HK1104055B - Photochromic materials - Google Patents

Description

Photochromic material

Background

Various non-limiting embodiments disclosed herein relate generally to materials having at least one soft segment bonded thereto, and more particularly to photochromic materials comprising at least one ring-opening cyclic monomer bonded thereto. Other non-limiting embodiments relate to photochromic compositions and optical elements, such as but not limited to ophthalmic lenses, comprising the disclosed photochromic materials.

Photochromic materials can be incorporated into polymeric materials to impart desired optical properties to the polymeric materials. For example, photochromic materials have been successfully incorporated into polymeric materials used to form ophthalmic lenses, as well as into polymeric coatings applied to such ophthalmic lenses. Typically, the polymeric material into which the photochromic material is incorporated is relatively soft and, therefore, susceptible to mechanical damage such as abrasion and scratching. Because it is generally undesirable for certain articles, such as ophthalmic lenses, to be susceptible to such damage, one or more "hard coatings" are often applied to the surfaces of the articles to, among other things, enhance their abrasion resistance. For example, hard coatings are often applied to the surfaces of ophthalmic lenses formed from "soft" polymeric materials to enhance their abrasion resistance.

However, it has been observed that under certain conditions, photochromic materials have a tendency to migrate from the soft polymeric material into which they are incorporated into these other hard coatings. Because the photochromic properties of a photochromic material (i.e., the rate of coloration (or activation) and fade of the photochromic material) are affected by the local environment surrounding the photochromic material, migration may deteriorate the photochromic properties. In general, for organic photochromic materials, the time required for coloration or discoloration to occur tends to increase as the hardness of the local environment surrounding the photochromic material increases. Thus, the photochromic performance of a photochromic material may deteriorate as the material migrates from a softer or more pliable environment to a harder or more rigid environment. Thus, migration may result in reduced applicability of the photochromic material, as well as the coating or article into which it is incorporated.

One method of reducing migration of photochromic materials in polymeric materials is to bond the photochromic materials to the polymeric materials. For example, photochromic materials containing shorter organic segments that can be polymerized into polymeric materials have been disclosed. Such photochromic materials have a reduced tendency to migrate in the polymeric material due to the physical constraints provided by the bonding of the photochromic material to the polymeric material. However, the use of such short organic segments to bond the photochromic material to the polymeric material may have the effect of slowing the rate of coloration and discoloration of the photochromic material as compared to similar photochromic materials that are not bonded to the polymeric material. Furthermore, for some photochromic materials, it is preferred to have the short organic segment located away from the "living" portion of the photochromic material, i.e., the portion of the photochromic material that undergoes a reversible transition from one state to another upon exposure to actinic radiation. That is, for some photochromic materials, the ability of the photochromic material to undergo a transformation may be hampered if the segment is too close to the reactive portion of the photochromic material. Therefore, the photochromic properties of the material may be impaired.

Other methods of improving the rate of fade of photochromic materials have focused on creating a relatively "soft" environment around the photochromic material, such that the photochromic properties of the material are less affected by the hardness of the polymeric material into which the photochromic material is incorporated, rather than reducing migration. For example, photochromic materials have been disclosed that are adducts of a photochromic moiety and at least one pendant oligomeric group. However, because such photochromic materials are generally not bonded to the polymeric material into which they are incorporated, phase separation may occur if the photochromic material is not compatible with the polymeric material. That is, the photochromic material may separate from the polymeric material, which may lead to undesirable properties such as fogging and blooming, which may limit the applicability of the material in many applications where transparency is important.

Accordingly, it would be advantageous to develop photochromic materials that can incorporate a variety of polymeric materials that have both a reduced tendency to migrate and a favorable rate of coloration and/or fade.

Summary of The Invention

Various non-limiting embodiments disclosed herein relate to photochromic materials. For example, one non-limiting embodiment provides a photochromic material comprising the reaction product of (a) at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates and (b) a photochromic initiator.

Another non-limiting embodiment provides a photochromic material represented by the general formula:

wherein (a) PC is a photochromic group; (b) n is an integer selected from 1 to 8; and (c) each occurrence of S' is independently selected from the group represented by the following general formula:

wherein (1) L is a linking group independently selected for each occurrence from the group consisting of-O-, -N-, and-S-, or L comprises a linear or branched organic bridging group comprising at least one linking group independently selected for each occurrence from the group consisting of-O-, -N-, and-S-; (2) 'a' is an integer independently selected at each occurrence from 1 to 500; (3) r¹Is independently selected at each occurrence from a ring-opened cyclic ester monomer and a ring-opened cyclic carbonate monomer; (4) r²An organic material independently selected for each occurrence from hydrogen and a residue comprising at least one reactive group; and (5) b is an integer independently selected at each occurrence from 1 to 20.

Another non-limiting embodiment provides a photochromic material represented by the general formula:

wherein (a) Y is selected from C and N; (b) a is selected from naphtho, benzo, phenanthro, fluorantheno, antheno, quino, thieno, furo, indolo, indolino, indeno, benzofuro, benzothieno, thieno, indenonaphtho, heterocyclic fused naphtho, and heterocyclic fused benzo; (c) n 'is an integer selected from 0 to 8, with the proviso that if n' is 0, at least one of B and B 'comprises the group S'; (d) s' is represented by the following general formula:

Wherein: (1) l is a linker independently selected at each occurrence from-O-, -N-, and-S-, or L comprises a linear or branched organic bridging group comprising at least one linker independently selected at each occurrence from-O-, -N-, and-S-; (2) a is an integer independently selected at each occurrence from 1 to 500; (3) r¹Is independently selected at each occurrence from a ring-opened cyclic ester monomer and a ring-opened cyclic carbonate monomer; (4) r²Independently at each occurrence, selected from hydrogen and organic materials comprising a residue of at least one reactive group, wherein the residue of at least one reactive group is selected from the group consisting of acrylates, alkyls, alkylphosphonates, alkyldialkoxysilyl groups, alkoxydialkylsilyl groups, allylcarbonates, amides, amines, anhydrides, aryl groups, aziridines, carboxylic acids, chloroformates, cycloaliphatic epoxides, isocyanates, isothiocyanates, epoxides, esters, halogens, hydroxyls, methacrylates, propenyl ethers, residues of ring-opening cyclic monomers, trialkoxysilyl groups, thiiranes, thiolsVinyl carbonates, vinyl ethers, vinyl benzyl ethers, and combinations thereof; (5) b is an integer independently selected at each occurrence from 1 to 20; and (e) B and B' are independently selected from: (1) a group S'; (2) mono-R ¹⁷-substituted phenyl, wherein R¹⁷Represented by one of the following general formulae: -G [ (OC)₂H₄)_q(OC₃H₆)_r(OC₄H₈)_s]J and- [ (OC)₂H₄)_q(OC₃H₆)_r(OC₄H₈)_s]J, wherein-G is selected from the group consisting of-C (O) -and-CH₂-, J is selected from C1-C12 alkoxy and polymerizable groups; q, r and s are each a number between 0 and 50, and the sum of q, r and s is from 2 to 50; (3) unsubstituted, mono-, di-or trisubstituted aryl; (4) 9-julolidine, an unsubstituted, mono-or di-substituted heteroaromatic group selected from the group consisting of pyridylfuryl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl and fluorenyl, each of the aryl and heteroaromatic substituents of (3) and (4) being independently selected from the group consisting of: (i) hydroxy, (ii) a group-C (O) R¹⁸Wherein R is¹⁸Is selected from-OR¹⁹、-N(R²⁰)R²¹Piperidino and morpholino wherein R¹⁹Selected from allyl, C1-C6 alkyl, phenyl, mono (C1-C6) alkyl substituted phenyl, mono (C1-C6) alkoxy substituted phenyl, phenyl (C1-C3) alkyl, mono (C1-C6) alkyl substituted phenyl (C1-C3) alkyl, mono (C1-C6) alkoxy substituted phenyl (C1-C3) alkyl, C1-C6 alkoxy (C2-C4) alkyl, and C1-C6 haloalkyl; r ²⁰And R²¹Each selected from the group consisting of C1-C6 alkyl, C5-C7 cycloalkyl, phenyl, monosubstituted phenyl, and disubstituted phenyl, the phenyl substituents being selected from the group consisting of C1-C6 alkyl and C1-C6 alkoxy, and the halo substituents being selected from the group consisting of chloro and fluoro; (iii) aryl, mono (C1-C12) alkoxyaryl, di (C1-C12) alkoxyaryl, mono (C1-C12) alkylaryl, di (C1-C12) alkylaryl, haloaryl, C3-C7 cycloalkylaryl, C3-C7 cycloalkyl, C3-C7 cycloalkoxy, C3-C7 cycloalkoxy (C1-C12) alkyl, C3-C7 cycloalkoxy(C1-C12) alkoxy, aryl (C1-C12) alkyl, aryl (C1-C12) alkoxy, aryloxy (C1-C12) alkyl, aryloxy (C1-C12) alkoxy, mono-or di-C1-C12) alkylaryl (C1-C12) alkyl, mono-or di-C1-C12) alkoxyaryl (C1-C12) alkyl, mono-or di-C1-C12) alkylaryl (C1-C12) alkoxy, mono-or di-C1-C12) alkoxyaryl (C1-C12) alkoxy, amino, mono (C1-C12) alkylamino, di (C1-C12) alkylamino, diarylamino, piperazinyl, N- (C1-C12) alkylpiperazinyl, N-arylpiperazinyl, aziridino, dihydropyrimidino, morpholino, and the like, Tetrahydroquinolinyl, tetrahydroisoquinolinyl, pyrrolidinyl, C1-C12 alkyl, C1-C12 haloalkyl, C1-C12 alkoxy, mono (C1-C12) alkoxy (C1-C12) alkyl, acryloyloxy, methacryloyloxy, and halogen; (5) an unsubstituted or mono-substituted group selected from pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl, and acridinyl, each of said substituents being independently selected from C1-C12 alkyl, C1-C12 alkoxy, phenyl, and halogen; (6) a mono-substituted phenyl group having a substituent at the para-position, wherein the substituent is selected from the group consisting of- (CH) ₂)_t-and-O- (CH)₂)_t-, where t is an integer selected from 1, 2, 3, 4, 5 and 6, the substituent being attached to an aryl group on another photochromic material; (7) a group represented by one of the following general formulae:

wherein K in each formula is independently selected from methylene and oxygen, and M in each formula is independently selected from oxygen and substituted nitrogen, with the proviso that when M is substituted nitrogen, K is methylene; the substituent of the substituted nitrogen is selected from hydrogen, C1-C12 alkyl and C1-C12 acyl; each R²²Independently at each occurrence in each formula selected from the group consisting of C1-C12 alkyl, C1-C12 alkoxy, hydroxy, and halogen; r in each formula²³And R²⁴Each independently selected from hydrogen and C1-A C12 alkyl group; u is an integer selected from 0, 1 and 2; (8) C1-C12 alkyl, C1-C12 haloalkyl, C1-C12 alkoxy (C1-C12) alkyl, C3-C7 cycloalkyl, mono (C1-C12) alkoxy (C3-C7) cycloalkyl, mono (C1-C12) alkyl (C3-C7) cycloalkyl, halo (C3-C7) cycloalkyl, and C4-C12 bicycloalkyl, with the proviso that B and B' are not both selected from (8); and (9) a group represented by the following general formula:

wherein R is²⁵Selected from hydrogen and C1-C12 alkyl, R²⁶Is an unsubstituted, mono-or di-substituted group selected from naphthyl, phenyl, furyl and thienyl, wherein the substituents are independently selected from the group consisting of C1-C12 alkyl, C1-C12 alkoxy and halogen; or (10) B and B' together form a fluoren-9-ylidene group, a mono-or disubstituted fluoren-9-ylidene group or a spirocyclic group selected from the group consisting of saturated C3-C12 spiro-monocyclic hydrocarbon rings, saturated C7-C12 spiro-bicyclic hydrocarbon rings, and saturated C7-C12 spiro-tricyclic hydrocarbon rings, with the proviso that said spirocyclic group is not norbornylidene or bicyclo [3.3.1 ]9-nonylidene, each of said fluoren-9-ylidene substituents being independently selected from C1-C12 alkyl, C1-C12 alkoxy, halogen, or group S'.

Another non-limiting embodiment provides a photochromic material represented by the general formula:

wherein:

(a)R³⁴and R³⁵Independently selected from: (1) a group S ', wherein S' is represented by the following general formula:

wherein: (A) l comprises at least one group selected from: C-C alkoxy, C-C alkylamino, C-C alkylthio, C-C β -oxypoly (ethoxy), C-C β -oxypoly (propoxy), C-C β 0-oxypoly (butoxy), C-C β 1-aminopoly (ethoxy), C-C β 2-aminopoly (propoxy), C-C β 3-aminopoly (butoxy), C-C β 4-thiopoly (ethoxy), C-C β 5-thiopoly (propoxy), C-C β 6-thiopoly (butoxy), arylC-C alkoxy, arylC-C alkylamino, arylC-C alkylthio, arylC-C β 7-oxypoly (ethoxy), arylC-C β 8-oxypoly (propoxy), Aryl C4-C40 beta 9-oxypoly (butoxy), aryl C2-C20 beta-aminopoly (ethoxy), aryl C3-C30 beta 0-aminopoly (propoxy), aryl C4-C40 beta 1-aminopoly (butoxy), aryl C2-C20 beta 2-thiopoly (ethoxy), aryl C20-C20 beta 3-thiopoly (propoxy), aryl C20-C20 beta 4-thiopoly (butoxy), heterocycle C20-C20 alkoxy, heterocycle C20-C20 alkylamino, heterocycle C20-C20 alkylthio, heterocycle C20-C20 beta 5-oxypoly (ethoxy), heterocycle C20-C20 beta 6-oxypoly (propoxy), heterocycle C20-C20 beta-oxypoly (butoxy), heterocycle C20-C20 beta-aminopoly (ethoxy), heterocycle C20-C20 beta-aminopoly (propoxy), Heterocycle C4-C40 β -aminopoly (butoxy), heterocycle C2-C20 β -thiopoly (ethoxy), heterocycle C3-C30 β -thiopoly (propoxy), and heterocycle C4-C40 β -thiopoly (butoxy); (B) 'a' is an integer independently selected at each occurrence from 1 to 500; (C) r ¹Independently at each occurrence, selected from the group consisting of a ring-opened cyclic ester monomer and a ring-opened cyclic carbonate monomer; (D) r²Independently at each occurrence, selected from hydrogen and organic materials comprising a residue of at least one reactive group, wherein the residue of at least one reactive group is selected from the group consisting of acrylates, alkyls, alkylphosphonates, alkyldialkoxysilyl groups, alkoxydialkylsilyl groups, allylcarbonates, amides, amines, anhydrides, aryl groups, aziridines, carboxylic acids, chloroformates, cycloaliphatic epoxides, isocyanates, isothiocyanates, epoxides, esters, halogens, hydroxyls, methacrylates, propenyl ethers, residues of ring-opening cyclic monomers, trialkoxysilyl groups, thiiranes, thiols, vinyl carbonates, vinyl ethers, vinylbenzyl ethersAnd combinations thereof; (E) b is an integer independently selected at each occurrence from 1 to 20; and (2) hydrogen, hydroxy, C1-C6 alkyl, C3-C7 cycloalkyl, allyl, phenyl, monosubstituted phenyl, benzyl, monosubstituted benzyl, chloro, fluoro, a group-C (O) R⁴⁰Wherein R is⁴⁰Is hydroxy, C1-C6 alkyl, C1-C6 alkoxy, phenyl, monosubstituted phenyl, amino, mono (C1-C6) alkylamino or di (C1-C6) alkylamino; or (3) R ³⁴And R³⁵Each being a group-OR⁴¹Wherein R is⁴¹Is C1-C6 alkyl, phenyl (C1-C3) alkyl, mono (C1-C6) alkyl-substituted phenyl (C1-C3) alkyl, mono (C1-C6) alkoxy-substituted phenyl (C1-C3) alkyl, C1-C6 alkoxy (C2-C4) alkyl, C3-C7 cycloalkyl, mono (C1-C4) alkyl-substituted C3-C7 cycloalkyl, C1-C6 chloroalkyl, C1-C6 fluoroalkyl, allyl, a group-CH (R1-C3) alkyl⁴²)R⁴³Wherein R is⁴²Is hydrogen or C1-C3 alkyl and R⁴³Is CN, CF₃Or COOR⁴⁴And R⁴⁴Is hydrogen or C1-C3 alkyl; or R⁴¹Is a group-C (O) R⁴⁵Wherein R is⁴⁵Is hydrogen, C1-C6 alkyl, C1-C6 alkoxy, unsubstituted, mono-or disubstituted arylphenyl or naphthyl, phenoxy, mono-or di (C1-C6) alkyl-substituted phenoxy, mono-or di (C1-C6) alkoxy-substituted phenoxy, amino, mono (C1-C6) alkylamino, di (C1-C6) alkylamino, phenylamino, mono-or di (C1-C6) alkyl-substituted phenylamino, or mono-or di (C1-C6) alkoxy-substituted phenylamino, each of said phenyl, benzyl and aryl substituents being C1-C6 alkyl or C1-C6 alkoxy; or (4) R³⁴And R³⁵Together form an oxy group, a spiro carbocyclic ring containing 3 to 6 carbon atoms, or a spiro heterocyclic group containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including a spiro carbon atom, said spiro carbocyclic and spiro heterocyclic groups being fused to 0, 1 or 2 benzene rings; (b) y and y' are integers independently selected from 0 to the total number of available positions; (c) each R ³⁶And R³⁷Independently selected from: a group S', hydrogen, C1-C6 alkyl, C3-C7 cycloalkyl, phenyl, monosubstituted phenyl, disubstituted phenyl and a group-OR⁵⁰and-OC (O) R⁵⁰Wherein R is⁵⁰Is C1-C6 alkyl, phenyl (C1-C3) -alkyl, mono (CC1-C6) alkyl substituted phenyl (C1-C3) alkyl, mono (C1-C6) alkoxy substituted phenyl (C1-C3) alkyl, C1-C6 alkoxy (C2-C4) alkyl, C3-C7 cycloalkyl or mono (C1-C4) alkyl substituted C3-C7 cycloalkyl, and the phenyl substituent is C1-C6 alkyl or C1-C6 alkoxy; (e) b and B' are as described above; with the proviso that the photochromic material comprises at least one group S'.

Other non-limiting embodiments relate to photochromic compositions and optical elements comprising the above photochromic materials and methods of making the same. One particular non-limiting embodiment provides a photochromic composition comprising: (a) a polymeric material; and (b) at least one photochromic material bonded to at least a portion of the polymeric material, the at least one photochromic material comprising: (1) a photochromic group, and (2) at least one segment comprising residues of a plurality of ring-opened cyclic monomers bonded to the photochromic group, the ring-opened cyclic monomers selected from the group consisting of cyclic esters, cyclic carbonates, cyclic ethers, cyclic siloxanes, and combinations thereof, wherein the at least one segment has a number average molecular weight of at least 1000 g/mol; and wherein the photochromic material, when bonded to the polymeric material, has a T1/2 value that is not greater than the T1/2 value of a corresponding photochromic material in the absence of a segment comprising residues of a plurality of ring-opened cyclic monomers.

Yet another non-limiting embodiment provides a method of inhibiting migration of a photochromic material in a polymeric material, the method comprising bonding the photochromic material to at least a portion of the polymeric material, wherein the photochromic material comprises: (1) a photochromic group, and (2) at least one segment comprising residues of a plurality of ring-opened cyclic monomers bonded to the photochromic group, the ring-opened cyclic monomers selected from the group consisting of cyclic esters, cyclic carbonates, cyclic ethers, cyclic siloxanes, and combinations thereof, wherein the at least one segment has a number average molecular weight of at least 1000 g/mol.

Another non-limiting embodiment provides a method of making a photochromic material, the method comprising: initiating ring opening of at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters, cyclic carbonates, cyclic ethers, and cyclic siloxanes with a photochromic initiator comprising at least one functional group suitable for initiating ring opening of the at least one ring-opening cyclic monomer, the at least one functional group selected from the group consisting of alcohols, amines, carboxylic acids, silanols, thiols, and combinations, salts, and complexes thereof.

Brief description of several views of the drawings

The various non-limiting embodiments disclosed herein will be better understood when read in conjunction with the appended drawings: wherein:

FIGS. 1 and 4-6 are schematic illustrations of various manufacturing routes for photochromic materials according to various non-limiting embodiments disclosed herein;

FIGS. 2 and 3 are schematic illustrations of various preparative routes for photochromic initiators that may be used in conjunction with the various non-limiting embodiments disclosed herein;

figures 7(a) -7(c) depict photochromic materials according to various non-limiting embodiments disclosed herein.

Detailed Description

The articles "a," "an," and "the" when used in this specification and the appended claims include plural referents unless expressly and unequivocally limited to one referent.

Moreover, for the purposes of this specification, unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth, and other properties or parameters used in the specification are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated otherwise, it is understood that the numerical parameters set forth in the following specification and attached claims are approximations. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, the numerical parameters should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

In addition, notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the examples section are reported as precisely as possible. It should be understood, however, that these numerical values inherently contain certain errors resulting from the measurement equipment and/or measurement techniques.

As discussed earlier, photochromic materials are often incorporated into polymeric materials to impart desired optical properties to the polymeric materials or articles made therefrom. Additionally, as discussed above, the photochromic performance (i.e., the rate of coloration and fade of the photochromic material) may be affected by the environment surrounding the photochromic material. Thus, when an organic photochromic material migrates from a relatively "soft" or "pliable" environment to a relatively "hard" or "rigid" environment, the photochromic properties of the material may be compromised. While bonding photochromic materials to polymeric materials can help reduce migration, previous attempts to do so have generally resulted in photochromic materials having lower photochromic performance than non-migrating, non-bonded photochromic materials.

Although not limited thereto, rigid or hard polymers tend to have a glass transition temperature higher than room temperature (e.g., 23 ℃); whereas polymers with glass transition temperatures below room temperature tend to be soft and flexible. It will be appreciated by those skilled in the art that by selecting suitable rigid and/or flexible polymer segments, polymers having a desired hardness or softness can be prepared. Rigid polymer segments are segments that tend to form a polymeric material that is hard and undergoes little plastic deformation prior to fracture. A flexible polymer segment is a segment that tends to form a polymeric material that is flexible and capable of plastic deformation without breaking. For example, methods of preparing urethane materials by selecting components (e.g., isocyanates and polyols) to form suitable segment types are known to those skilled in the art. See, for example, U.S. Pat. No. 6,187,444 at column 3, line 49 to column 4, line 46 for a discussion of hard and soft segments, the disclosure of which is expressly incorporated herein by reference.

As discussed herein below, the inventors have observed that when a photochromic material according to various non-limiting embodiments disclosed herein is bonded to a polymeric material, the tendency of the photochromic material to migrate may be reduced as compared to a similar conventional photochromic material that is not bonded to the polymeric material. In addition, it has been noted that even when bonded to the polymeric material, the photochromic performance of the photochromic materials according to the various non-limiting embodiments disclosed herein may be comparable to or better than the photochromic performance of similar conventional photochromic materials that are not bonded to the polymeric material.

Photochromic materials according to various non-limiting embodiments of the present invention will now be discussed. The term "photochromic" as used herein means having an absorption spectrum for at least visible radiation that changes in response to at least actinic radiation. Further, the term "photochromic material" as used herein refers to any substance suitable to exhibit photochromic properties, i.e. suitable to have an absorption spectrum for at least visible radiation, which changes at least in response to actinic radiation. Thus, the term "photochromic material" as used herein includes organic photochromic materials, inorganic photochromic materials, and combinations thereof. The term "organic photochromic material" as used herein refers to organic materials such as, but not limited to, photochromic groups, as well as polymers, prepolymers, monomers, and other compounds comprising at least one photochromic group. The term "photochromic group" as used herein refers to an organic photochromic entity comprising at least one photochromic moiety, and which may comprise other organic groups or compounds (e.g., functional groups, and/or aliphatic, alicyclic, aromatic and heterocyclic groups and compounds, and the like) attached or fused thereto. The term "photochromic moiety" as used herein refers to that portion of a photochromic group that can undergo a reversible transition from one state to another upon exposure to actinic radiation (i.e., the "active portion" of the photochromic material discussed earlier). The term "linked" as used herein means covalently bonded. In addition, the term "fused" as used herein means covalently bonded at least at two positions.

In addition, as used herein, the term "prepolymer" or "prepolymer material" refers to partially polymerized materials, including but not limited to, oligomeric and partially polymerized materials. The terms "polymer" and "polymeric material" as used herein refer to homopolymers and copolymers (e.g., block, random, and alternating copolymers), as well as blends and other combinations thereof.

Non-limiting examples of photochromic groups that may be used in conjunction with the various non-limiting embodiments disclosed herein include photochromic pyrans, photochromic oxazines, and photochromic fulgides. Non-limiting examples of photochromic pyrans that may be used herein include benzopyrans; naphthopyrans, e.g. naphtho [1, 2-b]Pyran, naphtho [2, 1-b ]]A pyran; indenonaphthopyrans, such as those disclosed in U.S. Pat. No. 5,645,767 at column 2, line 16 to column 12, line 57; heterocyclic fused naphthopyrans, e.g., U.S. Pat. No. 5,723,072 column 2, line 27 to column 15, line 55; U.S. patent No. 5,698,141, column 2, line 11 to column 19, line 45; those disclosed in U.S. patent No. 6,153,126, column 2, line 26 through column 8, line 60, and U.S. patent No. 6,022,497, column 2, line 21 through column 11, line 46, the disclosures of which are expressly incorporated herein by reference; spiro-9-fluoreno [1, 2-b ] ]A pyran; phenanthropyran; a quinolopyran; fluoranthenopyrans (fluoroanthrapyrans); and spiropyrans, such as spiro (benzindoline) naphthopyrans, spiro (indoline) benzopyrans, spiro (indoline) naphthopyrans and spiro (indoline) pyrans. More specific non-limiting examples of naphthopyrans are described in U.S. Pat. No. 5,658,501, column 1, line 64 to column 13, line 17, the disclosure of which is specifically incorporated herein by reference. Spiro (indoline) pyrans are also in textbooksTechniques in ChemistryVolume III, "Photochromym", Chapter3, Glenn H.Brown, Editor, John Wiley and Sons, Inc., New York, 1971, the disclosure of which is also expressly incorporated herein by reference.

Non-limiting examples of photochromic oxazines that may be used in conjunction with the various non-limiting embodiments disclosed herein include benzoxazines; naphthoxazines; and spiro oxazines such as spiro (indoline) naphthooxazine, spiro (indoline) pyridobenzoxazine, spiro (indoline) naphthooxazine, spiro (indoline) benzoxazine, spiro (indoline) fluoranthenooxazine and spiro (indoline) quinoxazine.

Non-limiting examples of thermally reversible photochromic fulgides or fulgimides (fulgimides) that may be used in conjunction with the various non-limiting embodiments disclosed herein include those fulgides and fulgimides disclosed in U.S. Pat. No. 4,685,783, column 1, line 57 to column 5, line 27, the disclosure of which is specifically incorporated herein by reference, and mixtures of any of the above photochromic materials.

Various non-limiting embodiments provided herein relate to photochromic materials comprising the reaction product of: (a) at least one ring-opening cyclic monomer, and (b) a photochromic initiator. The term "photochromic initiator" as used herein refers to a photochromic material comprising at least one functional group suitable for initiating the ring opening of at least one cyclic monomer. As discussed earlier, the term "photochromic material" as used herein refers to any substance suitable for exhibiting photochromic properties. Thus, the photochromic initiator according to the various non-limiting embodiments disclosed herein can be an organic photochromic material, an inorganic photochromic material, or a combination thereof, comprising at least one functional group suitable for initiating a ring-opening reaction. Suitable non-limiting organic photochromic materials include photochromic groups, as well as polymers, prepolymers, monomers, and other compounds comprising at least one photochromic group. Non-limiting examples of photochromic groups that may be used in conjunction with these and other non-limiting embodiments disclosed herein are set forth in detail above.

The term "ring-opening cyclic monomer" as used herein refers to a monomer having a cyclic structure capable of undergoing a ring-opening reaction or ring-opening polymerization. The terms "ring opening" and "ring opening reaction" as used herein refer to the conversion of a cyclic monomer to its acyclic form, typically after reaction with an initiator. In addition, the term "ring-opening polymerization" as used herein refers to the formation of a chain having a plurality of ring-opening cyclic monomers. The term "ring-opened cyclic monomer" as used herein refers to the acyclic form of the ring-opened cyclic monomer. The term "residue of a ring-opened cyclic monomer" as used herein refers to a residue remaining after the ring-opened cyclic monomer undergoes a ring-opening reaction. The term "plurality", as used herein, means at least two.

Examples of ring-opening cyclic monomers that may be used in conjunction with the various non-limiting embodiments disclosed herein include, without limitation, cyclic esters, cyclic carbonates, cyclic ethers, and cyclic siloxanes.

Non-limiting examples of suitable cyclic esters include those represented by the following general formula:

wherein c and d are integers from 1 to 8; each carbon unit (i.e. each (C)_cAnd (C)_dUnit) R ³、R⁴、R⁵And R⁶Independently selected from-H, -CH₃C2-C16 alkyl, C (CH)₃)₂And HO-CH₂-; e is 0 or 1; d is selected from-O-or-O-C (O) -. Alternatively, c is 1; d is-C (R)³′)(R⁴′)-；R³' and R⁴' may be with R³And R⁴Together form a fused aryl, fused heterocyclic aryl, or fused cyclic aliphatic group, as shown below.

Specific non-limiting examples of suitable cyclic esters include: epsilon-caprolactone; tert-butyl caprolactone; ζ -heptalactone; delta-valerolactone; monoalkyl delta-valerolactones such as, but not limited to, monomethyl, monoethyl, and monohexyl-delta-valerolactone; nonanyl, dialkyl and trialkyl-epsilon-caprolactones, such as, but not limited to, monomethyl, monoethyl, monohexyl, dimethyl, di-n-propyl, di-n-hexyl, trimethyl, triethyl and tri-n-epsilon-caprolactones, 5-nonyl-oxepan-2-one, 4, 4, 6-or 4, 6, 6-trimethyl-oxepan-2-one, 5-hydroxymethyl-oxepan-2-one; beta-lactones such as, but not limited to, beta-propiolactone, beta-butyrolactone; gamma-lactones such as, but not limited to, gamma-butyrolactone and pivalolactone; dilactones such as, but not limited to, lactide, dilactide, glycolides (e.g., tetramethyl glycolide); and ketodioxanones such as, but not limited to, 1, 4-dioxan-2-one and 1, 5-dioxepan-2-one.

Non-limiting examples of suitable cyclic carbonates include those represented by the general formula:

wherein f and g are integers from 1 to 3; each carbon unit (i.e., each (C)_fAnd (C)_gUnit) R⁷、R⁸、R⁹And R¹⁰Each independently selected from-H, -CH₃C2-C16 alkyl, C (CH)₃) ₂、HO-CH₂-, or-OC₆H₅(ii) a h is 0 or 1; e is-O-. Specific examples of suitable cyclic carbonates include, but are not limited to, ethylene carbonate, 3-ethyl-3-hydroxymethyltrimethylene carbonate, propylene carbonate, trimethylene carbonate, trimethylolpropane monocarbonate, 4, 6-dimethyl-1, 3-trimethylene carbonate, 2-dimethyltrimethylene carbonate, and 1, 2-dioxepan-2-one.

Non-limiting examples of suitable cyclic ethers include those represented by the general formula:

wherein 'i' is an integer of 2 to 5, each R¹¹May be the same or different and may be selected from hydrogen; halogens such as, but not limited to, fluorine, chlorine, bromine, and iodine; C1-C10 alkyl such as, but not limited to, linear or branched methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; phenyl, which may be substituted or unsubstituted; halogenated C1-C10 alkyls such as, but not limited to, chloromethyl, bromomethyl, iodomethyl, dichloromethyl, 2-chloromethyl and 3-chloromethyl; and C1-C6 hydroxyalkyl, e.g. hydroxymethyl (i.e. -CH) ₂OH). Specific non-limiting examples of cyclic ethers include, for example, ethylene oxide, 1, 2-propylene oxide, epichlorohydrin, epibromohydrin, 1, 2-butylene oxide, 2, 3-butylene oxide, isobutylene oxide, oxetane, 3-methyloxetane, 3-dimethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, and tetrahydrofuran.

Non-limiting examples of suitable cyclic siloxanes include those represented by the general formula:

wherein R of each siloxane unit¹²And R¹³Identical or different and are each independently selected from C1-C8 linear or branched alkyl, aryl (C1-C6) alkyl or (C1-C6) alkylaryl, and j is the number of siloxane units and is selected from 3 to 6. For example, although not limited herein, according to one non-limiting embodiment, R¹²And R¹³May each be methyl, and j may be 3 or 4. These cyclic siloxanesNon-limiting examples of alkanes include, but are not limited to, hexamethylcyclotrisiloxane (i.e., j ═ 3) and octamethylcyclotetrasiloxane (i.e., j ═ 4).

Although not limited thereto, according to one non-limiting embodiment disclosed herein, the photochromic material comprises the reaction product of: (a) at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates, and (b) a photochromic initiator. For example, although not limited herein, according to this non-limiting embodiment, the at least one cyclic monomer may be selected from epsilon-caprolactone and delta-valerolactone.

As mentioned above, ring opening of ring-opened cyclic monomers typically involves an initiator. It will be appreciated by those skilled in the art that the choice of initiator will depend in part on the cyclic monomer involved. For example, suitable initiators for ring opening of the cyclic ester may be selected from, but are not limited to, alcohols, amines, carboxylic acids, thiols, and combinations, salts, and complexes thereof. In addition, once the ring-opened cyclic monomer has undergone a ring-opening reaction with a suitable initiator, the ring-opened monomer can itself be used to initiate the ring-opening of another ring-opened cyclic monomer, which in turn can be used to initiate the ring-opening of yet another ring-opened cyclic monomer, and so on, thereby forming a chain having two (or more) ring-opened monomers. In other words, ring-opening polymerization of a plurality of ring-opening cyclic monomers can occur. Ring-opening polymerization may result in the formation of homopolymers or copolymers depending on the ring-opening cyclic monomer used. For example, a homopolymer may be formed by ring-opening polymerization of a plurality of ring-opening cyclic monomers of the same kind. Alternatively, the copolymer may be formed as follows: ring-opening polymerization of a plurality of ring-opening cyclic monomers, at least one of which is different from the others.

For example, although not limited thereto, as schematically depicted in fig. 1, a ring-opened cyclic monomer (generally designated 10 in fig. 1) may be ring-opened by reacting the ring-opened cyclic monomer with a photochromic initiator (generally designated 12) to form a photochromic material (generally designated 14) according to various non-limiting embodiments disclosed herein. As shown in fig. 1, the ring-opening cyclic monomer is a cyclic ester as described above where e is 0. In addition, as shown in FIG. 1, the photochromic initiator 12 includes at least one functional group suitable for initiating a ring-opening reaction (i.e., a hydroxyl group (-OH) as shown in FIG. 1). Although not required, as further described with respect to fig. 1, the photochromic material 14 can be a photochromic initiator of one or more additional ring-opening cyclic monomers (generally designated 16), which can be the same as or different from the cyclic monomer 10, to form a photochromic material (generally designated 18) according to various non-limiting embodiments disclosed herein. Although not limited thereto, for example, in fig. 1, k can be an integer from 0 to 499 and the photochromic material 18 can comprise residues from 1 to 500 ring-opened cyclic monomers, each of which can be the same or different from the remaining ring-opened cyclic monomers.

As discussed above, photochromic materials according to various non-limiting embodiments disclosed herein can comprise the reaction product of a plurality of ring-opened cyclic monomers and at least one photochromic initiator. Further, as discussed above, the ring-opening cyclic monomers may be the same or different. For example, although not limited herein, according to one non-limiting embodiment, each of the plurality of ring-opened cyclic monomers can be independently selected from epsilon-caprolactone and delta-valerolactone. In addition, according to this non-limiting embodiment, one of the ring-opened cyclic monomers may be epsilon-caprolactone, and the other may be delta-valerolactone. Thus, according to this non-limiting embodiment, the photochromic material can comprise a polymer segment that is a homopolymer of epsilon-caprolactone or delta-valerolactone, or a copolymer (e.g., a random, alternating, or block copolymer) of epsilon-caprolactone and delta-valerolactone.

As discussed earlier, photochromic initiators according to various non-limiting embodiments disclosed herein comprise at least one functional group adapted to initiate ring opening of at least one cyclic monomer and may be adapted to initiate ring opening polymerization of a plurality of ring-opened cyclic monomers. Examples of functional groups suitable for use in conjunction with the various non-limiting embodiments disclosed herein include, without limitation, alcohols, amines, carboxylic acids, silanols, thiols, and combinations, salts, and complexes thereof. According to one non-limiting embodiment, the photochromic initiator comprises at least one functional group selected from primary alcohol groups and secondary alcohol groups, and salts and complexes thereof. However, as discussed above, the choice of functional group will depend in part on the ring-opening cyclic monomer.

Specific non-limiting examples of photochromic initiators that may be used in conjunction with the various non-limiting embodiments disclosed herein are given in table 1 below. It is self-evident that table 1 is not an exhaustive list of all suitable photochromic initiators and is given for illustrative purposes only. Those skilled in the art will recognize a variety of other photochromic initiators and modifications of those photochromic initiators that are within the spirit and scope of the present disclosure and that may be used in conjunction with the various non-limiting embodiments disclosed herein.

TABLE 1

These and other non-limiting methods of forming photochromic initiators will be readily understood by those skilled in the art from a reading of the present disclosure and examples. For example, although not limited thereto, one formation process that can be used to prepare photochromic initiators such as 2, 2-bis (4-methoxyphenyl) -5-methoxycarbonyl-6-hydroxy- [2H ] -naphtho [1, 2-b ] pyran 1.18 and 1.84 (shown in Table 1 above) can be found in column 13, lines 15-52, example 1 of U.S. Pat. No. 5,458,814, which is specifically incorporated herein by reference.

General reaction routes to form photochromic pyran initiators and photochromic oxazine initiators that may be used in conjunction with the various non-limiting embodiments disclosed herein are given in fig. 2 and 3, respectively. It is understood that the general reaction schemes depicted in fig. 2 and 3 are not intended to be limiting herein and are for illustrative purposes only. Those skilled in the art will recognize that in addition to the general reaction schemes shown in fig. 2 and 3 and their modifications, other methods may be used to form suitable photochromic initiators that may be used in accordance with the various non-limiting embodiments disclosed herein.

FIG. 2 schematically depicts a general reaction scheme for preparing a photochromic pyran that comprises at least one functional group adapted to initiate ring opening of at least one ring-opening cyclic monomer. In FIG. 2, a 4-fluorobenzophenone, generally indicated as 220 in FIG. 2, can be reacted under nitrogen in an anhydrous solvent, dimethyl sulfoxide (DMSO), with an organic group containing at least one substituted ketone adapted to initiate at least one cyclic monomer ("R" is shown generally as 222 to form a substituted ketone¹⁴") functional group. For example, R, although not limited thereto¹⁴May be a linear or branched group comprising a functional group selected from alcohols, amines, carboxylic acids, silanols, thiols or combinations, salts and complexes thereof. It will be understood by those skilled in the art that 4-fluorobenzophenones may be purchased or prepared by the Friedel-Crafts method known in the artAnd (4) preparing. For example, see publicationsFriedel-Crafts and Related ReactionsOlah, Interscience Publishers, 1964, volume 3, chapter XXXI (Aromatic Ketone Synthesis) and Ishihara, Yugi et al, "geographic friend-Crafts activation of1, 2, 3, 4-Tetrahydroquinoline and Related Nitrogen heterocycles: effect on NH Protective Groups and RingSize ", J.chem.Soc, Perkin Trans.1, pages 3401 to 3406, 1992, which are specifically incorporated herein by reference. Thereafter, the substituted ketone 222 can be reacted with sodium acetylene in a suitable solvent, such as, but not limited to, anhydrous Tetrahydrofuran (THF) to form the corresponding propargyl alcohol (generally designated 224). Propargyl alcohol 224 can then be coupled with the hydroxy-substituted A' group (generally indicated as 226) to form a photochromic pyran initiator (generally indicated as 228). Suitable non-limiting examples of A' groups include naphtho, benzo, phenanthro, fluorantheno, antheno, quino, indenonaphtho, heterocyclic fused naphtho, and heterocyclic fused benzo. Further, as depicted in FIG. 2, optionally, the A' group may be substituted with one or more R ¹⁴Groups (e.g., m can be 0 to the total number of available positions) and each R is substituted¹⁴May be combined with the remaining R¹⁴The groups may be the same or different.

Fig. 3 schematically depicts a general reaction scheme for preparing photochromic oxazines comprising at least one functional group adapted to initiate ring opening of at least one ring-opened cyclic monomer. In FIG. 3, a general nitrosation and coupling process is shown wherein a hydroxylated A "group (generally designated 330) is reacted with sodium nitrite in the presence of an acid, such as but not limited to acetic acid, to produce a nitroso-substituted A" (generally designated 332). Suitable non-limiting examples of A' groups include naphtho, benzo, phenanthro, fluorantheno, antheno, quino, indeno-fused naphtho, heterocyclic-fused naphtho, and heterocyclic-fused benzo. Optionally, the A' group may be substituted with one or more organic groups containing a functional group adapted to initiate a ring-opening reaction ("R¹⁵"). The nitroso-substituted a "group 332 is then coupled with a Fischer base (generally indicated at 334),the latter may also contain one or more radicals R¹⁵. The coupling is carried out in a solvent such as, but not limited to, absolute ethanol and heated under reflux conditions to produce a photochromic oxazine initiator (generally designated 336). Additionally, in FIG. 3, p and p' can be 0 to the total number of available positions on the molecule to which the group is attached, provided that at least one functional group adapted to initiate ring opening is present, and each R ¹⁵The radicals may be substituted by radicals of the rest of R¹⁵The groups may be the same or different.

As discussed earlier, once a ring-opened cyclic monomer is opened with a suitable initiator, the ring-opened monomer can be used to initiate the opening of another ring-opened cyclic monomer, and so on. Thus, once the photochromic initiator initiates the ring opening of at least one ring-opening cyclic monomer, the resulting photochromic material can be used as a photochromic initiator for yet another ring-opening cyclic monomer. In this way, a photochromic material can be formed that comprises at least one polymer chain comprising a plurality of ring-opened cyclic monomers, which may be the same or different. Thus, for example, any of the photochromic initiators listed in table 1 above may be reacted with one or more cyclic monomers to form other photochromic initiators suitable for use in connection with the various non-limiting embodiments disclosed herein.

In addition, photochromic materials according to various non-limiting embodiments disclosed herein can be further reacted with an organic material comprising at least one reactive group such that the resulting photochromic material further comprises an organic material comprising a residue of at least one reactive group. The term "reactive group" as used herein refers to any group capable of reacting with a hydroxyl group, with or without a catalyst. In addition, the term "residue of a reactive group" as used herein refers to a group that remains after the reactive group has been reacted.

Non-limiting examples of suitable organic materials comprising at least one reactive group that may be used in conjunction with the various non-limiting embodiments disclosed herein include those set forth in table 2 below. Non-limiting examples of reactions that an organic material comprising at least one reactive group may take part in include addition reactions, elimination reactions, condensation reactions, substitution reactions, and Polymerization reactions (e.g., free radical Polymerization, anionic Polymerization, cationic Polymerization, ring opening Polymerization, polycondensation, addition Polymerization, and those Polymerization methods described in Ullmann's Encyclopedia of Industrial Chemistry, Vol. 21A, pp. 305 to 428, which are specifically incorporated herein by reference). Other specific non-limiting reactions are given in table 2 below. Non-limiting examples of the residue of the at least one reactive group obtained after the reaction of the at least one reactive group is also shown in table 2 below. It is self-evident that table 2 is not an exhaustive list of all suitable organic materials, possible reactions and/or residues comprising at least one reactive group and that table 2 is given for illustrative purposes only. Those skilled in the art will recognize a variety of other organic materials, possible reactions, and residues comprising at least one reactive group that are within the spirit and scope of the present disclosure and that may be used in conjunction with the various non-limiting embodiments disclosed herein.

As discussed above, after reaction with an organic material comprising at least one reactive group, photochromic materials according to various non-limiting embodiments disclosed herein will further comprise an organic material comprising a residue of at least one reactive group. Non-limiting examples of residues of at least one reactive group that photochromic materials according to various non-limiting embodiments disclosed herein may comprise include acrylates, alkyls, alkylphosphonates, alkyldialkoxysilyl groups, alkoxydialkylsilyl groups, allylcarbonate, amides, amines, anhydrides, aryls, aziridines, carboxylic acids, chloroformates, cycloaliphatic epoxides, esters, halogens, hydroxyls, isocyanates, isothiocyanates, methacrylates, propenyl ethers, residues of ring-opening cyclic monomers, trialkoxysilyl groups, thiiranes, thiols, vinyl carbonates, vinyl ethers, vinyl benzyl ethers, and combinations thereof. It will be understood by those skilled in the art that depending on the intended use of the photochromic material, the organic material comprising at least one reactive group may be selected such that the organic material comprising the residue of the reactive group may be further reacted with other materials or groups, such as, but not limited to, polymers, prepolymers, and monomeric materials. Alternatively, the organic material comprising at least one reactive group may be selected such that the organic material comprising the residue of the reactive group is substantially non-reactive in subsequent use.

TABLE 2

Organic materials comprising reactive groups	Type of reaction	Residues of reactive groups
			Methyl-3, 4-epoxycyclohexanecarboxylate	Transesterification	Cycloaliphatic epoxide
Epichlorohydrin	Alkylation	Glycidyl ethers
			Phosgene	Phosgenation	Chloroformate
Vinyl chloroformate	Acylation	Ethylene carbonate
			Allyl chloroformate	Acylation	Allyl carbonate
Chloroethyl vinyl ether	Alkylation	Vinyl ethers
			Allyl bromide	Alkylation	Allyl ethers
4-vinylbenzyl chloride	Alkylation	Styryl (styrene)
			Acryloyl chloride	Acylation	Acrylic esters
Methacrylic anhydride	Acylation	Methacrylic acid esters
			2-isocyanatoethyl methacrylate	Carbamylation of	Methacrylic acid esters
Isocyanatopropyltrimethoxysilane	Carbamylation of	Trimethoxysilyl group
			((chloromethyl) phenethyl) methyldimethoxysilane	Alkylation	Dimethoxysilyl group
Isophorone diisocyanate	Carbamylation of	Isocyanates
			3-isopropenyl-alpha, alpha-dimethylbenzyl isocyanate	Carbamylation of	Isopropenyl phenyl
2-bromoethyl isocyanate	Carbamylation of	Halogen element
			Phenyl isocyanate	Carbamylation of	Phenyl (aryl)
N-butyl bromide	Alkylation	Butyl (alkyl)

For example, although not limited thereto, as schematically depicted in fig. 4, a photochromic material according to various non-limiting embodiments disclosed herein (generally designated 440) can be further reacted with an organic material comprising reactive groups (generally designated 442) to form a photochromic material comprising an organic material (generally designated 444) comprising a residue of at least one reactive group. Although not limited thereto, as shown in fig. 4, the organic material 442 comprising at least one reactive group can be selected such that the resulting residue of the at least one reactive group is substantially non-reactive. For example, although not limited herein, the organic material 442 may be a polymer or prepolymer material that includes at least one reactive group, and the photochromic material may be bonded to the polymer material as follows: reacting the reactive groups of the polymeric or pre-polymeric material with the hydroxyl groups of the photochromic material. In addition, although not limited thereto, in fig. 4, k' may be 1 to 500.

Alternatively, as discussed above, according to other non-limiting embodiments, the organic material comprising at least one reactive group can be selected such that the resulting photochromic material comprises an organic material comprising a residue of at least one reactive group that can be further reacted with one or more additional materials or groups. For example, although not limited thereto, as schematically depicted in fig. 5, a photochromic material (generally designated 550) according to various non-limiting embodiments disclosed herein can be further reacted with an organic material (generally designated 552) comprising two reactive groups to form a photochromic material (generally designated 554) comprising an organic material comprising a residue of at least one reactive group and an unreacted reactive group. As shown in fig. 5, the organic material 552 is a diisocyanate, and the resulting photochromic material 554 comprises an organic material comprising a residue of isocyanate groups and unreacted isocyanate groups. In addition, although not shown in fig. 5, the unreacted isocyanate groups may further react with one or more additional materials or groups, such as to form a polymer segment or to bond or attach the photochromic material to another material, such as a polymeric material or surface.

It will be understood by those skilled in the art that other methods of reacting the photochromic materials disclosed herein with organic materials comprising reactive groups and/or bonding reactive groups (or other functionalities) to photochromic materials according to various non-limiting embodiments disclosed herein may be used, and that the above examples are provided for illustrative purposes only and are not intended to be limiting herein. For example, although not limited thereto, as shown in fig. 6, a photochromic material (generally designated 660) according to various non-limiting embodiments disclosed herein can be reacted in a halogenation reaction with an organic material comprising at least one reactive group (e.g., thionyl chloride (SOCl)) in a halogenation reaction₂) As shown in fig. 6) to form a photochromic material comprising an organic material (generally designated 664) comprising a residue of a ring-opening cyclic monomer in which the terminal hydroxyl group is substituted with a reactive group (e.g., chlorine, as shown in fig. 6).

Accordingly, one specific non-limiting embodiment disclosed herein provides a photochromic composition comprising the reaction product of (a) a photochromic material and (b) an organic material comprising at least one reactive group, the photochromic material being the reaction product of:

(1) At least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates; and (2) a photochromic initiator. As discussed above, according to various non-limiting embodiments disclosed herein, the organic material comprising at least one reactive group can be selected, for example, to provide a photochromic material having a desired functionality or to link or bond the photochromic material to another group or material. For example, according to this non-limiting embodiment, the organic material comprising at least one reactive group may be selected, such that after reaction the photochromic composition comprises an organic material comprising a residue of a reactive group bonded to the photochromic material, wherein the residue is selected from the group consisting of acrylate, alkyl, alkylphosphonate, alkyldialkoxysilyl, alkoxydialkylsilyl, allylcarbonate, amide, amine, anhydride, aryl, aziridine, carboxylic acid, chloroformate, cycloaliphatic epoxide, ester, halogen, hydroxyl, isocyanate, isothiocyanate, methacrylate, propenyl ether, residue of a ring-opening cyclic monomer, trialkoxysilyl, thiirane, thiol, vinyl carbonate, vinyl ether, vinylbenzyl ether, and combinations thereof.

Other non-limiting embodiments disclosed herein provide photochromic materials represented by the general formula:

general formula 1

Wherein PC is a photochromic group; n is an integer from 1 to 8; and each S' is independently at each occurrence selected from the group represented by:

general formula 2

Wherein (1) L is a linking group independently selected for each occurrence from the group consisting of-O-, -N-, and-S-, or L comprises a linear or branched organic bridging group comprising at least one linking group independently selected for each occurrence from the group consisting of-O-, -N-, and-S-; (2) radical R¹Is a cyclic monomer which has been opened, and (3) the radical R²Each occurrence is independently selected from hydrogen and organic materials comprising a residue of at least one reactive group. In addition, in formula 2, 'a' is an integer independently selected from 1 to 500 at each occurrence, and b is an integer independently selected from 1 to 20 at each occurrence.

As discussed earlier, the term "photochromic group" as used herein refers to an organic entity comprising at least one photochromic moiety, and which may comprise other organic groups or compounds (e.g., functional groups, and/or aliphatic, alicyclic, aromatic and heterocyclic groups and compounds, etc.) attached or fused thereto. Non-limiting examples of suitable photochromic groups include those described in detail above. For example and without limitation, the photochromic group PC according to various non-limiting embodiments disclosed herein may be selected from the photochromic pyrans, photochromic oxazines, and photochromic fulgides of those discussed earlier. According to a specific non-limiting embodiment, the PC is a photochromic pyran selected from the group consisting of benzopyrans, naphthopyrans, phenanthropyrans, quinopyrans, fluoranthenopyrans, and spiropyrans. According to another non-limiting embodiment, PC is a naphthopyran selected from the group consisting of naphtho [1, 2-b ] pyran, naphtho [2, 1-b ] pyran, indenonaphthopyran, and heterocyclic fused naphthopyran. According to yet another non-limiting embodiment, PC is an indenonaphthopyran.

As discussed earlier, prior attempts to limit migration of photochromic materials in polymeric materials have generally involved bonding the photochromic materials to the polymeric materials with short organic segments. However, such bonding of the photochromic material may cause deterioration of photochromic properties of the material. In addition, depending on the photochromic material involved, the placement of the organic segment on the photochromic material may be limited to a location remote from the active portion of the photochromic material.

In contrast, the present inventors have observed that photochromic materials according to various non-limiting embodiments disclosed herein can have good photochromic properties, even when the group S' is disposed proximate to the active portion of the photochromic material. In addition, according to various non-limiting embodiments disclosed herein, each PC may have more than one group S' (i.e., n may be 1 to 8).

For example, according to one specific non-limiting embodiment, n is 4 and the photochromic material may have four S' groups, for example, as shown below:

general formula 3

For example, according to another specific non-limiting embodiment, n is 2 and the photochromic material may have two S' groups, for example, as shown below:

S′-PC-S′

General formula 4

Although not limited thereto, one specific non-limiting example of a photochromic material having two S' groups according to various non-limiting embodiments disclosed herein is given in example 5 below.

According to yet another specific non-limiting embodiment, n is 1 and the photochromic material may have 1S' group, for example, as shown below:

PC-S′

general formula 5

While not limiting herein, non-limiting examples of various photochromic materials having one S' group according to various non-limiting embodiments disclosed herein are given in the following examples.

As discussed above, according to various non-limiting embodiments disclosed herein, L may be a linker independently selected from the group consisting of-O-, -N-, and-S-at each occurrence, or L may comprise a linear or branched organic bridging group that may comprise at least one linker independently selected from the group consisting of-O-, -N-, and-S-at each occurrence. The term "linker" as used herein means to R¹The group forms at least one covalent bond. As discussed earlier, the term "linked" as used herein refers to a covalent bond. For example, although not limited thereto, as schematically depicted in FIG. 7(a), L comprises an organic bridging group having one and R¹A linking-O-group to which the group is attached.

In addition, as indicated above, L may comprise a linear or branched organic bridging group comprising more than one linking group. For example, and as schematically depicted in fig. 7(b), one non-limiting embodiment disclosed herein provides a photochromic material represented by formulas 1 and 2 above, wherein b is 2 and L is a linear or branched organic bridging group comprising two linking groups. More specifically, and without limitation thereto, L may comprise an organic bridging group having two linking-O-groups, each of which is linked to R as depicted in FIG. 7(b)¹The groups are linked. Further, as schematically depicted in FIG. 7(c), b is 3, L is a branched organic bridging group having three attached-O-groups, each of which is linked to R¹The groups are linked. According to other non-limiting embodiments, the L group may be a bridging group comprising more than 3 linking groups. For example, although not limited thereto, as discussed above, b can be 1 to 20 and L can be an organic bridging group comprising 1 to 20 linking groups. According to other non-limiting embodiments, b may be 1 to 16, 1 to 10, or 1 to 3.

According to various non-limiting embodiments disclosed herein, wherein L is a linear or branched organic bridging group comprising at least one linking group, L may be selected from: C1-C10 alkoxy, C1-C10 alkylamino, C1-C10 alkylthio, C2-C20 β -oxypoly (ethoxy), C3-C30 β -oxypoly (propoxy), C4-C40 β -oxypoly (butoxy), C2-C20 β -aminopoly (ethoxy), C3-C30 β -aminopoly (propoxy), C4-C40 β -aminopoly (butoxy), C2-C20 β -thiopoly (ethoxy), C3-C30 β -thiopoly (propoxy), C4-C40 β -thiopoly (butoxy), aryl C1-C10 alkoxy, aryl C1-C10 alkylamino, aryl C10-C10 alkylthio, aryl C10-C10 β -oxypoly (ethoxy), aryl C10-C10 β -oxypoly (propoxy), aryl C10-C10 β -oxybutyloxy), poly (butoxy) poly (10-C10 β -10, Aryl C2-C20 beta-aminopoly (ethoxy), aryl C3-C30 beta-aminopoly (propoxy), aryl C4-C40 beta-aminopoly (butoxy), aryl C2-C20 beta-thiopoly (ethoxy), aryl C3-C30 beta-thiopoly (propoxy), aryl C4-C40 beta-thiopoly (butoxy), heterocycle C1-C10 alkoxy, heterocycle C1-C10 alkylamino, heterocycle C1-C10 alkylthio, heterocycle C2-C20 beta-oxypoly (ethoxy), heterocycle C3-C30 beta-oxypoly (propoxy), heterocycle C4-C40 beta-oxypoly (butoxy), heterocycle C2-C20 beta-aminopoly (ethoxy), heterocycle C3-C30 beta-aminopoly (propoxy), heterocycle C4-C40 beta-aminopoly (butoxy), Heterocycle C2-C20 β -thiopoly (ethoxy), heterocycle C3-C30 β -thiopoly (propoxy), heterocycle C4-C40 β -thiopoly (butoxy), and combinations thereof.

The term "heterocycle" as used herein refers to a compound having a ring of atoms in which at least one atom forming the ring is different from the other atoms forming the ring. Non-limiting examples of suitable heterocyclic groups include: azaindolyl, dibenzofuranyl, dibenzothienyl, benzofuranyl, benzothienyl, thienyl, furanyl, dioxanyl (dioxano), dioxolanyl (dioxanone), carbazolyl, benzoxazolyl, benzimidazole, benzothiazole, imidazolyl, indazolyl, isobenzooxazolyl, isoxazolyl, isoindolyl, isoxazolyl, isoquinolyl, isothiazolyl, morpholino, oxadiazolyl, thiazolyl, piperidinyl, purinyl (purinyl), phenazinyl, piperazinyl, pyrazinyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrrolidinyl, quinolinyl, isoquinolinyl, thiazolyl, triazinyl, thiomorpholinyl, thiadiazolyl, tetrahydroquinolinyl, and tetrahydroisoquinolinyl.

Non-limiting examples of aryl groups are selected from phenyl and naphthyl.

Specific non-limiting examples of suitable bridging groups comprising at least one linking group from which L may be selected include: those organic groups given in table 1 above that contain at least one functional group adapted to initiate ring opening of at least one cyclic monomer after the functional group has reacted with the cyclic monomer. For example, although not limited thereto, L can comprise an organic group comprising a hydroxyl or alcohol group shown in structure 1.4 (i.e., 4- (2-hydroxyethoxy) phenyl) after the functional group is reacted with the ring-opening cyclic monomer. That is, L may be a 4- (2-oxaethoxyphenyl) group.

As discussed above, R¹Is a cyclic monomer which has been ring-opened. In addition, as discussed earlier, the term "ring-opened cyclic monomer" as used herein refers to the acyclic form of the ring-opened cyclic monomer. Non-limiting examples of suitable ring-opening cyclic monomers are described in detail above. For example, according to one non-limiting embodiment, R¹The cyclic ester monomer which has been ring-opened, the cyclic carbonate monomer which has been ring-opened, the cyclic ether monomer which has been ring-opened, and the cyclic siloxane monomer which has been ring-opened may be selected. According to another non-limiting embodiment, R¹The cyclic ester monomer which is ring-opened by itself and the cyclic carbonate monomer which is ring-opened may be selected. According to yet another non-limiting embodiment, R¹May be selected from the group consisting of ring-opened epsilon-caprolactone monomers and ring-opened delta-valerolactone monomers.

In addition, as noted above, the photochromic materials can have from 1 to 8S 'groups, each S' group can have one R, according to various non-limiting embodiments disclosed herein¹A group or a plurality of R¹A group. Thus, according to various non-limiting embodiments disclosed herein, 'a' in formula 2 may be independently selected at each occurrence from 1 to 500. According to other non-limiting embodiments, 'a' may range from 1 to 100. According to other non-limiting embodiments, 'a' may range from 1 to 60. According to other non-limiting embodiments, 'a' may range from 20 to 60.

As discussed earlier, according to various non-limiting embodiments disclosed herein, the photochromic material can comprise a polymeric segment comprising a plurality of cyclic monomers that have been ring-opened. According to various non-limiting embodiments, the polymeric chain segment desirably has multiple R' s¹A flexible segment of a radical that allows flexible bonding of the photochromic material to the polymeric material. According to other non-limiting embodiments, the polymer segment is of 10 to 100 or 20 to 60R that allows the photochromic material to flexibly bond to the polymer material¹Flexible chain segments of radicals.In addition, as discussed in more detail below, according to these non-limiting embodiments, each R¹The radicals may be substituted by radicals of the rest of R¹The groups may be the same or different (i.e., the polymeric chain segments may be homopolymers or copolymers). While not wishing to be bound by any particular theory, it is contemplated that the pliable segment according to various non-limiting embodiments disclosed herein may be advantageous in: allowing the photochromic material to bond with the polymeric material without compromising the photochromic properties of the material.

When S' comprises a plurality of R¹When radical, these R ¹The groups may be linked together to form a segment. In addition, in the plurality of R¹Each R in the group¹The radicals may be substituted by radicals of the remaining radicals R¹The groups may be the same or different. Thus, for example, according to one non-limiting embodiment, where S 'has multiple R' S¹Group of each R¹The groups may be independently selected from self-opened epsilon-caprolactone monomers and self-opened delta-valerolactone monomers. According to another non-limiting embodiment, wherein S' comprises a plurality of R¹Group, at least one R¹May be an epsilon caprolactone monomer which has been ring opened and at least one R¹May be a delta valerolactone monomer which has been ring opened. Thus, according to this non-limiting embodiment, S' comprises a copolymeric segment. For example, one non-limiting example of a photochromic material according to various non-limiting embodiments disclosed herein is given in example 5 below, wherein the photochromic material comprises two S ' groups, each S ' group comprising a plurality of R ' groups that together form a copolymeric segment¹A group.

Further, according to various non-limiting embodiments disclosed herein, for each S', each- [ R ]¹]_aThe fragments may have a number average molecular weight of 100 to 22,000 grams per mole ("g/mol"). According to other non-limiting embodiments, for each S', each- [ R ] ¹]_aThe fragments may have a number average molecular weight of 2000 to 6000 g/mol. According to other non-limiting embodiments, for each S', each- [ R ]¹]_aThe fragments may have a size of 100 to 500Number average molecular weight of g/mol.

As discussed above, the group R²Each occurrence is independently selected from hydrogen and organic materials comprising a residue of at least one reactive group. As discussed earlier, the term "residue of a reactive group" as used herein refers to the group remaining after the reactive group has been reacted. Further, although not limited herein, according to various non-limiting embodiments, wherein R is²Is an organic material comprising a residue of at least one reactive group, which may be selected from: acrylate, alkyl, alkylphosphonate, alkyldialkoxysilyl, alkoxydialkylsilyl, allylcarbonate, amide, amine, anhydride, aryl, aziridine, carboxylic acid, chloroformate, cycloaliphatic epoxide, isocyanate, isothiocyanate, epoxide, ester, halogen, hydroxyl, methacrylate, propenyl ether, the residue of a ring-opening cyclic monomer, trialkoxysilyl, thiirane, thiol, vinyl carbonate, vinyl ether, vinylbenzyl ether, and combinations thereof. According to other non-limiting embodiments, R ²An organic material that may comprise a residue of at least one reactive group, wherein the residue of at least one reactive group is selected from: acrylate, alkyl, alkyldialkoxysilyl, alkoxydialkylsilyl, allyl carbonate, amide, amine, anhydride, aryl, carboxylic acid, chloroformate, cycloaliphatic epoxide, isocyanate, isothiocyanate, epoxide, halogen, hydroxyl, methacrylate, thiol, propenyl ether, residue of a ring-opening cyclic monomer, trialkoxysilyl, vinyl carbonate, vinyl ether, vinylbenzyl ether, and combinations thereof. Additionally, as discussed earlier, the organic material comprising a residue of at least one reactive group may further comprise at least one unreacted reactive group according to various non-limiting embodiments disclosed herein.

As discussed earlier, photochromic materials according to various non-limiting embodiments disclosed herein can comprise organic materialsAn organic material comprising a residue of at least one reactive group that is not used for further bonding or reaction. Thus, according to various non-limiting embodiments disclosed herein, R ²May be an organic material comprising a residue of at least one reactive group that is not used for further bonding or reaction. For example and without limitation, organic materials comprising a residue of at least one reactive group may be end-capped with a non-reactive functional group. Although not limited thereto, for example, R is shown as the photochromic material 444 in FIG. 4²There may be organic materials which contain residues of isocyanate groups which are not used for further bonding or reaction.

Alternatively, R according to various non-limiting embodiments disclosed herein²It may be an organic material comprising a residue of at least one reactive group for further bonding or reaction. For example, R, although not limited thereto²An organic material that may be a residue containing isocyanate groups and non-reactive isocyanate groups, such as shown by photochromic material 554 in fig. 5; or R as shown in the photochromic material 664 of FIG. 6²May be an organic material comprising the residue of a ring-opening cyclic monomer further comprising a reactive halogen group.

Other non-limiting embodiments disclosed herein provide photochromic materials represented by the general formula:

General formula 6

Wherein Y may be selected from carbon or nitrogen; the group A may be selected from naphtho, benzo, phenanthro, fluorantheno, antheno, quinolino, thieno, furo, indolo, indolino, indeno, benzofuro, benzothieno, thieno, indenonaphtho, heterocyclic fused naphtho and heterocyclic fused benzo; the group S' is as defined above; n 'is an integer selected from 0 to 8, with the proviso that if n' is 0, at least one of B or B 'comprises a group S' (defined above).

With continued reference to formula 6, B and B' may be independently selected from: (1) a group S' (defined above); (2) mono-R¹⁷-substituted phenyl, wherein R¹⁷Represented by one of the following general formulae: -G [ (OC)₂H₄)_q(OC₃H₆)_r(OC₄H₈)_s]J and- [ (OC)₂H₄)_q(OC₃H₆)_r(OC₄H₈)_s]J, wherein-G is selected from the group consisting of-C (O) -and-CH₂-, J is selected from C1-C12 alkoxy and polymerizable groups; q, r and s are each a number between 0 and 50, and the sum of q, r and s is from 2 to 50; (3) unsubstituted, mono-, di-or trisubstituted aryl; (4) 9-julolidine, an unsubstituted, mono-or di-substituted heteroatomic heteroaromatic group selected from the group consisting of pyridylfuranyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl and fluorenyl, each of the aryl and heteroaromatic substituents of (3) and (4) being independently selected from the group consisting of: (i) hydroxy, (ii) a group-C (O) R ¹⁸Wherein R18 is selected from-OR¹⁹、-N(R²⁰)R²¹Piperidino and morpholino wherein R¹⁹Selected from allyl, C1-C6 alkyl, phenyl, mono (C1-C6) alkyl substituted phenyl, mono (C1-C6) alkoxy substituted phenyl, phenyl (C1-C3) alkyl, mono (C1-C6) alkyl substituted phenyl (C1-C3) alkyl, mono (C1-C6) alkoxy substituted phenyl (C1-C3) alkyl, C1-C6 alkoxy (C2-C4) alkyl, and C1-C6 haloalkyl; r²⁰And R²¹Each selected from the group consisting of C1-C6 alkyl, C5-C7 cycloalkyl, phenyl, monosubstituted phenyl, and disubstituted phenyl, the phenyl substituents being selected from the group consisting of C1-C6 alkyl and C1-C6 alkoxy, and the halo substituents being selected from the group consisting of chloro and fluoro; (iii) aryl, mono (C1-C12) alkoxyaryl, di (C1-C12) alkoxyaryl, mono (C1-C12) alkylaryl, di (C1-C12) alkylaryl, haloaryl, C3-C7 cycloalkylaryl, C3-C7 cycloalkyl, C3-C7 cycloalkoxyAlkyl, C3-C7 cycloalkoxy (C1-C12) alkyl, C3-C7 cycloalkoxy (C1-C12) alkoxy, aryl (C1-C12) alkyl, aryl (C1-C12) alkoxy, aryloxy (C1-C12) alkyl, aryloxy (C1-C12) alkoxy, mono-or di (C1-C12) alkylaryl (C1-C12) alkyl, mono-or di (C1-C12) alkoxyaryl (C1-C12) alkyl, mono-or di (C1-C12) alkylaryl (C12-C12) alkoxy, mono-or di (C12-C12) alkoxyaryl (C12-C12) alkoxy, amino, mono (C12-C12) alkylamino, di (C12-C12) alkylamino, diarylamino- (C12) alkylamino, N- (N-piperazinyl) piperazinyl, Aziridinyl, indolino, piperidino, morpholino, thiomorpholino, tetrahydroquinolinyl, pyrrolidinyl, C1-C12 alkyl, C1-C12 haloalkyl, C1-C12 alkoxy, mono (C1-C12) alkoxy (C1-C12) alkyl, acryloyloxy, methacryloyloxy and halogen; (5) an unsubstituted or mono-substituted group selected from pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl, and acridinyl, each of said substituents being independently selected from C1-C12 alkyl, C1-C12 alkoxy, phenyl, and halogen; (6) a mono-substituted phenyl group having a substituent at the para-position, wherein the substituent is selected from the group consisting of- (CH) ₂)_t-and-O- (CH)₂)_t-, where t is an integer selected from 1, 2, 3, 4, 5 and 6, the substituent being attached to an aryl group on another photochromic material; (7) a group represented by one of the following general formulae:

general formula 7 general formula 8

Wherein K in each formula is independently selected from methylene and oxygen, and M in each formula is independently selected from oxygen and substituted nitrogen, with the proviso that when M is substituted nitrogen, K is methylene; the substituent of the substituted nitrogen is selected from hydrogen, C1-C12 alkyl and C1-C12 acyl; each R²²Each occurrence in each formula is independentlySelected from the group consisting of C1-C12 alkyl, C1-C12 alkoxy, hydroxy and halogen; r in each formula²³And R²⁴Each independently selected from hydrogen and C1-C12 alkyl; u is an integer selected from 0, 1 and 2; and (8) C1-C12 alkyl, C1-C12 haloalkyl, C1-C12 alkoxy (C1-C12) alkyl, C3-C7 cycloalkyl, mono (C1-C12) alkoxy (C3-C7) cycloalkyl, mono (C1-C12) alkyl (C3-C7) cycloalkyl, halo (C3-C7) cycloalkyl, and C4-C12 bicycloalkyl, with the proviso that B and B' are not both selected from (8); and (9) a group represented by the following formula 9:

general formula 9

Wherein R is²⁵Selected from hydrogen and C1-C12 alkyl, R²⁶Is an unsubstituted, mono-or di-substituted group selected from naphthyl, phenyl, furyl and thienyl, wherein the substituents are independently selected from the group consisting of C1-C12 alkyl, C1-C12 alkoxy and halogen.

Alternatively, according to various non-limiting embodiments disclosed herein, B and B 'may together form a fluoren-9-ylidene group, a mono-or di-substituted fluoren-9-ylidene group, or a spiro-cyclic group selected from a saturated C3-C12 spiro-monocyclic hydrocarbon ring, a saturated C7-C12 spiro-bicyclic hydrocarbon ring, or a saturated C7-C12 spiro-tricyclic hydrocarbon ring, with the proviso that the spiro-cyclic group is not norbornylidene or bicyclo [3.3.1] 9-nonylidene, each of the fluoren-9-ylidene substituents being independently selected from C1-C12 alkyl, C1-C12 alkoxy, halogen, or the group S' (defined above).

As discussed earlier, photochromic materials having a relatively short organic segment attached thereto have been described that can be polymerized into polymeric materials. However, for certain photochromic materials, the placement of such organic segments on the photochromic material may be limited to locations remote from the active portion of the photochromic material. If the segment is placed too close to the reactive portion of the photochromic material, the ability of the photochromic material to undergo a transformation may be compromised, thereby deteriorating the photochromic properties of the material. However, the present inventors have observed that the S' group according to various non-limiting embodiments disclosed herein does not generally compromise photochromic performance, even when disposed proximate to the active portion of the photochromic material. In addition, as discussed in more detail below, the photochromic materials according to various non-limiting embodiments disclosed herein may have better photochromic performance than similar photochromic materials that do not include the group S'.

Thus, in accordance with various non-limiting disclosures herein, wherein Y in formula 6 is carbon and A is indenonaphtho, the photochromic material is an indenonaphthopyran represented by the following formula:

general formula 10

Wherein v and v' are integers independently selected from 0 to the total number of available positions, provided that R³⁰At least one of the groups B and B 'comprises a group S'. For example, while not limited herein, according to one non-limiting embodiment, the photochromic material is an indenonaphthopyran represented by the general formula:

general formula 11

And R is³⁰At least one of the groups B and B 'comprises a group S'. R in position 13³⁰Other non-limiting examples of groups from which groups may be selected are given in U.S. Pat. No. 6,555,028, column 9, lines 4 to 42, the disclosure of which is specifically incorporated herein by reference. 6. R in positions 7, 10 and 11³⁰From which radicals can be derivedOther non-limiting examples of selected groups are given in U.S. Pat. No. 6,555,028, column 8, lines 62 to 9, line 4, the disclosure of which is specifically incorporated herein by reference. Further non-limiting examples of groups from which B and B' may be selected are defined above.

According to other non-limiting embodiments disclosed herein, wherein Y in formula 6 is carbon and A is naphtho derived from alpha-naphthol, the photochromic material is a 2H-naphtho [1, 2-b ] pyran represented by the following formula:

General formula 12

Wherein w is an integer from 0 to the total number of available positions, provided that R³¹At least one of the radicals B and B 'comprises a radical S'. For example, while not limited thereto, according to one non-limiting embodiment, the photochromic material is a 2H-naphtho [1, 2-b ] represented by the following formula]Pyran:

general formula 13

And R is³¹At least one of the groups B and B 'comprises a group S'. 7. R in positions 8 and 9³¹Other non-limiting examples of groups from which groups may be selected are given in U.S. Pat. No. 6,555,028, column 8, lines 62 to 9, line 4, the disclosure of which is specifically incorporated herein by reference. R in position 5³¹Other non-limiting examples of groups from which groups may be selected are given in U.S. Pat. No. 6,555,028, column 8, lines 40 to 51, the disclosure of which is specifically incorporated herein by reference. R in position 6³¹Other non-limiting examples of groups from which groups can be selected are in U.S. Pat. No. 6,555,028, column 8Given in lines 52 to 61, the disclosure of which is specifically incorporated herein by reference. Further non-limiting examples of groups from which B and B' may be selected are defined above.

According to other non-limiting embodiments disclosed herein, wherein Y in formula 6 is carbon and A is naphtho derived from β -naphthol, the photochromic material is 3H-naphtho [2, 1-b ] pyran represented by the following formula:

General formula 14

Wherein x is an integer selected from 0 to the total number of available selected positions, provided that R³²At least one of the radicals B and B 'comprises a radical S'. For example, while not limited thereto, in one non-limiting embodiment, the photochromic material is a 3H-naphtho [2, 1-b ] represented by the following formula]Pyran:

general formula 15

And R is³²At least one of the groups B and B 'comprises a group S'. R in positions 5 and 6³²Other non-limiting examples of groups from which groups may be selected are given in U.S. Pat. No. 6,555,028 at column 8, line 62 to column 9, line 4, the disclosure of which is expressly incorporated herein by reference. R in position 9³²Other non-limiting examples of groups from which groups may be selected are given in U.S. Pat. No. 6,555,028, column 8, lines 40 to 51, the disclosure of which is specifically incorporated herein by reference. R in position 8³²Other non-limiting examples of groups from which groups may be selected are given in U.S. Pat. No. 6,555,028 column 8, lines 52 to 61, the disclosure of which is specifically incorporated herein by referenceFor reference.

Other non-limiting embodiments disclosed herein provide photochromic materials represented by the general formula:

general formula 16

Wherein R is³⁴And R³⁵May be independently selected from the group S' (as defined above), hydrogen, hydroxy, C1-C6 alkyl, C3-C7 cycloalkyl, allyl, phenyl, monosubstituted phenyl, benzyl, monosubstituted benzyl, chloro, fluoro, the group-C (O) R⁴⁰Wherein R is⁴⁰Is hydroxy, C1-C6 alkyl, C1-C6 alkoxy, phenyl, monosubstituted phenyl, amino, mono (C1-C6) alkylamino or di (C1-C6) alkylamino.

Or, R³⁴And R³⁵May each be a group-OR⁴¹Wherein R is⁴¹Is C1-C6 alkyl, phenyl (C1-C3) alkyl, mono (C1-C6) alkyl-substituted phenyl (C1-C3) alkyl, mono (C1-C6) alkoxy-substituted phenyl (C1-C3) alkyl, C1-C6 alkoxy (C2-C4) alkyl, C3-C7 cycloalkyl, mono (C1-C4) alkyl-substituted C3-C7 cycloalkyl, C1-C6 chloroalkyl, C1-C6 fluoroalkyl, allyl, a group-CH (R1-C4)⁴²)R⁴³Wherein R is⁴²Is hydrogen or C1-C3 alkyl and R⁴³Is CN, CF₃Or COOR⁴⁴，R⁴⁴Is hydrogen or C1-C3 alkyl; or R⁴¹Is a group-C (O) R⁴⁵Wherein R is⁴⁵Is hydrogen, C1-C6 alkyl, C1-C6 alkoxy, unsubstituted, mono-or disubstituted arylphenyl or naphthyl, phenoxy, mono-or di (C1-C6) alkyl-substituted phenoxy, mono-or di (C1-C6) alkoxy-substituted phenoxy, amino, mono (C1-C6) alkylamino, di (C1-C6) alkylamino, phenylamino, mono-or di (C1-C6) alkyl-substituted phenylamino or mono-or di (C1-C6) alkoxy-substituted phenylamino, each of said phenyl, benzyl and aryl substituents being independently C1-C6 alkyl or C1-C6 alkoxy And (4) a base.

In addition, R³⁴And R³⁵Together may form an oxy group, a spiro carbocyclic ring containing 3 to 6 carbon atoms or a spiro heterocyclic group containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spiro carbon atom, said spiro carbocyclic and spiro heterocyclic groups being fused to 0, 1 or 2 benzene rings.

With continued reference to formula 16 above, each R³⁶And R³⁷Independently selected from the group S' (as defined above), hydrogen, C1-C6 alkyl, C3-C7 cycloalkyl, phenyl, mono-substituted phenyl, di-substituted phenyl and a group-OR⁵⁰and-OC (O) R⁵⁰Wherein R is⁵⁰Is C1-C6 alkyl, phenyl (C1-C3) -alkyl, mono (C1-C6) alkyl-substituted phenyl (C1-C3) alkyl, mono (C1-C6) alkoxy-substituted phenyl (C1-C3) alkyl, C1-C6 alkoxy (C2-C4) alkyl, C3-C7 cycloalkyl or mono (C1-C4) alkyl-substituted C3-C7 cycloalkyl, and the phenyl substituent is C1-C6 alkyl or C1-C6 alkoxy. The groups B and B' are as described above for formula 6. Further, in formula 16, y and y 'are each independently integers of 0 to the total number of available positions, provided that the photochromic material represented by formula 16 comprises at least one group S'

Other non-limiting embodiments disclosed herein provide methods of making the above-described photochromic materials. For example, one non-limiting embodiment provides a method of making a photochromic material, the method comprising: initiating ring opening of at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters, cyclic carbonates, cyclic ethers, and cyclic siloxanes with a photochromic initiator comprising at least one functional group adapted to initiate ring opening of the at least one ring-opening cyclic monomer. Suitable non-limiting examples of functional groups that can be used to initiate ring opening (and ring opening polymerization) of various ring-opening cyclic monomers include alcohols, amines, carboxylic acids, silanols, thiols, and combinations, salts and complexes thereof. Although not limited thereto, according to one non-limiting embodiment, the at least one functional group may be selected from primary alcohols, secondary alcohols, or salts or complexes thereof.

As discussed earlier, by initiating the ring opening of at least one cyclic monomer with a photochromic initiator comprising at least one suitable functional group, it is possible to form a photochromic material comprising the residue of at least one ring-opened cyclic monomer or at least one ring-opened cyclic monomer. In addition, as discussed earlier, once the photochromic initiator initiates ring opening of at least one cyclic monomer, the resulting photochromic material comprising the residue of the ring-opened cyclic monomer can further initiate ring opening of another ring-opened monomer (i.e., the photochromic material is a photochromic initiator), and so on, thereby forming a polymeric chain consisting of residues of multiple ring-opened cyclic monomers. In addition, although not required, initiation of the ring-opening reaction may be carried out in the presence of at least one catalyst. Non-limiting examples of suitable catalysts include aluminum isopropoxide, triethylaluminum, tin (II) 2-ethylhexanoate, trifluoroacetic acid, enzymes, potassium and suitable salts thereof, and trifluoromethanesulfonic anhydride. The selection of a suitable catalyst will be readily appreciated by those skilled in the art.

Photochromic materials according to various non-limiting embodiments disclosed herein can be incorporated into polymeric materials that can be used, for example and without limitation, to form articles, such as optical elements and coatings. Additionally, it should be appreciated that photochromic materials according to the various non-limiting embodiments disclosed can each be used alone, in combination with other photochromic materials according to the various non-limiting embodiments disclosed herein, or in combination with one or more other suitable complementary conventional photochromic materials. For example, photochromic materials according to various non-limiting embodiments disclosed herein can be used in combination with one or more other conventional photochromic materials having at least one active absorption maximum in the range of 300 to 1000 nanometers. Complementary conventional photochromic materials can include other polymerizable or compatibilized photochromic materials, such as those described in U.S. patent nos. 4,719,296; 5,166,345; 5,236,958; 5,252,742; 5,359,085; 5,488,119 and 6,113,814 (column 2, line 39 to line 8, line 416) and 6,555,028 (column 2, line 65 to column 12, line 56), the disclosures of which are expressly incorporated herein by reference.

Other examples of complementary conventional photochromic materials include other naphthopyrans and indenonaphthopyrans, benzopyrans and oxazines, substituted 2H-phenanthro [4, 3-b ] pyrans and 3H-phenanthro [1, 2-b ] pyrans, benzopyrans having a substituent at the 2-position of the pyran ring, and mixtures of these photochromic materials, such as those described in U.S. Pat. Nos. 3,562,172; 3,567,605, respectively; 3,578,602, respectively; 4,215,010, respectively; 4,342,668, respectively; 4,816,584, respectively; 4,818,096, respectively; 4,826,977, respectively; 4,880,667, respectively; 4,931,219, respectively; 5,066,818, respectively; 5,238,981, respectively; 5,274,132; 5,384,077, respectively; 5,405,958, respectively; 5,429,774; 5,458,814, 5,466, 398; 5,514,817, respectively; 5,552,090, respectively; 5,552,091, respectively; 5,565,147, respectively; 5,573,712, respectively; 5,578,252, respectively; 5,637,262, respectively; 5,645,767; 5,656,206, respectively; 5,658,500, respectively; 5,658,501, respectively; 5,674,432 and 5,698,141. Other complementary photochromic materials known are fulgides and fulgimides, for example, 3-furyl and 3-thienyl fulgides and fulgimides, which are described in U.S. Pat. No. 4,931,220 at column 20, lines 5 to 21, line 38.

Further, according to various non-limiting embodiments disclosed herein, the photochromic composition can comprise one photochromic material or a mixture of two or more photochromic materials, as desired. Mixtures of photochromic materials can be used to achieve certain activated colors such as near neutral gray or near neutral brown. See, for example, U.S. Pat. No. 5,645,767 at column 12, line 66 to column 13, line 19, which describe parameters defining neutral gray and brown colors and the disclosure of which is expressly incorporated herein by reference.

For example, various non-limiting embodiments disclosed herein provide photochromic compositions comprising (a) a polymeric material and (b) at least one photochromic material in contact with at least a portion of the polymeric material, the at least one photochromic material comprising the reaction product of (1) at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates and (2) a photochromic initiator. The term "photochromic composition" as used herein refers to at least one photochromic material in combination with at least one other material, which may or may not be a photochromic material. The term "contacting" as used herein includes both direct and indirect contact. For example, while not limited herein, according to various non-limiting embodiments disclosed herein, the at least one photochromic material may be in contact with at least a portion of the polymeric material by blending or bonding. As used herein, the term "blended" means that the photochromic material is blended with at least a portion of the polymeric material, rather than bonded to the polymeric material. In addition, the term "bonded" as used herein means that the photochromic material is directly attached to a portion of the polymeric material or indirectly attached to a portion of the polymeric material through one or more other groups.

For example, one non-limiting embodiment provides a photochromic composition comprising (a) a polymeric material and (b) at least one photochromic material blended with at least a portion of the polymeric material, the at least one photochromic material comprising the reaction product of (1) at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates and (2) a photochromic initiator. Another non-limiting embodiment provides a photochromic composition comprising (a) a polymeric material and (b) at least one photochromic material bonded to at least a portion of the polymeric material, the at least one photochromic material comprising the reaction product of (1) at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates and (2) a photochromic initiator.

Examples of polymeric materials that may be used in conjunction with the various non-limiting embodiments disclosed herein include, but are not limited to: a polymer of a bis (allyl carbonate) monomer; diethylene glycol dimethacrylate monomer; diisopropenyl benzene monomer; ethoxylated bisphenol a dimethacrylate monomer; ethylene glycol dimethacrylate monomer; a poly (ethylene glycol) dimethacrylate monomer; ethoxylated phenol dimethacrylate monomers; alkoxylated polyol acrylate monomers, such as ethoxylated trimethylolpropane triacrylate monomers; urethane acrylate monomers such as those described in U.S. Pat. No. 5,373,033; and vinylbenzene monomers such as those described in U.S. Pat. No. 5,475,074 and styrene. Other non-limiting examples of suitable polymeric materials include polyfunctional polymers, such as mono, di, or polyfunctional acrylate and/or methacrylate monomers; poly (C1-C12 alkyl methacrylates) such as poly (methyl methacrylate); poly (oxyalkylene) dimethacrylic acid; poly (alkoxylated phenol methacrylate); cellulose acetate; cellulose triacetate; cellulose acetate propionate; cellulose acetate butyrate; poly (vinyl acetate); poly (vinyl alcohol); poly (vinyl chloride); poly (vinylidene chloride); a polyurethane; polythiourethane; a thermoplastic polycarbonate; a polyester; poly (ethylene terephthalate); polystyrene; poly (alpha-methylstyrene); copolymers of styrene and methyl methacrylate; copolymers of styrene and acrylonitrile; polyvinyl butyral; and polymers of diallylidenepentaerythritol, especially copolymers with polyol (allyl carbonate) monomers such as diethylene glycol bis (allyl carbonate), and acrylate monomers such as ethyl acrylate, butyl acrylate. Other examples of polymeric materials are disclosed in U.S. Pat. No. 5,753,146 at column 8, line 62 to column 10, line 34, the disclosure of which is expressly incorporated herein by reference. Other suitable non-limiting examples of polymeric materials are those prepared from the monomers and mixtures of monomers disclosed in U.S. Pat. No. 5,962,617 at column 2, line 9 to line 5, 64 and U.S. Pat. No. 5,658,501 at column 15, line 28 to line 16, 17, the disclosures of which are expressly incorporated herein by reference. Also contemplated are copolymers of the above monomers and blends of the above polymers and copolymers with other polymers, for example to form interpenetrating network products.

In addition, the polymeric material can comprise transparent polymers, copolymers, and blends thereof, according to various non-limiting embodiments in which transparency of the photochromic composition is desired. For example, according to various non-limiting embodiments, the polymeric material may be: preparation from thermoplastic polycarbonate resins, e.g. resins derived from bisphenol A and phosgeneOf optically clear polymeric material, which is given the trade markSelling; polyesters, e.g. under the trade markThe material sold; poly (methyl methacrylate), e.g. under the trade markThe material sold; polyol (allyl carbonate) monomers, especially polymers of diethylene glycol bis (allyl carbonate), which monomers are known under the trade markSelling; and polyurea-polyurethane (polyurea-urethane) polymers, prepared, for example, by reacting a polyurethane prepolymer and a diamine curing agent, one such polymer composition being marketed by PPG Industries, incAnd (5) selling. Other non-limiting examples of suitable polymeric materials include polymers of copolymers of polyols (allyl carbonates), such as diethylene glycol bis (allyl carbonate), with other copolymerizable monomeric materials, such as, but not limited to: copolymers with vinyl acetate, for example copolymers of 80 to 90% diethylene glycol bis (allyl carbonate) and 10 to 20% vinyl acetate, in particular copolymers of 80 to 85% of this bis (allyl carbonate) and 15 to 20% vinyl acetate; copolymers with polyurethanes containing terminal diacrylate functionality, as described in U.S. Pat. Nos. 4,360,653 and 4,994,208; and copolymers with aliphatic urethanes that contain allyl or acryloyl functional groups at their terminal ends, as described in U.S. Pat. No. 5,200,483. Other suitable polymeric materials include, but are not limited to, poly (vinyl acetate), polyvinyl butyral, polyurethane, polythiourethane, selected from diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, ethoxylated bisphenol A dimethyl Acrylic monomers, ethylene glycol dimethacrylate monomers, poly (ethylene glycol) dimethacrylate monomers, polymers of ethoxylated phenol dimethacrylate monomers and ethoxylated trimethylolpropane triacrylate monomers, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene and copolymers of styrene with methyl methacrylate, vinyl acetate and acrylonitrile. Although not limited thereto, optically transparent polymeric materials typically have a refractive index that can range from about 1.48 to about 1.75.

According to one non-limiting embodiment, the polymeric material can be an optical resin sold by PPG industries, Inc. under the CR-designation, e.g., CR-307, CR-407, and CR-607, or a polymeric material prepared for use as a hard or soft contact lens. Methods for making both such contact lenses are disclosed in U.S. Pat. No. 5,166,345 at column 11, line 52 to column 12, line 52, the disclosure of which is specifically incorporated herein by reference. Additional polymeric materials that may be used in accordance with various non-limiting embodiments disclosed herein include: polymeric materials used to form soft contact lenses having high moisture content as described in U.S. patent No. 5,965,630 and extended wear contact lenses as described in U.S. patent No. 5,965,631, the disclosures of which are incorporated herein by reference.

According to a particular non-limiting embodiment, the polymeric material is selected from copolymers of ethylene and vinyl acetate; copolymers of ethylene and vinyl alcohol; copolymers of ethylene, vinyl acetate and vinyl alcohol (e.g., those resulting from partial saponification of copolymers of ethylene and vinyl acetate); cellulose acetate butyrate; poly (urethane); poly (acrylates); poly (methacrylates); an epoxy resin; an aminoplast-functionalized polymer; poly (anhydrides); poly (urea-urethanes); an N-alkoxymethyl (meth) acrylamide-functional polymer; poly (siloxanes) and poly (silanes).

According to other non-limiting embodiments, photochromic materials according to various non-limiting embodiments disclosed herein can be incorporated into a polymeric microparticle, for example, by bonding the photochromic material to a portion of the microparticle or encapsulating the photochromic material in the microparticle. For example, although not limited herein, the photochromic material may be bonded to the microparticles as follows: bonding the photochromic material to at least one component of a polymerizable system comprising at least one substantially hydrophobic polymer, prepolymer or monomer material, and at least one substantially hydrophilic polymer, prepolymer or monomer material, wherein the components of the polymerizable system are adapted to combine and form at least partially crosslinked photochromic polymeric microparticles. Alternatively, the photochromic material may be encapsulated in the microparticles without bonding. For example, the components of the polymerizable system can self-assemble into at least partially formed microparticles that encapsulate the photochromic material during formation.

Another non-limiting embodiment provides a photochromic composition comprising a polymeric material and at least one photochromic material in contact with at least a portion of the polymeric material, wherein the at least one photochromic material is represented by formula 1, which is described in detail above.

As discussed earlier, the inventors have observed that when photochromic materials according to the various non-limiting embodiments disclosed herein are incorporated into polymeric materials (such as those described above) with or without bonding, the photochromic properties of the materials, i.e., the activation or coloration and fade rates of the materials, may be comparable to or better than the photochromic properties of the corresponding photochromic materials. For example, while not limited herein, photochromic materials according to various non-limiting embodiments disclosed herein (e.g., those represented by formula 1) can have comparable or better photochromic performance when incorporated into a polymeric material than the corresponding photochromic material represented by PC but without the group S'. In addition, photochromic materials according to various non-limiting embodiments disclosed herein can exhibit photochromic properties comparable to or better than those of the corresponding photochromic materials, even when bonded to a polymeric material without bonding of the corresponding photochromic materials. As discussed earlier, prior attempts to bond photochromic materials to polymeric materials to prevent migration of the photochromic materials have generally resulted in deterioration of photochromic performance.

Additionally, a mixture of PC- [ S 'has been observed according to various non-limiting embodiments disclosed herein']_nThe photochromic materials represented, when bonded to polymeric materials, are associated with corresponding photochromic materials having short organic segments but no- [ R ]¹]_aThe photochromic materials of the segments (for example those represented by PC-L-H) may have comparable migration and improved photochromic properties when bonded to the same polymeric material.

For example, one non-limiting embodiment disclosed herein provides a photochromic composition comprising: (a) a polymeric material and (b) at least one photochromic material in contact with at least a portion of the polymeric material, the at least one photochromic material comprising the reaction product of (1) at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates and (2) a photochromic initiator, wherein the at least one photochromic material, when bonded to the polymeric material, has a fade rate that is equal to or faster than the fade rate of a corresponding photochromic material that is free of residues of cyclic monomers, when bonded to the polymeric material. According to other non-limiting embodiments, the at least one photochromic material, when bonded to the polymeric material, has a T1/2 value that is no greater than the T1/2 value of a corresponding photochromic material that does not comprise a residue of a cyclic monomer, when bonded to the polymeric material. According to other non-limiting embodiments, the at least one photochromic material, when bonded to the polymeric material, has a T1/2 value that is less than the T1/2 value of a corresponding photochromic material that does not comprise a residue of a cyclic monomer, when bonded to the polymeric material. As discussed in the examples, the term "T1/2 value" as used herein refers to the time interval (seconds) for the delta OD of the activated form of the photochromic material in the photochromic composition to reach half the fifteen minute delta OD at 73.4F (23℃) after removal of the activating light source.

Another non-limiting embodiment provides a photochromic composition comprising a polymeric material and at least one photochromic material bonded to at least a portion of the polymeric material, wherein the at least one photochromic material is comprised of PC- [ S']_nAnd wherein the at least one is selected from the group consisting of PC- [ S']_nThe photochromic materials represented are those which fade at a rate equal to or faster than the rate at which the corresponding photochromic material represented by PC (i.e., without S') in contact with the polymeric material, or the corresponding photochromic material represented by PC-L-H (i.e., without the residue of at least one cyclic monomer) fade at a rate equal to or faster than the rate at which the corresponding photochromic material represented by PC-L-H (i.e., without the residue of at least one cyclic monomer) fades when bonded to the polymeric material, wherein PC and L are as described above. According to other non-limiting embodiments, the at least one is selected from the group consisting of PC- [ S']_nThe value of T1/2 of the photochromic material represented when bonded to the polymeric material is not greater than the value of T1/2 of the corresponding photochromic material represented by PC in contact with the polymeric material or the value of T1/2 of the photochromic material represented by PC-L-H when bonded to the polymeric material. According to other non-limiting embodiments, the at least one is selected from the group consisting of PC- [ S' ]_nThe value of T1/2 of the photochromic material represented by (A) when bonded to the polymeric material is less than the value of T1/2 of the corresponding photochromic material represented by PC in contact with the polymeric material or the value of T1/2 of the photochromic material represented by PC-L-H when bonded to the polymeric material.

Another non-limiting embodiment provides a photochromic composition comprising (a) a polymeric material; and (b) at least one photochromic material bonded to at least a portion of the polymeric material, the at least one photochromic material comprising: (1) a photochromic group, and (2) at least one segment comprising residues of a plurality of ring-opened cyclic monomers bonded to the photochromic group, the ring-opened cyclic monomers selected from the group consisting of cyclic esters, cyclic carbonates, cyclic ethers, cyclic siloxanes, and combinations thereof, wherein the at least one segment has a number average molecular weight of at least 1000 g/mol; and wherein the photochromic material, when bonded to the polymeric material, has a T1/2 value that is not greater than the T1/2 value of a corresponding photochromic material in the absence of a segment comprising residues of a plurality of ring-opened cyclic monomers.

As discussed earlier, the present invention further provides optical elements made using photochromic materials and compositions according to various non-limiting embodiments disclosed herein. The term "optical" as used herein refers to reference to or relating to light and/or vision.

Optical elements according to various non-limiting embodiments disclosed herein may be selected from ophthalmic elements, display elements, windows, mirrors, and active and passive liquid crystal cell elements. The term "ophthalmic" as used herein refers to a reference to or relation to the eye and vision. Non-limiting examples of ophthalmic elements include corrective and non-corrective lenses, including single-vision or multi-vision lenses, which may be segmented or non-segmented multi-vision lenses (such as, but not limited to, bifocal, trifocal, and progressive lenses), as well as other elements used to correct, protect, or enhance (cosmetic or other) vision, including, but not limited to, contact lenses, intraocular lenses, magnifying lenses, protective lenses, and goggles. The term "display" as used herein refers to a visual or machine-readable representation of information in the form of words, values, indicia, designs or pictures. Non-limiting examples of display elements include screens, monitors, and security elements, such as security markers. The term "window" as used herein refers to an opening adapted to allow transmission of radiation therethrough. Non-limiting examples of windows include automotive and aircraft transparencies, filters, shutters and optical switches. The term "mirror" as used herein refers to a surface that specularly reflects a substantial portion of incident light. The term "liquid crystal cell" as used herein refers to a structure comprising a liquid crystal material capable of ordering. An active liquid crystal cell is a cell in which the liquid crystal material is capable of switching between ordered and disordered states or between two ordered states under an external force, such as an electric or magnetic field. Passive liquid crystal cells are cells in which the liquid crystal material maintains an ordered state. One non-limiting example of an active liquid crystal cell element or device is a liquid crystal display.

For example, one non-limiting embodiment provides an optical element comprising (a) a substrate and (b) at least one photochromic material attached to at least a portion of the substrate, the at least one photochromic material comprising the reaction product of (1) at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates and (2) a photochromic initiator.

The term "coupled" as used herein means in direct contact with a target or in indirect contact with a target. For example and without limitation, the photochromic materials disclosed herein can be in direct contact with a portion of the substrate, such as by bonding with a portion of the material from which the substrate is made, blending with the substrate material, or coating on the substrate. Alternatively, they may be in indirect contact with the substrate, for example, through an intermediate coating, film or layer. For example, according to one non-limiting embodiment, a substrate comprises a polymeric material and at least one photochromic material bonded to at least a portion of the polymeric material. According to another non-limiting embodiment, the substrate comprises a polymeric material and at least one other photochromic material blended with at least a portion of the polymeric material. Non-limiting examples of polymeric materials useful in forming substrates according to various non-limiting embodiments disclosed herein are described in detail above.

According to other non-limiting embodiments, the substrate may be a polymeric substrate or an inorganic substrate (e.g., without limitation, a glass substrate) and the at least one photochromic material may be present as part of an at least partial coating that is attached to at least a portion of the substrate. For example, one non-limiting embodiment provides an optical element comprising (a) a substrate and (b) an at least partial coating layer attached to at least a portion of the substrate, the at least partial coating layer comprising at least one photochromic material comprising the reaction product of (1) at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates, and (2) a photochromic initiator.

According to various non-limiting embodiments, a coating comprising at least a portion of at least one photochromic material can be directly attached to at least a portion of a substrate, for example, by directly applying a coating composition comprising the at least one photochromic material to at least a portion of a surface of the substrate and at least partially fixing the coating composition. The term "fixing" as used herein includes, but is not limited to, curing, polymerizing, crosslinking, cooling and drying. Additionally or alternatively, the at least partial coating layer comprising at least one photochromic material may be indirectly attached to the substrate, for example, by one or more additional coating layers. For example, but not limited thereto, according to various non-limiting embodiments, at least one additional coating composition can be applied to at least a portion of the surface of the substrate and at least partially fixed, after which a coating composition comprising at least one photochromic material can be applied to the substrate and at least partially fixed. Non-limiting methods of applying the coating to the substrate are discussed below.

Non-limiting examples of other coatings and films that may be used in conjunction with the optical elements disclosed herein include primer coatings; protective coatings, including transitional coatings and abrasion resistant coatings; an anti-reflective coating; and polarizing coatings and films. The term "protective coating" as used herein refers to a coating that exerts the following properties: resistance to wear or abrasion, provide a property transition from one coating to another, prevent the effects of polymerization chemistries and/or prevent deterioration due to environmental conditions such as moisture, heat, ultraviolet light, oxygen, and the like.

Non-limiting examples of primer coatings that may be used in conjunction with the various non-limiting embodiments disclosed herein include coatings comprising coupling agents, at least partially hydrolyzed products of coupling agents, and mixtures thereof. As used herein, "coupling agent" refers to a material having at least one group capable of reacting, bonding, and/or associating with a group on at least one surface. In one non-limiting embodiment, the coupling agent may act as a molecular bridge at the interface of at least two surfaces, which may be similar or dissimilar surfaces. In another non-limiting embodiment, the coupling agent may be a monomer, a prepolymer, and/or a polymer. Such materials include, but are not limited to, metal organic compounds such as silanes, titanates, zirconates, aluminates, zirconium aluminates, their hydrolysates, and mixtures thereof. The phrase "product of at least partial hydrolysis of a coupling agent" as used herein means that at least some to all of the hydrolyzable groups on the coupling agent have been hydrolyzed. Other non-limiting examples of primer coatings suitable for use in connection with the various non-limiting embodiments disclosed herein include those described in U.S. Pat. No. 6,025,026 at column 3, line 3 to column 11, line 40 and U.S. Pat. No. 6,150,430 at column 2, line 39 to column 7, line 58, the disclosures of which are expressly incorporated herein by reference.

The term "transitional coating" as used herein refers to a coating that helps create a gradient of properties between two coatings. For example, although not limited herein, a transitional coating may help create a hardness gradient between a harder coating and a softer coating. Non-limiting examples of transitional coatings include radiation-cured acrylate-based films as described in U.S. patent application publication 2003/0165686, the disclosure of which is specifically incorporated herein by reference.

Non-limiting examples of abrasion resistant coatings include: abrasion resistant coatings comprising organosilanes, organosiloxanes, abrasion resistant coatings based on inorganic materials such as silica, titania and/or zirconia, organic abrasion resistant coatings of the type that are UV curable, oxygen barrier coatings, UV barrier coatings, and combinations thereof. As used herein, the term "Abrasion resistant coating" refers to a coating of a protective polymeric material that exhibits a higher degree of Abrasion Resistance than a Standard reference material, such as that available from PPG Industries, Inc, as tested according to a Method comparable to ASTM F-735 Standard Test Method for Abrasion Resistance of transgenic Plastics and Coatings Using the same The polymer made of the monomer has high wear resistance.

Non-limiting examples of antireflective coatings include one or more layers of metal oxides, metal fluorides, or other such materials, which can be deposited onto the articles of the present invention by vacuum deposition, sputtering, or other methods. Non-limiting examples of polarizing coatings include, but are not limited to, coatings comprising dichroic compounds known in the art.

As discussed above, according to various non-limiting embodiments, coatings comprising at least a portion of at least one photochromic material may be applied to a substrate prior to application of such coatings. Alternatively or additionally, the coatings comprising at least part of the at least one photochromic material may be applied to the substrate after application of the coatings comprising at least part of the at least one photochromic material, for example as an overcoat on the coating comprising at least part of the at least one photochromic material. For example, while not limited herein, according to various other non-limiting embodiments, the above-described coating can be attached to at least a portion of the same surface of the substrate in the following order, starting from the surface: primer coatings, photochromic coatings, transitional coatings, abrasion resistant coatings, polarizing films or coatings, anti-reflective coatings, and abrasion resistant coatings; or primer coatings, photochromic coatings, transitional coatings, abrasion resistant coatings and antireflective coatings; or photochromic, transitional, and polarizing coatings; or primer coatings, photochromic coatings and polarizing coatings; or primer coatings, photochromic coatings and antireflective coatings. In addition, the above-described coatings can be applied to one or more surfaces of the substrate, such as both surfaces of an optical substrate.

Non-limiting embodiments of methods of manufacturing photochromic compositions and optical elements according to various non-limiting embodiments disclosed herein will now be discussed. One non-limiting embodiment provides a method of making a photochromic composition, the method comprising: attaching at least one photochromic material to at least a portion of the substrate, wherein the at least one photochromic material comprises the reaction product of: (1) at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates; and (2) a photochromic initiator.

Non-limiting methods of attaching the photochromic material to the polymeric material include, for example, mixing the photochromic material into a solution or melt of the polymeric, pre-polymeric, or monomeric material, followed by at least partially conditioning the polymeric, pre-polymeric, or monomeric material. It will be understood by those skilled in the art that, according to this non-limiting embodiment, the photochromic material may be blended with (i.e., blended with rather than bonded to) or bonded to the polymeric material in the resulting photochromic composition. For example, if the photochromic material comprises reactive functionality that is compatible with a polymeric, pre-polymeric, or monomeric material, the photochromic material can react with at least a portion of the material to bond the photochromic material to the resulting polymeric material during immobilization of the material.

Another method of attaching photochromic materials to polymeric materials that may be used in conjunction with the various non-limiting embodiments disclosed herein is imbibition. According to this method, the photochromic material is caused to diffuse into the polymeric material, for example by immersing the polymeric material in a solution containing the photochromic material, with or without heating. Thereafter, for example, if the photochromic material includes reactive functionality that is compatible with the polymeric material, the photochromic material can be bonded to the polymeric material.

Other non-limiting embodiments disclosed herein provide methods of making an optical element, the method comprising: attaching at least one photochromic material to at least a portion of the substrate, wherein the at least one photochromic material comprises the reaction product of: (1) at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates; and (2) a photochromic initiator. Non-limiting methods of attaching the photochromic material to at least a portion of the substrate include: infiltration (as described above), cast-in-place, in-mold casting, coating, and lamination.

According to one non-limiting embodiment, wherein the substrate comprises a polymeric material, the photochromic material can be attached to at least a portion of the substrate by a cast-in-place process. According to this non-limiting embodiment, the photochromic material is mixed with a polymer solution or melt, or other prepolymer and/or monomer solution or mixture, and then cast into a molded article having a desired shape and at least partially set to form a substrate. According to this non-limiting embodiment, the at least one photochromic material may be bonded to the polymeric material or it may be blended with (i.e., blended with rather than bonded to) the polymeric material of the substrate.

According to another non-limiting embodiment, wherein the substrate comprises a polymeric material, the photochromic material can be attached to at least a portion of the substrate by an in-mold casting process. According to this non-limiting embodiment, a coating composition (which may be a liquid coating composition or a powder coating composition) comprising a photochromic material is applied to the surface of the molded article and at least partially adjusted. Thereafter, a polymer solution or melt, or a prepolymer or monomer solution or mixture is cast on the coating and at least partially fixed. After the fixing, the coated substrate is removed from the mold. Non-limiting examples of powder coatings in which photochromic materials according to various non-limiting embodiments disclosed herein may be used are illustrated in U.S. Pat. No. 6,068,797 at column 7, line 50 to column 19, line 42, the disclosure of which is specifically incorporated herein by reference.

According to yet another non-limiting embodiment, wherein the substrate comprises a polymeric material or an inorganic material, such as glass, the photochromic material can be attached to at least a portion of the substrate by coating. Non-limiting examples of suitable coating methods include: spin coating, spray coating (e.g., using liquid or powder coatings), curtain coating, roll coating, spin and spray coating, in-mold casting, and overmolding. For example, according to one non-limiting embodiment, the photochromic material can be attached to the substrate by overmolding. According to this non-limiting embodiment, a coating composition comprising a photochromic material (which, as discussed earlier, can be a liquid coating composition or a powder coating composition) is applied to a mold, and then a substrate is plunged into the mold such that the substrate contacts the coating causing it to spread over at least a portion of the substrate surface. Thereafter, the coating composition is at least partially set and the coated substrate is removed from the mold. Alternatively, the over-molding may be performed as follows: the substrate is placed in the mold such that an open area is defined between the substrate and the mold, after which a coating composition comprising the photochromic material is injected into the open area. Thereafter, the coating composition can be at least partially set and the coated substrate removed from the mold.

According to yet another non-limiting embodiment, wherein the substrate comprises a polymeric material or an inorganic material, such as glass, the photochromic material can be attached to at least a portion of the substrate by lamination. According to this non-limiting embodiment, the film comprising the photochromic material can be adhered to a portion of the substrate with or without an adhesive and/or the application of heat and pressure. Thereafter, if desired, a second substrate can be applied over the first substrate and the two substrates can be laminated together (i.e., by using heat and pressure) to form an element with the film comprising the photochromic material interposed between the two substrates. The method of forming the film comprising the photochromic material may include, for example and without limitation, combining the photochromic material with a polymer solution or a prepolymer solution, thereby casting or extruding a film, and, if desired, at least partially fixing the film. Additionally or alternatively, the film (with or without the photochromic material) may be formed and infiltrated with the photochromic material (as discussed above).

In addition, it will be understood by those skilled in the art that the photochromic compositions and photochromic coating compositions according to the various non-limiting embodiments disclosed herein may further comprise other additives that aid in the processing and/or performance of the compositions. For example and without limitation, these additives may be selected from the group consisting of photoinitiators, thermal initiators, polymerization inhibitors, solvents, light stabilizers (such as, but not limited to, ultraviolet light absorbers and light stabilizers such as Hindered Amine Light Stabilizers (HALS)), heat stabilizers, mold release agents, rheology control agents, leveling agents (such as, but not limited to, surfactants), free radical scavengers, and adhesion promoters (such as hexanediol diacrylate and coupling agents).

As previously discussed, the inventors have observed that photochromic materials according to various non-limiting embodiments disclosed herein can have advantageous migration properties. Accordingly, one non-limiting embodiment disclosed herein provides a method of inhibiting migration of a photochromic material in a polymeric material, the method comprising bonding the photochromic material to at least a portion of the polymeric material, wherein the photochromic material comprises: (1) a photochromic group, and (2) at least one segment comprising residues of a plurality of ring-opened cyclic monomers bonded to the photochromic group, the ring-opened cyclic monomers selected from the group consisting of cyclic esters, cyclic carbonates, cyclic ethers, cyclic siloxanes, and combinations thereof, wherein the at least one segment has a number average molecular weight of at least 1000 g/mol. In addition, according to this non-limiting embodiment, the residue of the at least one ring-opened cyclic monomer may have a number average molecular weight of 2000 to 6000 g/mol.

Various non-limiting embodiments of the invention will be illustrated in the following non-limiting examples.

Examples

Preparation of photochromic materials

Example 1: example preparation of photochromic Material "PM-1

Part A:

a photochromic initiator (represented by structure 1.49 in table 1 above) was prepared as follows. 3-Piperidinemethanol (5.1 g) and anhydrous tetrahydrofuran (330ml) were added to the dried reaction flask. The reaction mixture was cooled in an ice bath. To this reaction mixture was slowly added dropwise 51ml of butyllithium (2.5M in hexane) over 20 minutes. The reaction mixture was allowed to warm to room temperature and the desired product of example 4, step 6 of U.S. Pat. No. 6,296,785 (3, 3-bis (4-methoxyphenyl) -6, 7-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran, 11.0 g) was added. The reaction mixture was stirred at room temperature overnight and then poured slowly into ice water (400 ml). Aqueous hydrochloric acid (10% v/v) was added until pH 5 and then diluted with ethyl acetate (200 ml). The layers were separated and the aqueous layer was partially extracted with three 175ml portions of ethyl acetate. The organic layers were combined and washed with saturated aqueous sodium bicarbonate (200 ml). The organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The resulting residue was purified by column chromatography on silica gel (300 g), eluting with 40% ethyl acetate in hexane. The photochromic fractions were combined and concentrated by rotary evaporation. The resulting residue was recrystallized from tert-butyl methyl ether to yield 5.6 g of an off-white solid. NMR and mass spectral analysis showed that the product had a structure and molecular weight consistent with 3, 3-bis (4-methoxyphenyl) -6-methoxy-7- (3-piperidinomethane) -13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran.

And part B:

an example photochromic material, "PM-1", was prepared using the photochromic initiators given in part a (above) as follows: 0.8038g of the photochromic initiator of part A above, 7.37g of epsilon-caprolactone monomer and a half-drop of tin (II) 2-ethyloctoate were charged under nitrogen into a three-necked flask equipped with a condenser, nitrogen inlet and stirring bar. The mixture was stirred at room temperature until a dark homogeneous solution formed. Polymerization was carried out at about 120 ℃ for 22 hours. Thereafter, the highly viscous mixture was cooled to about 80 ℃ and transferred to a glass bottle. The product is considered to be composed of a mixture of photochromic materials having a structure substantially represented by the following formula 19, wherein 'a' is an integer of 1 to 165. Mass spectrometry confirmed the structure.

General formula 17

Example 2: preparation of example photochromic Material "PM-2

Part A:

a photochromic initiator (represented by structure 1.51 in table 1 above) was prepared as follows. The product of example 5 of U.S. Pat. No. 5,645,767, which example is specifically incorporated herein by reference (3, 3-bis (4-methoxyphenyl) -6, 11, 13-trimethyl-13-hydroxy-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran, 200 grams) was added to a reaction flask containing 700ml of triethylene glycol and 750m l acetonitrile. The resulting mixture was stirred under a nitrogen atmosphere and heated to 80 ℃. Subsequently, 2 g of p-toluenesulfonic acid was added to the reaction mixture. After 30 minutes at 80 ℃, the reaction was quenched in 8L of water with vigorous stirring until a green solid precipitated out. The solid was filtered, washed with water, dried in air and purified by column chromatography. Subsequently, crystallization from diethyl ether yielded 152 g of a white solid. NMR analysis showed the product to have a structure consistent with 3, 3-bis (4-methoxyphenyl) -6, 11, 13-trimethyl-13- (2- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran.

And part B:

an example photochromic material, "PM-2", was prepared using the photochromic initiators given in part a (above) as follows: 40.3190g of the photochromic initiator of part A (above), 120.5558g of epsilon-caprolactone monomer and 0.4209g of tin 2-ethyloctoate (I I) were charged under nitrogen into a three-necked flask equipped with a condenser, nitrogen inlet and mechanical stirring bar. The mixture was stirred at room temperature until a dark homogeneous solution formed. The polymerization of epsilon-caprolactone was carried out at 120 ℃ for 5 hours. Thereafter, the highly viscous mixture was cooled to about 80 ℃ and transferred to a glass bottle. The product obtained is a solid at room temperature, having a number average and a weight average molecular weight, determined by GPC, of 3300 and 4500g/mol, respectively, relative to polystyrene standards. The product is considered to be composed of a mixture of photochromic materials having a structure substantially represented by the following formula 19, wherein 'a' is an integer of 1 to 307.

General formula 18

Example 3: preparation of example photochromic Material "PM-3

An example photochromic material, "PM-3", was prepared using the photochromic initiator given in part a (above) of example 2 as follows: 1.5822g of the photochromic initiator of example 2 part A (above), 4.7089g of delta-valerolactone monomer and 0.0157g of tin 2-ethyloctoate (I I) were charged under nitrogen into a three-necked flask equipped with a condenser, nitrogen inlet and magnetic stir bar. The polymerization procedure was the same as given in example 2 part B (above). The product obtained is a solid at room temperature, having a number average and a weight average molecular weight, determined by GPC, of 2800 and 3500g/mol, respectively, with respect to polystyrene standards. The product is considered to be composed of a mixture of photochromic materials having a structure substantially represented by the following formula 19, wherein 'a' is an integer of 1 to 166.

General formula 19

Example 4: example preparation of photochromic Material "PM-4

An example photochromic material, "PM-4", was prepared using the photochromic initiator given in part a (above) of example 2 as follows: 100.0114g of the photochromic initiator of example 2 part A (above), 139.0881g of delta-valerolactone, 158.5649g of epsilon-caprolactone and 0.9942g of tin (II) 2-ethyloctanoate were charged under nitrogen into a three-necked flask equipped with a condenser, nitrogen inlet and mechanical stirrer. The polymerization procedure was the same as given in example 2 part B (above). The product material was a viscous liquid at room temperature, having number average and weight average molecular weights of 2800 and 3600g/mol, respectively, as determined by GPC, relative to polystyrene standards. The product is believed to be comprised of a mixture of photochromic materials having a structure generally represented by the following formula 20, where the "random copolymer" is a random copolymer of epsilon-caprolactone and delta-valerolactone.

Insertion formula

General formula 20

Example 5: example preparation of photochromic Material "PM-5

Part A:

a photochromic radical initiator (represented by structure 1.3 in table 1 above) was prepared as follows. Step 1:4-fluoro-4' - (2-hydroxyethoxy) -benzophenone from example 7 (below) part A, step 1(7-974) (43.3 grams) and acetylene saturated N, N-dimethylformamide (130ml) were combined in a reaction flask. The reaction flask was cooled in an ice bath. Sodium acetylene solution (9 wt% in toluene, 221 g) was added dropwise to the cooled reaction mixture over 30 minutes. The ice bath was removed and the reaction mixture was allowed to warm back to room temperature. The reaction mixture was poured into ice water (450ml) and diethyl ether (300ml) was added thereto. The layers were separated and the aqueous layer was extracted once with diethyl ether (300ml) and twice with ethyl acetate (300ml each). The organic layers were combined, dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The resulting residue was purified by column chromatography on silica gel (600 g), eluting with a mixture of 45% ethyl acetate in hexane. The fractions containing the pure desired product were combined and concentrated by rotary evaporation to yield 30.1 g of 1- (4-fluorophenyl) -1- (4' - (2-hydroxyethoxy) phenyl) -2-propargyl-1-ol.

Step 2:will result from step 11- (4-fluorophenyl) -1- (4' - (2-hydroxyethoxy) phenyl) -2-propargyl-1-ol (19.9 g), 2, 3-dimethoxy-5, 7-dihydroxy-7-ethyl-7H-benzo [ C ] C from example 8 (below) part A, step 4 ]Fluorene (18.0 g), p-toluenesulfonic acid monohydrate (1.02 g) and chloroform (stored with pentene, 360ml) were combined in a reaction flask and stirred at room temperature for 2.5 hours. The reaction mixture was washed with 50% saturated aqueous sodium bicarbonate (300ml), dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The resulting residue was purified by column chromatography on silica gel (500 g), eluting with a mixture of 50% ethyl acetate in hexane. The fractions containing the desired photochromic substance were combined and concentrated by rotary evaporation to give 18.9 g of 3- (4-fluorophenyl) -3- (4- (2-hydroxyethoxy) phenyl) -6, 7-dimethoxy-13-ethyl-13-hydroxy-3H, 13H-indeno [2, 1-f ]]Naphtho [1, 2-b ]]A pyran.

And step 3:the 3- (4-fluorophenyl) -3- (4- (2-hydroxyethoxy) phenyl) -6, 7-dimethoxy-13-ethyl-13-hydroxy-3H, 13H-indeno [2, 1-f ] from step 2]Naphtho [1, 2-b ]]Pyran (18.9 grams), diethylene glycol (190ml), toluene (190ml), and p-toluenesulfonic acid monohydrate (0.60 gram) were combined in a reaction flask and heated to 85 ℃ for 2.5 hours. The reaction mixture was cooled to room temperature and diluted with toluene (190 ml). The reaction mixture was washed with saturated aqueous sodium bicarbonate (350ml) and saturated two portions of aqueous sodium chloride (350ml each). The organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The resulting residue was chromatographed on silica gel (650 g), eluting with a mixture of 65% ethyl acetate in hexane. The pure photochromic fractions were combined and concentrated by rotary evaporation to a dark green oil. NMR analysis showed that the product had a similar identity to 3- (4-fluorophenyl) -3- (4- (2-hydroxyethoxy) phenyl) -6, 7-dimethoxy-13-ethyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] ]Naphtho [1, 2-b ]]Pyrans have a consistent structure.

And part B:

an example photochromic material, "PM-5", was prepared using the photochromic initiators given in part a (above) as follows: 0.4194g of the photochromic initiator given in part A above, 1.6973g of delta-valerolactone, 1.9349g of epsilon-caprolactone and 0.0101g of tin (II) 2-ethyloctanoate were charged under nitrogen into a three-necked flask equipped with a condenser, nitrogen inlet and magnetic stirring bar. The polymerization procedure was the same as given in example 2 part B (above). The product was a viscous liquid at room temperature, having a number average and weight average molecular weight, determined by GPC, of 8800 and 9800g/mol, respectively, relative to polystyrene standards. The product is believed to be comprised of a mixture of photochromic materials having a structure generally represented by the following formula 21, where the "random copolymer" is a random copolymer of epsilon-caprolactone and delta-valerolactone.

General formula 21

Example 6: example preparation of photochromic Material "PM-6

An example photochromic material, "PM-6", was prepared using the photochromic initiator given in part a of example 2 (above) as follows: 12.1814g of the photochromic initiator of example 2 part A (above), 11.2488g of delta-valerolactone, 12.8240g of epsilon-caprolactone and 0.0906g of tin (II) 2-ethyloctanoate were charged under nitrogen into a three-necked flask equipped with a condenser, nitrogen inlet and mechanical stirrer. The polymerization procedure was the same as given in example 2 part B (above). After polymerization, the resulting mixture was cooled to 80 ℃, a drop of dibutyltin dilaurate was added and 2.8097g of 2-isocyanatoethyl methacrylate were added over 30 minutes at about 80 ℃. The reaction was maintained at 80 ℃ until no isocyanate groups could be detected by IR. The product was a viscous liquid at room temperature, having a number average and weight average molecular weight, determined by GPC, of 2400 and 3900/mol, respectively, relative to polystyrene standards. The product is believed to be comprised of a mixture of photochromic materials having a structure generally represented by formula 22 below, where the "random copolymer" is a random copolymer of epsilon-caprolactone and delta-valerolactone.

General formula 22

Example 7: preparation of example photochromic Material "PM-7

Part A:

a photochromic initiator (represented by structure 1.37 in table 1 above) was prepared as follows.Step 1:4-hydroxy-4' -fluoro-benzophenone (100 g), 2-chloroethanol (93 g), sodium iodide (14 g), potassium carbonate (128 g) were added to a reaction flask containing 400ml of N, N-dimethylformamide. The resulting mixture was heated to 95 ℃ and stirred under a nitrogen atmosphere. After 4 hours at 95 ℃, an additional 30 grams of 2-chloroethanol and 5 grams of sodium iodide were added to the reaction mixture. After a further 14 hours at 95 ℃, the reaction was quenched in a mixture of 50ml of 50% sodium hydroxide solution and 4L of water with vigorous stirring to precipitate a white solid. The solid was filtered, washed with water and dried under air to give 117 g of the desired product, 4- (2-hydroxyethoxy) -4' -fluoro-benzophenone. This material was used in the next step without further purification.

Step 2:the product of step 1, 4- (2-hydroxyethoxy) -4' -fluoro-benzophenone (90 grams), morpholine (75.3 grams), triethylamine (69.9 grams) were added to a reaction flask containing 160ml of dimethyl sulfoxide. The resulting mixture was heated to 95 ℃ and stirred under a nitrogen atmosphere. After 4 hours at 95 ℃, an additional 40 g of morpholine and 35 g of triethylamine were added to the reaction mixture. After a further 14 hours at 95 ℃, an additional 60 g of morpholine were added to the reaction mixture. After a further 24 hours at 95 ℃, the reaction was quenched in 5L of water with vigorous stirring, and a pale yellow solid was seen to precipitate out. The solid was filtered, washed with water and dried under air to give 105 g of The product, 4- (2-hydroxyethoxy) -4' -morpholino-benzophenone, is desired. This material was used in the next step without further purification.

And step 3:the product of step 2, 4- (2-hydroxyethoxy) -4' -morpholino-benzophenone (105 grams) was added to a reaction flask containing 600ml of N, N-dimethylformamide saturated with acetylene. The resulting mixture was stirred at room temperature under a nitrogen atmosphere using a mechanical stirrer. Sodium acetylene (214 grams of an 18 wt% solution) in xylene/mineral oil was added to the reaction mixture over thirty minutes while stirring. After stirring at room temperature for half an hour, the reaction was quenched in 4L of water with vigorous stirring to see a pale yellow solid precipitated out. The solid was filtered, washed with water and dried under air to give 111.1 g of the desired product, 1- (4- (2-hydroxyethoxy) -phenyl-1- (4-morpholinophenyl) -2-proparg-1-ol.

And 4, step 4:the product of example 1, step 2 of U.S. Pat. No. 5,645,767 (1-phenyl-2-methoxycarbonyl-4-acetoxynaphthalene, 50 grams) was added to a reaction flask containing 500ml tetrahydrofuran. The resulting mixture was cooled in an ice-water bath and stirred under a nitrogen atmosphere. 703ml of methylmagnesium chloride solution (1M in tetrahydrofuran) was added dropwise over forty-five minutes. The resulting yellow reaction mixture was stirred at 0 ℃ for 2 hours and slowly warmed to room temperature. The reaction mixture was poured into 2L of ice/water mixture. Ether (1L) was added and the layers were separated. The aqueous layer was extracted with two 500ml ether fractions, the organic fractions were combined and washed with 1L water. The organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The resulting oil was transferred to a reaction vessel (equipped with a dean-stark trap) containing 500ml of toluene to which ten drops of dodecylbenzene sulfonic acid were added. The reaction mixture was heated to reflux for 2 hours and cooled. Toluene was removed by rotary evaporation to yield 40.2 g of a pale yellow solid. NMR spectrum shows that the product has 7, 7-dimethyl-5-hydroxy-7H-benzo [ C ] ]Fluorene a consistent structure. This material was used directly in the next step without further purification.

And 5:the product of step 4, 7-dimethyl-5-hydroxy-7H-benzo [ C ] in a reaction flask]Fluorene (40 g), the product of step 3, 1- (4- (2-hydroxyethoxy) -phenyl-1- (4-morpholinophenyl) -2-proparg-n-1-ol (54.3 g), twenty drops of methanesulfonic acid and 800ml of chloroform were combined and stirred at reflux temperature under a nitrogen atmosphere after two hours an additional 5 g of 1- (4- (2-hydroxyethoxy) -phenyl-1- (4-morpholinophenyl) -2-proparg-n-1-ol were added to the reaction mixture followed by an additional 5 g after a further two hours the reaction mixture was heated at reflux for 16 hours then cooled to room temperature after which the organic layer was separated, the organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The residue was chromatographed on a column of silica gel using hexane, dichloromethane and ethyl acetate (50/40/10) as eluent. The photochromic fractions were collected and concentrated by rotary evaporation to give a bluish solid (66 g). NMR spectra showed that the product had a chemical identity to 3- (4- (2-hydroxyethoxy) -phenyl-3- (4-morpholinophenyl) -13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] ]Naphtho [1, 2-b ]]Pyrans have a consistent structure.

And part B:

an example photochromic material, "PM-7", was prepared using the photochromic initiators given in part a (above) as follows: 1.4230g of the photochromic initiator given in section A above, 4.7830g of epsilon caprolactone monomer, and 0.0064g of tin (II) 2-ethyloctoate were charged under nitrogen into a three-necked flask equipped with a condenser, nitrogen inlet and magnetic stir bar. The reaction mixture was stirred at room temperature until a dark homogeneous solubility had formed. Followed by polymerization at 140 ℃ for 10 hours. Thereafter, the highly viscous mixture was cooled to about 80 ℃ and transferred to a glass bottle. The product was a solid at room temperature, having a number average and weight average molecular weight of 1800 and 3100/mol, respectively, as determined by GPC, relative to polystyrene standards. The product is considered to be a mixture of photochromic materials having a general structure represented by the following formula 23, wherein 'a' is an integer of 1 to 228.

General formula 23

Example 8: example preparation of photochromic Material "PM-8

Part A: preparation of photochromic initiators

A photochromic initiator (represented by structure 1.32 in table 1 above) was prepared as follows. Step 1:the product of example 4, step 2 of U.S. Pat. No. 6,296,785 (a mixture of E and Z isomers of 4- (3, 4-dimethoxyphenyl) -4-phenyl-3-methoxycarbonyl-3-butenoic acid, 225 g) and acetic anhydride (900ml) were added to a reaction flask under a nitrogen atmosphere. The reaction mixture was heated to reflux for 5 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was collected by vacuum filtration and washed with cold methanol to obtain 211 g of 1-phenyl-2-methoxycarbonyl-4-acetoxy-6, 7-dimethoxynaphthalene. The product was used in the subsequent reaction without further purification.

Step 2:the 1-phenyl-2-methoxycarbonyl-4-acetoxy-6, 7-dimethoxynaphthalene from step 1 (100 g), water (675ml), methanol (35ml) and sodium hydroxide (75 g) were combined in a reaction flask and heated to reflux for 1 hour. The reaction mixture was cooled to room temperature and poured slowly into a 1.5L 4N HCl/ice mixture. Additional 4N HCl was added until the pH of the reaction mixture was 3. The resulting white precipitate was collected by vacuum filtration and washed with water to yield 96 g of 1-phenyl-2-hydroxycarbonyl-4-hydroxy-6, 7-dimethoxy-naphthalene. The product was used in the subsequent reaction without further purification.

And step 3:the 1-phenyl-2-hydroxycarbonyl-4-hydroxy-6, 7-dimethoxy-naphthalene from step 2 (105 g), acetic anhydride (420ml), acetic acid (630ml) and zinc chloride (7 g) were combined and heated to reflux in a reaction flask for 10 hThen (c) is performed. The reaction mixture was cooled and the resulting precipitate was collected by vacuum filtration and washed with acetic acid followed by water to give an orange solid. This solid was slurried in saturated aqueous sodium bicarbonate for 15 minutes, collected by vacuum filtration and washed with water to give an orange solid. The orange solid was slurried in hot methanol, cooled to room temperature, collected by vacuum filtration and washed with cold methanol to give 84.2 g of 2, 3-dimethoxy-5-acetoxy-7H-benzo [ C ] amine]Fluoren-7-one. The product was used in the subsequent reaction without further purification.

And 4, step 4:under a nitrogen atmosphere, the 2, 3-dimethoxy-5-acetoxy-7H-benzo [ C ] obtained from step 3]Fluoren-7-one was added to the reaction flask. Anhydrous tetrahydrofuran (1250ml) was added to the reaction flask. The reaction mixture was cooled in an ice bath and 178ml of ethyl magnesium bromide solution (3.0M in diethyl ether) were added dropwise over 30 minutes. The reaction mixture was allowed to warm slowly to room temperature and then poured into a saturated aqueous ammonium chloride and ice mixture (1.3L). The layers were separated and the aqueous layer was extracted with two 750ml portions of ethyl acetate. The organic fractions were combined and washed with saturated aqueous sodium bicarbonate (800 ml). The organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The orange solid was slurried in hot tert-butyl methyl ether, cooled to room temperature, collected by vacuum filtration and washed with cold tert-butyl methyl ether to give 41.3 g of 2, 3-dimethoxy-5, 7-dihydroxy-7-ethyl-7H-benzo [ C ] ]Fluorene. The product was used in the subsequent reaction without further purification.

And 5:2, 3-dimethoxy-5, 7-dihydroxy-7-ethyl-7H-benzo [ C ] from step 4 was placed in a reaction flask]Fluorene (30g), morpholine (46.7ml) and anhydrous tetrahydrofuran (900ml) were combined. The reaction mixture was cooled in an ice bath and an n-butyllithium solution (2.5M in hexane, 178ml) was added dropwise over 30 minutes. The ice bath was removed and the reaction mixture was heated to reflux for 3 hours. The reaction mixture was cooled to room temperature and then poured into a saturated aqueous ammonium chloride and ice mixture (1L). The layers were separated and the aqueous layer was extracted with two 350m l portions of ethyl acetate. Will be provided withThe organic fractions were combined and washed with saturated aqueous sodium bicarbonate (500 ml). The organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The orange solid was slurried in hot tert-butyl methyl ether, cooled to room temperature, collected by vacuum filtration and washed with cold tert-butyl methyl ether to give 26.6 g of 2-morpholino-3-methoxy-5, 7-dihydroxy-7-ethyl-7H-benzo [ C ] methyl ether]Fluorene. The product was used in the subsequent reaction without further purification.

Step 6:2-morpholino-3-methoxy-5, 7-dihydroxy-7-ethyl-7H-benzo [ C ] from step 5 was placed in a reaction flask ]Fluorene (20 g), the product of example 1, step 1 of U.S. Pat. No. 5,458,814 (1, 1-bis (4-methoxyphenyl) -2-propargyl-1-ol, 17.8 g), dodecylbenzenesulfonic acid (1.7 g) and chloroform (stored with pentene, 600ml) were combined and stirred at room temperature for 2 hours. The reaction mixture was washed with saturated aqueous sodium hydrogencarbonate solution (300ml) and the organic layer was dried over anhydrous sodium sulfate. The organic layer was concentrated by rotary evaporation. Hot methanol was added to the resulting residue and then cooled to room temperature. The resulting precipitate was collected by vacuum filtration and washed with cold methanol to give 26.8 g of 3, 3-bis (4-methoxyphenyl) -6-methoxy-7-morpholino-13-ethyl-13-hydroxy-3H, 13H-indeno [2, 1-f ]]Naphtho [1, 2-b ]]A pyran. The product was used in the subsequent reaction without further purification.

And 7:the 3, 3-bis (4-methoxyphenyl) -6-methoxy-7-morpholino-13-ethyl-13-hydroxy-3H, 13H-indeno [2, 1-f ] from step 6 was placed in a reaction flask]Naphtho [1, 2-b ]]Pyran (12 g), diethylene glycol (120ml), toluene (120ml) and p-toluenesulfonic acid monohydrate (0.36 g) were combined and heated to 85 ℃ for 4 hours. The reaction mixture was cooled to room temperature and diluted with toluene (120 ml). The reaction mixture was washed with saturated aqueous sodium bicarbonate (100ml) and four portions of saturated aqueous sodium chloride (100ml each). The organic layer was dried over anhydrous sodium sulfate and concentrated to a dark oil. The oil was chromatographed on a silica gel column, eluting with a 40% ethyl acetate in hexane mixture. The photochromic fractions were collected and concentrated by rotary evaporation. At 40% hexane in tert The resulting residue was recrystallized from a mixture of butyl methyl ether to yield 5g of an off-white solid. NMR analysis showed that the product had a chemical identity to 3, 3-bis (4-methoxyphenyl) -6-methoxy-7-morpholino-13-ethyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ]]Naphtho [1, 2-b ]]Pyrans have a consistent structure.

And part B:

an example photochromic material, "PM-8", was prepared using the photochromic initiators given in part a (above) as follows: under nitrogen, 1.695g of the photochromic initiator given in section A above, 4.6440g of epsilon caprolactone monomer and 0.0062g of tin (II) 2-ethyloctanoate were charged into a three-necked flask equipped with a condenser, nitrogen inlet and magnetic stir bar. The reaction mixture was stirred at room temperature until a dark homogeneous solubility had formed. Polymerization was carried out at 140 ℃ for 6 hours. Thereafter, the highly viscous mixture was cooled to about 80 ℃ and transferred to a glass bottle. The product was a solid at room temperature, having a number average and a weight average molecular weight, determined by GPC, of 2000 and 3100/mol, respectively, relative to polystyrene standards. The product is considered to be a mixture of photochromic materials having a general structure represented by the following formula 24, wherein 'a' is an integer of 1 to 166.

General formula 24

Example 9: example preparation of photochromic Material "PM-9

Part A: preparation of photochromic initiators

A photochromic initiator (represented by structure 1.31 in table 1 above) was prepared as follows.Step 1:anisole (27.5 grams), 4-fluorobenzoyl chloride (35 grams) and methylene chloride (250ml) were combined in a reaction flask. Aluminum chloride (30.8 g) was added slowly to the reaction mixture over 20 minutes. Stirring the reaction at room temperatureThe mixture should be allowed to stand for two hours and then poured into a mixture of 70ml of concentrated hydrochloric acid and 500ml of water. The layers were separated and the aqueous layer was extracted with two portions of dichloromethane (300ml per portion). The organic fractions were combined and washed with saturated aqueous sodium bicarbonate (400 ml). The organic layer was dried over anhydrous sodium sulfate and evaporated to give 48.0 g of 4-fluoro-4' -methoxy-benzophenone as a white solid. This material was used directly in the next step without further purification.

Step 2:the 4-fluoro-4' -methoxy-benzophenone from step 1 (126.7 g) and acetylene saturated N, N-dimethylformamide (380ml) were combined in a reaction flask. Sodium acetylene solution (9 wt% in toluene, 343 g) was added dropwise to the reaction mixture over 45 minutes. The reaction mixture was stirred at room temperature for 1 hour and then poured into ice water (600 ml). The layers were phase separated and the aqueous layer was extracted with three portions of diethyl ether (200 ml). The organic layers were combined and washed with saturated aqueous ammonium chloride (200ml), saturated aqueous sodium chloride (200ml) and saturated aqueous sodium bicarbonate (200 ml). The organic layer was dried over anhydrous sodium sulfate and evaporated to give 136.6 g of 1- (4-fluorophenyl) -1- (4-methoxyphenyl) -2-proparg-1-ol as a pale yellow oil. This material was used directly in the next step without further purification.

And step 3:in a reaction flask 1- (4-fluorophenyl) -1- (4-methoxyphenyl) -2-propargyl-1-ol from step 2 (26.3 g), 2, 3-dimethoxy-5, 7-dihydroxy-7-ethyl-7H-benzo [ C ] from example 8 part A, step 4]Fluorene (30.0 g), dodecylbenzenesulfonic acid (2.9 g) and chloroform (stored with pentene, 600ml) were combined and stirred at room temperature for 1 hour. The reaction mixture was washed with saturated aqueous sodium hydrogencarbonate solution (300ml) and the organic layer was dried over anhydrous sodium sulfate. The organic layer was evaporated to a dark oil to which warm methanol was added. The resulting precipitate was collected by vacuum filtration and washed with cold methanol to give 34.5 g of 3- (4-fluorophenyl) -3- (4-methoxyphenyl) -6, 7-dimethoxy-13-ethyl-13-hydroxy-3H, 13H-indeno [2, 1-f)]Naphtho [1, 2-b ]]A pyran. This material was used directly in the next step without further purification.

And 4, step 4:3- (4-fluorophenyl) -3- (4-methoxyphenyl) -6, 7-dimethoxy-13-ethyl-13-hydroxy-3H, 13H-indeno [2, 1-f ] from step 7 was placed in a reaction flask]Naphtho [1, 2-b ]]Pyran (35.0 g), diethylene glycol (350ml), toluene (350ml) and p-toluenesulfonic acid monohydrate (1.73 g) were combined and heated to 85 ℃ for 6 hours. The reaction mixture was cooled to room temperature and diluted with toluene (350 ml). The reaction mixture was washed with saturated aqueous sodium bicarbonate (300ml) and four portions of saturated aqueous sodium chloride (300ml per portion). The organic layer was dried over anhydrous sodium sulfate and concentrated to a dark oil. The oil was chromatographed on silica gel, eluting with a mixture of 25% ethyl acetate in hexane. The photochromic fractions were collected and concentrated by rotary evaporation. The resulting residue was recrystallized from a mixture of 10% hexane in t-butyl methyl ether to yield 16.6 g of a white solid. NMR analysis showed that the product had a chemical identity to 3- (4-fluorophenyl) -3- (4-methoxyphenyl) -6, 7-dimethoxy-13-ethyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] ]Naphtho [1, 2-b ]]Pyrans have a consistent structure.

And part B:

an example photochromic material, "PM-9", was prepared using the photochromic initiators given in part a (above) as follows: 1.6577g of the photochromic initiator given in section A above, 5.0002g of epsilon-caprolactone monomer and 0.0067g of 2-ethyltin (II) octanoate were charged under nitrogen into a three-necked flask equipped with a condenser, nitrogen inlet and magnetic stirring bar. The reaction mixture was stirred at room temperature until a dark homogeneous solution formed. Followed by polymerization at 140 ℃ for 8 hours. Thereafter, the highly viscous mixture was cooled to about 80 ℃ and transferred to a glass bottle. The product was a solid at room temperature, having a number average and a weight average molecular weight, determined by GPC, of 2200 and 3700/mol, respectively, relative to polystyrene standards. The product is considered to be a mixture of photochromic materials having a general structure represented by the following formula 25, wherein 'a' is an integer of 1 to 382.

General formula 25

Example 10: example preparation of photochromic Material "PM-10

An example photochromic material, "PM-10", was prepared using the photochromic initiator given in part a of example 8 (above) as follows: 1.6310g of the photochromic initiator of example 8 part A, 8.9370g of epsilon caprolactone monomer and 0.0120g of tin (II) 2-ethyloctanoate were charged under nitrogen into a three-necked flask equipped with a condenser, nitrogen inlet and magnetic stir bar. The reaction mixture was stirred at room temperature until a dark homogeneous solution formed. Polymerization was carried out at 140 ℃ for 10 hours. Thereafter, the highly viscous mixture was cooled to about 80 ℃ and transferred to a glass bottle. The product was a solid at room temperature, having a number average and a weight average molecular weight, determined by GPC, of 3100 and 7200/mol, respectively, relative to polystyrene standards. The product is considered to be a mixture of photochromic materials having a general structure represented by the general formula 25 (above), wherein 'a' is an integer of 1 to 665.

Example 11: example preparation of photochromic Material "PM-11

An example photochromic material, "PM-11", was prepared using the photochromic initiator given in part a of example 7 (above) as follows: 1.8334g of the photochromic initiator given in example 7 part A, 3.080g of epsilon caprolactone monomer and 0.0041g of tin (II) 2-ethyloctoate were charged under nitrogen into a three-necked flask equipped with a condenser, nitrogen inlet and magnetic stirring bar. The reaction mixture was stirred at room temperature until a dark homogeneous solution was formed and polymerized at 140 ℃ for 7 hours. Thereafter, the very viscous mixture was cooled to about 80 ℃ and transferred to a glass bottle. The product was a solid at room temperature, having a number average and weight average molecular weight, determined by GPC, of 1300 and 1900g/mol, respectively, relative to polystyrene standards. The product is considered to be a mixture of photochromic materials having the general structure represented by formula 25 (above), wherein 'a' is an integer from 1 to 117.

Example 12: example preparation of photochromic Material "PM-12

An example photochromic material, "PM-12", was prepared using the photochromic initiator given in part a of example 9 (above) as follows: 1.2358g of the photochromic initiator given in example 9 part A above, 7.4580g of epsilon caprolactone monomer and 0.0100g of tin 2-ethyl octanoate (I I) were charged under nitrogen into a three-necked flask equipped with a condenser, nitrogen inlet and magnetic stir bar. The reaction mixture was stirred at room temperature until a dark homogeneous solution formed. Followed by polymerization at 140 ℃ for 10 hours. Thereafter, the highly viscous mixture was cooled to about 80 ℃ and transferred to a glass bottle. The product was a solid at room temperature, having a number average and a weight average molecular weight determined by GPC of 3100 and 8100/mol, respectively, relative to polystyrene standards. The product is considered to be a mixture of photochromic materials having the general structure represented by formula 25 (above), wherein 'a' is an integer from 1 to 853.

Example 13: example preparation of photochromic Material "PM-13

Part A: preparation of photochromic initiators

A photochromic initiator (represented by structure 1.18 in table 1 above) was prepared as follows: in a 300ml round bottom flask, 9.4g (0.02 mol) of 2, 2-bis (4-methoxyphenyl) -5-methoxycarbonyl-6-hydroxy- [2H ] -naphtho [1, 2-b ] pyran were dissolved in 100ml of DMF Dimethylformamide (DMF). Powdered anhydrous potassium carbonate (13.8g, 0.1 mole) was added and the mixture stirred and heated to 80 ℃ while 5g (0.04 mole) of 2-bromoethanol was added dropwise. The reaction was monitored by TLC (thin layer chromatography) and after 4 hours, in which no more starting material was present, the reaction was quenched by pouring one liter of water. The product was extracted into chloroform, concentrated and chromatographed on silica using 2: 1 ethyl acetate: hexane as eluent. The red photochromic fraction was collected and the product was crystallized from a diethylether: hexane mixture. The resulting material was 2, 2-bis (4-methoxyphenyl) -5-methoxycarbonyl-6- (2-hydroxyethoxy) - [2H ] -naphtho [1, 2-b ] pyran represented by structure 1.18 in table 1 above.

And part B:

an example photochromic material, "PM-13", was prepared using the photochromic initiators given in part a (above) as follows: 1.4580g of the photochromic initiator given in part A above, 3.0340g of epsilon-caprolactone, 2.6613g of delta-valerolactone and 0.0179g of tin 2-ethyloctoate (I I) were charged under nitrogen into a three-necked flask equipped with a condenser, nitrogen inlet and magnetic stir bar. The reaction mixture was stirred at room temperature until a dark homogeneous solution formed. Followed by polymerization at 120 ℃ for 7 hours. Thereafter, the highly viscous mixture was cooled to about 80 ℃ and transferred to a glass bottle. The product was liquid at room temperature, having a number average and weight average molecular weight of 2900 and 3400/mol, respectively, as determined by GPC, relative to polystyrene standards. The product is considered to be a mixture of photochromic materials having a general structure represented by the following formula 26, wherein the "random copolymer" is a random copolymer of epsilon-caprolactone and delta-valerolactone.

General formula 26

Example 14: example preparation of photochromic Material "PM-14

The photochromic material PM-14 was prepared as follows: 6.5g of the photochromic material PM-2 described in example 2 above was dissolved in 50ml of chloroform with stirring. A molar excess of triethylamine and a catalytic amount of 4-Dimethylaminopyridine (DMAP) were then added, followed by five drops of 4-methoxybenzoyl chloride. The progress of the reaction was monitored by TLC. After two hours, five more drops of the benzoyl chloride were added. This process was repeated until TLC showed no more starting material present. At this point, the reaction mixture was poured into 250ml of water. The organic portion was separated, concentrated and then chromatographed on silica using a 2: 1 mixture of hexane: ethyl acetate. The photochromic portions were collected, combined and concentrated to obtain an oil that solidified upon standing. The resulting material has the structure given above in formula 18, except that the hydroxyl groups are capped with p-anisoyl groups.

Example 15: example preparation of photochromic Material "PM-15

An example photochromic material, "PM-15", was prepared using the photochromic initiator given in part a of example 2 (above) as follows: 1.2475g of the photochromic initiator given in example 2 (above) part A, 3.7128g of trimethylene carbonate (TMC) monomer and 0.0124g of tin (II) 2-ethyloctanoate were charged under nitrogen into a three-necked flask equipped with a condenser, nitrogen inlet and magnetic stir bar. The polymerization procedure was the same as given in example 2 part B (above). The product was a solid at room temperature, having a number average and weight average molecular weight, determined by GPC, of 2700 and 4700g/mol, respectively, relative to polystyrene standards. The product is considered to be a mixture of photochromic materials having a general structure represented by the following formula 27, wherein 'a' is an integer of 1 to 402.

General formula 27

Example 16: example preparation of photochromic Material "PM-16

An example photochromic material, "PM-16", was prepared using the photochromic initiator given in part a of example 2 (above) as follows: 2.1127g of the photochromic initiator given in example 2 (above) part A, 6.2878g of Lactide (LT) monomer and 0.0210g of 2-ethyltin (II) octanoate were charged under nitrogen into a three-necked flask equipped with a condenser, nitrogen inlet and magnetic stirring bar. The polymerization procedure was the same as given in example 2 part B (above). The product was a solid at room temperature, having a number average and weight average molecular weight determined by GPC of 1756 and 3840g/mol, respectively, relative to polystyrene standards. The product is considered to be a mixture of photochromic materials having a general structure represented by the following formula 28, wherein 'a' is an integer of 1 to 209.

General formula 28

Testing

Example 17:

a photochromic coating composition (represented as "example coating 1" in table 3 below) was prepared using the photochromic material PM-1 given in example 1. In addition, two comparative photochromic coating compositions, designated "comparative coating A" and "comparative coating B" in Table 3, were prepared using the following comparative photochromic materials "CPM-A" and "CPM-B", respectively. The comparative example photochromic material CPM-a (which is represented by the following formula 29) was prepared as follows. Piperidine (1.5ml) and anhydrous tetrahydrofuran (150ml) were added to the oven dried reaction flask. The reaction mixture was cooled in an ice bath. To this reaction mixture 7ml of butyllithium (2.5M in hexane) was added slowly dropwise over 20 minutes. The reaction mixture was allowed to warm to room temperature and the desired product of example 4, step 6 of U.S. Pat. No. 6,296,785 (3, 3-bis (4-methoxyphenyl) -6, 7-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran, 5.0 g) was added. The reaction mixture was stirred at room temperature overnight and then poured slowly into ice water (250 ml). Aqueous hydrochloric acid (10% v/v) was added until pH 4 and then diluted with ethyl acetate (100 ml). The layers were separated and the aqueous layer was extracted with three 100ml portions of ethyl acetate. The organic layers were combined and washed with saturated aqueous sodium bicarbonate (200 ml). The organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The resulting residue was recrystallized from tert-butyl methyl ether to obtain 1.6 g of a white solid. NMR and mass spectral analysis showed that the product had a structure and molecular weight consistent with that of 3, 3-bis (4-methoxyphenyl) -6-methoxy-7-piperidino-13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran.

General formula 29

Comparative example photochromic material CPM-B is the photochromic material given in example 1 part a.

Each coating composition was prepared as follows: the appropriate photochromic materials were pre-dissolved in N-methylpyrrolidone ("NMP") and the remaining components given in table 3 were then added to this solution in the amounts listed. The resulting mixture was stirred using a magnetic stir bar for approximately 30 minutes until a homogeneous mixture was obtained. After mixing, each coating composition was applied by spin coating at 1500rpm for 6 seconds to a wet weight of about 0.2g on a Gentex PDQ hard coated polycarbonate lens (1.5X 70mm) which had been previously plasma treated. The coating was cured at 120 ℃ for 1 hour to a final thickness of about 20 microns. The components of the coating composition were adjusted so that each of the three coatings had substantially the same Fischer hardness (as shown in table 3). The Fischer hardness and photochromic performance of each of the coated lenses were measured according to the following discussion.

TABLE 3

¹HDI Biuret B17960 is a blocked hexamethylene diisocyanate available from Baxenden Chemical Co., Lancaster, England.

²HC-86-7776 is a polyacrylate polymer available from PPG Industries, Inc., Pittsburgh, Pennsylvania.

³PC-1122 is an aliphatic carbonate diol available from Stahl USA.

^4，5Available from Aldrich of Milwaukee, Wisconsin. NMP is biotechnological grade.

Fischer microhardness tests were performed using Fischer scope HCV, Model H-100, available from Fischer Technology, Inc. The Fischer microhardness (or "Fischer hardness") of the coating was determined in Newton/mm under the following conditions²: 100 millinewton load, 30 loading steps and a 0.5 second pause between loading steps. The Fischer hardness data reported herein were measured at an indenter depth of 2 μm.

The photochromic properties of each of the above coating compositions were carried out as follows. The coated lenses prepared above were tested for photochromic response on an optical bench of the optical bench ("BMP") for measuring photochromic properties manufactured by Essilor, ltd. The optical bench was maintained at a constant temperature of 73.4 ° F (23 ℃) during the test.

Each of the coated lenses was exposed to 365 nm uv light for about 10 minutes at a distance of about 14 cm to activate the photochromic material prior to testing on the optical bench. UVA (315 to 380nm) irradiance at the lens was measured using a Licormodel Li-1800 spectroradiometer and found to be 22.2 watts per square meter. The lens was then placed under a 500 watt high intensity halogen lamp for about 10 minutes at a distance of about 36 centimeters to discolor (passivate) the photochromic material. The illuminance at the lens was measured with a Licor spectroradiometer and found to be 21.4 Klux. The lens is then kept in a dark environment at room temperature (70 to 75F, or 21 to 24℃) for at least 1 hour before testing on the optical bench. The ultraviolet absorbance of the lens at 390 and 405 nanometers was measured prior to the optical bench measurements.

The BMP optical bench was equipped with two 150 watt Oriel Model #66057 xenon arc lamps at right angles to each other. The light path of the lamp 1 is guided through a 3mm Schott KG-2 band filter and a suitable medium density filter which helps to achieve the required UV and partial visible light irradiance levels. The light path of the lamp 2 is directed through a 3mm Schott KG-2 band pass filter, a Schott short wave 400nm cut-off filter and a suitable medium density filter to provide supplemental visible light illuminance. The two beams were mixed using a 2 inch x 2 inch 50% circular beam splitter at 45 ° to each lamp. The combination of the medium density filter and the voltage control of the xenon arc lamp is used to adjust the intensity of the irradiance. Proprietary software was used on the BMP to control time, irradiance, air cell (air cell) and sample temperature, shutter, filter selection and response measurement. A Zeiss spectrophotometer (Model MCS 501) in which the optical cable for light transmission passes through the lens is used for the measurement of response and color. Light adaptive response measurements were collected on each lens, as well as responses at four selected wavelengths.

The power output of the optical bench, i.e., the light dose to which the lens is exposed, was adjusted to 6.7 watts per square meter (W/m)²) UVA, integrated from 315-380nm and 50Klux illumination, integrated from 380-780 nm. The measurement of the power output was performed using a photometer and software contained inside the BMP.

Response measurements, i.e. the change in optical density (Δ OD) from an unactivated or faded state to an activated or colored state, were determined as follows: an initial unactivated transmittance is established, the shutter of the xenon lamp is opened and the activated transmittance is measured at selected time intervals. The optical density change was determined according to the following formula: Δ OD log₁₀(% Tb/% Ta), where% Tb is the percent transmission in the faded state and% Ta is the percent transmission in the activated state. Optical density measurements are based on optically adapted optical density.

The results of this test are given in table 4 below, where the first fade half-life ("T1/2") value is the time interval (seconds) for the delta OD of the activated form of photochromic material in the coating to reach half the fifteen minute delta OD at 73.4 ° F (23 ℃) after removal of the activating light source. The second fade half-life ("2T 1/2") value is the time interval (seconds) for the delta OD of the activated form of the photochromic material in the coating to reach one-quarter of the fifteen minutes delta OD at 73.4 ° F (23 ℃) after removal of the activating light source. The third half-life ("3T 1/2") value is the time interval (seconds) for the delta OD of the activated form of the photochromic material in the coating to reach one-eighth of the fifteen minutes delta OD at 73.4 ° F (23 ℃) after removal of the activating light source. In addition, the "AT 3/4" value is the time interval (seconds) for the delta OD of the photochromic material in faded form in the coating to reach three-quarters of a fifteen minute delta OD AT 73.4F (23℃) after exposure to an activating light source.

TABLE 4

Response to	Example coating 1	Comparative coating A	Comparative coating B
				T1/2 (seconds)	207	245	375
2T1/2 (seconds)	453	551	894
				3T1/2 (seconds)	727	968	1743
AT 3/4 (seconds)	42	43	63

From the results in Table 4, it can be seen that the T1/2, 2T1/2, and 3T1/2 values for example coating 1 (which included the photochromic material PM-1 of example 1) were less than those for comparative coating A or comparative coating B (which included the comparative photochromic materials CPM-A and CPM-B, respectively) (i.e., the fade rate of example coating 1 was faster than either comparative coating). Further, the AT 3/4 value for example paint 1 was less than the AT 3/4 activation rate of comparative paint B and was substantially the same as the AT 3/4 activation rate of comparative paint a.

Example 18:

two photochromic coating compositions (denoted "example coating 2" and "example coating 4" in table 5 below) were prepared using the example photochromic material PM-2 given in example 2 and the example photochromic material PM-4 given in example 4. In addition, two comparative example photochromic coating compositions (designated "comparative coating C" and "comparative coating D" in Table 5 below) were prepared using comparative photochromic materials CPM-C and CPM-D, respectively.

A comparative photochromic material CPM-C, which is represented by formula 30 below, is 3, 3-bis (4-methoxyphenyl) -6, 11, 13-trimethyl-13-hydroxy-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran, prepared as described in example 5 of U.S. Pat. No. 5,645,767.

General formula 30

Comparative photochromic material CPM-D is the photochromic material given in example 2 part a. As described above in example 17, each coating composition was prepared by mixing the components given in Table 5 in the amounts listed. After preparation, each coating was coated onto a plasma treated Gentex PDQ hard coat flat polycarbonate lens and cured as described above in example 15, except that spin coating was performed at 1500rpm for 5 seconds. The components of example coating 2 and the comparative coating were adjusted so that each of the three coatings had substantially the same Fischer hardness (as shown in table 5 below). Example coating 4 had a higher Fischer hardness.

TABLE 5

The Fischer hardness test and photochromic performance test were performed on each of the coated lenses as discussed in example 17 above. In addition, the lenses with example coating 2 and the two comparative coatings were subjected to an NMP soak test to determine the amount of photochromic material that could leach out of the coating. More specifically, each coating was applied to a hard coated polycarbonate lens and cured in an NMP soak test. Thereafter, each lens was soaked in NMP for 1 hour. UV absorbance at 390nm was measured before and after NMP soaking. % photochromic loss was determined by measuring% loss of UV absorbance after soaking. NMP was used in this test because the photochromic material could be extracted into the solvent.

The results of the above tests are given in table 6 below.

TABLE 6

Response to	Example coating 2	Comparative coating C	Comparative coating D	Example coating 4
					T1/2 (seconds)	37	54	63	31
2T1/2 (seconds)	94	152	222	67
					3T1/2 (seconds)	-	-	-	145
AT3/4 (seconds)	4.6	5.9	6.6	4.3
					NMP soak (light induced deformation)% color loss)	0	90	10	-*

None of the tests

From the results in Table 6, it can be seen that the AT3/4, T1/2, and 2T1/2 values for the example coatings 1 and 4, which comprise the example photochromic materials PM-2 (example 2) and PM-4 (example 4), respectively, are less than the AT3/4, T1/2, and 2T1/2 values of either of the comparative coating compositions (i.e., the example coatings activate and fade more quickly than those of the comparative coatings). Additionally, example coating 4 had smaller T1/2, 2T1/2, and AT3/4 values than the comparative coating, and the Fischer hardness of this example coating 4 was AT least twice that of the comparative coating composition. Further, during the NMP soak, substantially no leaching of the photochromic material from the example paint 2 was detected after the NMP soak, however, leaching of the photochromic material from the comparative paint was detected.

Example 19:

an example photochromic coating composition (represented as "example coating 5" in table 7 below) was prepared using the example photochromic material PM-5 given in example 5. In addition, a comparative example photochromic coating composition (represented as "comparative coating H '" in table 7 below) was prepared using a comparative photochromic material "CPM-H'" (which is given in example 20 below).

As described above in example 17, each coating composition was prepared by mixing the components given in Table 7 in the amounts listed. After preparation, each coating was applied to a plasma treated Gentex PDQ hard coated flat polycarbonate lens and cured as described in example 18 above. The composition of example coating 5 and comparative coating H' were adjusted so that each of the coatings had substantially the same Fischer hardness (as shown in table 7 below).

TABLE 7

The Fischer hardness test and photochromic performance test were performed on each of the coated lenses as discussed in example 17. In addition, the NMP soak test was performed as discussed in example 18 above.

The results of the above tests are given in table 8 below.

TABLE 8

Response to	Example coating 5	Comparative coating E
			T1/2 (seconds)	72	70
2T1/2 (seconds)	173	168
			AT3/4	46	49

From the results in Table 8, it can be seen that T1/2, 2T1/2, and AT3/4 of the example coating 5, which comprises the example photochromic material PM-5 (example 5), are similar to those of the comparative coating H ', which coating H' comprises the comparative photochromic material CPM-H.

Example 20:

the migration performance of the following photochromic materials was tested as follows: two coating compositions ("example coating 789" and "comparative coating FGH") were prepared by mixing the components given in table 9. Example coating 789 includes three example photochromic materials, PM-7, PM-8, and PM-9, which are described above in examples 7, 8, and 9, respectively. The comparative coating FGH contains three comparative example photochromic materials (CPM-F, -G, and-H), which are not bonded to the polymer coating.

Comparative example photochromic material CPM-F was prepared as follows: 7, 7-dimethyl-5-hydroxy-7H-benzo [ C ] fluorene (2.6g, 0.01 mole) from part A, step 4 of example 7 was dissolved in 100ml of toluene together with 3.5g (slight molar excess) of 1- (4-methoxyphenyl-1- (4-morpholinophenyl) -2-propargyl-1-ol, the mixture was stirred at 40 ℃ and dodecylbenzenesulfonic acid was added dropwise until a consistent dark color was obtained after 2 hours TLC showed that the reaction was substantially complete, after which 300ml of water was added to the stirred mixture, the organic layer was separated and the solvent was removed on a rotary evaporator, the crude product was chromatographed on a silica column using a hexane: ethyl acetate 2: 1 mixture, the photochromic fractions were collected, combined and the solvent was removed on a rotary evaporator, the residue was crystallized from methanol, 1.8g of white crystals are obtained, the NMR of which is in accordance with the structure 3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran.

Comparative example photochromic material CPM-G was prepared as follows: the 3, 3-bis (4-methoxyphenyl) -6-methoxy-7-morpholino-13-ethyl-13-hydroxy-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran from example 8 part a, step 6 (68.7 g), anhydrous methanol (685ml), toluene (685ml), and p-toluenesulfonic acid monohydrate (5.1 g) were combined in a reaction flask and heated to reflux. After four hours of reflux, and after eight hours of reflux, additional p-toluenesulfonic acid monohydrate was added in two 0.5 gram portions. The reaction mixture was then refluxed overnight. Subsequently, the reaction mixture was cooled to room temperature and diluted with toluene (400 ml). The reaction mixture was washed with 50% saturated aqueous sodium bicarbonate (800 ml). The organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The resulting residue was chromatographed on silica gel (1,300 g), eluting with 25% ethyl acetate in hexane. The photochromic fractions were combined and concentrated by rotary evaporation. The resulting residue was recrystallized from 20% hexane in t-butyl methyl ether to yield 62.6 g of a tan solid. Mass spectrometry and NMR spectroscopy indicated that the product had a structure consistent with 3, 3-bis (4-methoxyphenyl) -6-methoxy-7-morpholino-13-ethyl-13-methoxy-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran.

Comparative example photochromic material CPM-H was prepared as follows: 3- (4-fluorophenyl) -3- (4-methoxyphenyl) -6, 7-dimethoxy-13-ethyl-13-hydroxy-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran (14.9 g), diethylene glycol monomethyl ether (150ml), toluene (150ml) and p-toluenesulfonic acid monohydrate (0.495 g) from example 9 part A, step 3 were combined in a reaction flask and heated to 95 ℃ for 6 hours. The reaction mixture was cooled to room temperature and diluted with toluene (150 ml). The reaction mixture was washed with 50% saturated aqueous sodium bicarbonate (200ml) and four portions of saturated aqueous sodium chloride (175ml per portion). The organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The resulting residue was chromatographed on silica gel, eluting with 25% ethyl acetate in hexane. The photochromic fractions were collected and concentrated by rotary evaporation. The resulting residue was recrystallized from 20% hexane in t-butyl methyl ether to yield 9.3 g of a white crystalline solid. NMR mass spectrometry and NMR spectroscopy indicated that the product had a structure consistent with 3- (4-fluorophenyl) -3- (4-methoxyphenyl) -6, 7-dimethoxy-13-ethyl-13- (2- (2-methoxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran.

Each coating composition was then spin coated onto each of two plasma treated Gentex PDQ hard coated flat polycarbonate lenses and cured as described above in example 18. One coated lens of each pair of coated lenses was further treated with plasma and a protective coating having the composition given in table 10 below was spin coated over the photochromic coating to a wet film weight of about 0.6 grams and to a thickness of about 10-12 microns by UV curing in a nitrogen atmosphere. Each of the protective coated lenses was then post-baked at 105 ℃ for 3 hours to simulate the conditions seen in a typical hard coating curing process.

TABLE 9

Watch 10

Components	Amount (wt%)
		SR-3996	5
SR-3507	30
		SR-3488	35
Part (A)Methacrylated bisphenol A diepoxide9	30
		SILQUESTTMA-18710	20
Irgacure 81911	0.1
		CD-101112	4

⁶SR-399 is dipentaerythritol pentaacrylate available from Sartomer Company, Exton, Pennsylvania.

⁷SR-305 is trimethylolpropane trimethacrylate, available from Sartomer Company.

⁸SR-348 is an ethoxylated bisphenol A dimethacrylate available from Sartomer Company.

⁹Obtained as ADME #302 from Echo Resins and Laboratories, Versailles, Missouri.

¹⁰SILQUEST A-187 is gamma-glycidoxypropyltrimethoxysilane available from Osi specificities, Paris, France.

¹¹Irgacure 819 is a bisacryloylphosphine oxide photoinitiator available from Ciba-Geigy, Basel, Switzerland.

¹²CD-1011 is a triarylsulfonium hexafluorophosphate cation light guide available from Sartomer CompanyA hair agent.

Photochromic performance tests were performed on each lens in the coated lens pair (i.e., with and without the protective coating) as described in example 17 above. The results of this test are given in table 11 below.

TABLE 11

From Table 11 above, it can be seen that the T1/2 and 2T1/2 values for the example coating 789 coating (with and without the protective coating) are less than those for the comparative coating FGH with and without the protective coating, respectively. In addition, as shown in table 11, the values of 2T1/2, T70%, and T75% for example coating 789 (i.e., the time intervals (minutes) at which the lens reached 70% and 75% light transmittance, respectively) were substantially the same with and without the protective coating. This indicates that: the photochromic materials bound to the coating composition in the example coating 789 have less migration into the harder protective coating. In contrast, the t-70% and t-75% values of the comparative coating FGH are longer with the protective coating than without it. This indicates that: some portion of the comparative photochromic material of the comparative coating FGH migrates into the harder protective coating, which causes the photochromic properties of the comparative coating FGH to deteriorate.

Example 21:

the example coatings and comparative coatings given in table 12 below were prepared as described above in example 17 and applied to lenses as described above in example 18. Each photochromic coating was formulated to have approximately 15N/mm²The Fischer hardness of (2).

TABLE 12

Photochromic coatings	HDI biuret B17960	PC-1122	HC-86-7726	NMP	DBTDL	BYK3331	Photochromic material
								Comparative coating F	2.5	1.25	1.25	2	0.08	0.003	0.08g CPM-F
Comparative coating I	2.5	1.25	1.25	2	0.08	0.003	0.084g CPM-I2
								Example coating 11	1.25	0.39	0.45	0.92	0.04	0.002	0.219g PM-11
Example coating 7	1.25	0.04	0.45	0.92	0.04	0.002	0.183g PM-7
								Comparative coating H	2.5	1.25	1.25	2	0.08	0.003	0.0914g CPM-H
Comparative coating J	2.5	1.25	1.25	2	0.08	0.003	0.0895g CPM-J3
								Example coating 9	1.25	0.425	0.45	0.92	0.04	0.002	0.19g PM-9
Example coating 12	1.25	0.39	0.45	0.92	0.04	0.002	0.219g PM-12
								Comparative coating G	2.5	1.25	1.25	2	0.08	0.003	0.0887g CPM-G
Comparative coating K	2.5	1.25	1.25	2	0.08	0.003	0.0986g CPM-K4
								Example coating 8	2.5	0.85	0.9	1.84	0.08	0.003	0.388g PM-8
Example coating 10	1.25	0.39	0.45	0.92	0.04	0.002	0.232g PM-10

¹BYK 333 is a polyether modified dimethylpolysiloxane copolymer available from BYK-Chemie, Wallingford, Connecticut.

²Example 7 part a photochromic material.

³Example 9 part a photochromic material.

⁴Example 8 part a photochromic material.

The number average molecular weight of each of the photochromic materials used in the photochromic coatings listed in table 12 was determined using GPC or by theoretical calculation (according to the description). The T1/2 and 2T 1/2 fade rates for each of the photochromic coatings listed in table 12 were measured as discussed in example 17 above. These results are given in table 13 below.

Watch 13

Photochromic coating	MW(g/mol)	T1/2 (seconds)	T1/2 (seconds)
				Comparative coating F	565*	34	78
Comparative coating I	595*	70	225
				Example coating 11	1300	37	95
Example coating 7	1800	30	70
				Comparative coating H	677*	61	150
Comparative coating J	663*	97	315
				Example coating 9	2200	54	130
Example coating 12	3100	50	117
				Comparative coating G	656*	49	120
Comparative coating K	730*	77	265
				Example coating 8	2000	34	78
Example coating 10	3100	32	75

MW determined by theoretical calculation and rounded.

As can be appreciated from table 13, example coatings comprising photochromic materials according to various non-limiting embodiments disclosed herein generally have shorter T1/2 and 2T1/2 values (i.e., faster fade rates) than photochromic coatings comprising comparative photochromic materials.

Example 22:

an example photochromic coating composition (represented as "example coating 13" in table 14 below) was prepared using the example photochromic material PM-13 given in example 13. In addition, two comparative example photochromic coating compositions (designated "comparative coating L" and "comparative coating M" in Table 14 below. in addition, each of the photochromic materials PM-13 and CPM-M is bonded to the polymeric material of their respective coatings (example coating 13 and comparative coating M.) were prepared using the comparative photochromic material CPM-L and comparative photochromic material CPM (which are the photochromic materials given in example 13, part A, above) given below, whereas the photochromic material CPM-L did not.

A comparative photochromic material CPM-L having a structure represented by formula 31 below was prepared as described in example 2 of U.S. Pat. No. 5,458,814 column 13, line 55 to column 14, line 7, which example is specifically incorporated herein by reference.

General formula 31

As described above in example 17, each coating composition was prepared by mixing the components given in Table 14 in the amounts listed. After preparation, each coating was applied to a plasma treated Gentex PDQ hard coated flat polycarbonate lens and cured as described in example 18 above. As shown in table 14 below, the compositions of the example 13 and comparative L and M coatings were adjusted so that each of the coating layers had substantially the same Fischer hardness.

TABLE 14

The coatings discussed above were tested for photochromic performance as described in example 17. The results of the photochromic testing are given in table 15 below.

Watch 15

Response to	Example coating 13	Comparative coating L	Comparative coating M
				T1/2 (seconds)	75	100	160
2T1/2 (seconds)	230	350	1100

[0396] From the results in Table 15, it can be seen that example paint 13 had shorter T1/2 and 2T1/2 values (i.e., faster fade rates) than either comparative paint L or comparative paint M.

Example 23:

An example photochromic coating composition (represented as "example coating 14" in table 16 below) was prepared using the example photochromic material PM-14 given in example 14. A second example photochromic coating composition (represented as "example coating 2'" in table 16 below) was prepared using the example photochromic material PM-2 given in example 2 above. Further, a comparative example photochromic coating composition (indicated as "comparative coating C'" in table 14 below) was prepared using the comparative photochromic material CPM-C as described in example 18 above.

As described above in example 17, each coating composition was prepared by mixing the components given in Table 16 in the amounts listed. After preparation, each coating was applied to a plasma treated Gentex PDQ hard coated flat polycarbonate lens and cured as described in example 17 above. As shown in table 16 below, the components of each coating composition were adjusted so that each of the coating layers had substantially the same Fischer hardness. The two photochromic materials PM-14 and CPM-C were blended in, rather than bonded to, the polymeric materials of their respective photochromic coating compositions (i.e., example coating 14 and comparative coating C'). The photochromic material PM-2 is bonded to the polymeric material of the example coating 2'.

TABLE 16

The coatings discussed above were subjected to photochromic performance and NMP soak tests as described in example 18. The results of these tests are given in table 17 below.

TABLE 17

Response to	Example coating 14	Comparative dope 2'	Comparative coating C'
				T1/2 (seconds)	31	35	64
2T1/2 (seconds)	120	95	177
				Loss in NMP soak%	61	0	55

From the results in Table 17, it can be seen that the two example coatings 14 and 2 'have lower T1/2 and 2T1/2 values (i.e., faster fade rates) than the comparative coating C'. Further, no leaching of the photochromic material from the example paint 2 'was detected after NMP soaking, however, leaching of the photochromic material from the comparative paint C' and the example paint 14 was detected. Additionally, the example coating 14, in which the photochromic material is not bonded to the polymer coating, exhibits blooming after curing.

It is to be understood that this specification illustrates aspects of the invention relevant to a clear understanding of the invention. Certain aspects of the present invention that will be apparent to those of ordinary skill in the art and that, therefore, will not facilitate a better understanding of the invention have not been presented in order to simplify the present description. While the invention has been described in connection with certain embodiments, the invention is not limited to the particular embodiments disclosed, but is intended to cover modifications within the spirit and scope of the invention as defined by the appended claims.

Claims (87)

1. A photochromic material comprising the reaction product of:

(a) at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates; and

(b) a photochromic initiator.

2. The photochromic material of claim 1 wherein at least one ring-opening cyclic monomer is a cyclic ester represented by the general formula:

wherein c and d are integers from 1 to 8; each carbon unit, i.e. each (C)_cAnd (C)_dR of unit³、R⁴、R⁵And R⁶Independently selected from-H, -CH₃C2-C16 alkyl, C (CH)₃)₂And HO-CH₂-; e is 0 or 1; d is selected from-O-or-O-C (O); or wherein c is 1; d is-C (R)³′)(R⁴′)-；R³' and R⁴' and R³And R⁴Together form a fused aryl, fused heterocyclic aryl, or fused cyclic aliphatic group.

3. The photochromic material of claim 1 wherein at least one ring-opening cyclic monomer is a cyclic ester selected from the group consisting of: epsilon-caprolactone; tert-butyl caprolactone; ζ -heptalactone; delta-valerolactone; monoalkyl delta-valerolactone; nonanyl-, dialkyl-, or trialkyl-epsilon-caprolactone; a beta-lactone; a gamma-lactone; dilactones and ketolidesAn alkanone.

4. The photochromic material of claim 1 wherein at least one ring-opening cyclic monomer is a cyclic carbonate represented by the general formula:

wherein f and g are integers from 1 to 3; r per carbon unit ⁷、R⁸、R⁹And R¹⁰Each independently selected from-H, -CH₃C2-C16 alkyl, C (CH)₃)₂、H0-CH₂-, or-0C₆H₅(ii) a h is 0 or 1; e is-0-.

5. The photochromic material of claim 1, wherein the photochromic material comprises the reaction product of a plurality of ring-opening cyclic monomers.

6. The photochromic material of claim 5 wherein each of the plurality of ring-opening cyclic monomers is independently selected from the group consisting of epsilon-caprolactone and delta-valerolactone.

7. The photochromic material of claim 1, wherein the photochromic initiator comprises a photochromic material selected from the group consisting of pyrans, oxazines, and fulgides.

8. The photochromic material of claim 1, wherein the photochromic initiator comprises a pyran selected from the group consisting of benzopyrans, naphthopyrans, phenanthropyrans, quinopyrans, fluoranthenopyrans (fluoroanthrapyrans), and spiropyrans.

9. The photochromic material of claim 1 wherein the photochromic initiator comprises a naphthopyran selected from the group consisting of naphtho [1, 2-b ] pyrans, naphtho [2, 1-b ] pyrans, indenonaphthopyrans, and heterocyclic fused naphthopyrans.

10. The photochromic material of claim 1, wherein the photochromic initiator comprises at least one functional group suitable for initiating the ring opening of at least one ring-opening cyclic monomer, the at least one functional group being selected from the group consisting of alcohols, amines, carboxylic acids, silanols, thiols and combinations, salts and complexes thereof.

11. The photochromic material of claim 10 wherein the at least one functional group is selected from the group consisting of primary alcohol groups, secondary alcohol groups, and salts and complexes thereof.

12. The photochromic material of claim 1, wherein the photochromic initiator is selected from the group consisting of:

(1)3, 3-bis (4-methoxyphenyl) -6, 7-dimethoxy-13-methyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(2)3, 3-bis (4-methoxyphenyl) -6-methoxy-7- ((3-hydroxymethyl) piperidinyl) -13-ethyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(3)3- (4- (2-hydroxyethoxy) phenyl) -3- (4-fluorophenyl) -6, 7-dimethoxy-13-ethyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(4) 3-phenyl-3- (4- (2-hydroxyethoxy) phenyl) -6-methoxy-7- (3-methylpiperidinyl) -13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(5)3- (4-methoxyphenyl) -3- (4-fluorophenyl) -6-methoxy-7- (piperidino) -13-butyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(6) 3-phenyl-3- (4- (2-hydroxyethoxy) phenyl) -6-methoxy-7-piperidino-13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(7) 3-phenyl-3- (4-methoxyphenyl) -6, 11-dimethoxy-13- (2-hydroxyethyl) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(8) 3-phenyl-3- (4-morpholinophenyl) -6, 7-dimethoxy-13-hydroxymethyl-13- (2-hydroxyethyl) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(9)3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -6-methoxy-7-pyrrolidinyl-13-ethyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(10)3- (4-methoxyphenyl) -3- (4-fluorophenyl) -6-methoxy-7-morpholino-13-ethyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(11)3, 3-bis (4-methoxyphenyl) -13-propyl-13-hydroxymethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(12)3, 3-bis (4-methoxyphenyl) -6, 7-dimethoxy-11-fluoro-13-butyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(13) 3-phenyl-3- (4- (2-hydroxyethoxy) phenyl) -6, 11-dimethoxy-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(14)3, 3-bis (4-methoxyphenyl) -6, 7-dimethoxy-13-hydroxymethyl-13- (2-hydroxyethyl) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(15) 3-phenyl-3- (4- (2-hydroxyethoxy) phenyl) -6, 11-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(16) 3-phenyl-3- (4-methoxyphenyl) -6, 11-dimethoxy-13-ethyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(17)3, 3-bis (4-methoxyphenyl) -6, 11, 13-trimethyl-13- (2, 2-bis (hydroxymethyl) butoxy-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(18)2, 2-bis (4-methoxyphenyl) -5-methoxycarbonyl-6- (2-hydroxyethoxy) - [2H ] -naphtho [1, 2-b ] pyran;

(19) 3-phenyl-3- (4- (2-hydroxyethoxy) phenyl) -6, 11-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(20) 3-phenyl-3- (4-methoxyphenyl) -6-methoxy-7- ((3-hydroxymethyl) piperidino) -13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(21)3- (4-methoxyphenyl) -3 (4-morpholin-1-yl-phenyl) -6, 11-dimethyl-13-butyl-13- (2- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(22) 3-phenyl-3- (4- (2-hydroxyethoxy) phenyl) -6-methoxy-7- (morpholino) -13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(23) 3-phenyl-3- (4- (2-hydroxyethoxy) phenyl) -6, 7-dimethoxy-13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(24)3- (4-methoxyphenyl) -3- (4-fluorophenyl) -6-methoxy-7- ((4-hydroxymethyl) piperidino) -13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(25)3, 3-bis (4-methoxyphenyl) -6-methoxy-7- (piperidin-1-yl) -13-butyl-13- (2- (2-hydroxyethoxy) ethoxy-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(26)3, 3-bis (4-methoxyphenyl) -6, 11-dimethyl-13-hydroxymethyl-13- (2-hydroxypropyl) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(27) 3-phenyl-3- (4-morpholinophenyl) -6-methoxy-7- ((3-hydroxymethyl) piperidino) -13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(28)3- (4-methoxyphenyl) -3- (4-fluorophenyl) -6-methoxy-7- (morpholin-1-yl) -13-butyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(29)3- (4-fluorophenyl) -3- (4- (2-hydroxyethoxy) phenyl) -13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(30)2, 2-bis (4-methoxyphenyl) -5- (2- (2-hydroxyethoxy) ethoxycarbonyl) -6-phenyl- [2H ] -naphtho [1, 2-b ] pyran;

(31)3- (4-fluorophenyl) -3- (4-methoxyphenyl) -6, 7-dimethoxy-13-ethyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(32)3, 3-bis (4-methoxyphenyl) -6-methoxy-7-morpholino-13-ethyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(33)3- (4-morpholinophenyl) -3-phenyl-6, 7-dimethoxy-13-butyl-13- (2- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-bpyran;

(34)3- (4-fluorophenyl) -3- (4- (3-hydroxymethyl) piperidinophenyl) -6-methoxy-7-hydroxy-13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(35)3- (4-morpholinophenyl) -3-phenyl-6, 7-dimethoxy-13-ethyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(36)2, 2-diphenyl-5-hydroxymethyl-8-methyl-2H-naphtho [1, 2-b ] pyran;

(37)3- (4- (2-hydroxyethoxy) phenyl) -3- (4-morpholinophenyl) -13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(38)3- (4- (2-hydroxyethoxy) phenyl) -3-phenyl-13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(39)2, 2-diphenyl-5- (2- (2-hydroxyethoxy) ethoxycarbonyl) -8, 9-dimethoxy-2H-naphtho [1, 2-b ] pyran;

(40)3, 3-bis (4-fluorophenyl) -6, 7-dimethoxy-13-butyl-13- (2- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(41)3- (4-fluorophenyl) -3- (4-methoxyphenyl) -6, 7-dimethoxy-13-ethyl-13- (2- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(42)2, 2-diphenyl-5-methoxycarbonyl-6-phenyl-9- (2-hydroxyethoxy) -2H-naphtho [1, 2-b ] pyran;

(43)3, 3-bis (4-methoxyphenyl) -6, 7-dimethoxy-13-ethyl-13- (2- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(44)3- (4-methoxyphenyl) -3-phenyl-6, 11-dimethoxy-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(45)3- (4- (2-hydroxyethyl) piperazinylphenyl) -3-phenyl-13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(46)2, 2-bis (4-methoxyphenyl) -5- (2-hydroxyethoxy) carbonyl-6-phenyl-2H-naphtho [1, 2-b ] pyran;

(47)2, 2-diphenyl-5-hydroxymethyl-6-methyl-9-methoxy-2H-naphtho [1, 2-b ] pyran;

(48)3- (4-morpholinophenyl) -3-phenyl-13-ethyl-13- (2- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(49)3, 3-bis (4-methoxyphenyl) -6-methoxy-7- (3-hydroxymethyl) piperidinophenyl) -13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(50)2, 2-diphenyl-5- (2- (2-hydroxyethoxy) ethoxycarbonyl) -7, 8-dimethoxy-2H-naphtho [1, 2-b ] pyran;

(51)3, 3-bis (4-methoxyphenyl) -6, 11, 13-trimethyl-13- (2- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(52)2, 2-diphenyl-5- (2- (2-hydroxyethoxy) ethoxycarbonyl) -6- (4-methoxy) phenyl-9-methoxy-2H-naphtho [1, 2-b ] pyran;

(53)2, 2-diphenyl-5-hydroxymethyl-7, 8-dimethoxy-2H-naphtho [1, 2-b ] pyran;

(54)3, 3-bis (4-methoxyphenyl) -6, 11, 13-trimethyl-13 (10-hydroxydecyloxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(55)2, 2-bis (4-methoxyphenyl) -5-methoxycarbonyl-6- (4- (2-hydroxyethoxy) phenyl-2H-naphtho [1, 2-b ] pyran;

(56)3, 3-bis (4-methoxyphenyl) -6, 11-dimethoxy-13- (2-hydroxyethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(57) 3-phenyl-3- (4-morpholinophenyl) -6, 11-dimethoxy-13- (2-hydroxyethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(58)2, 2-bis (4-methoxyphenyl) -5-methoxycarbonyl-6-phenyl-9- (2-hydroxyethoxy) -2H-naphtho [1, 2-b ] pyran;

(59)3, 3-bis (4-methoxyphenyl) -6, 11-dimethyl-13-hydroxy-13- (2-hydroxyethyl) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(60)3, 3-bis (4-methoxyphenyl) -6, 11, 13-trimethyl-13- (5-hydroxypentoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(61)3, 3-bis (4-methoxyphenyl) -11- (2-hydroxyethoxy) -13, 13-dimethyl-3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(62)3, 3-bis (4-methoxyphenyl) -6, 11-dimethyl-13-hydroxy-13- (3-hydroxypropyl) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(63)3, 3-bis (4-methoxyphenyl) -6, 11-dimethyl-13- (2-hydroxyethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(64) 3-phenyl-3- (4-methoxyphenyl) -6, 11-dimethoxy-13-methyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(65)3, 3-bis (4-methoxyphenyl) -6, 11-dimethyl-13-hydroxy-13-hydroxymethyl) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(66)3, 3-bis (4-methoxyphenyl) -6, 11-dimethoxy-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(67)3, 3-bis (4-methoxyphenyl) -6, 11-dimethoxy-13-methyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(68)2, 2-diphenyl-5- (2, 3-dihydroxy) propoxycarbonyl-8-methyl-2H-naphtho [1, 2-b ] pyran;

(69)3, 3-bis (4-methoxyphenyl) -6, 11-dimethoxy-13-hydroxy-13- (4-hydroxybutyl) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(70)5, 5-bis (4- (2- (2-hydroxyethoxy) ethoxy) phenyl) -8- (3-chloropropoxy) carbonyl-5H-fluorantheno [3, 2-b ] pyran;

(71)3, 3-bis (4-methoxyphenyl) -6, 11-dimethoxy-13-butyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(72)3, 3-bis (4-methoxyphenyl) -6, 11-dimethoxy-13-hydroxy-13- (3-hydroxypropyl) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(73) 3-phenyl-3- (4-morpholinophenyl) -13-methyl-13- (2, 3-dihydroxypropoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(74)3, 3-bis (4-methoxyphenyl) -6, 11, 13-trimethyl-13- (2, 3-dihydroxypropoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(75)3, 3-bis (4-methoxyphenyl) -6, 11-dimethoxy-13-methyl-13- (2, 3-dihydroxypropoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(76)3, 3-bis (4-methoxyphenyl) -6, 11, 13-trimethyl-13- (2-hydroxyethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(77)2- (4- (2- (2-hydroxyethoxy) ethoxy) phenyl-2-phenyl-5-methoxycarbonyl-6-methyl-9-methoxy-2H-naphtho [1, 2-b ] pyran;

(78)3, 3-bis (4-methoxyphenyl) -6, 11, 13-trimethyl-13- (2- (2, 2-bis [ 2-hydroxyethoxy) methyl ] -3-hydroxypropoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(79)3, 3-bis (4-methoxyphenyl) -6, 11, 13-trimethyl-13- (2- (2- (2- (2- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(80)2, 2-diphenyl-5- (2- (2-hydroxyethoxy) ethoxycarbonyl) -8-methyl-2H-naphtho [1, 2-b ] pyran;

(81)3, 3-bis (4-methoxyphenyl) -6, 11, 13-trimethyl-13- (2- (2- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(82)3, 3-bis (4-methoxyphenyl) -6, 11, 13-trimethyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2, 1-f ] naphtho [1, 2-b ] pyran;

(83)2, 2-bis (4-methoxyphenyl) -5- (2- (2- (2-hydroxyethoxy) ethoxy) ethoxycarbonyl) -6-phenyl-2H-naphtho [1, 2-b ] pyran;

(84)2, 2-bis (4-methoxyphenyl) -5-methoxycarbonyl-6- (2-hydroxyethoxy) ethoxy-2H-naphtho [1, 2-b ] pyran;

(85)2, 2-bis (4-methoxyphenyl) -5- (2- (2- (2- (2-hydroxyethoxy) ethoxy) ethoxycarbonyl) -6-phenyl-2H-naphtho [1, 2-b ] pyran;

(86)2, 2-bis (4-methoxyphenyl) -5-hydroxy-6- (2-hydroxyphenyl) -2H-naphtho [1, 2-b ] pyran.

13. A photochromic composition comprising the reaction product of:

(a) a photochromic material comprising the reaction product of:

(1) at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates; and

(2) A photochromic initiator; and

(b) an organic material comprising at least one reactive group.

14. The photochromic composition of claim 13, wherein the photochromic composition comprises an organic material comprising a residue of at least one reactive group bonded to the photochromic material, wherein the residue of the at least one reactive group is selected from the group consisting of alkyl, alkyldialkoxysilyl, alkoxydialkylsilyl, amide, amine, anhydride, aryl, aziridine, carboxylic acid, cycloaliphatic epoxide, ester, halogen, hydroxyl, propenyl ether, residue of a ring-opening cyclic monomer, trialkoxysilyl, thiirane, thiol, vinyl ether, vinylbenzyl ether, and combinations thereof.

15. The photochromic composition of claim 14 wherein said ester is selected from the group consisting of acrylates, alkyl phosphonates, allyl carbonates, isocyanates, chloroformates, isothiocyanates, methacrylates, vinyl carbonates.

16. A photochromic material represented by the formula:

wherein:

(a) PC is a photochromic base;

(b) n is an integer from 1 to 8; and

(c) each S' is independently at each occurrence selected from the group represented by the formula:

Wherein:

(1) l is a linker independently selected at each occurrence from-O-, -N-, and-S-, or L comprises a linear or branched organic bridging group comprising at least one linker independently selected at each occurrence from-O-, -N-, and-S-;

(2) a is an integer independently selected at each occurrence from 1 to 500;

(3)R¹is independently selected at each occurrence from a ring-opened cyclic ester monomer and a ring-opened cyclic carbonate monomer;

(4)R²is an organic material independently selected for each occurrence from hydrogen and a residue comprising at least one reactive group; and

(5) b is an integer independently selected at each occurrence from 1 to 20.

17. The photochromic material of claim 16 wherein the PC is selected from the group consisting of pyrans, oxazines, and fulgides.

18. The photochromic material of claim 16 wherein PC is a pyran selected from the group consisting of benzopyrans, naphthopyrans, phenanthropyrans, quinopyrans, fluoranthenopyrans, and spiropyrans.

19. The photochromic material of claim 16 wherein PC is a naphthopyran selected from the group consisting of naphtho [1, 2-b ] pyran, naphtho [2, 1-b ] pyran, indenonaphthopyran, and heterocyclic fused naphthopyran.

20. The photochromic material of claim 16 wherein n is 1 to 4.

The photochromic material of claim 16 wherein n is 1 to 2.

22. The photochromic material of claim 16 wherein n is 1.

23. The photochromic material of claim 16 wherein L is selected from: C1-C10 alkoxy, C1-C10 alkylamino, C1-C10 alkylthio, C2-C20 beta-oxypoly (ethoxy), C3-C30 beta-oxypoly (propoxy), C4-C40 beta-oxypoly (butoxy), C2-C20 beta-aminopoly (ethoxy), C3-C30 beta-aminopoly (propoxy), C4-C40 beta-aminopoly (butoxy), C2-C20

Beta-thiopoly (ethoxy), C3-C30 beta-thiopoly (propoxy), C4-C40 beta-thiopoly (butoxy), aryl C1-C10 alkoxy, aryl C1-C10 alkylamino, aryl C1-C10 alkylthio, aryl C2-C20 beta-oxypoly (ethoxy), aryl C3-C30 beta-oxypoly (propoxy), aryl C4-C40 beta-oxypoly (butoxy), aryl C2-C20 beta-aminopoly (ethoxy), aryl C3-C30

Beta-aminopoly (propoxy), aryl C4-C40 beta-aminopoly (butoxy), aryl C2-C20

Beta-thiopoly (ethoxy), aryl C3-C30 beta-thiopoly (propoxy), aryl C4-C40 beta-thiopoly (butoxy), heterocycle C1-C10 alkoxy, heterocycle C1-C10 alkylamino, heterocycle C1-C10 alkylthio, heterocycle C2-C20 beta-oxypoly (ethoxy), heterocycle C3-C30 beta-oxypoly (propoxy), heterocycle C4-C40 beta-oxypoly (butoxy), heterocycle C2-C20 beta-aminopoly (ethoxy), heterocycle C3-C30 beta-aminopoly (propoxy), heterocycle C4-C40 beta-aminopoly (butoxy), heterocycle C2-C20 beta-thiopoly (ethoxy), heterocycle C3-C30 beta-thiopoly (propoxy), heterocycle C4-C40 beta-thiopoly (propoxy)

β -sulfur poly (butoxy) and combinations thereof.

24. The photochromic material of claim 23, wherein the heterocyclic group is selected from azaindolyl, dibenzofuranyl, dibenzothienyl, benzofuranyl, benzothienyl, thienyl, furanyl, dibenzfuranylAlkyl (dioxano), dioxolanyl (dioxanone), carbazolyl, benzoAzolyl, benzimidazolyl, benzothiazolyl, imidazolyl, indazolyl, isoxazolylBenzo (b) isAzolyl radical, isoAzolyl, isoindolylOxazolyl, isoquinolyl, isothiazolyl, morpholino,A diazolyl group,Thiazolyl, piperidino, purinyl (purinyl), phenazinyl, piperazinyl, pyrazinyl, pyrazolyl, pyridyl, pyrimidinyl, pyrrolidinyl, quinolinyl, isoquinolinyl, thiazolyl, triazinyl, thiomorpholino, thiadiazolyl, tetrahydroquinolinyl, and tetrahydroisoquinolinyl.

25. The photochromic material of claim 23 wherein the aryl group is selected from phenyl and naphthyl.

26. The photochromic material of claim 16 wherein b is 1 to 10.

27. The photochromic material of claim 16 wherein b is 1 to 3.

28. The photochromic material of claim 16 wherein b is 2 and L is a linear or branched organic bridging group comprising two linking groups.

29. The photochromic material of claim 16 wherein R¹Selected from the group consisting of ring-opened epsilon-caprolactone monomers and ring-opened delta-valerolactone monomers.

30. The photochromic material of claim 16 wherein a is at least 2, at least one R¹Is a ring-opened epsilon-caprolactone monomer, and at least one R¹Is a ring-opened delta-valerolactone monomer.

31. The photochromic material of claim 16 wherein for each S', a is an integer selected from 1 to 100.

32. The photochromic material of claim 16 wherein for each S', a is an integer selected from 1 to 60.

33. The photochromic material of claim 16 wherein for each S', a is an integer selected from 10 to 100.

34. The photochromic material of claim 16 wherein for each S', a is an integer selected from 20 to 60.

35. The photochromic material of claim 16 wherein for each S', each- [ R [ ]¹]_aThe segment has a number-average molecular weight of from 100 to 22,000 g/mol.

36. The photochromic material of claim 16 wherein for each S', each- [ R [ ]¹]_aThe segment has a number average molecular weight of 2000 to 6000 g/mol.

37. The photochromic material of claim 16 wherein for each S', each- [ R [ ]¹]_aThe segments have a number-average molecular weight of from 100 to 500 g/mol.

38. The photochromic material of claim 16 wherein R²Comprising an organic material comprising a residue of at least one reactive groupWherein the residue of the at least one reactive group is selected from the group consisting of alkyl, alkyldialkoxysilyl, alkoxydialkylsilyl, amide, amine, anhydride, aryl, aziridine, carboxylic acid, cycloaliphatic epoxide, ester, halogen, hydroxy, propenyl ether, residue of a ring-opening cyclic monomer, trialkoxysilyl, thiirane, thiol, vinyl ether, vinylbenzyl ether, and combinations thereof.

39. The photochromic material of claim 38, wherein said ester is selected from the group consisting of acrylates, alkyl phosphonates, allyl carbonates, isocyanates, chloroformates, isothiocyanates, methacrylates, vinyl carbonates.

40. The photochromic material of claim 38 or 39 wherein the organic material comprising the residue of at least one reactive group further comprises at least one unreacted reactive group.

41. A photochromic material represented by the formula:

wherein:

(a) y is selected from C and N;

(b) a is selected from naphtho, benzo, phenanthro, fluorantheno, quinolino, thieno, furo, indolo, indolino, indeno, benzofuro, benzothieno, thieno, indenonaphtho, heterocyclic fused naphtho, and heterocyclic fused benzo;

(c) n 'is an integer selected from 0 to 8, with the proviso that if n' is 0, at least one of B and B 'comprises the group S';

(d) s' is represented by the following general formula:

wherein:

(1) l is a linker independently selected at each occurrence from-O-, -N-, and-S-, or L comprises a linear or branched organic bridging group comprising at least one linker independently selected at each occurrence from-O-, -N-, and-S-;

(2) a is independently at each occurrence an integer selected from 1 to 500;

(3)R¹independently at each occurrence, selected from the group consisting of a ring-opened cyclic ester monomer and a ring-opened cyclic carbonate monomer;

(4)R²independently at each occurrence, selected from hydrogen and organic materials comprising a residue of at least one reactive group, wherein the residue of at least one reactive group is selected from the group consisting of alkyl, alkyldialkoxysilyl, alkoxydialkylsilyl, amide, amine, anhydride, aryl, aziridine, carboxylic acid, cycloaliphatic epoxide, ester, halogen, hydroxyl, propenyl ether, residue of ring-opening cyclic monomer, trialkoxysilyl, thiirane, thiol, vinyl ether, vinylbenzyl ether, and combinations thereof;

(5) b is independently at each occurrence an integer selected from 1 to 20; and

(e) B and B' are independently selected from:

(1) a group S';

(2) mono-R¹⁷-substituted phenyl, wherein R¹⁷Represented by one of the following general formulae:

-G[(OC₂H₄)_q(OC₃H₆)_r(OC₄H₈)_s]j and

-[(OC₂H₄)_q(OC₃H₆)_r(OC₄H₈)_S]J，

wherein-G is selected from the group consisting of-C (O) -and-CH₂-, J is selected from C1-C12 alkoxy and polymerizable groups; q, r and s are each a number between 0 and 50, and the sum of q, r and s is from 2 to 50;

(3) unsubstituted, mono-, di-or trisubstituted aryl;

(4) 9-julolidine, an unsubstituted, mono-or di-substituted heteroaromatic group selected from the group consisting of pyridylfuryl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl and fluorenyl, each of the aryl and heteroaromatic substituents of (3) and (4) being independently selected from the group consisting of:

(i) a hydroxyl group(s),

(ii) group-C (O) R¹⁸Wherein R is¹⁸Is selected from-OR¹⁹、-N(R²⁰)R²¹Piperidino and morpholino wherein R¹⁹Selected from allyl, C1-C6 alkyl, phenyl, mono (C1-C6) alkyl substituted phenyl, mono (C1-C6) alkoxy substituted phenyl, phenyl (C1-C3) alkyl, mono (C1-C6) alkyl substituted phenyl (C1-C3) alkyl, mono (C1-C6) alkoxy substituted phenyl (C1-C3) alkyl, C1-C6 alkoxy (C2-C4) alkyl, and C1-C6 haloalkyl; r ²⁰And R²¹Each selected from the group consisting of C1-C6 alkyl, C5-C7 cycloalkyl, phenyl, monosubstituted phenyl, and disubstituted phenyl, the phenyl substituents being selected from the group consisting of C1-C6 alkyl and C1-C6 alkoxy, and the halo substituents being selected from the group consisting of chloro and fluoro;

(iii) aryl, mono (C1-C12) alkoxyaryl, di (C1-C12) alkoxyaryl, mono (C1-C12) alkylaryl, di (C1-C12) alkylaryl, haloaryl, C3-C7 cycloalkylaryl, C3-C7 cycloalkyl, C3-C7 cycloalkoxy, C3-C7 cycloalkoxy (C7-C7) alkyl, C7-C7 cycloalkoxy (C7-C7) alkoxy, aryl (C7-C7) alkyl, aryl (C7-C7) alkoxy, aryloxy (C7-C7) alkyl, aryloxy (C7-C7) alkoxy, mono or di (C7-C7) alkylaryl (C7-C7) alkyl, mono or di (C7) alkoxyaryl (C7-C7) alkoxy (C7-C7) alkyl, mono or di (C7) alkyl 7) alkoxy (C7) alkyl, Mono-or di (C1-C12) alkoxyaryl (C1-C12) alkoxy, amino, mono (C1-C12) alkylamino, di (C1-C12) alkylamino, diarylamino, piperazinyl, N- (C1-C12) alkylpiperazinyl, N-arylpiperazinyl, aziridinyl, indolino, piperidino, morpholino, thiomorpholino, tetrahydroquinolinyl, tetrahydroisoquinolinyl, pyrrolidinyl, C1-C12 alkyl, C1-C12 haloalkyl, C1-C12 alkoxy, mono (C1-C12) alkoxy (C1-C12) alkyl, acryloyloxy, methacryloyloxy, and halogen;

(5) Selected from pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, and thiophenylAn unsubstituted or mono-substituted group of an oxazinyl group, a phenazinyl group and an acridinyl group, each of said substituents being independently selected from the group consisting of C1-C12 alkyl, C1-C12 alkoxy, phenyl and halogen;

(6) a mono-substituted phenyl group having a substituent at the para-position, wherein the substituent is selected from the group consisting of- (CH)₂)_t-and-O- (CH)₂)_t-, where t is an integer selected from 1, 2, 3, 4, 5 and 6, the substituent being attached to an aryl group on another photochromic material;

(7) a group represented by one of the following general formulae:

wherein K in each formula is independently selected from methylene and oxygen, and M in each formula is independently selected from oxygen and substituted nitrogen, with the proviso that when M is substituted nitrogen, K is methylene; the substituent of the substituted nitrogen is selected from hydrogen, C1-C12 alkyl and C1-C12 acyl; each R²²Independently at each occurrence in each formula selected from the group consisting of C1-C12 alkyl, C1-C12 alkoxy, hydroxy, and halogen; r in each formula²³And R²⁴Each independently selected from hydrogen and C1-C12 alkyl; u is an integer selected from 0, 1 and 2;

(8) C1-C12 alkyl, C1-C12 haloalkyl, C1-C12 alkoxy (C1-C12) alkyl, C3-C7 cycloalkyl, mono (C1-C12) alkoxy (C3-C7) cycloalkyl, mono (C1-C12) alkyl (C3-C7) cycloalkyl, halo (C3-C7) cycloalkyl, and C4-C12 bicycloalkyl, with the proviso that B and B' are not both selected from (8); and

(9) A group represented by the following general formula:

wherein R is²⁵Selected from hydrogen and C1-C12 alkyl, R²⁶Is an unsubstituted, mono-or di-substituted group selected from naphthyl, phenyl, furyl and thienyl, wherein the substituents are independently selected from the group consisting of C1-C12 alkyl, C1-C12 alkoxy and halogen; or

(10) B and B 'together form a fluoren-9-ylidene group, a mono-or disubstituted fluoren-9-ylidene group or a spirocyclic group selected from a saturated C3-C12 spiromonocyclic hydrocarbon ring, a saturated C7-C12 spirobicyclic hydrocarbon ring, or a saturated C7-C12 spirotricyclic hydrocarbon ring, with the proviso that said spirocyclic group is not norbornylidene or bicyclo [3.3.1] 9-nonylidene, each of said fluoren-9-ylidene substituents being independently selected from C1-C12 alkyl, C1-C12 alkoxy, halogen, or the group S'.

42. A photochromic material according to claim 41 wherein for (4) R²Wherein the ester is selected from the group consisting of acrylates, alkyl phosphonates, allyl carbonates, chloroformates, isocyanates, isothiocyanates, methacrylates, vinyl carbonates.

43. The photochromic material of claim 41 or 42 wherein L comprises at least one group selected from the group consisting of: C1-C10 alkoxy, C1-C10 alkylamino, C1-C10 alkylthio, C2-C20

Beta-oxypoly (ethoxy), C3-C30 beta-oxypoly (propoxy), C4-C40 beta-oxypoly (butoxy), C2-C20 beta-aminopoly (ethoxy), C3-C30 beta-aminopoly (propoxy), C4-C40 beta-aminopoly (butoxy), C2-C20 beta-thiopoly (ethoxy), C3-C30 beta-thiopoly (propoxy), C4-C40 beta-thiopoly (butoxy), aryl C1-C10 alkoxy, aryl C1-C10 alkylamino, aryl C1-C10 alkylthio, aryl C2-C20 beta-oxypoly (ethoxy), aryl C3-C30 beta-oxypoly (propoxy), aryl C4-C40 beta-oxypoly (butoxy), aryl C2-C20 beta-aminopoly (ethoxy), Aryl C3-C30 beta-aminopoly (propoxy), aryl C4-C40 beta-aminopoly (butoxy), aryl C2-C20 beta-thiopoly (ethoxy), aryl C3-C30

β -thiopoly (propoxy), aryl C4-C40 β -thiopoly (butoxy), heterocycle C1-C10 alkoxy, heterocycle C1-C10 alkylamino, heterocycle C1-C10 alkylthio, heterocycle C2-C20 β -oxypoly (ethoxy), heterocycle C3-C30 β -oxypoly (propoxy), heterocycle C4-C40 β -oxypoly (butoxy), heterocycle C2-C20 β -aminopoly (ethoxy), heterocycle C3-C30 β -aminopoly (propoxy), heterocycle C4-C40 β -aminopoly (butoxy), heterocycle C2-C20 β -thiopoly (ethoxy), heterocycle C3-C30 β -thiopoly (propoxy), and heterocycle C4-C40 β -thiopoly (butoxy).

44. The photochromic material of claim 41 or 42 wherein Y is C, A is indenonaphtho, and the photochromic material is an indenonaphthopyran represented by the general formula:

wherein v and v' are integers independently selected from 0 to the total number of available positions, provided that R³⁰At least one of the groups B and B 'comprises a group S'.

45. The photochromic material of claim 44 wherein the photochromic material is represented by the general formula:

wherein R in the 6-position³⁰Substituent, R in the 7-position³⁰R in the 10-position³⁰Substituent, R in the 11-position³⁰Substituent, R3 in the 13-position⁰At least one of the substituents, B and B 'comprises a group S'.

46. The photochromic material of claim 41 or 42 wherein Y is C, A is naphtho derived from α -naphthol, and the photochromic material is a 2H-naphtho [1, 2-b ] pyran represented by the following general formula:

wherein w is an integer from 0 to the total number of available positions, provided that R³¹At least one of the radicals B and B 'comprises a radical S'.

47. The photochromic material of claim 46 wherein the photochromic material is represented by the general formula:

wherein R in the 5-position³¹Substituent, R in the 6-position³¹Substituent, R in the 7-position³¹Substituent, R in the 8-position³¹Substituent, R in the 9-position³¹At least one of the substituents, B and B 'comprises a group S'.

48. The photochromic material of claim 41 or 42 wherein Y is C, A is naphtho derived from β -naphthol, and the photochromic material is 3H-naphtho [2, 1-b ] pyran represented by the general formula:

wherein x is an integer from 0 to the total number of available positions, provided that R³²At least one of the radicals B and B 'comprises a radical S'.

49. The photochromic material of claim 48 wherein the photochromic material is represented by the general formula:

wherein R in the 5-position³²Substituent, R in the 6-position³²Substituent, R in the 8-position ³²Substituent, R in the 9-position³²At least one of the substituents, B and B 'comprises a group S'.

50. The photochromic material of claim 41 or 42 wherein R²Is an organic material comprising a residue of at least one reactive group, wherein the residue of at least one reactive group is selected from the group consisting of acrylates, alkyls, alkyldialkoxysilyl groups, alkoxydialkylsilyl groups, allylcarbonate, amides, amines, anhydrides, aryl groups, carboxylic acids, chloroformates, cycloaliphatic epoxides, isocyanates, isothiocyanates, epoxides, halogens, hydroxyls, methacrylates, thiols, propenyl ethers, residues of ring-opening cyclic monomers, trialkoxysilyl groups, vinyl carbonates, vinyl ethers, vinylbenzyl ethers, and combinations thereof.

51. The photochromic material of claim 50 wherein the organic material comprising the residue of at least one reactive group further comprises at least one unreacted reactive group.

52. A photochromic material represented by the formula:

wherein:

(a)R³⁴and R³⁵Independently selected from:

(1) a group S ', wherein S' is represented by the following general formula:

wherein:

(A) l comprises at least one group selected from: C1-C10 alkoxy, C1-C10 alkylamino, C1-C10 alkylthio, C2-C20 beta-oxypoly (ethoxy), C3-C30 beta-oxypoly (propoxy), C4-C40 beta-oxypoly (butoxy), C2-C20 beta-aminopoly (ethoxy), C3-C30

Beta-aminopoly (propoxy), C4-C40 beta-aminopoly (butoxy), C2-C20 beta-thiopoly (ethoxy), C3-C30 beta-thiopoly (propoxy), C4-C40 beta-thiopoly (butoxy), aryl C1-C10 alkoxy, aryl C1-C10 alkylamino, aryl C1-C10 alkylthio, aryl C2-C20

Beta-oxypoly (ethoxy), aryl C3-C30 beta-oxypoly (propoxy), aryl C4-C40 beta-oxypoly (butoxy), aryl C2-C20 beta-aminopoly (ethoxy), aryl C3-C30 beta-aminopoly (propoxy), aryl C4-C40 beta-aminopoly (butoxy), aryl C40-C40 beta-thiopoly (ethoxy), aryl C40-C40 beta-thiopoly (propoxy), aryl C40-C40 beta-thiopoly (butoxy), heterocycle C40-C40 alkoxy, heterocycle C40-C40 alkylamino, heterocycle C40-C40 alkylthio, heterocycle C40-C40 beta-oxypoly (ethoxy), heterocycle C40-C40 beta-oxypoly (propoxy), heterocycle C40-C40 beta-oxypoly (butoxy), heterocycle C40-C40 beta-aminopoly (ethoxy), Heterocycle C3-C30 β -aminopoly (propoxy), heterocycle C4-C40 β -aminopoly (butoxy), heterocycle C2-C20 β -thiopoly (ethoxy), heterocycle C3-C30 β -thiopoly (propoxy), and heterocycle C4-C40 β -thiopoly (butoxy);

(B) a is independently at each occurrence an integer selected from 1 to 500;

(C)R¹independently at each occurrence, selected from the group consisting of a ring-opened cyclic ester monomer and a ring-opened cyclic carbonate monomer;

(D)R²Independently at each occurrence, selected from hydrogen and organic materials comprising a residue of at least one reactive group, wherein the residue of at least one reactive group is selected from the group consisting of alkyl, alkyldialkoxysilyl, alkoxydialkylsilyl, amide, amine, anhydride, aryl, aziridine, carboxylic acid, cycloaliphatic epoxide, ester, halogen, hydroxy, propenyl ether, residue of ring-opening cyclic monomer, trialkylAlkoxysilyl, thiirane, thiol, vinyl ether, vinylbenzyl ether, and combinations thereof;

(E) b is independently at each occurrence an integer selected from 1 to 20; and

(2) hydrogen, hydroxy, C1-C6 alkyl, C3-C7 cycloalkyl, allyl, phenyl, monosubstituted phenyl, benzyl, monosubstituted benzyl, chloro, fluoro, the radical-C (O) R⁴⁰Wherein R is⁴⁰Is hydroxy, C1-C6 alkyl, C1-C6 alkoxy, phenyl, monosubstituted phenyl, amino, mono (C1-C6) alkylamino or di (C1-C6) alkylamino; or

(3)R³⁴And R³⁵Each being a group-OR⁴¹Wherein R is⁴¹Is C1-C6 alkyl, phenyl (C1-C3) alkyl, mono (C1-C6) alkyl-substituted phenyl (C1-C3) alkyl, mono (C1-C6) alkoxy-substituted phenyl (C1-C3) alkyl, C1-C6 alkoxy (C2-C4) alkyl, C3-C7 cycloalkyl, mono (C1-C4) alkyl-substituted C3-C7 cycloalkyl, C1-C6 chloroalkyl, C1-C6 fluoroalkyl, allyl, a group-CH (R1-C4) ⁴²)R⁴⁵Wherein R is⁴²Is hydrogen or C1-C3 alkyl and R⁴³Is CN, CF₃Or COOR⁴⁴，R⁴⁴Is hydrogen or C1-C3 alkyl; or R⁴¹Is a group-C (O) R⁴⁵Wherein R is⁴⁵Is hydrogen, C1-C6 alkyl, C1-C6 alkoxy, unsubstituted, mono-or disubstituted arylphenyl or naphthyl, phenoxy, mono-or di (C1-C6) alkyl-substituted phenoxy, mono-or di (C1-C6) alkoxy-substituted phenoxy, amino, mono (C1-C6) alkylamino, di (C1-C6) alkylamino, phenylamino, mono-or di (C1-C6) alkyl-substituted phenylamino, or mono-or di (C1-C6) alkoxy-substituted phenylamino, each of said phenyl, benzyl and aryl substituents being C1-C6 alkyl or C1-C6 alkoxy; or

(4)R³⁴And R³⁵Together form an oxy group, a spiro carbocyclic ring containing 3 to 6 carbon atoms, or a spiro heterocyclic group containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including a spiro carbon atom, said spiro carbocyclic and spiro heterocyclic groups being fused to 0, 1 or 2 benzene rings;

(b) y and y' are integers independently selected from 0 to the total number of available positions;

(c) each one of which isR³⁶And R³⁷Independently selected from: a group S', hydrogen, C1-C6 alkyl, C3-C7 cycloalkyl, phenyl, monosubstituted phenyl, disubstituted phenyl and a group-OR⁵⁰and-OC (O)⁵⁰Wherein R is⁵⁰Is C1-C6 alkyl, phenyl (C1-C3) alkyl, mono (C1-C6) alkyl substituted phenyl (C1-C3) alkyl, mono (C1-C6) alkoxy substituted phenyl (C1-C3) alkyl, C1-C6 alkoxy (C2-C4) alkyl, C3-C7 cycloalkyl or mono (C1-C4) alkyl substituted C3-C7 cycloalkyl, and the phenyl substituent is C1-C6 alkyl or C1-C6 alkoxy;

(e) B and B' are independently selected from:

(1) a group S';

(2) mono-R¹⁷-substituted phenyl, wherein R¹⁷Represented by one of the following general formulae:

-G[(OC₂H₄)_q(OC₃H₆)_r(OC₄H₈)_s]j and

-[(OC₂H₄)_q(OC₃H₆)_r(OC₄H₈)_S]J，

wherein-G is selected from the group consisting of-C (O) -and-CH₂-, J is selected from C1-C12 alkoxy and polymerizable groups; q, r and s are each a number between 0 and 50, and the sum of q, r and s is from 2 to 50;

(3) unsubstituted, mono-, di-or trisubstituted aryl;

(4) 9-julolidine, an unsubstituted, mono-or di-substituted heteroaromatic group selected from the group consisting of pyridylfuryl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl and fluorenyl, each of the aryl and heteroaromatic substituents of (3) and (4) being independently selected from the group consisting of:

(i) a hydroxyl group(s),

(ii) group-C (O) R¹⁸Wherein R is¹⁸Is selected from-OR¹⁹、-N(R²⁰)R²¹Piperidino and morpholino wherein R¹⁹Selected from allyl, C1-C6 alkyl, phenyl, mono (C1-C6) alkyl substituted benzenePhenyl substituted by mono (C1-C6), phenyl (C1-C3) alkyl, phenyl (C1-C3) alkyl substituted by mono (C1-C6) alkyl, phenyl (C1-C3) alkyl substituted by mono (C1-C6) alkoxy, C1-C6 alkoxy (C2-C4) alkyl and C1-C6 haloalkyl; r ²⁰And R²¹Each selected from the group consisting of C1-C6 alkyl, C5-C7 cycloalkyl, phenyl, monosubstituted phenyl, and disubstituted phenyl, the phenyl substituents being selected from the group consisting of C1-C6 alkyl and C1-C6 alkoxy, the halo substituents being selected from the group consisting of chloro and fluoro;

(iii) aryl, mono (C1-C12) alkoxyaryl, di (C1-C12) alkoxyaryl, mono (C1-C12) alkylaryl, di (C1-C12) alkylaryl, haloaryl, C3-C7 cycloalkylaryl, C3-C7 cycloalkyl, C3-C7 cycloalkoxy, C3-C7 cycloalkoxy (C7-C7) alkyl, C7-C7 cycloalkoxy (C7-C7) alkoxy, aryl (C7-C7) alkyl, aryl (C7-C7) alkoxy, aryloxy (C7-C7) alkyl, aryloxy (C7-C7) alkoxy, mono or di (C7-C7) alkylaryl (C7-C7) alkyl, mono or di (C7) alkoxyaryl (C7-C7) alkoxy (C7-C7) alkyl, mono or di (C7) alkyl 7) alkoxy (C7) alkyl, Mono-or di (C1-C12) alkoxyaryl (C1-C12) alkoxy, amino, mono (C1-C12) alkylamino, di (C1-C12) alkylamino, diarylamino, piperazinyl, N- (C1-C12) alkylpiperazinyl, N-arylpiperazinyl, aziridinyl, indolino, piperidino, morpholino, thiomorpholino, tetrahydroquinolinyl, tetrahydroisoquinolinyl, pyrrolidinyl, C1-C12 alkyl, C1-C12 haloalkyl, C1-C12 alkoxy, mono (C1-C12) alkoxy (C1-C12) alkyl, acryloyloxy, methacryloyloxy, and halogen;

(5) Selected from pyrazolyl, imidazolyl, pyrazolyl, imidazolinyl, pyrrolinyl, phenothiazinyl, and thiophenylAn unsubstituted or mono-substituted group of an oxazinyl group, a phenazinyl group and an acridinyl group, each of said substituents being independently selected from the group consisting of C1-C12 alkyl, C1-C12 alkoxy, phenyl and halogen;

(6) a mono-substituted phenyl group having a substituent at the para-position, wherein the substituent is selected from the group consisting of- (CH)₂)_t-and-O-(CH₂)_t-, where t is an integer selected from 1, 2, 3, 4, 5 and 6, the substituent being attached to an aryl group on another photochromic material;

(7) a group represented by one of the following general formulae:

wherein K in each formula is independently selected from methylene and oxygen, and M in each formula is independently selected from oxygen and substituted nitrogen, with the proviso that when M is substituted nitrogen, K is methylene; the substituent of the substituted nitrogen is selected from hydrogen, C1-C12 alkyl and C1-C12 acyl; each R²²Independently at each occurrence in each formula selected from the group consisting of C1-C12 alkyl, C1-C12 alkoxy, hydroxy, and halogen; r in each formula²³And R²⁴Each independently selected from hydrogen and C1-C12 alkyl; u is an integer selected from 0, 1 and 2;

(8) C1-C12 alkyl, C1-C12 haloalkyl, C1-C12 alkoxy (C1-C12) alkyl, C3-C7 cycloalkyl, mono (C1-C12) alkoxy (C3-C7) cycloalkyl, mono (C1-C12) alkyl (C3-C7) cycloalkyl, halo (C3-C7) cycloalkyl, and C4-C12 bicycloalkyl, with the proviso that B and B' are not both selected from (8); and

(9) A group represented by the following general formula:

wherein R is²⁵Selected from hydrogen and C1-C12 alkyl, R²⁶Is an unsubstituted, mono-or di-substituted group selected from naphthyl, phenyl, furyl and thienyl, wherein the substituents are independently selected from the group consisting of C1-C12 alkyl, C1-C12 alkoxy and halogen; or

(10) B and B 'together form a fluoren-9-ylidene group, a mono-or disubstituted fluoren-9-ylidene group, or a spirocyclic group selected from a saturated C3-C12 spiromonocyclic hydrocarbon ring, a saturated C7-C12 spirobicyclic hydrocarbon ring, or a saturated C7-C12 spirotricyclic hydrocarbon ring, with the proviso that said spirocyclic group is not norbornylidene or bicyclo [3.3.1] 9-nonylidene, each of said fluoren-9-ylidene substituents being independently selected from C1-C12 alkyl, C1-C12 alkoxy, halogen, or group S';

with the proviso that the photochromic material comprises at least one group S'

53. A photochromic material according to claim 52 wherein for (D) R²Wherein the ester is selected from the group consisting of acrylates, alkyl phosphonates, allyl carbonates, chloroformates, isocyanates, isothiocyanates, methacrylates, vinyl carbonates.

54. A photochromic composition comprising:

(a) a polymeric material; and

(b) at least one photochromic material in contact with at least a portion of the polymeric material, the at least one photochromic material comprising the reaction product of:

(1) At least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates; and

(2) a photochromic initiator.

55. The photochromic composition of claim 54 wherein the polymeric material is selected from the group consisting of polymeric microparticles; copolymers of ethylene and vinyl acetate; copolymers of ethylene and vinyl alcohol; copolymers of ethylene, vinyl acetate and vinyl alcohol; cellulose acetate butyrate, poly (urethane); poly (acrylates); poly (methacrylates); epoxy resins; an aminoplast-functionalized polymer; poly (anhydrides); poly (urea-urethanes); an N-alkoxymethyl (meth) acrylamide-functional polymer; poly (siloxanes) and poly (silanes).

56. The photochromic composition of claim 54, wherein the at least one photochromic material is blended with at least a portion of the polymeric material.

57. The photochromic composition of claim 54, wherein the at least one photochromic material is bonded to at least a portion of the polymeric material.

58. The photochromic composition of claim 54, wherein the at least one photochromic material, when bonded to the polymeric material, has a fade rate that is equal to or faster than the fade rate of a corresponding photochromic material, which does not have a residue of a cyclic monomer, when bonded to the polymeric material.

59. The photochromic composition of claim 58, wherein the at least one photochromic material has a T1/2 value when bonded to the polymeric material that is not greater than the T1/2 value of the corresponding photochromic material bonded to the polymeric material that does not comprise a residue of a cyclic monomer.

60. The photochromic composition of claim 58, wherein the at least one photochromic material has a T1/2 value when bonded to the polymeric material that is less than the T1/2 value of a corresponding photochromic material bonded to the polymeric material that does not comprise a residue of a cyclic monomer.

61. A photochromic composition comprising:

(a) a polymeric material; and

(b) at least one photochromic material in contact with at least a portion of the polymeric material, wherein the at least one photochromic material is represented by the general formula:

wherein:

(1) PC is a photochromic base;

(2) n is an integer from 1 to 8; and

(3) each S' is independently at each occurrence selected from the group represented by the formula:

wherein:

(A) l is a linker independently selected at each occurrence from-O-, -N-, and-S-, or L comprises a linear or branched organic bridging group comprising at least one linker independently selected at each occurrence from-O-, -N-, and-S-;

(B) a is an integer independently selected at each occurrence from 1 to 500;

(C)R¹independently at each occurrence, selected from the group consisting of a ring-opened cyclic ester monomer and a ring-opened cyclic carbonate monomer;

(D)R²an organic material independently selected for each occurrence from hydrogen and a residue comprising at least one reactive group; and

(E) b is a independently at each occurrence an integer selected from 1 to 20.

62. The photochromic composition of claim 61 wherein the polymeric material is selected from the group consisting of polymeric microparticles; copolymers of ethylene and vinyl acetate; copolymers of ethylene and vinyl alcohol; copolymers of ethylene, vinyl acetate and vinyl alcohol; cellulose acetate butyrate, poly (urethane); poly (acrylates); poly (methacrylates); epoxy resins; an aminoplast-functionalized polymer; poly (anhydrides); poly (urea-urethanes); an N-alkoxymethyl (meth) acrylamide-functional polymer; poly (siloxane); and poly (silanes).

63. The photochromic composition of claim 61, wherein the at least one is selected from PC- [ S']_nThe photochromic material represented has a fade rate when bonded to the polymeric material equal to or faster than the corresponding photochromic material represented by PC or the corresponding photochromic material represented by PC-L-H in contact with the polymeric material when bonded to the polymeric material.

64. The photochromic composition of claim 63, wherein the at least one is selected from the group consisting of PC-[S′]_nThe photochromic material represented has a T1/2 value when bonded to the polymeric material that is not greater than the T1/2 value of the corresponding photochromic material represented by PC or the corresponding photochromic material represented by PC-L-H when bonded to the polymeric material in contact with the polymeric material.

65. The photochromic composition of claim 63, wherein the at least one photochromic material represented by PC- [ S' ] n has a T1/2 value when bonded to the polymeric material that is less than the T1/2 value of the corresponding photochromic material represented by PC in contact with the polymeric material or the corresponding photochromic material represented by PC-L-H when bonded to the polymeric material.

66. A photochromic composition comprising:

(a) a polymeric material; and

(b) at least one photochromic material bonded to at least a portion of the polymeric material, the at least one photochromic material comprising:

(1) a photochromic group, and

(2) at least one segment comprising a residue of a plurality of ring-opened cyclic monomers bonded to the photochromic group, the ring-opened cyclic monomers selected from the group consisting of cyclic esters, cyclic carbonates, cyclic ethers, cyclic siloxanes, and combinations thereof, wherein the at least one segment has a number average molecular weight of at least 1000 g/mol; and

Wherein the photochromic material, when bonded to the polymeric material, has a T1/2 value that is not greater than the T1/2 value of a corresponding photochromic material in the absence of a segment comprising residues of a plurality of ring-opened cyclic monomers.

67. An optical element comprising:

(a) a substrate; and

(b) at least one photochromic material attached to at least a portion of the substrate, the at least one photochromic material comprising the reaction product of:

(1) at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates; and

(2) a photochromic initiator.

68. The optical element of claim 67 wherein the optical element is selected from the group consisting of: ophthalmic elements, display elements, windows, mirrors, active liquid crystal cell elements and passive liquid crystal cell elements.

69. The optical element of claim 67 wherein the optical element is an ophthalmic element selected from the group consisting of corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying lenses, protective lenses, and visors.

70. The optical element of claim 67 wherein the substrate comprises a polymeric material and the at least one photochromic material is blended with at least a portion of the polymeric material.

71. The optical element of claim 67 wherein the substrate comprises glass.

72. The optical element of claim 67 further comprising an at least partial coating layer coupled to at least a portion of the substrate, wherein the at least partial coating layer comprises at least one photochromic material.

73. The optical element of claim 67 further comprising at least one coating selected from at least portions of a primer coating, a protective coating, an anti-reflective coating, and a polarizing coating, the coatings being attached to at least a portion of at least one surface of the substrate.

74. An optical element comprising:

(a) a substrate; and

(b) at least one photochromic material attached to at least a portion of the substrate, wherein the at least one photochromic material is represented by the general formula:

wherein:

(1) PC is a photochromic base;

(2) n is an integer from 1 to 8; and

(3) each S' is independently at each occurrence selected from the group represented by the formula:

wherein:

(A) l is a linker independently selected at each occurrence from-O-, -N-, and-S-, or L comprises a linear or branched organic bridging group comprising at least one linker independently selected at each occurrence from-O-, -N-, and-S-;

(B) a is an integer independently selected at each occurrence from 1 to 500;

(C)R¹independently at each occurrence, selected from the group consisting of a ring-opened cyclic ester monomer and a ring-opened cyclic carbonate monomer;

(D)R²An organic material independently selected for each occurrence from hydrogen and a residue comprising at least one reactive group; and

(E) b is an integer independently selected at each occurrence from 1 to 20.

75. The optical element of claim 74 further comprising an at least partial coating coupled to at least a portion of the substrate, wherein the at least partial coating comprises the at least one photochromic material.

76. An optical element comprising:

(a) a substrate; and

(b) an at least partial coating associated with at least a portion of the substrate, the at least partial coating comprising at least one photochromic material comprising the reaction product of:

(1) at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates; and

(2) a photochromic initiator.

77. The optical element of claim 76 wherein the at least partial coating comprises a polymeric material and the at least one photochromic material is blended with at least a portion of the polymeric material.

78. The optical element of claim 76 wherein the at least partial coating comprises a polymeric material and the at least one photochromic material is bonded to at least a portion of the polymeric material.

79. A method of making a photochromic composition, comprising: attaching at least one photochromic material to at least a portion of the polymeric material, wherein the at least one photochromic material comprises the reaction product of:

(1) At least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates; and

(2) a photochromic initiator.

80. A method of manufacturing an optical element, comprising: attaching at least one photochromic material to at least a portion of the substrate, wherein the at least one photochromic material comprises the reaction product of:

(1) at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters and cyclic carbonates; and

(2) a photochromic initiator.

81. The method of claim 80, wherein attaching the photochromic material to at least a portion of the substrate comprises at least one of infiltrating, casting-in-place, in-mold casting, coating, and laminating.

82. A method of inhibiting migration of a photochromic material in a polymeric material, the method comprising bonding the photochromic material to at least a portion of the polymeric material, wherein the photochromic material comprises: (1) a photochromic group, and (2) at least one segment comprising residues of a plurality of ring-opened cyclic monomers bonded to the photochromic group, the ring-opened cyclic monomers selected from the group consisting of cyclic esters, cyclic carbonates, cyclic ethers, cyclic siloxanes, and combinations thereof, wherein the at least one segment has a number average molecular weight of at least 1000 g/mol.

83. The method of claim 82, wherein the at least one segment has a number average molecular weight of 2000 to 6000 g/mol.

84. A method of making a photochromic material, comprising: initiating ring opening of at least one ring-opening cyclic monomer selected from the group consisting of cyclic esters, cyclic carbonates, cyclic ethers, and cyclic siloxanes with a photochromic initiator comprising at least one functional group suitable for initiating ring opening of the at least one ring-opening cyclic monomer, the at least one functional group selected from the group consisting of alcohols, amines, carboxylic acids, silanols, thiols, and combinations, salts, and complexes thereof.

85. The process of claim 84, wherein the ring-opening polymerization is initiated in the presence of at least one catalyst selected from the group consisting of aluminum isopropoxide, triethylaluminum, tin 2-ethylhexanoate (I I), trifluoroacetic acid, an enzyme, potassium and salts thereof, and trifluoromethanesulfonic anhydride.

86. The method of claim 84, wherein said functional group is selected from the group consisting of primary alcohols, secondary alcohols, and combinations, salts, and complexes thereof.

87. A photochromic material made by the process of claim 84.