HK1153765B - Compositions and articles prepared from thioether functional oligomeric polythiols - Google Patents

Description

Compositions and articles prepared from thioether-functional, oligomeric polythiols

This application is a divisional application filed according to rules of practice 42 of the patent Law, the original application being the application No. 200780016260.6 entitled "compositions and articles prepared from thioether-functional, oligomeric polythiols" filed on 4.5.2007.

Cross Reference to Related Applications

This application claims priority to U.S. provisional patent application 60/797,985 filed on 5/2006.

Technical Field

The present invention relates to oligomeric polythiols having thioether functionality, and their use in the manufacture of polymers and sulfur-containing polyurethane and poly (urea-urethane) articles having useful optical properties.

Background

Many applications such as windshields, sunglasses, fashion lenses, zero and powered lenses, sport masks, protective masks and goggles seek optical elements that provide acceptable optical performance while maintaining durability and abrasion resistance. In response to this need, optical elements made from a variety of durable organic polymers have been developed.

In applications such as optical lenses, optical fibers, windows, and automotive, marine and aerospace transparencies (auto and aviation transparencies), a number of organic polymeric materials, such as plastics, have been developed as alternatives and substitutes for glass. These polymeric materials can provide advantages over glass including shatter resistance, lighter weight for a particular application, ease of molding and ease of dyeing. However, many polymeric materials have refractive indices lower than that of glass. In ophthalmic applications, the use of polymeric materials having a lower refractive index will require thicker lenses relative to higher refractive index materials, which is generally undesirable.

Accordingly, there is a need in the art to develop polymeric materials with sufficient refractive index and good impact resistance/strength for practical use in optical articles at a reasonable cost.

Summary of The Invention

The present invention relates to a composition comprising the reaction product of:

(A) a reactive compound comprising a substance having a functional group reactive with active hydrogen;

(B) a thioether-functional, oligomeric polythiol prepared by reacting together:

(1) a compound having at least two thiol functional groups;

(2) a compound having triple bond functionality; and optionally

(3) A compound having at least two double bonds; and, optionally,

(C) an active hydrogen-containing compound different from (B).

The present invention also relates to a method of making a hard article comprising the reaction product of:

(A) a reactive compound comprising a substance having a functional group reactive with active hydrogen;

(B) a thioether-functional, oligomeric polythiol prepared by reacting together:

(1) a compound having at least two thiol functional groups;

(2) a compound having triple bond functionality; and optionally

(3) A compound having at least two double bonds; and

(C) an active hydrogen-containing compound different from (B);

the method comprises the following steps:

(i) introducing (A), (B) and (C) simultaneously into a reaction vessel; and

(ii) reacting them together to form the reaction product.

In addition, the present invention provides a method of making a hard article comprising the reaction product of:

(A) a reactive compound comprising a substance having a functional group reactive with active hydrogen;

(B) a thioether-functional, oligomeric polythiol prepared by reacting together:

(1) a compound having at least two thiol functional groups;

(2) a compound having triple bond functionality; and optionally (c) a second set of instructions,

(3) a compound having at least two double bonds; and

(C) an active hydrogen-containing compound different from (B);

the method comprises the following steps:

(i) introducing a reactive compound (a) and an oligomeric polythiol (B) into a reaction vessel;

(ii) reacting a reactive compound (a) first with an oligomeric polythiol (B) to prepare a prepolymer; and

(iii) post-reacting an active hydrogen-containing compound (C) with the prepolymer to produce the reaction product.

Detailed Description

It is noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent.

For the purposes of this specification, unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and other parameters used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

All numerical ranges herein include all numbers and all numerical ranges within the listed numerical ranges. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the square root standard deviation (standard variation) found in their respective testing measurements.

The various embodiments and examples of the invention provided herein are each to be construed as non-limiting with respect to the scope of the invention.

As used in the following specification and claims, the following terms have the meanings indicated below:

the terms "acrylic" and "acrylate" are used interchangeably (unless doing so would change the intended meaning) and includeIncluding acrylics, anhydrides, and derivatives thereof, e.g. C₁-C₅Alkyl esters, lower alkyl-substituted acrylic acids, e.g. C₁-C₅Substituted acrylic acids, e.g. methacrylic acid, ethacrylic acid, etc., and C thereof₁-C₅Alkyl esters, unless expressly indicated otherwise. The term "(meth) acrylic" or "(meth) acrylate" is intended to include both acrylic/acrylate and methacrylic/methacrylate forms of the material, such as (meth) acrylate monomers.

The terms "oligo" and "oligomeric" are intended to mean compounds made by addition polymerization to produce materials having repeating units and a number average molecular weight of at most 5000, or at most 2000, or 200-1200. The number average molecular weight can be determined by gel permeation chromatography using polystyrene standards.

The term "curable" as used, for example, in connection with a curable composition means that the composition can be polymerized or crosslinked via functional groups, for example, by methods including, but not limited to: thermal, catalytic, electron beam, chemical free radical initiation, and/or photoinitiation such as exposure to ultraviolet light or other actinic radiation.

As used in connection with a cured or curable composition, the terms "cure," "cured," or similar terms, such as some specifically described "cured compositions," mean that at least a portion of the polymerizable and/or crosslinkable components forming the curable composition are polymerized and/or crosslinked. Additionally, curing of a polymerizable composition refers to subjecting the composition to curing conditions such as, but not limited to, thermal curing, thereby causing the reactive functional groups of the composition to react and result in polymerization and formation of a polymerized product. When the polymerizable composition is subjected to curing conditions, the reaction rate of the remaining unreacted reactive end groups becomes progressively slower after polymerization and after most of the reactive end groups have reacted. The polymerizable composition may be subjected to curing conditions until it is at least partially cured. The term "at least partially cured" means subjecting a polymerizable composition to curing conditions wherein at least a portion of the reactive groups of the composition react to form a polymerized product, such that the polymerized product can be demolded and cut into test pieces, or such that it can be subjected to mechanical processing, including optical lens processing. The polymerizable composition may also be subjected to curing conditions such that substantially complete curing is achieved and wherein further curing does not result in a significant further improvement in polymer properties such as hardness.

The term "reactive compound" refers to a compound that is capable of chemically reacting with itself and/or other compounds, either spontaneously or upon application of heat, actinic radiation, or in the presence of a catalyst or by any other method known to those skilled in the art.

The terms "on.. or," attached to.. or, "" affixed to.. or "attached to.. or the like," mean that the specified item, e.g., coating, film or layer, is directly attached to (e.g., superimposed on) the target surface or is indirectly attached to the target surface, e.g., by one.

The term "ophthalmic" refers to elements and devices relating to the eye and vision, such as, but not limited to, spectacle lenses, e.g., corrective and non-corrective lenses, and magnifying lenses.

For example, as used in connection with a polymeric material, the term "optical quality" (e.g., "resin having optical quality" or "organic polymeric material having optical quality") means that the material (e.g., polymeric material, resin, or resin composition) is or forms a substrate, layer, film, or coating that can be used as or in combination with an optical article, such as a lens.

The term "rigid", as used, for example, in connection with an optical substrate or optical article, means that the article is self-supporting; that isIs capable of retaining its shape and supporting any applied coating and/or film. The optical substrate itself may be in the form of a film or sheet. Hard articles can also be defined as being capable of being demolded and cut into test pieces or subjected to machining without permanent deformation. Alternatively, the hard article may be described as having at least 20N/mm as defined herein²The hardness in mahalanobis.

The term "optical article" means that the article exhibits a visible light transmission (through incident light) of at least 4%, such as at least 50%, or at least 70%, or at least 85%; and exhibit a Haze of less than 5%, such as less than 1% or less than 0.5%, when measured at 550nm, for example by a Haze Gard Plus Haze meter. Optical articles may include, but are not limited to, optical fibers, windows and automotive, marine and aerospace transparencies, lenses, optical layers such as optical resin layers, optical films such as films and/or sheets suitable for electronic displays such as monitors, luminescent screens or security elements, optical coatings, and optical substrates having light influencing properties (light influencing properties).

The term "photochromic receptive" means that the article has sufficient free volume to allow the photochromic material incorporated into the article to transform from its colorless form to its colored form (and then revert back to its colorless form) to the extent required for commercial optical applications.

The term "colored" as used, for example, in connection with ophthalmic devices and optical substrates, means that the article contains a fixed light radiation absorber, such as, but not limited to, conventional colored dyes and/or pigments, infrared and/or ultraviolet light absorbing materials, on or in the article. The colored article has an absorption spectrum of visible radiation that does not vary significantly with actinic radiation.

The term "colorless," as used, for example, in connection with ophthalmic devices and optical substrates, means that the article is substantially free of immobilized optical radiation absorber. Colorless articles have an absorption spectrum of visible radiation that does not change significantly with actinic radiation.

The term "radiation curable" refers to compositions that can be cured by means of ionizing radiation, such as electron beams, actinic radiation, and the like.

The term "actinic radiation" includes light having a wavelength of electromagnetic radiation ranging from the ultraviolet ("UV") light range through the visible range to the infrared range. Actinic radiation that may be used to cure coating compositions used in the present invention typically has electromagnetic radiation wavelengths of 150-2,000 nanometers (nm), 180-1,000nm, or 200-500 nm. In one embodiment, ultraviolet radiation having a wavelength of 10 to 390nm may be used. Examples of suitable ultraviolet light sources include xenon arc lamps, mercury arcs, carbon arcs, low, medium or high pressure mercury lamps, swirl-flow plasma arcs and ultraviolet light emitting diodes. Suitable ultraviolet light-emitting lamps are medium pressure mercury vapor lamps having an output of 200 and 600 watts/inch (79-237 watts/cm) over the entire length of the lamp tube.

The term "transparent" as used, for example, in connection with a substrate, film, material, and/or coating, means that the substrate, coating, film, and/or material has light transmissive properties without significant scattering so that objects located at a distance are fully visible.

The present invention relates to thioether-functional, oligomeric polythiols having pendant hydroxyl groups. In addition, the present invention relates to compositions comprising thioether-functional, oligomeric polythiols, including, but not necessarily limited to, those having pendant hydroxyl groups mentioned above. The above compositions may be used to prepare coating compositions and polymerizates used in the manufacture of articles such as optical articles. In addition, the present invention provides a method of making a rigid article, such as a rigid optical article, comprising a thioether-functional, oligomeric polythiol, such as those previously mentioned.

Thioether-functional, oligomeric polythiols having pendant hydroxyl groups:

as noted above, the present invention provides a thioether-functional, oligomeric polythiol having pendant hydroxyl functional groups, prepared by reacting together:

(a) a compound having at least two thiol functional groups; and

(b) a hydroxy-functional compound having triple bond functionality.

The compound (a) having at least two thiol functional groups may comprise a polythiol, such as a dithiol, a compound having more than two thiol functional groups (higher polythiols), or a mixture thereof. The mixture may comprise a mixture of dithiols, a mixture of higher polythiols, or a mixture of dithiols and higher polythiols. The thiol functional groups are typically terminal groups, although a minor portion (e.g., less than 50% of the total groups) may be pendant along the chain. Compound (a) may additionally contain a minor proportion of other active hydrogen functional groups (i.e. different from thiols), such as hydroxyl functional groups. The compound (a) may be linear or branched and may contain a cyclic group, an alkyl group, an aryl group, an aralkyl group or an alkaryl group.

The compound (a) may be selected to produce a substantially linear oligomeric polythiol. Thus, when compound (a) comprises a mixture of a dithiol and a compound having more than two thiol functional groups, the compound having more than two thiol functional groups may be present in an amount of up to 10wt% of the mixture.

Suitable dithiols may include linear or branched aliphatic, cycloaliphatic, aromatic, heterocyclic, polymeric, oligomeric dithiols and mixtures thereof. Dithiols may contain a variety of linkages including, but not limited to, ether linkages (-O-), thioether linkages (-S-), polysulfide linkages (-S-), and the like_x-, where x is at least 2, or 2-4), ester linkages, amide linkages, and combinations of the foregoing.

Non-limiting examples of dithiols suitable for use in the present invention may include, but are not limited to, 2, 5-dimercaptomethyl-1, 4-dithiane, dimercaptodiethylsulfide (DMDS), ethanedithiol, 3, 6-dioxa-1, 8-octanedithiol, ethylene glycol di (2-mercaptoacetate), ethylene glycol di (3-mercaptopropionate), polyethylene glycol di (2-mercaptoacetate) and polyethylene glycol di (3-mercaptopropionate), benzenedithiol, 4-tert-butyl-1, 2-benzenedithiol, 4' -thiodithiol, and mixtures thereof.

The dithiols may include dithiol oligomers having disulfide bonds, such as those represented by the following formula I:

wherein n may represent an integer of 1 to 21.

Dithiol oligomers represented by formula I can be prepared, for example, by reacting 2, 5-dimercaptomethyl-1, 4-dithiane with sulfur in the presence of a basic catalyst, as is known in the art.

The nature of the SH groups in polythiols allows oxidative coupling to occur readily, resulting in the formation of disulfide bonds. Various oxidizing agents can cause the oxidative coupling described above. Oxygen in air can sometimes cause the above-mentioned oxidative coupling during storage of the polythiol. It is believed that one possible mechanism for oxidative coupling of thiol groups involves the formation of sulfur-centered radicals (thio radials) which then couple to form disulfide bonds. It is further believed that disulfide bond formation may occur under conditions that result in the formation of a sulfur-centered radical, including but not limited to reaction conditions involving free radical initiation. Polythiols suitable for use as compound (a) in the preparation of polythiols of the invention can include species that contain disulfide bonds formed during storage. Polythiols suitable for use as compound (a) in the preparation of any oligomeric polythiol of the invention can also include species containing disulfide bonds formed during the synthesis of the polythiol.

In certain embodiments, dithiols suitable for use in the present invention may include at least one dithiol represented by the following formula:

dithiols containing thioether linkages comprising 1, 3-dithiolanes (e.g., formulas II and III) or 1, 3-dithianes (e.g., formulas IV and V) can be prepared by reacting unsymmetrical-dichloroacetone with a dithiol and then reacting the reaction product with a dimercaptoalkyl sulfide, dithiol, or mixtures thereof, as described in U.S. patent 7,009,032B 2.

Non-limiting examples of dithiols suitable for reaction with asymmetric-dichloroacetone may include, but are not limited to, those represented by the following formula VI:

wherein Y may represent CH₂Or (CH)₂-S-CH₂) And n' may be an integer of 0 to 5. Dithiols suitable for reaction with unsymmetrical-dichloroacetone in the present invention may be selected from, for example, ethanedithiol, propanedithiol, and mixtures thereof.

The amounts of unsymmetrical dichloroacetone and dithiol suitable for carrying out the above reaction may vary. For example, the unsymmetrical-dichloroacetone and dithiol may be present in the reaction mixture in amounts such that the molar ratio of dichloroacetone to dithiol may be in the range of from 1:1 to 1: 10.

The temperature suitable for the reaction of unsymmetrical-dichloroacetone with dithiol can vary, often from 0 to 100 ℃.

Non-limiting examples of dithiols suitable for reaction with the reaction product of asymmetric-dichloroacetone and dithiol may include, but are not limited to, the species represented by formula VI above, aromatic dithiols, cycloalkyl dithiols, heterocyclic dithiols, branched dithiols, and mixtures thereof.

Non-limiting examples of dimercaptoalkyl sulfides suitable for reaction with the reaction product of unsymmetrical-dichloroacetone and a dithiol may include, but are not limited to, those represented by the following formula:

wherein X may represent O, S or Se, n 'may be an integer from 0 to 10, m may be an integer from 0 to 10, p may be an integer from 1 to 10, and q may be an integer from 0 to 3, provided that (m + n') is an integer from 1 to 20.

Non-limiting examples of dimercaptoalkyl sulfides suitable for use in the present invention may include branched dimercaptoalkyl sulfides.

The amount of dithiols, dimercaptoalkylthioethers, or mixtures thereof suitable for reaction with the reaction product of unsymmetrical-dichloroacetone and dithiols may vary. Generally, the dithiols, dimercaptoalkylsulfides, or mixtures thereof may be present in the reaction mixture in an amount such that the equivalent ratio of reaction product to dithiols, dimercaptoalkylsulfides, or mixtures thereof may be from 1: 1.01 to 1: 2. In addition, the temperature suitable for carrying out the reaction may vary from 0 to 100 ℃.

The reaction of unsymmetrical-dichloroacetone with dithiol may be carried out in the presence of an acid catalyst. The acid catalyst may be selected from a wide variety known in the art, such as, but not limited to, lewis acids and bronsted acids. Non-limiting examples of suitable acid catalysts may include those described in Ullmann's Encyclopedia of Industrial Chemistry, fifth edition, 1992, volume A21, pages 673-. The acid catalyst is often selected from boron trifluoride etherate, hydrogen chloride, toluene sulfonic acid, and mixtures thereof. The amount of acid catalyst may be from 0.01 wt% to 10wt% of the reaction mixture.

The reaction product of unsymmetrical-dichloroacetone and a dithiol may alternatively be reacted with a dimercaptoalkyl sulfide, a dithiol, or a mixture thereof in the presence of a base. The base may be selected from a wide variety known in the art, such as, but not limited to, lewis bases and bronsted bases. Non-limiting examples of suitable bases may include those described in Ullmann's encyclopedia of Industrial Chemistry, fifth edition, 1992, volume A21, pages 673 and 674. The base is often sodium hydroxide. The amount of base may vary. In general, a suitable equivalent ratio of base to reaction product of the first reaction may be from 1:1 to 10: 1.

The reaction of unsymmetrical-dichloroacetone with dithiol may be carried out in the presence of a solvent. The solvent may be selected from, but is not limited to, organic solvents. Non-limiting examples of suitable solvents may include, but are not limited to, chloroform, dichloromethane, 1, 2-dichloroethane, diethyl ether, benzene, toluene, acetic acid, and mixtures thereof.

In another embodiment, the reaction product of asymmetric-dichloroacetone and a dithiol may be reacted with a dimercaptoalkyl sulfide, a dithiol, or a mixture thereof in the presence of a solvent, wherein the solvent may be selected from, but is not limited to, organic solvents. Non-limiting examples of suitable organic solvents may include alcohols such as, but not limited to, methanol, ethanol, and propanol; aromatic hydrocarbon solvents such as, but not limited to, benzene, toluene, xylene; ketones such as, but not limited to, methyl ethyl ketone; water; and mixtures thereof.

The amount of solvent can vary widely and is from 0% to 99% by weight of the reaction mixture. Alternatively, the reaction can be carried out neat (i.e., without solvent).

The reaction of unsymmetrical-dichloroacetone with dithiol can also be carried out in the presence of a dehydrating agent. The dehydrating agents may be selected from a wide variety known in the art. Suitable dehydrating agents for use in this reaction may include, but are not limited to, magnesium sulfate. The amount of dehydrating agent can vary widely depending on the stoichiometry of the dehydration reaction.

In certain non-limiting embodiments, the compound (a) having at least two thiol functional groups used to prepare the oligomeric polythiols of the invention can be prepared by reacting 2-methyl-2-dichloromethyl-1, 3-dithiolane with dimercaptodiethylsulfide to produce the dimercapto-1, 3-dithiolane derivative of formula III. Alternatively, 2-methyl-2-dichloromethyl-1, 3-dithiolane can be reacted with 1, 2-ethanedithiol to produce the dimercapto-1, 3-dithiolane derivative of formula II. 2-methyl-2-dichloromethyl-1, 3-dithiane can be reacted with dimercaptodiethylsulfide to produce the dimercapto-1, 3-dithiane derivative of formula V. Alternatively, 2-methyl-2-dichloromethyl-1, 3-dithiane can be reacted with 1, 2-ethanedithiol to produce the dimercapto-1, 3-dithiane derivative of formula IV.

Another non-limiting example of a dithiol suitable for use as compound (a) in the preparation of an oligomeric polythiol of the invention can include at least one dithiol oligomer made by reacting a dichloro derivative with a dimercaptoalkyl sulfide in reaction scheme a, as follows:

reaction scheme A

Wherein R may represent CH₃、CH₃CO、C₁-C₁₀Alkyl, cycloalkyl, arylalkyl or alkyl-CO; y' may represent C₁-C₁₀Alkyl, cycloalkyl, C₆-C₁₄Aryl group, (CH)₂)_p′(S)_m′(CH₂)_q′、(CH₂)_p′(Se)_m′(CH₂)_q′、(CH₂)_p′(Te)_m′(CH₂)_q′Wherein m ' may be an integer of 1 to 5 and p ' and q ' may each be an integer of 1 to 10; n' "can be an integer from 1 to 20; and x may be an integer from 0 to 10.

The reaction of the dichloro derivative with the dimercaptoalkyl sulfide may be carried out in the presence of a base. Suitable bases include any base known to those skilled in the art in addition to those disclosed above.

The reaction of the dichloro derivative with the dimercaptoalkylthioether may be carried out in the presence of a phase transfer catalyst. Phase transfer catalysts suitable for use in the present invention are known and widely varied. Non-limiting examples may include, but are not limited to, tetraalkylammonium salts and tetraalkylphosphonium salts. The reaction is often carried out in the presence of tetrabutylphosphonium bromide as phase transfer catalyst. The amount of phase transfer catalyst may vary widely, for example from 0 to 50 equivalent%, or from 0 to 10 equivalent%, or from 0 to 5 equivalent%, relative to the dimercaptosulfide reactant.

The compound (a) having at least two thiol functional groups may further contain a hydroxyl functional group. Non-limiting examples of suitable materials having both hydroxyl and multiple (greater than one) thiol groups can include, but are not limited to, glycerol bis (2-mercaptoacetate), glycerol bis (3-mercaptopropionate), 1, 3-dimercapto-2-propanol, 2, 3-dimercapto-1-propanol, trimethylolpropane bis (2-mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate), pentaerythritol bis (2-mercaptoacetate), pentaerythritol tris (2-mercaptoacetate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), and mixtures thereof.

In addition to the dithiols described above, specific examples of dithiols suitable for use as compound (a) or for preparing compound (a) may include 1, 2-ethanedithiol, 1, 2-propanedithiol, 1, 3-butanedithiol, 1, 4-butanedithiol, 2, 3-butanedithiol, 1, 3-pentanethiol, 1, 5-pentanethiol, 1, 6-hexanedithiol, 1, 3-dimercapto-3-methylbutane, dipentene dithiol, ethylcyclohexyl dithiol (ECHDT), dimercaptodiethylsulfide (DMDS), methyl-substituted dimercaptodiethylsulfide, dimethyl-substituted dimercaptodiethylsulfide, 3, 6-dioxa-1, 8-octanethiol, 1, 5-dimercapto-3-oxapentane, 2, 5-dimercaptomethyl-1, 4-dithiane (DMMD), ethylene glycol di (2-mercaptoacetate), ethylene glycol di (3-mercaptopropionate), and mixtures thereof.

Trifunctional or higher-functional polythiols suitable for use as compound (a) or for preparing compound (a) can be selected from a wide variety known in the art. Non-limiting examples may include pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), and/or thioglycerol bis (2-mercaptoacetate).

For example, the polythiol may be selected from those represented by the following formula VIII,

wherein R is₁And R₂May each be independently selected from linear or branched alkylene, cyclic alkylene, phenylene and C₁-C₉Alkyl-substituted phenylene radicals. Non-limiting examples of the linear or branched alkylene group may include methylene, ethylene, 1, 3-propylene, 1, 2-propylene, 1, 4-butylene, 1, 2-butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, octadecylene and eicosylene. Non-limiting examples of cyclic alkylene groups may include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, and alkyl-substituted derivatives thereof. Divalent linking group R₁And R₂May be selected from methylene, ethylene, phenylene and alkyl substituted phenylene, such as methyl, ethyl, propyl, isopropyl and nonyl substituted phenylene.

In a particular embodiment, compound (a) having at least two thiol functional groups may be prepared by reacting together (1) any of the above dithiols and (2) a compound having at least two double bonds (e.g., a diene). The compound having at least two double bonds is described in more detail below, as is the reaction method.

The compound (b) having triple bond functionality used to prepare the oligomeric polythiols of the invention can include any alkyne known to those skilled in the art. In the preparation of thioether-functional, oligomeric polythiols having pendant hydroxyl functional groups, compound (b) can comprise any hydroxyl-functional alkyne known in the art, such as those described immediately below. Since a triple bond can react twice with a thiol functional group, a triple bond is understood to be an equivalent of 2 double bonds when determining the reaction stoichiometry for the purposes of the present invention.

Suitable non-limiting examples of hydroxyl functional compounds having triple bond functionality include propargyl alcohol, but-2-yne-1, 4-diol, but-3-yne-2-ol, hex-3-yne-2, 5-diol, and/or mixtures thereof. A portion of the hydroxyl functionality on compound (b) may be esterified. For example, a portion of compound (b) may comprise C₁-C₁₂Alkyne-functional esters of carboxylic acids, such as propargyl acetate, propargyl propionate, propargyl benzoate, and the like. Furthermore, in the preparation of thioether-functional, oligomeric polythiols having pendant hydroxyl groups, a portion of the triple bond-containing compounds (b) may comprise, in addition to the hydroxyl-functional triple bond-containing compounds, triple bond-containing compounds that do not contain hydroxyl functional groups, such as those described below.

In the preparation of the oligomeric polythiols of the invention, the ratio of thiol functional groups in compound (a) to triple bonds in compound (b) is generally from 1.01:1 to 2.0: 1, for example from 1.3: 1 to 2.0: 1 and from 1.5: 1 to 2.0: 1. The presence of excess thiol functionality in the reaction product, sometimes during the reaction and as unreacted compound (a), may be desirable. For example, the presence of excess thiol during the reaction can increase the reaction rate. Further unreacted thiol (e.g. in the form of unreacted compound (a)) may be present in the final reaction product and thus available for subsequent reaction with e.g. a reactive compound having functional groups reactive towards active hydrogen (e.g. as described below). Thus, in one embodiment of the invention, the ratio of the reaction of thiol functional groups in compound (a) with triple bonds in compound (b) may be from 1.01:1 to 20: 1, such as from 1.01:1 to 10: 1, or from 1.01:1 to 5:1, or from 1.5: 1 to 3: 1.

To prepare the oligomeric polythiols of the present invention, the reaction of compound (a) with compound (b) containing a triple bond can be carried out in the presence of a free radical initiator. Free radical initiators suitable for use in the present invention may vary widely and may include those known to those skilled in the art. Non-limiting examples of free radical initiators may include, but are not limited to, azo or peroxide type free radical initiators such as azobisalkylidenenitrile (azobiskallene). The free radical initiator may be VAZO, which is available from DuPont under the trade name VAZO^TMCommercially available azobisalkylene nitriles. VAZO-52, VAZO-64, VAZO-67, VAZO-88 and mixtures thereof may also be used as free radical initiators.

The choice of free radical initiator may depend on the reaction temperature. The reaction temperature may vary, for example, from room temperature to 120 ℃. VAZO52 can be used at 50-60 ℃. VAZO64 and VAZO67 may be used at 60-100 deg.C, while VAZO 88 may be used at 70-120 deg.C.

The amount of free radical initiator used in the reaction of the present invention may vary widely and may depend on the free radical initiator selected. Typically, the free radical initiator is present in an amount of 0.01% to 5% by weight of the reaction mixture.

The reaction of the compound (a) with the triple bond-containing compound (b) may be carried out under various reaction conditions. The conditions may depend on the degree of reactivity of the triple bond-containing compound and the desired structure of the resulting polythiol oligomer. In one reaction scheme, the reactants and the free radical initiator may be combined together while heating the mixture. Alternatively, the triple bond containing compound may be added to a mixture of polythiol and free radical initiator at a temperature and in relatively small amounts over a period of time. In addition, the triple bond-containing compound may be combined with the compound (a) having at least two thiol functional groups step by step under free radical initiation. In addition, the radical initiator may be dissolved in the triple bond-containing compound (b), and the resulting solution may be added dropwise to the compound (a).

The present invention also relates to a composition, such as a coating composition, comprising any of the thioether-functional, oligomeric polythiols described above. The composition may further comprise a reactive compound comprising a material having a functional group reactive with active hydrogen, such as any such compound described in detail below.

The present invention also relates to thioether-functional, oligomeric polythiols having pendant hydroxyl functional groups, prepared by reacting together:

(a) a compound having at least two thiol functional groups, such as any of those described above;

(b) compounds having triple bond functionality, such as any of those described above; and

(c) a compound having at least two double bonds.

The compound (a) having at least two thiol functional groups may be any of the thioether-functional, oligomeric polythiols mentioned above, including those described above, which are prepared according to the invention. In one embodiment of the present invention, compound (a) comprises the reaction product of (1) any of the above dithiols and (2) a compound having at least two double bonds which may be the same as or different from compound (c). The compound (b) may be any of the aforementioned compounds having triple bond functionality, including the hydroxyl functional compounds having triple bond functionality.

The compound (c) having at least two double bonds may be selected from acyclic dienes including linear and/or branched aliphatic acyclic dienes, non-aromatic ring containing dienes including non-aromatic ring containing dienes wherein the double bonds may or may not be contained within the rings, or any combination thereof, and non-aromatic ring containing dienes wherein the non-aromatic ring containing dienes may contain non-aromatic monocyclic groups or non-aromatic polycyclic groups, or combinations thereof; dienes containing aromatic rings; or a diene containing a heterocycle; or a diene containing any combination of the above acyclic and/or cyclic groups. The diene may optionally contain a thioether, disulfide, polysulfide, sulfone, ester, thioester, carbonate, thiocarbonate, carbamate or thiocarbamate, or halogen substituent, or combinations thereof; provided that the diene contains at least some double bonds capable of reacting with the SH groups of the polythiol and forming covalent C-S bonds. The compounds (c) having at least two double bonds often comprise mixtures of dienes which are different from one another.

The compound (c) having at least two double bonds may comprise an acyclic non-conjugated diene, an acyclic polyvinyl ether, an allyl (meth) acrylate, a vinyl (meth) acrylate, a di (meth) acrylate of a diol, a di (meth) acrylate of a dithiol, a di (meth) acrylate of a poly (alkylene glycol) diol, a monocyclic non-aromatic diene, a polycyclic non-aromatic diene, an aromatic ring-containing diene, a diallyl ester of an aromatic ring dicarboxylic acid, a divinyl ester of an aromatic ring dicarboxylic acid, and/or mixtures thereof.

Non-limiting examples of acyclic non-conjugated dienes can include those represented by the following formula IX:

wherein R is₃Can represent C₁-C₃₀Linear or branched divalent saturated alkylene, or C₂-C₃₀Divalent organic groups including groups such as, but not limited to, those containing ethers, thioethers, esters, thioesters, ketones, polysulfides, sulfones, and combinations thereof. The acyclic non-conjugated diene may be selected from 1, 5-hexadiene, 1, 6-heptadiene, 1, 7-octadiene, and mixtures thereof.

Non-limiting examples of suitable acyclic polyvinyl ethers may include those represented by the following formula X:

CH₂＝CH--O---(---R₄-O---)_m″---CH＝CH₂

(X)

wherein R is₄May be C₂-C₆N-alkylene group, C₃-C₆Branched alkylene, or- - [ (CH)₂--)_p″--O--]_q″--(--CH₂--)_r′-, m "may be a rational number from 0 to 10, often 2; p "may be an integer from 2 to 6, q" may be an integer from 1 to 5 and r' may be an integer from 2 to 10.

Non-limiting examples of polyvinyl ether monomers suitable for use can include divinyl ether monomers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and mixtures thereof.

The di (meth) acrylate of a linear diol may include ethylene glycol di (meth) acrylate, 1, 3-propylene glycol dimethacrylate, 1, 2-propylene glycol di (meth) acrylate, 1, 4-butylene glycol di (meth) acrylate, 1, 3-butylene glycol di (meth) acrylate, 1, 2-butylene glycol di (meth) acrylate, and mixtures thereof.

The di (meth) acrylate of dithiol may include, for example, di (meth) acrylate of 1, 2-ethanedithiol including its oligomer, di (meth) acrylate of dimercaptodiethylsulfide including its oligomer (i.e., 2 '-thioethanedithiol di (meth) acrylate), di (meth) acrylate of 3, 6-dioxa-1, 8-octanedithiol including its oligomer, di (meth) acrylate of 2-mercaptoethylether including its oligomer, di (meth) acrylate of 4, 4' -thiodiphenylsulfide including its oligomer, and mixtures thereof.

Other non-limiting examples of suitable dienes can include monocyclic aliphatic dienes such as those represented by the following formula XI:

wherein X 'and Y' each independently may represent C_1-10A divalent saturated alkylene group; or C_1-5A divalent saturated alkylene group containing at least one element selected from the group consisting of sulfur, oxygen, and silicon in addition to carbon and hydrogen atoms; and R₅May represent H or C₁-C₁₀An alkyl group; and those represented by formula XII below:

wherein X' and R₅May be as defined above and R₆Can represent C₂-C₁₀An alkenyl group. Monocyclic aliphatic dienes may include 1, 4-cyclohexadiene, 4-vinyl-1-cyclohexene, dipentene and terpinene.

Non-limiting examples of polycyclic aliphatic dienes can include 5-vinyl-2-norbornene, 2, 5-norbornadiene, dicyclopentadiene, and mixtures thereof.

Non-limiting examples of the aromatic ring-containing diene may include those represented by the following formula XIII:

wherein R is₄May represent hydrogen or methyl. The aromatic ring-containing diene may include monomers such as diisopropenylbenzene, divinylbenzene, and mixtures thereof.

Examples of the diallyl ester of the aromatic cyclic dicarboxylic acid may include, but are not limited to, those represented by the following formula XIV:

wherein each m' "independently can be an integer from 0 to 5. The diallyl esters of the aromatic cyclic dicarboxylic acids may include diallyl phthalate, diallyl isophthalate, diallyl terephthalate and mixtures thereof.

The compound (c) having at least two double bonds usually contains 5-vinyl-2-norbornene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, butanediol divinyl ether, vinylcyclohexene, 4-vinyl-1-cyclohexene, dipentene, terpinene, dicyclopentadiene, cyclododecadiene, cyclooctadiene, 2-cyclopenten-1-yl-ether, 2, 5-norbornadiene, divinylbenzene including 1, 3-divinylbenzene, 1, 2-divinylbenzene and 1, 4-divinylbenzene, diisopropenylbenzene including 1, 3-diisopropenylbenzene, 1, 2-diisopropenylbenzene and 1, 4-diisopropenylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1, 3-propanediol di (meth) acrylate, 1, 2-propanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 2-butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dimercaptodiethylsulfide di (meth) acrylate, 1, 2-ethanedithiol di (meth) acrylate, and/or mixtures thereof.

Other non-limiting examples of suitable di (meth) acrylate monomers may include ethylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 2, 3-dimethyl-1, 3-propanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, alkoxylated neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth), Diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, thiodiethylene glycol di (meth) acrylate, 1, 3-propanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, alkoxylated hexanediol di (meth) acrylate, alkoxylated neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, and ethoxylated bisphenol a di (meth) acrylate.

For the purposes of the present invention, in the preparation of any oligomeric polythiol comprising reactants (a), (b), and (c), the reactants (a), (b), and (c) can all be reacted together simultaneously (as in a "one-pot" process) or incrementally mixed together in various combinations. For example, the compound (a) having at least two thiol functional groups and the compound (b) having a triple bond functional group may be first reacted in a first reaction vessel to produce a first reaction product, followed by adding the compound (c) having at least two double bonds to the reaction mixture to react with the first reaction product and obtain the oligomeric polythiol of the invention (or adding the first reaction product to a second reaction vessel containing the compound (c)). Alternatively, the compound (a) may be first reacted with the compound (c) having at least two double bonds to produce a first reaction product, followed by the addition of the compound (b) to obtain an oligomeric polythiol. In this embodiment, an additional compound (c) having at least two double bonds may optionally be added simultaneously with or after compound (b), which may be the same or different from compound (c) previously reacted with compound (a) to form the first reaction product.

When compound (a) is first combined with compound (c), it is believed that they react by a thiol-ene type reaction of the SH group of (a) with the double bond group of (c). The above reaction may generally take place in the presence of a radical initiator as described above, or in the presence of a base catalyst, particularly when the compound (c) comprises a compound having at least one (meth) acrylate-type double bond. Suitable base catalysts for this reaction may vary widely and may be selected from those known in the art. Non-limiting examples can include tertiary amine bases such as 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) and N, N-dimethylbenzylamine. The amount of base catalyst used may vary widely but is generally present in an amount of from 0.001 to 5.0% by weight of the mixture of (a) and (c).

The stoichiometric ratio of the sum of the number of thiol equivalents of all polythiols (compound (a)) present to the sum of the number of equivalents of all double bonds (including alkyne functionality effective as two double bond equivalents as described above) present is greater than 1: 1. In non-limiting embodiments, the ratio may be from greater than 1:1 to 3: 1, alternatively from 1.01:1 to 2: 1, alternatively from 1.05: 1 to 2: 1, alternatively from 1.1: 1 to 1.5: 1, alternatively from 1.25: 1 to 1.5: 1.

Various methods of reacting a multivinyl monomer and one or more dithiol species are described in detail in U.S. Pat. No.6,509,418B 1, column 4, line 52-column 8, line 25, the disclosure of which is incorporated herein by reference. Various methods of reacting allyl sulfide and dimercaptodiethyl sulfide are described in detail in WO 03/042270, page 2, line 16 to page 10, line 7, the disclosure of which is incorporated herein by reference. Various methods for reacting dithiols with aliphatic, ring-containing, non-conjugated dienes in the presence of free radical initiators are described in detail in WO/01/66623A1, page 3, line 19 to page 6, line 11, the disclosure of which is incorporated herein by reference.

In reacting compounds (a) and (c), it may be advantageous to use one or more free radical initiators. Non-limiting examples of suitable free radical initiators may include azo compounds such as those described above; organic peroxides such as, but not limited to, benzoyl peroxide and t-butyl peroxide; an inorganic peroxide; and similar free radical generating species.

Alternatively, the reaction of compounds (a) and (c) may be effected by irradiation with ultraviolet light, with or without a photoinitiating moiety.

The mixture of (a) and (c) may be reacted for a period of 1 hour to 5 days and at 20 ℃ to 100 ℃. The mixture is generally heated until a predetermined theoretical value of the SH content is reached.

The stoichiometric ratio of the sum of the number of equivalents of triple bond functional groups in compound (b) to the sum of the number of equivalents of double bonds in compound (c) is often 0.01: 0.99 to 1.00: 0, alternatively 0.10: 0.90 to 1.00: 0, alternatively 0.20: 0.80 to 1.00: 0.

The present invention also relates to a composition, such as a coating composition, comprising any of the thioether-functional, oligomeric polythiols comprising compounds (a), (b), and (c) described immediately above. The composition may further comprise any compound having a functional group reactive with active hydrogen, as described in detail below.

Compositions and articles comprising thioether-functional, oligomeric polythiols:

as noted above, the present invention provides a composition comprising the reaction product of:

(A) a reactive compound comprising a substance having a functional group reactive with active hydrogen, such as any of those described below;

(B) a thioether-functional, oligomeric polythiol prepared by reacting together:

(1) a compound having at least two thiol functional groups, such as any of those described above;

(2) a compound having triple bond functionality, such as any of those described hereinabove and hereinbelow and, optionally,

(3) a compound having at least two double bonds, such as any of those described above; and, optionally,

(C) an active hydrogen-containing compound other than (B), as described below.

Compounds having triple bond functionality may include any of the known alkynes, such as propargyl alcohol, propargyl chloride, propargyl bromide, propargyl acetate, propargyl propionate, propargyl benzoate, phenylacetylene, phenylpropargyl sulfide, 1, 4-dichloro-2-butyne, 2-butyne-1, 4-diol, 3-butyne-2-ol, 2-pentyne, 1-hexyne, 2-hexyne, 3-hexyne-2, 5-diol, and/or mixtures thereof.

The compositions can be used to make any of the articles described below, such as optical articles, including films and sheets; articles for non-optical applications, such as solar panels, body armor, aircraft and automotive interior and exterior parts such as doors, dashboards, and propellers, housings for hand-held electronic devices such as mobile phones, and windmill blades; and coating compositions for forming various coatings, adhesives and/or sealants. In a particular embodiment, the composition comprises a coating composition capable of providing a coating with excellent properties including, inter alia, impact and chemical resistance, flexibility, antimicrobial and fungicidal properties, and anti-ballistic (anti-ballistic) and flame retardant properties.

Any of the thioether-functional, oligomeric polythiols described herein can produce a polymerization product having a refractive index of at least 1.50, or at least 1.52, or at least 1.55, or at least 1.60, or at least 1.65, or at least 1.67 when reacted with a reactive compound having a functional group reactive with active hydrogen. In addition, the thioether-functional, oligomeric polythiols of the invention can produce a polymerization product having an Abbe number of at least 30, or at least 35, or at least 38, or at least 39, or at least 40, or at least 44, when reacted with a reactive compound having a functional group reactive with active hydrogen. The refractive index and Abbe number can be determined by methods known in the art, such as the American Standard Test Method (ASTM) D542-00, using various known instruments. The refractive index and Abbe number can also be measured according to ASTM D542-00 with the following exceptions: (i) testing 1-2 samples/specimen instead of the minimum 3 specimens specified in section 7.3; and (ii) testing the unconditioned sample rather than conditioning the sample/specimen prior to testing as specified in section 8.1. In addition, an Atago DR-M2 model Multi-wavelet Digital Abbe Refractometer (Multi-Wavelength Digital Abbe Refractometer) can be used to measure the refractive index and Abbe number of the sample/specimen.

In addition, any of the thioether-functional, oligomeric polythiols described herein can produce a mahalanobis hardness of at least 20N/mm when reacted with a reactive compound having a functional group reactive with active hydrogen²Or often at least 50, or more typically 70 to 200. Such polymeric products are generally not elastomeric; i.e., they are not substantially reversibly deformable (e.g., stretchable) due to their rigidity and do not generally exhibit the performance characteristics of rubber and other elastomeric polymers.

These polymerization products described above can be used to prepare articles according to the present invention, such as films, coatings and molded articles such as optical articles, having similar properties as described above.

The present invention further relates to a hard article, such as a hard optical article, comprising the reaction product of:

(A) a reactive compound comprising a substance having a functional group reactive with active hydrogen;

(B) thioether-functional, oligomeric polythiols having pendant hydroxyl functional groups as described above; and optionally

(C) An active hydrogen-containing compound different from (B).

Optical articles of the invention include ophthalmic articles such as plano (no optical power) lenses and vision correcting (prescription) lenses (finished or semi-finished) including multifocal lenses (bifocal, trifocal and progressive multifocal lenses); and ocular devices (oculardevices) such as contact lenses and intraocular lenses, sunglasses, fashion glasses, sports masks, protective masks and goggles. The optical article may also be selected from glazing such as architectural windows and vehicle transparencies such as automotive or aircraft windshields and side windows.

In the preparation of the reaction product used to prepare the optical article of the present invention, reactants (a), (B), and (C) may all be reacted together simultaneously ("one-pot") or mixed together incrementally in various combinations ("one-pot or two-pot"). Alternatively, the reactive compound (a) may be first reacted with the oligomeric polythiol (B) to make a prepolymer, such as a sulfur-containing isocyanate functional polyurethane, followed by post-reaction of the active hydrogen-containing compound (C) with the prepolymer to obtain the reaction product of the present invention. In another alternative, the reactive compound (a) can comprise an isocyanate functional polyurethane prepolymer made by reacting a polyisocyanate with any of the thioether-functional, oligomeric polythiols disclosed herein (e.g., the reaction product of a compound having at least two thiol functional groups, a compound having triple bond functional groups, and optionally a compound having at least two double bonds) and optionally other active hydrogen-containing materials. In this alternative, the reactive compound (a) may be reacted in any combination or sequence with the oligomeric polythiol (B) and the active hydrogen-containing compound (C). In embodiments where any of the reactants comprise two or more different compounds, these different compounds may be reacted as a mixture or added separately or even at different times/stages of the reaction. For example, the reaction product can be made by combining a polyisocyanate and/or polyisothiocyanate, a polythiol oligomer, optionally a first active hydrogen-containing material, and optionally a urethanization catalyst to form a sulfur-containing polyurethane prepolymer, then adding a second, different active hydrogen-containing material and optionally a urethanization catalyst to the sulfur-containing polyurethane prepolymer, and polymerizing the resulting mixture.

Note that the polyurethane prepolymer may contain disulfide bonds due to disulfide bonds contained in polythiols and/or polythiol oligomers used to prepare the polyurethane prepolymer.

The reactants (a), (B) and (C) may each be degassed (e.g. under vacuum) prior to mixing them and carrying out the polymerization. The reactants may be mixed in a variety of ways and devices, such as, but not limited to, a rotary mixer or an extruder.

The reactive compound (a) comprising a substance having a functional group reactive with active hydrogen may include, for example, polyisocyanates, blocked polyisocyanates, polyisothiocyanates, polyepoxides, polyepisulfides, polyacids, anhydrides, polyanhydrides, polyethylenically unsaturated substances such as polyvinyl ethers or poly (meth) acrylates, and/or mixtures of the aforementioned substances.

The term "polyisocyanate" as used herein is intended to include blocked (or blocked) polyisocyanates as well as unblocked polyisocyanates. The polyisocyanates and polyisothiocyanates which can be used in the reactive compounds (A) vary widely. Polyisocyanates suitable for use in the present invention can include, but are not limited to, polymeric and C₂-C₂₀Linear, branched, cyclic and aromatic polyisocyanates. Polyisothiocyanates suitable for use in the present invention can include, but are not limited to, polymeric and C₂-C₂₀Linear, branched, cyclic and aromatic polyisothiocyanates.

Non-limiting examples of suitable polyisocyanates and polyisothiocyanates can include polyisocyanates having at least two isocyanate groups; a polyisothiocyanate having at least two isothiocyanate groups; mixtures thereof; and combinations thereof, such as those having isocyanate and isothiocyanate functional groups.

Non-limiting examples of the polyisocyanate may include aliphatic polyisocyanates, alicyclic polyisocyanates in which one or more isocyanate groups are directly attached to an alicyclic ring, alicyclic polyisocyanates in which one or more isocyanate groups are not directly attached to an alicyclic ring, aromatic polyisocyanates in which one or more isocyanate groups are directly attached to an aromatic ring, and aromatic polyisocyanates in which one or more isocyanate groups are not directly attached to an aromatic ring. When aromatic polyisocyanates are used, care should generally be taken to select materials which do not impart color (e.g., yellow) to the final reaction product.

Examples of suitable polyisocyanates can include, but are not limited to, DESMODUR N3300 (hexamethylene diisocyanate trimer) and DESMODUR N3400 (60% hexamethylene diisocyanate dimer and 40% hexamethylene diisocyanate trimer) which are commercially available from Bayer corporation.

The polyisocyanate may include dicyclohexylmethane diisocyanate and isomer mixtures thereof. The term "isomer mixture" as used herein and in the claims refers to a mixture of cis-cis, trans-trans, and cis-trans isomers of polyisocyanates. Non-limiting examples of isomer mixtures useful in the present invention may include the trans-trans isomer of 4, 4' -methylenebis (cyclohexyl isocyanate), hereinafter referred to as "PICM" (p-isocyanatocyclohexyl methane), the cis-trans isomer of PICM, the cis-cis isomer of PICM, and mixtures thereof.

Other aliphatic and cycloaliphatic diisocyanates that can be used include 3-isocyanato-methyl-3, 5, 5-trimethylcyclohexyl-isocyanate ("isophorone diisocyanate" or "IPDI") available from Arco chemical, available as TMXDI from Cytec Industries Inc(Meta) Meta-tetramethylxylylene diisocyanate (1, 3-bis (1-isocyanato-1-methylethyl) -benzene) available from Aliphatic Isocynate, and Meta-xylylene diisocyanate (MXDI). Mixtures of any of the foregoing may also be used.

The terms aliphatic and cycloaliphatic diisocyanate as used herein and in the claims refer to straight chained linked or cyclized 6 to 100 carbon atoms having two diisocyanate reactive end groups. The aliphatic and cycloaliphatic diisocyanates for use in the present invention may include TMXDI and R- (NCO)₂Wherein R represents an aliphatic group or a cycloaliphatic group.

Other non-limiting examples of suitable polyisocyanates and polyisothiocyanates can include aliphatic polyisocyanates and polyisothiocyanates; ethylenically unsaturated polyisocyanates and polyisothiocyanates; alicyclic polyisocyanates and polyisothiocyanates; aromatic polyisocyanates and polyisothiocyanates in which the isocyanate groups are not directly bound to aromatic rings, such as m-xylylene diisocyanate; aromatic polyisocyanates and polyisothiocyanates in which the isocyanate groups are bonded directly to the aromatic ring, such as, for example, phenylene diisocyanate; aliphatic polyisocyanates and polyisothiocyanates containing thioether linkages; aromatic polyisocyanates and polyisothiocyanates containing thioether or disulfide bonds; aromatic polyisocyanates and polyisothiocyanates containing sulfone linkages; sulfonate type polyisocyanates and polyisothiocyanates such as 4-methyl-3-isocyanatobenzenesulfonyl-4' -isocyanatophenol ester; aromatic sulfonamide polyisocyanates and polyisothiocyanates; sulfur-containing heterocyclic polyisocyanates and polyisothiocyanates, such as thiophene-2, 5-diisocyanate; halogenated, alkylated, alkoxylated, nitrated, carbodiimide-modified, urea-modified and biuret-modified derivatives of these polyisocyanates; and also dimerization and trimerization products of these polyisocyanates.

In particular embodiments of the present invention, the polyisocyanate may include toluene diisocyanate, 4 '-diphenylmethane diisocyanate, m-xylylene diisocyanate, hydrogenated m-xylylene diisocyanate (1, 3-isocyanato-methylcyclohexane), 3-isocyanato-methyl-3, 5, 5-trimethylcyclohexyl-isocyanate, hexamethylene diisocyanate, m-tetramethylxylylene diisocyanate (1, 3-bis (1-isocyanato-1-methylethyl) -benzene) and/or 4, 4' -methylenebis (cyclohexyl isocyanate).

In certain embodiments, the reactive compound (a) comprises a diisocyanate or a mixture of a diisocyanate and a polyisocyanate having more than two isocyanate functional groups. In such cases, the polyisocyanate is present in an amount of up to 10 weight percent of the mixture. In one embodiment, the reactive compound (a) comprises isophorone diisocyanate, m-tetramethylxylylene diisocyanate (1, 3-bis (1-isocyanato-1-methylethyl) -benzene), and/or methylenebis (4-cyclohexyl diisocyanate), which is commercially available as DESMODUR W from bayer corporation.

Non-limiting examples of the substance having isocyanate and isothiocyanate groups may include substances having aliphatic, alicyclic, aromatic or heterocyclic groups and optionally containing sulfur atoms in addition to those in the isothiocyanate groups. Non-limiting examples of the above-mentioned substances may include 1-isocyanato-3-isothiocyanatopropane, 1-isocyanato-5-isothiocyanatopentane, 1-isocyanato-6-isothiocyanatohexane, isocyanatocarbonyl isothiocyanate, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-isocyanato-1-isothiocyanatobenzene, 2-isocyanato-4, 6-diisothiocyanato-1, 3, 5-triazine, 4-isocyanato-4 '-isothiocyanato-diphenyl sulfide and 2-isocyanato-2' -isothiocyanatodiethyl disulfide.

The isocyanate groups may be blocked or unblocked as desired. If the polyisocyanates are to be blocked or blocked, any suitable aliphatic, cycloaliphatic or aromatic alkyl monoalcohols or phenolic compounds known to the person skilled in the art can be used as blocking agents for the polyisocyanates.

The molecular weights of the polyisocyanates and polyisothiocyanates can vary widely. Their respective number average molecular weights (Mn) may be at least 100 g/mole, alternatively at least 150 g/mole, alternatively less than 15,000 g/mole, alternatively less than 5000 g/mole. The number average molecular weight can be determined by known methods. The number average molecular weight values listed herein and in the claims are determined by Gel Permeation Chromatography (GPC) using polystyrene standards.

When used to prepare an isocyanate-terminated polyurethane prepolymer or a sulfur-containing polyurethane prepolymer, the amount of polyisocyanate compound (A) and the amount of oligomeric polythiol (B) can be selected such that the equivalent ratio of (NCO): (SH + OH) can be greater than 1.0: 1.0, alternatively at least 2.0: 1.0, alternatively at least 2.5: 1.0, alternatively less than 4.5: 1.0, alternatively less than 6.5: 1.0. Also, in the prepolymer preparation, the amount of polyisothiocyanate and the amount of oligomeric polythiol (B) used as compound (A) may be selected such that the equivalent ratio of (NCS): (SH + OH) may be greater than 1.0: 1.0, alternatively at least 2.0: 1.0, alternatively at least 2.5: 1.0, alternatively less than 4.5: 1.0, alternatively less than 6.5: 1.0. The amount of polyisothiocyanate and polyisocyanate combination used as compound (a) and the amount of oligomeric polythiol (b) in the preparation of the prepolymer may be selected such that the equivalent ratio of (NCS + NCO): (SH + OH) may be greater than 1.0: 1.0, or at least 2.0: 1.0, or at least 2.5: 1.0, or less than 4.5: 1.0, or less than 6.5: 1.0.

In embodiments where the reactive compound (a) comprises a polyisothiocyanate and/or a polyisocyanate, a thermal stabilizer such as an antioxidant as is well known in the art is often included in the reaction mixture. The heat stabilizer may comprise a phosphite, for example a triaryl phosphite, in particular trisnonylphenyl phosphite, which is added as a stabilizer. A thermal stabilizer may be added to the reaction mixture at any stage of the reaction. For example, a thermal stabilizer may be added during the preparation of the oligomeric polythiol (B) and carried over to the reaction with the polyisocyanate and/or polyisothiocyanate. Alternatively, the heat stabilizer may be mixed with polyisocyanate and/or polyisothiocyanate and then reacted with compounds (B) and (C).

Polyepoxides and polyepisulfide compounds are also suitable for use in the reactive compounds (A). Examples of suitable polyepoxides include low molecular weight polyepoxides such as 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate and bis (3, 4-epoxy-6-methylcyclohexyl-methyl) adipate. Higher molecular weight polyepoxides, including polyglycidyl ethers of polyhydric phenols and alcohols, are also suitable.

Other specific examples of polyepoxide materials are disclosed in U.S. Pat. Nos. 5,369,141, 5,374,668, and others. Epoxy-containing materials are often made by reacting an active hydrogen-containing compound with an epihalohydrin, such as epichlorohydrin or epibromohydrin, using any method known in the art, including but not limited to those disclosed in US 2,324,483 and US5,807,975. Non-limiting examples of the classes of active hydrogen-containing compounds that can be chain extended with epihalohydrins include compounds having two or more thiol groups, compounds having one or more amino groups, compounds having two or more hydroxyl groups, compounds having combinations of the foregoing groups, or mixtures of compounds containing the foregoing groups, bisphenols, chlorinated bisphenols, brominated bisphenols, polyphenols, and novolac resins. Epoxy-containing materials can also be prepared by reacting ethylenically unsaturated compounds with suitable oxidizing agents, such as hydrogen peroxide or m-chloroperbenzoic acid. Suitable such epoxy-containing materials may include, but are not limited to, diepoxides derived from 4-vinyl-1-cyclohexene.

Non-limiting examples of aliphatic acyclic epoxy-containing materials include diglycidyl ethers of ethylene glycol, butanediol, diethylene glycol, 1, 2-ethanedithiol, and 2-mercaptoethyl sulfide.

Non-limiting examples of epoxy-containing materials containing non-aromatic rings are polyepoxides of cyclic polyenes, including but not limited to diepoxides of 4-vinyl-1-cyclohexene.

Non-limiting examples of epoxy-containing materials containing aromatic rings include polyglycidyl ethers of bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, resorcinol, hydroquinone, and novolac resins.

Suitable episulfide-containing materials can vary and can include, but are not limited to, materials having two or more episulfide functional groups. For example, the episulfide-containing material can have two or more moieties represented by the following formula XV:

wherein X "may be S or O; y' may be C₁-C₁₀Alkyl, O or S; p '"can be an integer from 0 to 2, and q'" can be an integer from 0 to 10. In a non-limiting embodiment, the quantitative ratio of S is 50% or more on average of the total amount of S and O constituting the three-membered ring.

The episulfide-containing material having two or more structural moieties represented by formula (VIII) may be attached to an acyclic and/or cyclic skeleton. The acyclic backbone may be branched or unbranched, and it may contain thioether and/or ether linkages. The episulfide-containing material can be obtained by replacing the oxygen in the epoxy ring-containing material with sulfur, thiourea, triphenylphosphine sulfide or other such reagents known in the art. The epoxy substance of the alkylsulfide type can be obtained by reacting various known polythiols with epichlorohydrin in the presence of an alkali; the oxygen in the epoxy ring is then replaced as described above to obtain an alkylsulfide-type episulfide-containing material.

In alternative non-limiting embodiments, the cyclic backbone may include the following:

(a) an episulfide-containing material in which the cyclic skeleton may be an alicyclic skeleton,

(b) an episulfide-containing substance, wherein the cyclic skeleton may be an aromatic skeleton, and

(c) an episulfide-containing material, wherein the cyclic skeleton may be a heterocyclic skeleton including a sulfur atom as a hetero atom.

Each of the above substances may contain a thioether bond, an ether bond, a sulfone bond, a ketone bond, and/or an ester bond.

Non-limiting examples of suitable episulfide-containing substances having an alicyclic skeleton may include 1, 3-and 1, 4-bis (. beta. -episulfide propylthio) cyclohexane, 1, 3-and 1, 4-bis (. beta. -episulfide propylthiomethyl) cyclohexane, bis [4- (. beta. -episulfide propylthio) cyclohexyl ] methane, 2-bis [4- (. beta. -episulfide) cyclohexyl ] propane, bis [4- (. beta. -episulfide propylthio) cyclohexyl ] sulfide, 4-vinyl-1-cyclohexene bicyclic sulfide, 4-episulfide ethyl-1-cyclohexene sulfide, 4-epoxy-1, 2-cyclohexene sulfide, 2, 5-bis (. beta. -episulfide propylthio) -1, 4-dithiane, and 2, 5-bis (. beta. -epithiopropylthioethylthiomethyl) -1, 4-dithiane.

Non-limiting examples of suitable episulfide-containing materials having an aromatic skeleton may include 1, 3-and 1, 4-bis (. beta. -episulfide propylthio) benzene, 1, 3-and 1, 4-bis (. beta. -episulfide propylthiomethyl) benzene, bis [4- (. beta. -episulfide propylthio) phenyl ] methane, 2-bis [4- (. beta. -episulfide propylthio) phenyl ] propane, bis [4- (. beta. -episulfide propylthio) phenyl ] sulfide, bis [4- (. beta. -episulfide propylthio) phenyl ] sulfone, and 4, 4-bis (. beta. -episulfide propylthio) biphenyl.

Non-limiting examples of suitable episulfide-containing materials having a heterocyclic skeleton including a sulfur atom as a hetero atom may include materials represented by the following general formula:

wherein r can be an integer from 1 to 5; s can be an integer from 0 to 4; a may be an integer of 0 to 5; u may be a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; y "" may be- (CH)₂CH₂S) -; z may be selected from a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or- (CH)₂)_rSY″″_sW; w may be an epithiopropyl group represented by the following formula XIX:

wherein X' may be O or S.

Other non-limiting examples of suitable episulfide-containing materials can include 2, 5-bis (. beta. -epithiopropylthiomethyl) -1, 4-dithiane; 2, 5-bis (β -epithiopropylthioethylthiomethyl) -1, 4-dithiane; 2, 5-bis (β -epithiopropylthioethyl) -1, 4-dithiane; 2,3, 5-tris (. beta. -epithiopropylthioethyl) -1, 4-dithiane; 2,4, 6-tris (. beta. -epithiopropylthiomethyl) -1, 3, 5-trithiane; 2,4, 6-tris (. beta. -epithiopropylthioethyl) -1, 3, 5-trithiane; 2,4, 6-tris (. beta. -epithiopropylthiomethyl) -1, 3, 5-trithiane; 2,4, 6-tris (. beta. -epithiopropylthioethylthioethyl) -1, 3, 5-trithiane; for example, those represented by formulas XX, XXI, XXII and XXIII:

wherein X "may be as defined above.

Polyacids, in particular polycarboxylic acids, are also suitable for use in the reactive compounds (A). Non-limiting examples of unsaturated polycarboxylic acids, such as dicarboxylic acids, include maleic acid, fumaric acid, citraconic acid, itaconic acid, and mecconic acid, anhydrides thereof, and lower alkyl esters or acid halides thereof. Non-limiting examples of saturated polycarboxylic acids include aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, pimelic acid, and sebacic acid; aromatic acids such as phthalic acid, terephthalic acid, isophthalic acid and anhydrides of said aromatic acids such as phthalic anhydride and maleic anhydride, as well as lower alkyl esters or acid halides of these acids or mixtures thereof. Non-limiting examples of suitable cyclic anhydrides include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, maleic anhydride adduct of cyclopentadiene, maleic anhydride adduct of methylcyclopentadiene, chlorendic anhydride, pyromellitic dianhydride, and others disclosed in US5,369,141.

Mixtures of acids and/or anhydrides may also be used.

Polyethylenically unsaturated reactive compounds, i.e. substances having a plurality of ethylenically unsaturated groups (double bonds), are particularly useful in compositions which are cured with actinic radiation, for example UV-curable compositions. Any of the above-mentioned substances having at least two double bonds are suitable. Polyvinyl ethers are examples of suitable reactive compounds. The poly (meth) acrylate reactive compounds include ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, 1, 3-propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 1, 4-butylene glycol di (meth) acrylate, 1,2, 4-butanetriol tri (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 4-cyclohexanediol di (meth) acrylate, 1, 4-benzenediol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 5-pentanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylolpropane tri (meth) acrylate.

The active hydrogen-containing compound (C) (other than B) used to prepare any of the compositions and articles of the present invention can be any compound or mixture of compounds that contain active hydrogens (e.g., active hydrogens of hydroxyl, thiol, or amino groups). The compound (C) may include a compound having at least two active hydrogens, the compound containing primary amine groups, secondary amine groups, hydroxyl groups, thiol groups, and/or a combination thereof. A single polyfunctional compound having a single type of functional group may be used; also, a single polyfunctional compound having a mixed functional group (e.g., hydroxyl and amino groups) may be used. Several different compounds may be used in mixtures with the same or different functional groups; for example, two different polyamines can be used, polythiols mixed with polyamines can be used, or polyamines mixed with hydroxyl-functional polythiols, for example, are suitable.

The compound (C) may have at least two primary and/or secondary amine groups (polyamine). Non-limiting examples of suitable polyamines include primary or secondary diamines or polyamines in which the groups attached to the nitrogen atom can be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic-substituted aliphatic, aliphatic-substituted aromatic, and heterocyclic. Non-limiting examples of suitable aliphatic and cycloaliphatic diamines include 1, 2-ethylenediamine, 1, 2-propylenediamine, 1, 8-octanediamine, isophoronediamine, propane-2, 2-cyclohexanediamine, and the like. Non-limiting examples of suitable aromatic diamines include phenylenediamine and toluenediamine, such as o-phenylenediamine and p-toluenediamine. Also suitable are polynuclear aromatic diamines such as 4,4 ' -biphenyldiamine, 4 ' -methylenedianiline and monochloro and dichloro derivatives of 4,4 ' -methylenedianiline.

Polyamines suitable for use in the present invention may include, but are not limited to, those having the following formula XXIV:

wherein R is₈And R₉May each be independently selected from methyl, ethyl, propyl, and isopropyl, and R₁₀May be selected from hydrogen and chlorine. Non-limiting examples of polyamines useful in the present invention include the following compounds manufactured by Lonza Ltd. (basell, switzerland):

LONZACURE.RTM.M-DIPA：R₈＝C₃H₇；R₉＝C₃H₇；R₁₀＝H

LONZACURE.RTM.M-DMA：R₈＝CH₃；R₉＝CH₃；R₁₀＝H

LONZACURE.RTM.M-MEA：R₈＝CH₃；R₉＝C₂H₅；R₁₀＝H

LONZACURE.RTM.M-DEA：R₈＝C₂H₅；R₉＝C₂H₅；R₁₀＝H

LONZACURE.RTM.M-MIPA：R₈＝CH₃；R₉＝C₃H₇；R₁₀＝H

LONZACURE.RTM.M-CDEA：R₈＝C₂H₅；R₉＝C₂H₅；R₁₀＝Cl

wherein R is₈、R₉And R₁₀Corresponding to the above formula.

The polyamine may include diamine reactive compounds such as 4, 4' -methylenebis (3-chloro-2, 6-diethylaniline), (b), (c) and (d)M-CDEA), available from Air Products and Chemical, Inc. (Allentown, Pa.); 2, 4-diamino-3, 5-diethyl-toluene, 2, 6-diamino-3, 5-diethyl-toluene, and mixtures thereof (collectively "diethyl toluene diamine" or "DETDA"), commercially available from Albemarle Corporation under the tradename Ethacure 100; dimethylthiotoluenediamine (DMTDA), which is available from Albemarle Corporation under the trade name Ethacure 300; 4, 4' -methylene-bis- (2-chloroaniline) commercially available as MOCA from Kingyorker Chemicals. DETDA can be a liquid at room temperature with a viscosity of 156cPs at 25 ℃. DETDA can be isomeric in which the 2, 4-isomer range is 75-81% and the 2, 6-isomer range can be 18-24%. The color stabilized form of Ethacure 100 (i.e., the formulation containing the yellow-reducing additive) available under the trade name Ethacure 100S can be used in the present invention.

Other examples of polyamines may include ethylene amines. Suitable ethylene amines may include, but are not limited to, Ethylene Diamine (EDA), diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA), piperazine, morpholine, substituted morpholines, piperidine, substituted piperidine, diethylene diamine (DEDA), and 2-amino-1-ethyl piperazine. In particular embodiments, the polyamine may be selected from C₁-C₃One or more isomers of dialkyltoluenediamines, such as, but not limited to, 3, 5-dimethyl-2, 4-toluenediamine, 3, 5-dimethyl-2, 6-toluenediamine, 3, 5-diethyl-2, 4-toluenediamine, 3, 5-diethyl-2, 6-toluenediamine, 3, 5-diisopropyl-2, 4-toluenediamine, 3, 5-diisopropyl-2, 6-toluenediamine, and mixtures thereof. Methylenedianiline and 1, 3-propanediol di (p-aminobenzoate) are also suitable.

Other examples of suitable polyamines include methylenedianilines, aniline sulfides, and benzidines, any of which may be hetero-substituted, provided that the substituent does not interfere with any reaction occurring among the reactants. Specific examples include 4,4 '-methylene-bis (2, 6-dimethylaniline), 4' -methylene-bis (2, 6-diethylaniline), 4 '-methylene-bis (2-ethyl-6-methylaniline), 4' -methylene-bis (2, 6-diisopropylaniline), 4 '-methylene-bis (2-isopropyl-6-methylaniline) and 4, 4' -methylene-bis (2, 6-diethyl-3-chloroaniline).

Diaminotoluenes such as diethyltoluenediamine (DETDA) are also suitable.

In certain embodiments, when the reactive compound (A) comprises isocyanate functional groups, the amounts of (A), (B) and (C) may be selected such that the equivalent ratio of (NH + SH + OH) to (NCO) may be from 0.80: 1.0 to 1.1: 1.0, alternatively from 0.85: 1.0 to 1.0: 1.0, alternatively from 0.90: 1.0 to 0.95: 1.0, alternatively from 0.95: 1.0 to 1.0: 1.0.

In embodiments where the reactive compound (A) comprises a polyisocyanate and/or a polyisothiocyanate, the amounts of (A), (B) and (C) may be selected such that the equivalent ratio of (NH + SH + OH) to (NCO + NCS) may be from 0.80: 1.0 to 1.1: 1.0, alternatively from 0.85: 1.0 to 1.0: 1.0, alternatively from 0.90: 1.0 to 0.95: 1.0, alternatively from 0.95: 1.0 to 1.0: 1.0.

The active hydrogen-containing compound (C) may have at least two primary hydroxyl groups and/or secondary hydroxyl groups (polyhydric alcohols). Suitable polyols include glycols such as ethylene glycol and higher polyols. Hydroxy-functional polyesters known to the person skilled in the art are also suitable as compounds (C). In alternative non-limiting embodiments, the active hydrogen-containing materials useful in the present invention may be selected from polyether polyols and polyester polyols having a number average molecular weight of at least 200 grams/mole, alternatively at least 300 grams/mole, alternatively at least 750 grams/mole; alternatively no greater than 1,500 g/mole, alternatively no greater than 2,500 g/mole, alternatively no greater than 4,000 g/mole.

Any of the above-mentioned polythiols, including those having hydroxyl functional groups, are suitable for use as compound (C).

With the use of a catalyst, the reaction of the various compounds (A), (B) and (C) can be enhanced, as can be determined by the person skilled in the art. Suitable catalysts may be selected from those known in the art. Non-limiting examples may include tertiary amine catalysts, organophosphorus compounds, tin compounds, or mixtures thereof, depending on the nature of the various reactive components. In alternative embodiments, the catalyst may comprise dimethylcyclohexylamine or dibutyltin dilaurate, or mixtures thereof. Degassing may be carried out before or after the addition of the catalyst.

When the reactive compound (a) comprises a polyisocyanate, a urethanization catalyst may be used in the present invention to enhance the reaction of the polyurethane-forming materials. Suitable urethanization catalysts may vary; for example, suitable urethanization catalysts may include those useful for urethane formation from the reaction of NCO and OH containing species and/or NCO and SH containing species. Non-limiting examples of suitable catalysts may be selected from Lewis bases, Lewis acids and insertion catalysts, as described in Ullmann's encyclopedia of Industrial Chemistry, fifth edition, 1992, volume A21, page 673-. The catalyst may be a stannous salt of an organic acid such as, but not limited to, stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin mercaptide, dibutyltin dimaleate, dimethyltin diacetate, dimethyltin dilaurate, dibutyltin dichloride, 1, 4-diazabicyclo [2.2.2] octane, and mixtures thereof. The catalyst may alternatively be zinc octoate, bismuth, or iron acetylacetonate.

Other non-limiting examples of suitable catalysts may include tin compounds such as dibutyltin dilaurate, phosphines, tertiary ammonium salts, and tertiary amines such as, but not limited to, triethylamine, triisopropylamine, dimethylcyclohexylamine, N-dimethylbenzylamine, and mixtures thereof. Such suitable tertiary amines are disclosed in U.S. Pat. No. 5,693,738 at column 10, lines 6-38, the disclosure of which is incorporated herein by reference.

When used, the catalyst level can vary widely and can depend on a variety of factors such as the type and amount of reactive compounds used to prepare the compositions and articles of the present invention, as well as the reaction conditions, reaction rate, and extent of reaction desired.

In one embodiment of the invention in which the optical article is a lens, the mixture (which may optionally be degassed) may be introduced into a mold and the mold may be heated (i.e., using a thermal curing cycle) using various conventional techniques known in the art. The thermal curing cycle may vary depending on the reactivity and molar ratio of the reactants and the presence of a catalyst. In particular embodiments, the thermal curing cycle can include heating a mixture of the polyurethane prepolymer (the reaction product of (a) and (B)) and the amine-containing curing agent compound (C), wherein the curing agent can include a primary diamine or a mixture of a primary diamine and a trifunctional or higher-functional polyamine and optionally a polyol and/or polythiol oligomer; or heating a mixture of polyisocyanate and/or polyisothiocyanate, polyol and/or polythiol and/or oligomeric polythiol, and amine-containing material; wherein the heating from room temperature to 200 ℃ is carried out for a period of 0.5 to 120 hours; or from 80 to 150c for a period of 5 to 72 hours.

The invention further relates to a hard article, such as an optical article, comprising the reaction product of:

(A) a substance having a functional group reactive with active hydrogen;

(B) a thioether-functional, oligomeric polythiol prepared by reacting together:

(1) a compound having at least two thiol functional groups; and

(2) a compound having triple bond functionality; and optionally

(C) An active hydrogen-containing compound different from (B).

These articles may be prepared as described above so as to have any of the aforementioned physical properties.

In accordance with the present invention, there is also provided an article comprising the reaction product of:

(A) a reactive compound comprising a substance having a functional group reactive with active hydrogen;

(B) a thioether-functional, oligomeric polythiol prepared by reacting together:

(1) a compound having at least two thiol functional groups;

(2) a compound having triple bond functionality; and

optionally, optionally

(3) A compound having at least two double bonds; and, optionally

(C) An active hydrogen-containing compound different from (B).

Any of the above-described materials (A), (B) and (C) may be used to prepare the articles of the present invention. In accordance with the present invention, these articles may include films, coatings, and molded articles such as optical articles.

In a specific non-limiting embodiment of the invention, a reaction product comprising a sulfur-containing polyurethane can be prepared as follows:

1. a sulfur-containing polyurethane prepolymer was prepared by the reaction of:

A) at least one material comprising a polyisocyanate, a polyisothiocyanate, or a mixture thereof;

B) at least one polythiol comprising any oligomeric polythiol of the invention; and

C) optionally, other active hydrogen-containing materials including polyols, polythiols, or mixtures thereof.

2. Mixing the sulfur-containing polyurethane prepolymer with at least one substance containing an episulfide group, an epoxy group, or a mixture of these groups.

3. The sulfur-containing polyurethane is then prepared by the reaction of:

a) the product of the above step 2, and

b) comprising at least one active hydrogen-containing material of a polyol, a polythiol, or a mixture thereof.

In another specific non-limiting embodiment of the invention, a reaction product comprising a sulfur-containing polyurethaneurea can be prepared as follows:

1. a sulfur-containing polyurethane prepolymer was prepared by the reaction of:

A) at least one material comprising a polyisocyanate, a polyisothiocyanate, or a mixture thereof;

B) at least one polythiol comprising any oligomeric polythiol of the invention;

C) optionally, other active hydrogen-containing materials including polyols, polythiols, or mixtures thereof.

2. Mixing the sulfur-containing polyurethane prepolymer with at least one substance containing an episulfide group, an epoxy group, or a mixture of these groups.

3. The sulfur-containing polyurethaneurea is then prepared by the reaction of:

a) the product of step 2 above;

b) a compound having at least two amine groups; and

c) optionally, an active hydrogen-containing material comprising a polyol, a polythiol, or a mixture thereof.

In alternative non-limiting embodiments, various known additives can be incorporated into the articles of the present invention. The additives may include, but are not limited to, light stabilizers, heat stabilizers, antioxidants, ultraviolet light absorbers, mold release agents, static (non-photochromic) dyes, pigments, and toughening additives such as, but not limited to, alkoxylated phenol benzoates and poly (alkylene glycol) dibenzoates. Non-limiting examples of anti-yellowing additives can include 3-methyl-2-butenol, organo pyrocarbonates, and triphenyl phosphite (CAS registry number 101-02-0). The above additives may be present in an amount such that the additives comprise less than 10wt%, or less than 5 wt%, or less than 3 wt%, based on the total weight of the reaction product. The above optional additives may be mixed with the polyisocyanate and/or polyisothiocyanate. Alternatively, optional additives may be mixed with the active hydrogen-containing material.

In certain embodiments, the articles of the present invention may further comprise a material that provides a light influencing property. The material may be inorganic or organic and may be present in the substrate and/or in a superposed coating or film as described below.

Numerous polarizing and/or photochromic materials can be used in the articles of the present invention, such as optical articles, to provide light influencing properties. The photochromic material can be provided in a variety of forms. Examples include: a single photochromic compound; a mixture of photochromic compounds; materials containing photochromic compounds, such as monomeric or polymeric ungelled solutions; a material to which the photochromic compound is chemically bonded such as a monomer or a polymer; a material comprising and/or having a photochromic compound chemically bonded thereto, the outer surface of which is encapsulated (the encapsulate being a form of coating), for example with a polymeric resin or a protective coating such as a metal oxide, which can prevent the photochromic material from contacting external substances such as oxygen, moisture and/or chemicals which have an adverse effect on the photochromic material; the material may be formed into particles prior to application of the protective coating, as described in U.S. Pat. nos. 4,166,043 and 4,367,170; photochromic polymers, such as photochromic polymers comprising photochromic compounds bonded together; or mixtures thereof.

The inorganic photochromic material can comprise crystallites of silver halide, cadmium halide, and/or copper halide. Other inorganic photochromic materials can be made by adding europium (II) and/or cerium (III) to an inorganic glass, such as sodium silicate glass.

The photochromic material can be an organic photochromic material with a maximum activation absorption wavelength of 300-1000 nm. In one embodiment, the organic photochromic material comprises a mixture of (a) and (b): an organic photochromic material having a visible light lambda maximum of from 400 to less than 550nm, and (b) an organic photochromic material having a visible light lambda maximum of from 550 to 700 nm.

The photochromic material may alternatively comprise an organic photochromic material which may be selected from pyrans, oxazines, fulgides, fulgimides, diarylethenes and mixtures thereof.

Non-limiting examples of photochromic pyrans that can be used herein include benzopyrans and naphthopyrans, such as naphtho [1, 2-b ] pyrans, naphtho [2, 1-b ] pyrans, indene-fused naphthopyrans, and heterocycle-fused naphthopyrans, spiro 9-fluoreno [1, 2-b ] pyrans, phenanthropyrans, quinolinopyrans; fluoranthenopyrans and spiropyrans, for example spiro (benzindolino) naphthopyrans, spiro (indoline) benzopyrans, spiro (indoline) naphthopyrans, spiro (indoline) quinopyrans and spiro (indoline) pyrans and mixtures thereof. Non-limiting examples of benzopyrans and naphthopyrans are disclosed below: U.S. Pat. No. 5,645,767, column 2, line 16 to column 12, line 57; U.S. patent 5,723,072, column 2, line 27-column 15, line 55; U.S. patent 5,698,141, column 2, line 11-column 19, line 45; U.S. patent 6,022,497, column 2, line 21-column 11, line 46; U.S. patent 6,080,338, column 2, line 21-column 14, line 43; U.S. patent 6,136,968, column 2, line 43-column 20, line 67; U.S. patent 6,153,126, column 2, line 26-column 8, line 60; column 2, line 47-column 31, line 5 of U.S. patent 6,296,785; U.S. patent 6,348,604, column 3, line 26-column 17, line 15; U.S. patent 6,353,102, column 1, line 62-column 11, line 64; U.S. Pat. No.6,630,597, column 2, line 16-column 16, line 23; and U.S. patent 6,736,998, column 2, line 53-column 19, line 7, the citations of which are incorporated herein by reference. Other non-limiting examples of naphthopyrans and complementary organic photochromic substances are described in U.S. patent 5,658,501, column 1, line 64-column 13, line 17, the disclosure of which is incorporated herein by reference. Spiro (indoline) pyrans are also described in the following text books: techniques in Chemistry, Volume III, "Photochromym", Chapter 3, Glenn H.Brown, Editor, John Wiley and Sons, Inc., New York, 1971.

Examples of photochromic oxazines that may be used include benzoxazines, naphthoxazines, and spirooxazines, such as spiro (indoline) naphthoxazines, spiro (indoline) pyridobenzoxazines, spiro (benzindoline) naphthoxazines, spiro (indoline) benzoxazines, spiro (indoline) fluoranthenooxazines, spiro (indoline) quinoxazines, and mixtures thereof.

Examples of photochromic fulgides or fulgimides that may be used include: fulgides and fulgimides disclosed in U.S. Pat. No. 4,685,783 at column 1, line 57 to column 5, line 27 and in U.S. Pat. No. 4,931,220 at column 1, line 39 to column 22, line 41, the disclosures of which are incorporated herein by reference. Non-limiting examples of diarylethenes are disclosed in U.S. patent application 2003/0174560 paragraphs [0025] - [0086 ].

Polymerizable organic photochromic materials may be used, such as the polymerizable naphthoxazines disclosed in U.S. Pat. No. 5,166,345 at column 3, line 36-column 14, line 3; polymerizable spirobenzopyrans disclosed in U.S. Pat. No. 5,236,958 at column 1, line 45 to column 6, line 65; polymerizable spirobenzopyrans and spirobenzothiopyrans disclosed in U.S. Pat. No. 5,252,742 at column 1, line 45 to column 6, line 65; polymerizable fulgides disclosed in U.S. Pat. No. 5,359,085, column 5, line 25 to column 19, line 55; polymerizable tetracenediones disclosed in U.S. Pat. No. 5,488,119 at column 1, line 29 to column 7, line 65; polymerizable spirooxazines disclosed in U.S. Pat. No. 5,821,287 at column 3, line 5 to column 11, line 39; polymerizable polyalkoxylated naphthopyrans disclosed in U.S. Pat. No.6,113,814 at column 2, line 23 to column 23, line 29; and polymeric matrix-compatibilized naphthopyrans disclosed in U.S. Pat. No.6,555,028, column 2, line 40 to column 24, line 56. The disclosures of the above patents on polymerizable organic photochromic materials are incorporated herein by reference.

Photochromic materials can be incorporated into articles, such as optical articles, by a variety of methods. For example, the photochromic material can be incorporated, e.g., dissolved and/or dispersed, into the composition, or polymerized with other components of the composition. Alternatively, the photochromic material can be incorporated into the composition by imbibition, permeation, or other delivery methods known to those skilled in the art.

Typically the photochromic material is present in the article in a photochromic amount; that is, the amount of color change that is discernible to the naked eye upon exposure to radiation. The amount of photochromic material incorporated into the curable film-forming composition can be from 0.5 to 40 weight percent based on the weight of solids in the curable film-forming composition. The amount of photochromic material can be 1 to 30 weight percent, 3 to 20 weight percent, or 3 to 10 weight percent. The amount of photochromic material in the optical article can range between any combination of these values, inclusive of the ranges set forth.

The article of the present invention may further comprise an at least partial film or coating superimposed thereon. The coating or film may include, inter alia, a photochromic coating, a tinted coating, a polarized coating, and/or an abrasion resistant coating or other protective coating.

The type of material used for the film or coating can vary widely and is a polymeric organic material selected from the group consisting of the substrates and protective films described below. In addition, the film or coating may comprise the aforementioned reaction product comprising thioether-functional, oligomeric polythiols. The film thickness of the polymeric organic material can vary widely. The thickness may be, for example, 0.1 mils to 40 mils and any range of thicknesses between these values, inclusive. However, greater thicknesses may be used if desired.

The polymeric organic material may be selected from thermosetting materials, thermoplastic materials and mixtures thereof. Examples of polymeric organic material films are disclosed in U.S. patent publication 2004/0096666 paragraphs [0082] - [0098], the disclosure of which is incorporated herein by reference.

In certain embodiments, the film or coating comprises a thermoplastic polymeric organic material such as nylon, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyacrylic acid C₁-C₈Alkyl esters, polymethacrylic acid C₁-C₈Alkyl esters, styrene-butadiene copolymer resins, poly (urea-urethanes), polyurethanes, polyparaphenyleneterephthalatesAcid esters, polycarbonates, polycarbonate-siloxane copolymers, and mixtures thereof.

Optionally, compatible (chemically and color) fixed dyes (fixed tint dyes) may be added to or applied to the optical article and/or the superimposed film to achieve a more aesthetic result, for medical reasons, or for fashion reasons. For example, the dye may be selected to complement the color produced by the activated photochromic material, such as to achieve a more neutral color or to absorb a particular wavelength of incident light. In another embodiment, the dye may be selected to provide a desired hue to the host material when the photochromic material is in an unactivated state.

Often a protective film may be applied to the surface of the article, for example to prevent scratches from the effects of friction and abrasion. The protective film in combination with the optical article of the present invention is typically an at least partially abrasion resistant film. The term "at least partially abrasion resistant film" refers to an at least partial film of an at least partially cured coating or sheet of a protective polymeric material that exhibits an abrasion resistance greater than that of a standard reference material, typically CR-39 from PPG Industries, IncPlastics made from monomers as tested in a Method comparable to the ASTM F-735 Standard test Method for Abrasion Resistance of clear Plastics and coatings Using the swing sandbag Method (ASTM F-735 Standard test Method for Abrasion Resistance of Transmission Plastics and coatings Using the Oscillating Sand Method).

The protective film may be selected from the group consisting of protective sheets, protective gradient films (which also provide a hardness gradient to the film between which they are interposed), protective coatings, and combinations thereof. A protective coating, such as a hardcoat, can be applied to the surface of the polymer film, substrate, and/or any applied film, such as over the protective transitional film.

When the protective film is selected from protective sheets, it can be selected, for example, from the protective polymeric sheets disclosed in U.S. patent publication 2004/0096666 paragraphs [0118] - [0126], which is incorporated herein by reference. In addition, the protective film may comprise a film or sheet of: which contains any of the aforementioned reaction products comprising any of the thioether-functional, oligomeric polythiols of the invention.

The protective gradient film provides a film that is at least partially resistant to abrasion and may be subsequently coated with other protective films. The protective gradient film may be used to protect the article during shipping or subsequent handling prior to application of additional protective films. The protective gradient film provides a hardness gradient from one applied film layer to another after the application of additional protective films. The hardness of the film can be determined by methods known to those skilled in the art. The protective film may also overlie the protective gradient film. Non-limiting examples of protective films that provide the above gradient properties include radiation-cured (meth) acrylate-based coatings described in U.S. patent application publication 2003/0165686, paragraphs [0010] - [0023] and [0079] - [0173], which are incorporated herein by reference.

The protective film may also include a protective coating. Examples of protective coatings known in the art to provide abrasion and scratch resistance are selected from multifunctional acrylic hardcoats, melamine based hardcoats, polyurethane based hardcoats, alkyd based coatings, and organosilane based coatings. Non-limiting examples of such abrasion-resistant coatings are disclosed in U.S. patent application 2004/0096666, paragraphs [0128] - [0149] and U.S. patent application 2004/0207809, paragraphs [0205] - [0249], the disclosures of both of which are incorporated herein by reference.

The optical article of the present invention may optionally further comprise an at least partially polarized surface treatment, coating or film. The phrase "at least partially polarize" means that some to all of the vibrations of the electric field vector of a light wave are confined to one direction or plane by surface treatment. The polarizing effect described above can be achieved by applying a film of dichroic material having an orientation to the optical element to at least partially polarize the penetrating radiation. In one non-limiting embodiment, the polymer sheet is stretched to orient the dichroic material applied on the polymer sheet. In another non-limiting embodiment, the coating is cured in an oriented manner, for example using polarized ultraviolet radiation, to orient the dichroic material in the coating.

The optical article may further comprise an at least partially antireflective surface treatment. The expression "at least partially antireflective surface treatment" means that there is at least a partial improvement in the antireflective properties of the optical element to which it is applied. In non-limiting embodiments, the amount of glare reflected by the treated optical element surface can be reduced and/or the percent transmission of the treated optical element can be increased as compared to an untreated optical element.

In other non-limiting embodiments, an at least partially antireflective surface treatment, such as a single layer or multiple layers of metal oxides, metal fluorides, or other such materials, can be attached to a surface of an optical article of the invention, such as a lens, by vacuum evaporation, sputtering, or some other method.

The optical article of the present invention may further comprise a surface treatment that is at least partially hydrophobic. The expression "at least partially hydrophobic surface" is a film as follows: it at least partially increases the water repellency properties of the substrate to which it is applied by reducing the amount of water that can attach to the substrate from the surface as compared to an untreated substrate.

When the optical article is a lens, a mixture of reactants can be introduced into a mold and the mold can be heated using various conventional techniques known in the art. The thermal curing cycle may vary depending on, for example, the reactivity and molar ratio of the reactants and the presence of a catalyst. In one example, the thermal curing cycle can include heating the reactants from room temperature to 200 ℃ over a period of 0.5 hours to 72 hours.

The present invention is more particularly described in the following examples, which are intended as illustrations only, since numerous changes and modifications will be apparent to those skilled in the art without departing from the spirit and scope of the invention.

Examples

In the following examples, unless otherwise specified, the refractive indices are reported as D-line (nD) and/or E-line (nE) and the abbe number is determined on a multiple wavelength abbe refractometer model DR-M2 manufactured by ATAGO co., ltd.; measuring the refractive index and Abbe number of the liquid according to ASTM-D1218; the refractive index and Abbe number of the solid were measured according to ASTM-D-542.

The viscosity was measured with a Brookfield CAP 2000+ viscometer.

According to ISO standard test method BS EN ISO 14577-1: 2002, hardness was measured using a Fischer Scope H-100 instrument supplied by Fischer technology, Inc., and reported as Marangoni hardness (HM 0.3/15/0) in units of bovine (N)/mm². The following test parameters were specified as required in the standard test method: the maximum total load applied to the specimen was 0.3 newtons (N), the time elapsed for the maximum total load to be applied to the specimen was 15 seconds, and the duration of the maximum total load followed by the application to the specimen was 0 seconds. Therefore, to reflect these three test parameters, the test results are designated by the term "HM 0.3/15/0".

The Impact Test was done according to the Impact Energy Test (Impact Energy Test) as described herein, and the results are reported in units of Energy (joules). The impact energy test involves testing flat plate samples of the polymer product, 3mm thick and cut to approximately 4cmx4cm squares. The flat sample of the polymerized product was supported on a flat O-ring attached to the base of a steel bracket as described below. The O-ring is composed of chloroprene rubber having a hardness of 40 + -5 Shore A durometer, a minimum tensile strength of 8.3MPa, and a minimum elongation at break of 400%, and has an inner diameter of 25mm, an outer diameter of 31mm, and a thickness of 2.3 mm. The steel pallet consists of a steel base having a mass of about 12kg and a steel base frame fixed to the steel base. The shape of the steel base frame approximates a three-dimensional shape that would result from: a frustum of a right circular cone with a base diameter of 75mm, a top diameter of 25mm and a height of 8mm is attached to the top of a cylinder with an outer diameter of 75mm and a height of 10mm, wherein the center of the frustum coincides with the center of the cylinder. The bottom of the steel base frame is secured to the steel base and the neoprene O-ring is centered and secured to the top of the steel base frame. A flat sample of the polymerization product was centered on the O-ring. The impact energy test was performed by dropping a steel ball of increasing weight from a distance of 50 inches (1.27 meters) to the center of the flat plate specimen. The panel was determined to pass the test if it did not crack. The panel was determined to fail the test when the panel broke. The term "fracture" as used herein refers to a crack through the entire thickness of the plate into two or more separate pieces, or the detachment of one or more pieces of material from the back side of the plate (i.e., the side of the plate opposite the side of impact). The impact strength of the panel is reported as the impact energy corresponding to the highest level (i.e., the largest ball) that the panel passes the test, which is calculated according to the following formula:

E＝mgd

where E represents impact energy in joules (J), m represents the mass of the ball in kilograms (kg), and g represents acceleration due to gravity (i.e., 9.80665 m/sec)²) And d represents the ball drop distance in meters (i.e., 1.27 m).

The NCO concentration of the prepolymer (component A) was determined by reaction with an excess of n-Dibutylamine (DBA) to form the corresponding urea followed by titration of the unreacted DBA with HCl according to the following procedure.

Reagent

1. Tetrahydrofuran (THF), reagent grade

2.80/20 THF/Propylene Glycol (PG) mixture.

The solution was made up in the laboratory by mixing 800ml of PG with 3.2 l of THF in a 4 l bottle.

And 3, authenticating DBA, dibutylamine and ACS.

DBA/THF solution. Combine 150mL DBA with 750mL THF; it was mixed well and transferred to an amber bottle.

5. Concentrated hydrochloric acid. And (5) ACS authentication.

6. Isopropanol, technical grade.

7. Hydrochloric acid containing alcohol, 0.2N. 75ml of concentrated HCl was added slowly to a 4 liter bottle of technical grade isopropanol while stirring with a magnetic stirrer; it was mixed for a minimum of 30 minutes. This solution was standardized with THAM (trihydroxymethylaminomethane) as follows: to a 100-mL glass beaker, approximately 0.6g (HOCH) was weighed to the nearest 0.1mg₂)₃CNH₂The standard was original and the weight was recorded. 100mL DI water was added and mixed to dissolve and titrate with the prepared alcoholic HCl.

This process is repeated a minimum of times and its values are averaged as follows.

Device

1. Polyethylene beaker, 200-mL, Falcon

Sample beaker, No. 354020.

2. Polyethylene lid for the above beaker, Falcon No.

354017。

3. Magnetic stirrers and stir bars.

4. The dispensation was with a Brinkmann dosimeter or a 10-mL pipette.

5. An automatic titrator equipped with a pH electrode.

6. The solvent is dispensed from a 25-mL, 50-mL dispenser or 25-mL and 50-mL pipette.

Process for producing a metal oxide

1. Blank test: 50mL of THF followed by 10.0mL of DBA/THF solution was added to a 220-mL polyethylene beaker.

The solution was capped and mixed with magnetic stirring for 5 minutes. 50mL of 80/20 THF/PG mixture was added and the volume was titrated with a standardized alcohol-containing HCl solution and recorded. The process was repeated and the values averaged to serve as the blank test value.

2. A1.0 g sample of the prepolymer was weighed into a polyethylene beaker and the weight recorded by taking the nearest 0.1 mg. 50mL of THF was added, the sample capped and dissolved with magnetic stirring.

3. 10.0mL of DBA/THF solution was added, the sample capped and stirred

Then, the reaction was carried out for 15 minutes.

4. 50mL of 80/20 THF/PG solution was added.

5. The beaker was placed on a titrator and titration was started. The process is repeated.

Computing

IEW-isocyanate equivalent weight

The SH groups in the product were determined by the following procedure. An aliquot (0.1mg) of the product was combined with 50mL of Tetrahydrofuran (THF)/propylene glycol (80/20) and stirred at room temperature until the aliquot was substantially dissolved. While stirring, 25.0mL of a 0.1N iodine solution (which is commercially available from Aldrich 31, 8898-1) was added to the mixture and allowed to react for a period of 5-10 minutes. To this mixture was added 2.0mL of concentrated HCl. The mixture was then potentiometrically titrated with 0.1N sodium thiosulfate in millivolt (mV) mode. A blank value was initially obtained by titrating 25.0mL iodine (including 1mL concentrated hydrochloric acid) with sodium thiosulfate in the same manner as performed with the product sample.

EXAMPLE 1 Synthesis of 2/1(mol/mol) adduct of Dimercaptodiethylsulfide (DMDS) and Propynol (PA)

154.0g, 1.0mol of dimercaptodiethylsulfide from Nisso Maruzen, Japan and 28.0g, 0.5mol of Propargyl Alcohol (PA) from Aldrich were mixed at room temperature in a glass jar with a magnetic stirrer. The mixture was then heated with an oil bath until 60 ℃. The mixture was kept at this temperature for 30 minutes with stirring. An exothermic reaction started to occur, causing the temperature of the reaction mixture to rise for a short time up to 80 ℃. After 30 minutes the exothermic reaction was complete and the reaction temperature was reduced to 60 ℃, the temperature of the heating bath. While the mixture was stirred at 60 ℃,50 mg, 275ppm of the radical initiator Vazo64 was added three times at 5 hour intervals. Then, an equivalent weight of 181.5 g/equivalent (theoretical 182 g/equivalent) was measured, based on which Mn 363 (expected in theory 364) was calculated. 50mg, 275ppm of Vazo64 are again added and the mixture is heated at 60 ℃ for a further 5 hours with stirring. Equivalent weight measurements showed no change and the reaction was considered complete. The viscosity of the clear water-white product thus obtained was 258cP (25 ℃), nD ═ 1.627, abbe number 36, nE ═ 1.631, abbe number 36.

EXAMPLE 2 Synthesis of 3/2(mol/mol) adduct of Dimercaptodiethylsulfide (DMDS) and Propynol

346.5g, 2.25mol of DMDS from Nisso Maruzen, Japan and 84.0g, 1.5mol of propargyl alcohol from Aldrich were mixed at room temperature in a glass jar with a magnetic stirrer. The mixture was then heated up to 50 ℃ with an oil bath. The mixture was kept at this temperature for 1.5 hours with stirring. An exothermic reaction started to occur, causing the temperature of the reaction mixture to rise for a short time up to 70 ℃ and then to drop to 50 ℃, the temperature of the heating bath. 120mg, 275ppm of the free radical initiator Vazo52 are added twice at 15-hour intervals and the mixture is stirred at 50 ℃. The SH equivalent weight was then determined to be 214. 120mg, 275ppm of Vazo52 are again added and the mixture is heated at 55 ℃ for a further 15 hours with stirring. An equivalent weight of 283 g/equivalent (theoretical 287 g/equivalent) was measured. The viscosity of the clear fluid white viscous product thus obtained was 115cP (73 ℃), nD ═ 1.631, abbe number 38, nE ═ 1.635, abbe number 38.

EXAMPLE 3 Synthesis of 2/1(mol/mol) adduct of Dimercaptodiethylsulfide (DMDS) and Phenylacetylene (PHA)

77.0g, 0.5mol of DMDS from Nisso Maruzen, Japan and 25.5g, 0.25mol of phenylacetylene from Aldrich were mixed at room temperature in a glass jar with a magnetic stirrer. The mixture was then heated with an oil bath until 70 ℃.20 mg of the free-radical initiator Vazo64 of 200ppm are added four times at 15-hour intervals and the mixture is stirred at 70 ℃. The SH equivalent weight was then determined to be 173 g/equivalent. 20mg, 200ppm of Vazo64 are again added and the mixture is heated at 70 ℃ for a further 15 hours with stirring. An equivalent weight of 173 g/equivalent (theoretical 205 g/equivalent) was measured. The product obtained was a clear yellow viscous liquid with nD ═ 1.635, abbe number 26, nE ═ 1.641, abbe number 26.

EXAMPLE 4 Synthesis of 2/1(mol/mol) adduct of dimercaptodiethylsulfide (DMDS) and 1, 3-Diisopropenylbenzene (DIPEB)

524.6g DMDS (3.4mol) were charged into a glass jar and the contents were heated to 60 ℃. Slowly add to the tank with mixing269.0g of DIPEB (1.7 mol). Once the addition of DIPEB was complete, the cans were placed in an oven heated to 60 ℃ for 2 hours. Then, 0.1g of VAZO52 was dissolved into the contents of the can and the can was placed back in the oven. After 20 hours, the resulting sample was titrated to determine the SH equivalent weight and the equivalent weight was found to be 145 g/mol. 0.1g of VAZO52 was dissolved into the reaction mixture, which was then placed back in the oven. During 8 hours, 0.2g VAZO52 was added twice and the reaction mixture was kept in an oven at 60 ℃ over this time frame. 17 hours after the final addition of VAZO52 was complete, the resulting coupon was titrated to an equivalent weight of 238 g/eq (233 g/eq theoretical). The viscosity of the material at 25 ℃ was measured and found to be 490 cps. The product obtained is a clear liquid, n_D1.611, Abbe number 35, n_E1.615, abbe number 35.

EXAMPLE 5 Synthesis of 2/1(mol/mol) adduct of Dimercaptodiethylsulfide (DMDS) and 5-vinyl-2-norbornene (VNB)

77g DMDS (0.5mol) were charged to a glass jar and the contents were heated to 60 ℃. To the tank was slowly added 30g VNB (0.25mol) with mixing while maintaining the mixture temperature-60 ℃. After the addition was complete the mixture was heated at 60 ℃ for another 30 minutes, then 0.2g VAZO67 was dissolved into the contents of the can and the can was heated at 65 ℃ for 20 hours. The resulting product was analyzed for SH content by titration with iodine as previously described. The SH equivalent weight was found to be 216 g/equivalent (theoretical value 214 g/equivalent). The viscosity of the material at 25 ℃ was measured and found to be 460 cps. The product obtained is a clear, colorless liquid, n_D1.607, Abbe number 39, n_E1.610, abbe number 39. The yield was quantitative.

Example 6 one-pot Synthesis of an adduct of oligomer polythiol, dimercaptodiethylsulfide (DMDS), 1, 3-Diisopropenylbenzene (DIPEB) and Propargyl Alcohol (PA)

127.6g of DMDS (0.828mol), 65.5gDIPEB (0.415mol) and 6.8g PA (0.121mol) were charged into glass jars. The mixture was stirred at room temperature for 30 minutes. After heating the mixture at 60 ℃ for another 30 minutes, 0.1g VAZO67 was dissolved into the contents of the can and the can was heated at 65 ℃ for 15 hours. Two additional portions of 0.100g VAZO67 were added at 6 hour intervals. The resulting product was analyzed for SH content by titration with iodine as previously described. The SH equivalent weight was found to be 335 g/equivalent (theoretical 341 g/equivalent). The viscosity of the material at 73 ℃ was measured and found to be 150 cps. The product obtained is a clear, colorless liquid, n_D1.6152 Abbe number 37, n_E1.620, abbe number 36.

Example 7 Synthesis of 2/1(mol/mol) adducts of the product of example 4 and propargyl alcohol 5)

200.0g, 0.42mol of the product from example 4 and 11.6g, 0.21mol of propargyl alcohol are mixed at room temperature. The mixture was then heated until 65 ℃. While the mixture was stirred at 65 ℃ 42mg of the free-radical initiator Vazo52 was added three times at 5-hour intervals. The SH equivalent weight was then determined to be 499 g/equivalent. The mixture was heated at 65 ℃ for a further 5 hours and the SH equivalent weight was again determined to be 499 g/equivalent, based on which Mn was calculated to be 998 (theoretically expected to be 1008). The viscosity of the clear water-white oligomer mixture thus obtained was 463cP (73 ℃), nD ═ 1.620, abbe number 36, nE ═ 1.624, abbe number 35.

Example 8 Synthesis of the product of example 4, a 2/0.32/0.68(mol/mol/mol) adduct of propargyl alcohol and 5-vinyl-2-norbornene (VNB)

238.0g, 0.5mol of the product of example 4, 4.48g, 0.08mol of propargyl alcohol and 20.4g, 0.17mol of 5-vinyl-2-norbornene are mixed at room temperature. The mixture was then heated to 60 ℃ until it became homogeneous. While the mixture was stirred at 60 ℃, 20mg, 76ppm of the radical initiator Vazo52 was added three times at 5-hour intervals. The SH equivalent weight was then determined to be 511 g/equivalent, based on which Mn — 1022 (theoretically expected to be 1051) was calculated. The equivalent weight did not change after heating and stirring at 60 ℃ for another 5 hours. The viscosity of the clear fluid white oligomer mixture thus obtained was 468cP (73 ℃), nD ═ 1.615, abbe number 37, nE ═ 1.619, abbe number 36.

Example 9 Synthesis of the product of example 4, a 2/0.5/0.5(mol/mol/mol) adduct of propargyl alcohol and 1, 3-Diisopropenylbenzene (DIPEB)

238.0g, 0.5mol of the product of example 4, 7.0g, 0.125mol of propargyl alcohol and 19.75g, 0.125 g of 1, 3-diisopropenylbenzene were mixed at room temperature. The mixture was then heated to 65 ℃ until it became homogeneous. While the mixture was stirred at 65 ℃, 20mg, 76ppm of the radical initiator Vazo52 was added three times at 5-hour intervals. The SH equivalent weight was then determined to be 510 g/equivalent, based on which Mn was calculated to be 1020 (theoretically expected to be 1059). The equivalent weight did not change after heating and stirring at 60 ℃ for another 5 hours. The viscosity of the clear water-white oligomer mixture thus obtained was 452cP (73 ℃), nD ═ 1.617, abbe number 36, nE ═ 1.621, abbe number 35.

EXAMPLE 10 Synthesis of polythiourethane prepolymer Using the product of example 7

4, 4-dicyclohexylmethane diisocyanate (Desmodur W) (135.0g, 1.03mol equivalent), from Bayer Corp. the product of example 7 (70.0g, 0.2102mol equivalent) was mixed and degassed in vacuo at room temperature for 2.5 h. The mixture was flushed with nitrogen and heated at 120 ℃ for 18 hours. Analysis of the SH groups showed complete exhaustion of the SH groups. The heating was terminated. The viscosity (73 ℃) of the clear mixture was 928cP, nE was 1.551(20 ℃), Abbe number was 45; and 16.73% NCO groups.

EXAMPLE 11 Synthesis of polythiourethane prepolymer Using the product of example 8

4, 4-dicyclohexylmethane diisocyanate (Desmodur W) (115.4g, 0.881mol equivalents) from Bayer Corp, isophorone diisocyanate (IPDI) (12.8g, 0.115mol equivalents) from Bayer Corp, and the product of example 8 (100.0g, 0.226mol equivalents) were mixed and degassed in vacuo at room temperature for 2.5 hours. N, N-dimethylcyclohexylamine (0.06g, 263ppm) was added to the mixture. The mixture was flushed with nitrogen and heated at 65 ℃ for 5 hours. Analysis of the SH groups thereafter showed complete exhaustion of the SH groups. The heating was terminated. The viscosity (73 ℃) of the clear mixture was 1403cP, nE was 1.561(20 ℃), Abbe number was 43; and NCO groups 13.36%.

EXAMPLE 12 Synthesis of polythiourethane prepolymer Using the product of example 9

4, 4-dicyclohexylmethane diisocyanate (Desmodur W) (126.5g, 0.965mol equivalent) from Bayer Corp, isophorone diisocyanate (IPDI) (14.1g, 0.127mol equivalent) from Bayer Corp and the product of example 9 (100.0g, 0.245mol equivalent) were mixed and degassed in vacuo at room temperature for 2.5 hours. To the mixture was added N, N-dimethylcyclohexylamine (0.075g, 312 ppm). The mixture was flushed with nitrogen and heated at 65 ℃ for 5 hours. Analysis of the SH groups thereafter showed complete exhaustion of the SH groups. The heating was terminated. The viscosity (73 ℃) of the clear mixture was 1320cP, nE was 1.558(20 ℃), and Abbe number was 44; and 14.99% of NCO groups.

Example 13 example 10 chain extension of polythiourethane prepolymer

The product of example 10 (50g) was degassed in vacuo at 60 ℃ for 4 h. Diethyltoluenediamine (trade name Ethacure 100, from Albemarle Corporation) (DETDA) (9.76g), the product of example 4 (19.28g), and N, N-dimethylcyclohexylamine (0.030g) were mixed and degassed in vacuo at 60 ℃ for 2 hours. The two mixtures were then mixed together at the same temperature and fed between preheated glass plate molds. The material was cured in a preheated oven at 110 ℃ for 72 hours. The cured material was clear and had an nE of 1.595(20 ℃), an Abbe number of 38 and a Mohs hardness of 110.

Example 14 chain extension of the prepolymer of example 11

The product of example 11 (40g) was degassed in vacuo at 60 ℃ for 4 h. Diethyltoluenediamine (trade name Ethacure 100, from Albemarle Corporation) (DETDA) (6.79g) and the product of example 4 (10.77g) were mixed and degassed in vacuo at 60 ℃ for 2 hours. The two mixtures were then mixed together at the same temperature and fed between preheated glass plate molds. The material was cured in a preheated oven at 110 ℃ for 72 hours. The cured material was clear and had an nE of 1.596(20 ℃), an Abbe number of 38 and a Martin hardness of 84.

EXAMPLE 15 chain extension of the prepolymer of example 12

The product of example 12 (40g) was degassed in vacuo at 60 ℃ for 4 h. Diethyltoluenediamine (trade name Ethacure 100, from Albemarle Corporation) (DETDA) (7.63g) and the product of example 4 (12.04g) were mixed and degassed in vacuo at 60 ℃ for 2 hours. The two mixtures were then mixed together at the same temperature and fed between preheated glass plate molds. The material was cured in a preheated oven at 120 ℃ for 24 hours. The cured material was clear and had an nE of 1.596(20 ℃), an Abbe number of 38 and a Martin hardness of 97.

Example 16 one-pot Synthesis of a polyurethane Polymer Using the product of example 1

The product of example 1 (27.8g) was degassed in vacuo at 60 ℃ for 4 h. 4, 4-dicyclohexylmethane diisocyanate (Desmodur W) (30.0g) from Bayer was mixed thoroughly with N, N-dimethylcyclohexylamine (0.020g) and the mixture was degassed in vacuo at 60 ℃ for 2 h. The two mixtures are then mixed together at the same temperature and fed between preheated glass plate molds. The material was cured in a preheated oven at 125 ℃ for 24 hours. The cured material was clear and had a refractive index (e-line) of 1.595(20 ℃), an Abbe number of 41 and a Mohs hardness of 109.

EXAMPLE 17 one-pot Synthesis of polyurethane/urea Polymer Using the product of example 2

Diethyltoluene diamine (DETDA) (1.7g) from Albemarle Corporation was mixed with the product of example 2 (24.6g) and degassed in vacuo at 75 deg.C for 4 hours. 4, 4-dicyclohexylmethane diisocyanate (Desmodur W) (25.0g) from Bayer was mixed thoroughly with N, N-dimethylcyclohexylamine (0.020g) and the mixture was degassed in vacuo at 60 ℃ for 2 h. The two mixtures are then mixed together and fed between preheated glass plate molds. The material was cured in a preheated oven at 120 ℃ for 48 hours. The cured material was clear and had an nE of 1.593(20 ℃), an Abbe number of 40 and a Martin hardness of 112.

Example 18 one-pot Synthesis of polyurethane Polymer Using the product of example 1

The product of example 1 (29.7g) was degassed in vacuo at 75 ℃ for 4 h. 4, 4-dicyclohexylmethane diisocyanate (Desmodur W) (30.0g) from Bayer, 1, 3-bis (1-isocyanato-1-methylethyl) -benzene) (TMXDI) (3.02g) from Cytec Industries Inc were thoroughly mixed with N, N-dimethylcyclohexylamine (0.020g), and the mixture was degassed in vacuo at 60 ℃ for 2 hours. The two mixtures are then mixed together and fed between preheated glass plate molds. The material was cured in a preheated oven at 125 ℃ for 48 hours. The cured material was clear, yellowish and nE was 1.596(20 ℃ C.), Abbe number 41, and Mohs hardness 123.

Example 19 one-pot Synthesis of polyurethane Polymer Using the product of example 1

The product of example 1 (22.90g) was degassed in vacuo at 75 ℃ for 4 h. Isophorone diisocyanate (IPDI) (21.18g) from Bayer was mixed thoroughly with N, N-dimethylcyclohexylamine (0.020g), and the mixture was degassed in vacuo at 60 ℃ for 2 hours. The two mixtures are then mixed together and fed between preheated glass plate molds. The material was cured in a preheated oven at 125 ℃ for 24 hours. The cured material was clear and had an nE of 1.595(20 ℃), an Abbe number of 40 and a Mohs hardness of 141.

Example 20 one-pot Synthesis of a polyurethane Polymer Using the product of example 1

The product of example 1 (30.95g) was degassed in vacuo at 75 ℃ for 4 h. Isophorone diisocyanate (IPDI) from Bayer (15.00g), 4-dicyclohexylmethane diisocyanate (Desmodur W) from Bayer (15.0g) and N, N-dimethylcyclohexylamine (0.020g) were mixed thoroughly and the mixture was degassed in vacuo at 60 ℃ for 2 hours. The two mixtures are then mixed together and fed between preheated glass plate molds. The material was cured in a preheated oven at 125 ℃ for 24 hours. The cured material was clear and had an nE of 1.595(20 ℃), an Abbe number of 40 and a Mohs hardness of 127.

Example 21 one-pot Synthesis of polyurethane/urea Polymer Using the products of examples 2 and 4

The product of example 2 (9.75g) was mixed with the product of example 4 (19.0g) and diethyltoluenediamine (DETDA) from Albemarle Corporation (7.92 g). The mixture was degassed in vacuo at 75 ℃ for 4 hours. 4, 4-dicyclohexylmethane diisocyanate (Desmodur W) (30.0g) from Bayer was mixed thoroughly with N, N-dimethylcyclohexylamine (0.020g) and the mixture was degassed in vacuo at 60 ℃ for 2 h. The two mixtures are then mixed together and fed between preheated glass plate molds. The material was cured in a preheated oven at 125 ℃ for 24 hours. The cured material was clear and had an nE of 1.592(20 ℃), an Abbe number of 39 and a Mohs hardness of 125.

EXAMPLE 22 one-pot Synthesis of polyurethane/urea Polymer Using the product of example 6

The product of example 6 (36.7g) was degassed in vacuo at 60 ℃ for 4 h. 4, 4-dicyclohexylmethane diisocyanate (Desmodur W) (33.3g) from Bayer was mixed thoroughly with N, N-dimethylcyclohexylamine (0.020g) and the mixture was degassed in vacuo at 60 ℃ for 2 h. Diethyltoluenediamine (DETDA) (9.73g) from Albemarle Corporation was degassed in vacuo at room temperature for 2 hours. The three mixtures were then mixed together and fed between preheated glass plate molds. The material was cured in a preheated oven at 110 ℃ for 24 hours. The cured material was clear and had an nE of 1.595(20 ℃), an Abbe number of 38 and a Mohs hardness of 109.

Example 23 one-pot Synthesis of polyurethane/Urea polymers based on the products described in example 4, example 7, DETDA and Desmodur W

The components listed in Table 1 were used in the amounts indicated for the preparation of polymer sheets 3.5mm thick, the test results of which are reported in Table 2. The polymer sheet was prepared from a mixture of 3 components injected into a specially designed molding machine from Max Machinery. The first component is Desmodur W. The second component is a combination of catalyst, N-dimethylcyclohexylamine, and the products of examples 4 and 7. The first component was degassed in vacuo at room temperature for 16 hours. The second component was degassed under vacuum at 44 ℃ for 16 hours prior to use. The third component was DETDA obtained from Albemarle Corporation, which was degassed in vacuo at room temperature for 16 hours prior to use. The molding machine was a Urethane Processor Model No. 601-. The blended mixture is then injected into a preheated glass plate mold treated with an external mold release agent. The mold was placed in a conventional oven at 110 ℃ for 24 hours. The temperature was then reduced to 85 ℃ before demoulding. The resulting sheet was cut to a size suitable for the test described above and reported in table 2.

TABLE 1

TABLE 2

Polyurethane and polyureaurethane formulations based on the products described in examples 1 and 5, DMDS, DETDA, and Desmodur W, examples 24A-O

The components listed in table 3 were used in the amounts indicated for the preparation of polymer sheets 3.5mm thick, the test results of which are reported in table 4. The polymer sheet was prepared from a mixture of 3 components injected into a specially designed molding machine from Maxmachinery as described in example 23. The first component was Desmodur W. The second component is a combination of the catalyst, N-dimethylcyclohexylamine, and the dithiols and/or DMDS of examples 1, 5. Each of these components was degassed under vacuum at 50 ℃ for 16 hours prior to use. The third component was DETDA obtained from Albemarle Corporation, which was degassed in vacuo at room temperature for 16 hours prior to use. The blended mixture is then injected into a preheated glass plate mold treated with an external mold release agent. The mold was placed in a convection oven at 110 ℃ for 24 hours. Then, the temperature was ramped down (ramp down) to 85 ℃ prior to demolding. The resulting sheet was cut to a size suitable for the test described above and reported in table 4.

TABLE 3

TABLE 4

Although specific embodiments of the invention have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present invention may be made without departing from the invention as defined in the appended claims.

Claims (13)

1. A thioether-functional, oligomeric polythiol having pendant hydroxyl functional groups, prepared by reacting together:

(a) a compound having at least two thiol functional groups;

(b) a hydroxy-functional compound having triple bond functionality; and optionally

(c) A compound having at least two double bonds;

wherein the term "oligomeric" is intended to mean compounds prepared by addition polymerization to produce a material having repeating units and a number average molecular weight of up to 5000, and the number average molecular weight is determined by gel permeation chromatography using polystyrene standards,

wherein the compound (a) having at least two thiol functional groups comprises a dithiol, a compound having more than two thiol functional groups, or a mixture of a dithiol and a compound having more than two thiol functional groups,

wherein the thiol functional group in the compound (a) is a terminal group.

2. The oligomeric polythiol of claim 1 wherein the compound (a) comprises a mixture of a dithiol and a compound having more than two thiol functional groups, wherein the compound having more than two thiol functional groups is present in an amount up to 10 weight percent of the mixture.

3. The oligomeric polythiol of claim 1 wherein the compound (a) having at least two thiol functional groups further contains hydroxyl functional groups.

4. The oligomeric polythiol of claim 1 wherein the ratio of thiol functional groups to triple bonds is from 1.01:1 to 5: 1.

5. The oligomeric polythiol of claim 1 wherein the hydroxyl functional compound (b) having triple bond functionality comprises propargyl alcohol, but-2-yne-1, 4-diol, but-3-yne-2-ol, hex-3-yne-2, 5-diol, and/or mixtures thereof.

6. The oligomeric polythiol of claim 1 wherein at least a portion of the hydroxyl functional groups on the compound (b) are esterified.

7. The oligomeric polythiol of claim 1 wherein the compound (c) having at least two double bonds comprises an acyclic nonconjugated diene, an acyclic polyvinyl ether, an allyl (meth) acrylate, a vinyl (meth) acrylate, a di (meth) acrylate ester of a diol, a di (meth) acrylate ester of a dithiol, a di (meth) acrylate ester of a poly (alkylene glycol) diol, a monocyclic non-aromatic diene, a polycyclic non-aromatic diene, an aromatic ring-containing diene.

8. The oligomeric polythiol of claim 1 wherein the compound (c) having at least two double bonds is a diallyl ester of an aromatic cyclic dicarboxylic acid, and/or a divinyl ester of an aromatic cyclic dicarboxylic acid.

9. The oligomeric polythiol of claim 7 wherein the compound (c) having at least two double bonds comprises 5-vinyl-2-norbornene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, butanediol divinyl ether, vinylcyclohexene, dipentene, terpinene, dicyclopentadiene, cyclododecadiene, cyclooctadiene, 2-cyclopenten-1-yl-ether, 2, 5-norbornadiene, divinylbenzene, diisopropenylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1, 3-propanediol di (meth) acrylate, 1, 2-propanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, butadiene rubber, rubber, 1, 2-butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 2' -thioethanedithiol di (meth) acrylate, and/or 1, 2-ethanedithiol di (meth) acrylate.

10. The oligomeric polythiol of claim 9 wherein the vinylcyclohexene is 4-vinyl-1-cyclohexene.

11. Use of the thioether-functional, oligomeric polythiol having pendant hydroxyl functional groups according to any one of claims 1 to 10 in a composition for the preparation of an optical article.

12. The use of claim 11, wherein the optical article has at least one light influencing property.

13. The use of claim 11, wherein the optical article is photochromic.