HK1077312B

HK1077312B - Impact resistant polyureaurethane and method of preparation

Info

Publication number: HK1077312B
Application number: HK05109357.3A
Authority: HK
Inventors: V．J．纳格帕尔; W．H．麦克唐纳; R.A.史密斯
Original assignee: Ppg工业俄亥俄公司
Priority date: 2001-11-16
Filing date: 2002-11-14
Publication date: 2010-04-16

Description

Impact-resistant polyureaurethane and method of making

This application is a converted version of US provisional patent application serial No. 60/332,827 (the 2001.11.16 application).

The present invention relates to a polyether-containing polyureaurethane.

In general, optically clear plastic materials are characterized by impact resistance and the temperature and pressure at which the material undergoes deformation.

It is necessary for the polyureaurethane to have a high degree of impact resistance.

It should be 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.

In this specification, unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth 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 sought 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.

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 standard deviation found in their respective testing measurements.

The present invention includes a polyether-containing polyureaurethane that when at least partially cured and when tested in The form of a lens has an impact resistance of at least 148 feet per second, wherein both surfaces of said lens have a hard coating in a planar configuration having a maximum central thickness of 2.2mm, said impact resistance being determined by The high speed impact Test (The HighImpact Test).

In addition, the present invention includes a polyether-containing polyureaurethane comprising the reaction product of:

a. a polyureaurethane prepolymer comprising a polyisocyanate and at least one polyether-containing polyol material; and

b. an amine-containing curing agent is included in the curing agent,

wherein said prepolymer has an NCO/OH equivalent ratio of from 2.0 to less than 4.5.

In addition, the present invention includes a method of preparing a polyether-containing polyureaurethane comprising the steps of:

a. reacting a polyisocyanate with at least one polyether-containing polyol to form a polyether-containing polyureaurethane prepolymer; and is

b. Reacting said prepolymer with an amine-containing curing agent,

In non-limiting embodiments, the polyether-containing polyureaurethane of the present invention can be used in transparency applications such as architectural glazings, automotive glazings, storm protection screens, aircraft awnings, face masks, visors, opthalmic and sunglasses, protective eyewear and transparent armor. It has been found that the polyether-containing polyureaurethane of the present invention can exhibit at least one of the following characteristics: optical clarity, good impact, good chemical resistance and acceptable heat distortion temperature.

The polyisocyanates that can be used in the preparation of the polyureaurethane of the present invention are numerous and varied. Non-limiting examples may include, but are not limited to, aliphatic polyisocyanates; a cycloaliphatic polyisocyanate in which one or more isocyanate groups are attached directly to the cycloaliphatic ring; a cycloaliphatic polyisocyanate in which one or more isocyanate groups are not directly attached to the cycloaliphatic ring; an aromatic polyisocyanate in which one or more isocyanate groups are attached directly to the aromatic ring; and an aromatic polyisocyanate in which one or more of the isocyanate groups are not directly attached to an aromatic ring; and mixtures thereof. In a non-limiting embodiment, when an aromatic polyisocyanate is used, materials that do not cause the polyureaurethane to discolor (e.g., yellow) should generally be carefully selected.

In alternative non-limiting embodiments of the present invention, the polyisocyanate can include, but is not limited to, aliphatic or cycloaliphatic diisocyanates, aromatic diisocyanates, cyclic dimers and cyclic trimers thereof, and mixtures thereof. Non-limiting examples of suitable polyisocyanates can include, but are not limited to, Desmodur N3300 (hexamethylene diisocyanate trimer), which is commercially available from Bayer; desmodur N3400 (60% hexamethylene diisocyanate dimer and 40% hexamethylene diisocyanate trimer). In a non-limiting embodiment, the polyisocyanate can include dicyclohexylmethyl diisocyanate and isomeric mixtures thereof. The term "isomeric mixture" as used herein and in the claims refers to a mixture of cis-cis, trans-trans and/or cis-trans isomers of polyisocyanates. Non-limiting examples of isomeric mixtures for use in the present invention may include the trans-trans isomer of 4, 4 '-methylenebis (cyclohexyl isocyanate), wherein 4, 4' -methylenebis (cyclohexyl isocyanate) is hereinafter referred to as "PICM" (p-isocyanatocyclohexylmethane), the cis-trans isomer of PICM, the cis-cis isomer of PICM, and mixtures thereof.

Suitable isomers for use in the present invention include, but are not limited to, the following three isomers of 4, 4' -methylenebis (cyclohexyl isocyanate).

In a non-limiting embodiment, the PICM used in the present invention can be prepared by phosgenating 4, 4' -methylenebis (cyclohexylamine) (PACM) according to various processes known in the art, such as those described in US patent 2,644,007; 2,680,127 and 2,908,703; which is incorporated herein by reference. The PACM isomer mixture, when phosgenated, can produce PICM in liquid, partially liquid, or solid phase form at room temperature. In alternative non-limiting embodiments, the PACM isomer mixture may be obtained by hydrogenation of methylenedianiline and/or by fractional crystallization of the PACM isomer mixture in the presence of water and alcohols such as methanol and ethanol.

In another alternative non-limiting embodiment of the invention, other aliphatic and cycloaliphatic diisocyanates that may be used include 3-isocyanato-methyl-3, 5, 5-trimethylcyclohexyl-isocyanate ("IPDI"), which is commercially available from Arco Chemical, and m-tetramethylxylene diisocyanate (1, 3-bis (1-isocyanato-1-methylethyl) -benzene), which is commercially available from Cytec Industries Inc., under the trade name TMXD I.RTM. (Meta) aliphatic isocyanate.

The term "aliphatic and cycloaliphatic diisocyanates" as used herein and in the claims means having from 6 to 100 carbon atoms attached in a linear or cyclic chain having two terminal diisocyanate reactive groups. In one non-limiting embodiment of the invention, the aliphatic and cycloaliphatic diisocyanates for use in the present invention may comprise TMXDI and the formula R- (NCO)₂Wherein R represents an aliphatic group or a cycloaliphatic group.

Polyether-containing polyols and processes for their preparation are well known to those skilled in the art. Many polyether-containing polyols of various types and molecular weights are commercially available from various manufacturers. Non-limiting examples of polyether-containing polyols may include, but are not limited to, polyoxyalkylene polyols and polyalkoxylated polyols. The polyoxyalkylene polyol can be prepared according to known methods. In a non-limiting embodiment, the polyoxyalkylene polyol can be prepared by condensing an alkylene oxide or mixture of alkylene oxides, using acid-or base-catalyzed addition, with a polyhydroxy initiator or mixture of polyhydroxy initiators, such as, but not limited to, ethylene glycol, propylene glycol, glycerol, and sorbitol. Non-limiting examples of alkylene oxides may include ethylene oxide, propylene oxide, butylene oxide, pentene oxide, aralkylene oxides such as, but not limited to, styrene oxide, mixtures of ethylene oxide and propylene oxide. In another non-limiting embodiment, the polyoxyalkylene polyol can be prepared using random or step-wise alkoxylation with a mixture of alkylene oxides. Non-limiting examples of such polyoxyalkylene polyols include polyoxyethylene, such as but not limited to polyethylene glycol, polyoxypropylene, such as but not limited to polypropylene glycol.

In one non-limiting embodiment, the polyalkoxylated polyol can be represented by the following general formula I:

wherein m and n may each be a positive integer, and the sum of m and n is 5 to 70; r₁And R₂May each be hydrogen, methyl or ethyl; and A may be a divalent linking group, such as a linear or branched alkylene group, which may contain from 1 to 8 carbon atoms; a phenylene group; and C₁-C₉Alkyl-substituted phenylene radicals. The choice of the values of m and n, combined with the choice of divalent linking groups, can determine the molecular weight of the polyol.

Polyalkoxylated polyols can be prepared by methods known in the art. In a non-limiting embodiment, a polyol such as 4, 4' -isopropylidenediphenol may be reacted with an ethylene oxide containing material such as, but not limited to, ethylene oxide, propylene oxide, and butylene oxide to form what is commonly referred to as an ethoxylated, propoxylated or butoxylated polyol having hydroxyl functionality. Non-limiting examples of polyols suitable for use in preparing polyalkoxylated polyols can include the polyols described in U.S. Pat. No. 6,187,444B1 at column 10, lines 1-20, which is incorporated herein by reference.

The term "polyether-containing polyol" as used herein and in the claims may include the commonly known poly (oxytetramethylene) glycols prepared by polymerizing tetrahydrofuran in the presence of lewis acid catalysts such as, but not limited to, boron trifluoride, tin (IV) chloride, and sulfonyl chloride. Also included are polyethers prepared by copolymerizing cyclic ethers such as, but not limited to, ethylene oxide, propylene oxide, trimethylene oxide and tetrahydrofuran with aliphatic diols such as, but not limited to, ethylene glycol, 1, 3-butanediol, 1, 4-butanediol, diethylene glycol, dipropylene glycol, 1, 2-propanediol and 1, 3-propanediol. Compatible mixtures of polyether-containing polyols may also be used. The term "compatible" as used herein means that the polyols are mutually soluble in each other to form a single phase.

In a non-limiting embodiment, the polyether-containing polyols useful in the present invention can include polyester polyols, polycaprolactone polyols, polycarbonate polyols, and mixtures thereof.

Polyester polyols such as, but not limited to, polyester diols may include the esterification products of one or more dicarboxylic acids having 4 to 10 carbon atoms, such as adipic acid, succinic acid, or sebacic acid, with one or more low molecular weight diols having 2 to 10 carbon atoms, such as ethylene glycol, propylene glycol, diethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, and 1, 10-decanediol. Known esterification processes for producing polyester polyols are described, for example, in the article "Polyesters from cellulose" Union Carbide F-40, p.147 by D.M. Young, F.Hostettler et al.

Polycarbonate polyols are known in the art and are commercially available, e.g.107(Enichem s.p.a.). In a non-limiting embodiment, the polycarbonate polyols can be produced by reacting an organic diol, such as a diol, such as those described below and in connection with the diol component of the polyureaurethane, and a dialkyl carbonate, such as those described in U.S. Pat. No. 4,160,853. In a non-limiting embodiment, the polyol can include polyhexamethylene carbonate, such as H- (O-C (O) -O- (CH)₂)₆)_n-OH, wherein n is an integer from 4 to 24, or an integer from 4 to 10 or from 5 to 7.

In a non-limiting embodiment, the glycol material can include low molecular weight polyols, such as polyols having a molecular weight of less than 500, and compatible mixtures thereof. The term "compatible" as used herein means that the glycols are mutually soluble in each other, thereby forming a single phase. Non-limiting examples of such polyols can include, but are not limited to, low molecular weight diols and triols. In another non-limiting embodiment, the amount of triol selected is such that a high degree of crosslinking of the polyurethane is avoided. A high degree of crosslinking may result in a thermoset polyurethane that cannot be formed by moderate heat and pressure. The organic diol typically has from 2 to 16 or from 2 to 6 or from 2 to 10 carbon atoms. Non-limiting examples of such diols may include, but are not limited to, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1, 2-, 1, 3-and 1, 4-butanediol, 2, 2, 4-trimethyl-1, 3-pentanediol, 2-methyl-1, 3-pentanediol, 1, 3-, 2, 4-and 1, 5-pentanediol, 2, 5-and 1, 6-hexanediol, 2, 4-heptanediol, 2-ethyl-1, 3-hexanediol, 2, 2-dimethyl-1, 3-propanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, 1, 2-bis (hydroxyethyl) -cyclohexane, glycerol, tetramethylolmethane such as but not limited to pentaerythritol, trimethylolethane and trimethylolpropane; and isomers thereof.

In alternative non-limiting embodiments, the polyether-containing polyol material has a weight average molecular weight of at least 200 or at least 1000 or at least 2000. In alternative non-limiting embodiments, the polyether-containing polyol material has a weight average molecular weight of less than 10000 or less than 15000 or less than 20000 or less than 32000.

In a non-limiting embodiment, the polyether-containing polyol materials useful in the present invention may include triesters (ters) derived from at least one low molecular weight dicarboxylic acid, such as adipic acid.

Polyether glycols that may be used in the present invention may include, but are not limited to, polytetramethylene ether glycol.

In a non-limiting embodiment, the polyether-containing polyol can include block polymers including blocks of ethylene oxide-propylene oxide and/or ethylene oxide-butylene oxide. In one non-limiting embodiment, the polyether-containing polyol can comprise a block polymer of the formula:

HO-(CRRCRR-Y_n-O)_a-(CRRCRR-Y_n-O)_b-(CRRCRR-Y_n-O)_c-H

wherein R may represent hydrogen or C₁-C₆An alkyl group; y may represent CH₂(ii) a n may be an integer from 0 to 6; a. b and c can each be an integer from 0 to 300, where a, b, and c can be selected such that the weight average molecular weight of the polyol does not exceed 32,000.

In another non-limiting embodiment, Pluronic R, Pluronic L62D, Tetronic R and Tetronic, commercially available from BASF, can be used as the polyether-containing polyol material in the present invention.

In the present invention, the equivalent ratio of NCO (i.e., isocyanate) to OH present in the polyether-containing polyureaurethane prepolymer can be in an amount of from 2.0 to less than 4.5NCO/1.0 OH.

Suitable amine-containing curing agents useful in the present invention are numerous and varied. Non-limiting examples include, but are not limited to, polyamines having more than one amino group per molecule, each amino group being independently selected from primary amino groups (-NH)₂) And secondary amine (-NH-) groups. In alternative non-limiting embodiments, the amine-containing curing agent can be selected from aliphatic polyamines, cycloaliphatic polyamines, aromatic polyamines, and mixtures thereof. In another non-limiting embodiment, the amino groups are all primary amino groups. In one embodiment, where it is desirable to produce a polyureaurethane having a low color, the amine-curing agent can be selected such that it has a relatively low color and/or can be manufactured and/or stored in a manner that prevents discoloration (e.g., yellowing) of the amine.

Suitable amine-containing curing agents that can be used in the present invention can include, but are not limited to, materials having the following chemical formula:

wherein R is₁And R₂May each be independently selected from methyl, ethyl, propyl and isopropyl, and R₃May be selected from hydrogen and chlorine. Non-limiting examples of amine-containing curing agents useful in the present invention include the following compounds, manufactured by Lonza Ltd. (Basel, switzerland):

LONZACURE.RTM.M-DIPA：R₁＝C₃H₇；R₂＝C₃H₇；R₃＝H

LONZACURE.RTM.M-DMA：R₁＝CH₃；R₂＝CH₃；R₃＝H

LONZACURE.RTM.M-MEA：R₁＝CH₃；R₂＝C₂H₅；R₃＝H

LONZACURE.RTM.M-DEA：R₁＝C₂H₅；R₂＝C₂H₅，R₃＝H

LONZACURE.RTM.M-MI PA：R₁＝CH₃；R₂＝C₃H₇；R₃＝H

LONZACURE.RTM.M-CDEA：R₁＝C₂H₅；R₂＝C₂H₅；R₃＝Cl

wherein R is₁、R₂And R₃Corresponding to the chemical formula described above.

In a non-limiting embodiment, the amine-containing curing agent can include, but is not limited to, diamine curing agents such as 4, 4' -methylenebis (3-chloro-2, 6-diethylaniline), (Lonzacur. RTM. M-CDEA), available in the United states from Air Products and Chemical, Inc. (Allentown, Pa.). In an alternative non-limiting embodiment, the amine-containing curing agent useful in the present invention can include 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 trade name Ethacure 100; dimethylthiotoluenediamine (DMTDA), commercially available from albemarle corporation under the trade name Ethacure 300; 4, 4' -methylene-bis (2-chloroaniline) commercially available from Kingyorker Chemicals under the trade name MOCA. DETDA can be a liquid at room temperature and has a viscosity of 156 cPs at 25 ℃. DETDA can be isomeric, with the 2, 4-isomer being in the 75-81% range and the 2, 6-isomer being in the 18-24% range.

In one non-limiting embodiment, a color stabilized version of Ethacure100 (i.e., a formulation containing a yellow color reducing additive), which is available under the trade name Ethacure 100S, can be used in the present invention.

In another embodiment, the amine-containing curing agent used in the present invention can be selected from DEDTA, a compound having the structure:

and mixtures thereof.

The polyureaurethane of the present invention can be prepared by a one-step molding, quasi-prepolymer, or full prepolymer process, all of which are known in the art and disclosed in U.S. Pat. No. 5,962,617; which is incorporated herein by reference. In a one-step forming process, all of the reactants may be mixed together at once. In the quasi-prepolymer method, typically 30-80% of the total polyol is reacted with the polyisocyanate to form the prepolymer, and then the remaining 20-70% of the polyol can be added to the prepolymer along with the amine-containing curing agent. In an alternative non-limiting embodiment, the polyisocyanate (i.e., NCO) can be mixed with the polyether-containing polyol material in an equivalent ratio of greater than 1 to less than 4.5NCO/1.0OH or 2.0 to 4.0NCO/1.0OH and heated to a temperature in the range of 190F to 300F. The time for which the mixture is heated can vary widely. Generally, at lower temperatures, the mixture can be heated for a longer period of time than when using higher temperatures. For example, the mixture can be heated at a temperature of 260 to 265 ° F for 5 to 10 hours, and at a temperature of 275 to 290 ° F for 3 to 5 hours. In a non-limiting embodiment, the mixture can be heated under dry nitrogen to facilitate reaction of the polyisocyanate with the polyether-containing polyol material to form a prepolymer. The heating source is then removed and the prepolymer may be cooled. In another non-limiting embodiment, the prepolymer can be cooled to 160 ° F. The prepolymer is allowed to stand at this temperature for about 24 hours. After cooling, the amount of NCO present in the prepolymer can be determined by various methods known in the art. In a non-limiting embodiment, the NCO present in the prepolymer is determined by various methods known in the art, such as ASTM-D-2572-91.

In one non-limiting embodiment of the invention, the NCO present in the prepolymer can be determined as follows. A2 gram sample of polyureaurethane was added to an Erlenmeyer flask. The sample can be purged with nitrogen and then several glass beads (5mm) added. To this mixture 20mL of 1N dibutylamine (in toluene) can be added with a pipette. The mixture can be spun and capped. The flask may then be placed on a heating source and the flask may be heated to a slight reflux, held at this temperature for 15 minutes, and then cooled to room temperature. A piece of Teflon can be placed between the plug and the fitting to prevent pressure build-up when heated. During the heating cycle, the contents are frequently swirled in an attempt to completely dissolve and react. Blank values were obtained by direct titration of 20mL of pipetted 1N Dibutylamine (DBA) plus 50mL of methanol and 1N hydrochloric acid (HCl) using a Titrino 751 dynamic autotitrator. The average of HCl standard concentration and DBA blank can be calculated and the values input into the auto-titrator. After the sample is cooled, the contents can be transferred to a beaker containing approximately 50-60mL of methanol. A magnetic stir bar may be added and the sample may be titrated with 1N HCl using a pre-entered Titrino 751 autotitrator. The percent NCO and IEW (isocyanate equivalent weight) can be calculated according to the following formula:

% NCO ═ g (mLs blank-mLs sample) (standard concentration HCl) (4.2018)/sample wt,/g;

IEW ═ (sample wt., g) 1000/(mLs blank-mLs sample) (standard concentration HCl)

The "standard HCl" value can be determined as follows. To a pre-weighed beaker was added 0.4 g of Na₂CO₃Primary standard and record weight. To this was added 50mL of deionized water and the Na was magnetically stirred₂CO₃And (4) dissolving. The Titrino 751 autotitrator was used to titrate the primary standard with 1N HCl and the volume was recorded. This procedure was repeated two additional times, three titrations in total, and the average value can be used as the standard concentration according to the following formula:

standard concentration HCl ═ standard wt., g/(mLs HCl) (0.053)

In one non-limiting embodiment of the invention, additional polyisocyanate may be added to the prepolymer to achieve a different (e.g., higher or lower) equivalent weight of NCO/OH. The prepolymer can then be reacted at about 160 ° F to 180 ° F with an amine-containing curing agent, such as a diamine curing agent. In an alternative non-limiting embodiment, the amine-containing curing agent can be 0.60 to 1.20NH₂1.0NCO or 0.90-1.0NH₂1.0NCO or 0.92-0.96NH₂The equivalent ratio of/1.0 NCO is present. The polyureaurethane can then be cured at a temperature of 230 ℃ and 300 ℃ F. for a period of 4 to 24 hours.

In a non-limiting embodiment, the polyether-containing polyureaurethane prepolymer can be prepared by reacting an excess of polyisocyanate with a polyether-containing polyol material at a temperature of 130 ℃ or less to produce a free-flowing prepolymer. The term "free flowing" as used herein and in the claims refers to a material that is not gelled. Heating the prepolymer to a temperature above 130 ℃ can accelerate the rate of reaction between the polyisocyanate and the polyether-containing polyol material, resulting in premature gelation of the prepolymer and subsequent premature gelation of the polyureaurethane. In the case of the lens casting process, premature gelation of the prepolymer and subsequent polyureaurethane can produce defective lenses.

In an alternative non-limiting embodiment, the polyisocyanate can be present in excess to produce a prepolymer having a viscosity of less than 2000cPs, or less than 600cPs, or less than 300cPs with the polyether-containing polyol material, wherein said viscosity is measured using a brookfield viscometer at 73 ℃. The excess polyisocyanate used may be in an equivalent ratio of 2.0 to less than 4.5NCO/1.0 OH. The viscosity of the prepolymer may depend on the particular polyisocyanate and polyether-containing polyol materials selected. In one non-limiting embodiment, mixtures having the higher end of the aforementioned range of NCO/OH equivalent ratios can form prepolymers having lower end viscosities of the aforementioned range.

In the present invention, a suitable catalyst for polyurethane formation may be used in order to enhance the reaction of the materials for polyurethane formation. Suitable polyurethane-forming catalysts may be those which are specific to polyurethane formation by reaction of NCO and OH-containing materials and which have little tendency to accelerate side reactions leading to allophanate (allophonate) and isocyanate formation. 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, 5 th edition, 1992, Volume A21, pp.673-674. In a non-limiting embodiment, the catalyst can 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, 1, 4-diazabicyclo [2.2.2] octane, and mixtures thereof. In alternative non-limiting embodiments, the catalyst may be zinc octoate, bismuth acetylacetonate, or iron.

Other non-limiting examples of suitable catalysts can include tertiary amines such as, but not limited to, triethylamine, triisopropylamine and N, N-dimethylbenzylamine. 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.

In a non-limiting embodiment, a catalyst can be incorporated into the amine-containing curing agent. The amount of catalyst may vary greatly depending on the particular catalyst selected. In alternative non-limiting embodiments, the amount of catalyst can be less than 5 wt%, or less than 3 wt%, or less than 1 wt%, based on the total weight of the reaction mixture. For example, dibutyltin dilaurate can be used in amounts of 0.0005 to 0.02 parts per 100 parts of the polyurethane-forming material. The amount of catalyst used may depend on the curing temperature used.

The polyether-containing polyureaurethane of the present invention can be processed into articles by a variety of methods including, but not limited to, casting, compression molding, extrusion, or injection molding. In a non-limiting embodiment, the polyether-containing polyureaurethane can be cast into a lens. Casting of the polyether-containing polyureaurethane can produce lenses with good optical properties.

In one non-limiting embodiment of the casting process, a mixture of the polyether-containing polyureaurethane prepolymer and the amine-containing curing agent can be cast into a mold and then cured. In another non-limiting embodiment, the polyether-containing polyureaurethane of the present invention can be partially cured by selecting an appropriate curing time and temperature, and the polyether-containing polyureaurethane can then be removed from the casting mold and processed into a desired shape. The polyether-containing polyureaurethane can be formed into simple or complex shapes and then can be fully cured.

The front and/or back of the lens may be coated with an abrasion resistant coating, such as an organosilane type abrasion resistant coating, which is known in the art for protecting plastic surfaces from abrasion and scratching. Organosilane abrasion resistant coatings can be referred to as hardcoats and are known in the art. Various organosilane hardcoats are described in U.S. Pat. No. 4,756,973 at column 5, lines 1-45; and U.S. Pat. No. 5,462,806, column 1, line 58 to column 2, line 8 and column 3, line 52 to column 5, line 50, the disclosures of which are incorporated herein by reference. Other non-limiting examples of organosilane hard-coats are disclosed in US patents 4,731,264; 5,134,191 and 5,231,156, the disclosures of which are also incorporated herein by reference. In one non-limiting embodiment, the front and back surfaces of the lens can be coated with SDC 1154, which is commercially available from SDC Coatings, Incorporated, or HiGard 1080, which is commercially available from PPG Industries, Incorporated.

Other coatings that provide abrasion and scratch resistance may be used as abrasion resistant coatings, such as multifunctional acrylic based hard coatings, melamine based hard coatings, polyurethane based hard coatings, alkyl coatings, silica sol based hard coatings or other organic or hybrid inorganic/organic hard coatings.

In another non-limiting embodiment, the hard coating can be coated with an additional coating, such as an anti-reflective coating. Examples of antireflective coatings are described in US patent 6,175,450, the disclosure of which is incorporated herein by reference. In one non-limiting embodiment, the front and/or back of the lens can be coated with Essilor's Reflection Free anti-reflective coating, which can be applied using Essilor's Reflection Free Process.

In a non-limiting embodiment, the front and/or back of the lens may be coated with a UV curable hard coat, such as but not limited to UVX and UVNVS, commercially available from UltraOptics.

In general, the impact resistance of an uncoated lens may be higher than the impact resistance of a coated lens. Applying a hard coating to a lens can result in a reduction in the impact strength of the lens. The impact strength can be further reduced by applying an anti-reflective coating on the hard coated lens. The degree of reduction in impact strength may depend on the particular hard coating and antireflective coating selected for application to the lens.

The polyether-containing polyureaurethane of the present invention can have good impact resistance. In another alternative non-limiting embodiment, the polyether-containing polyureaurethane when at least partially cured and tested in the form of a lens having a thickness of from 2.0 to 2.2mm and having a hard coating on both surfaces can withstand an impact of at least 148 feet per second or at least 170 feet per second or at least 300 feet per second as determined by the high speed impact test procedure. As used herein and in the claims, the term "High speed Impact Test procedure" refers to the following procedures performed in accordance with Z87.1-200X, Committee ball Draft review of ANSI Z87.1-1989(R1998), part 7.5.2.1, "High Velocity Impact" and 14.3 "Test for High Impact descriptions stresses". A Universal lens tester (ULT-II) manufactured by International Certification Services Laboratories, Incorporated was used in this process. Plano power lenses with a maximum base curve of 6.25 were edge rounded with industrial safety bevel gears to 55mm +0.04mm/-0.25mm diameter. Each lens can be tested once, with each additional impact using a new lens. Each lens can be mounted in the test holder such that the test lens is held firmly in the bevel gear of the lens holder. The high speed impact test involved projecting a projectile at a velocity of 150 feet per second into the middle of each lens. The projectile consisted of a 6.35mm (0.25 inch) diameter steel ball weighing 1.06g (0.037 ounce). The test can be repeated with two additional lens samples. If there is any rearward movement of the lens as a whole in the test holder; any breakage of the lens; a lens having any portion detached from its inner surface or having any full thickness penetration of the lens may be considered to have failed the test. As used herein, "fracture" means that the entire thickness of the lens is broken into two or more separate pieces or detached from the inner surface of any lens material, as visible to the naked eye. Failure of any one lens means failure. If all of the tested lenses pass the test, any given lens, having the same or greater thickness at its thinnest point, made by the same manufacturer, from the same material, with the same coating and process, may carry a "+" mark.

In a non-limiting embodiment, a small amount of at least one tri-or higher functional polyol, such as, but not limited to, triols, tetraols, pentaols, and mixtures thereof, can be added to the polyether-containing polyureaurethane prepolymer in an amount sufficient to effect crosslinking (based on equivalent weight of reactants). In another non-limiting embodiment, at least one of these materials is added so as to produce at least 0.01% or at least 0.5% or less than 99% or less than 5% crosslinking, by weight of the total reactants. Suitable non-limiting examples include trimethylolpropane, trimethylolethane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, sucrose, mannitol, and mixtures thereof. Other non-limiting examples include material chains amplified with ethylene oxide, propylene or butylene. The addition of at least one such material to the prepolymer can increase the heat distortion temperature and in some cases can improve the smoothness (ballastic) properties of the cured polyurethane.

In alternative non-limiting embodiments of the present invention, various additives known in the art can be used in the preparation of the polyether-containing polyureaurethane of the present invention. Non-limiting examples include various antioxidants, ultraviolet stabilizers, color retarders, optical brighteners, and mold release agents. In a non-limiting embodiment, 5% or less of at least one antioxidant can be added to the prepolymer, wherein the amount added is based on the weight of the total reactants. Suitable antioxidants that can be used in the present invention include, but are not limited to, multifunctional hindered phenol type materials. One non-limiting example of a multifunctional hindered phenol type antioxidant can include Irganox1010, which is commercially available from Ciba Geigy.

In alternative non-limiting embodiments, a UV-stabilizer can be added to the polyether-containing polyureaurethane prepolymer prior to or during the curing step in an amount of 5.0% or less by weight of the total reactants, alternatively from 0.5 to 4.0% by weight of the total reactants. UV-stabilizers suitable for use in the present invention include, but are not limited to, benzotriazole. Non-limiting examples of benzotriazole UV-stabilizers include Cyasorb5411, Cyasorb 3604, and Tinuvin 328. Cyasorb5411 and 3604 are commercially available from American Cyanamid, and Tinuvin 328 is commercially available from Ciba Geigy.

In an alternative non-limiting embodiment, hindered amine light stabilizers can be added to increase UV protection. Non-limiting examples of hindered amine light stabilizers may include Tinuvin 765, which is commercially available from Ciba-Geigy.

The polyether-containing polyureaurethane of the present invention can be used in the production of photochromic articles. U.S. patent applications serial nos. 09/793,886 and 09/794,026 (both 2000.3.20 applications and not filed in the US patent and trademark office) disclose the production of photochromic articles. Both of these applications are incorporated herein by reference.

When used to prepare photochromic articles (e.g., lenses), the polyureaurethane should be transparent to the portion of the electromagnetic spectrum that can activate the photochromic substance incorporated in the matrix, i.e., the Ultraviolet (UV) wavelengths that can produce a colored or open (open) form of the photochromic substance, and the portion of the visible spectrum that includes the absorption maximum wavelength for the photochromic substance in its UV-activated form (i.e., the open form). Photochromic substances that can be used with the polyureaurethane of the present invention are organic photochromic compounds or substances containing such compounds, which can be incorporated, for example, dissolved, dispersed or diffused into the polyureaurethane.

A first class of organic photochromic substances useful in forming the photochromic articles of the present invention are those having an activated absorption maximum in the visible range greater than 590 nanometers, such as 590-700 nanometers. These materials typically exhibit a blue, bluish green, or bluish-purple color when exposed to ultraviolet light in a suitable solvent or matrix. Non-limiting examples of such materials that can be used in the present invention include, but are not limited to, spiro (indoline) phenoxazines and spiro (indoline) benzoxazines. These and other classes of photochromic substances are known. See, for example, US patents: 3,562,172, respectively; 3,578,602, respectively; 4,215,010, respectively; 4,342,668, respectively; 5,405,958, respectively; 4,637,698, respectively; 4,931,219, respectively; 4,816,584, respectively; 4,880,667, respectively; 4,818,096.

A second class of organic photochromic substances useful in forming the photochromic articles of the present invention are those having at least one absorption maximum and two absorption maxima in the visible range between 400 and less than 500 nanometers. Such materials typically exhibit a yellow-orange color when exposed to ultraviolet light in a suitable solvent or matrix. Such compounds include, but are not limited to, certain chromenes, i.e., benzopyrans and naphthopyrans. Many such chromenes are known, for example, US patent 3,567,605; 4,826,977, respectively; 5,066,818, respectively; 4,826,977, respectively; 5,066,818, respectively; 5,466,398, respectively; 5,384,077, respectively; 5,238,931, respectively; and 5,274,132.

A third class of organic photochromic substances that can be used to form the photochromic articles of the present invention are those having one absorption maximum in the visible range between 400-500 nm and another absorption maximum in the visible range of 500-700 nm. Such materials typically exhibit a color ranging from yellow/brown to violet/gray when exposed to ultraviolet light in a suitable solvent or matrix. Non-limiting examples of such materials include certain benzopyran compounds, having a substituent at the 2-position of the pyran ring; and substituted or unsubstituted heterocyclic rings, such as benzothieno or benzofuro rings fused to the benzene portion of the benzopyran. Such materials are described in US patent 5,429,774.

Other photochromic substances include photochromic organometallic dithizonates, i.e., (arylazo) -thioformic arylhydrazides, e.g., mercury dithizonates, e.g., as described in U.S. Pat. No. 3,361,706. Fulgides and fulgimides, such as 3-furyl and 3-thienyl fulgides and fulgimides, are described in U.S. Pat. No. 4,931,220 at column 20, line 5 to column 21, line 38.

The disclosures in the aforementioned patents relating to such photochromic substances are incorporated herein by reference. The photochromic articles of the present invention may contain one photochromic substance or a mixture of photochromic substances. Mixtures of photochromic substances can be used to achieve certain activated colors, such as a nearly colorless gray or brown.

Each of the photochromic substances described herein may be used in an amount or in a proportion (when mixtures are used) such that the polyurethane/polymer to which the compound mixture is applied or into which they are incorporated, when activated with unfiltered sunlight, exhibits a desirable resulting color, e.g., a substantially colorless color, such as a gray or brown undertone, i.e., a color that brings the color of the activated photochromic substance as close as possible to colorless. The relative amounts of the aforementioned photochromic substances used will vary and will depend in part on the relative intensities of the colors of the species activated by such compounds and the desired final color.

The photochromic compounds or substances described herein may be applied or incorporated into the polyurethane/polymer by various methods described in the prior art. These methods include, but are not limited to, dissolving or dispersing the substance within the polyurethane/polymer, for example, by immersing the polyurethane/polymer in a hot solution of the photochromic substance or by heat transfer, allowing the photochromic substance to imbibe into the polyurethane/polymer; providing the photochromic substance in the form of a separate layer between adjacent layers of polymer, for example, as part of a polymer film; and applying the photochromic substance as a coating or as a portion of a coating on the polyurethane/polymer surface. The terms "imbibe" or "imbibe" are intended to mean and include penetration of the photochromic substance alone into the polyurethane/polymer, solvent assisted transfer absorption of the photochromic substance into the porous polymer, vapor phase transfer, and other such transfer mechanisms. One non-limiting example of an imbibing method includes coating a photochromic article with a photochromic substance; a step of heating the surface of the photochromic article and removing the residual coating from the surface of the photochromic article.

The amount of photochromic substance or composition containing it applied to or incorporated into the polyurethane/polymer is not critical, provided that a sufficient amount is used so that when activated a photochromic effect is produced which is visible to the naked eye. Generally, this amount can be described as a photochromic amount. The specific amount used will generally depend on the intensity of the color desired when irradiated and on the method used to incorporate or apply the photochromic substance. Generally, the more photochromic substance applied or incorporated, the greater the intensity of the color. Generally, the total photochromic substance amount incorporated or applied to the photochromic optical polyurethane/polymer can be from 0.15 to 0.35 milligrams per square centimeter of surface to which the photochromic substance is incorporated or applied.

Photochromic substances can also be added to multi-component organic compositions prior to polymerization, e.g., cast curing, of the composition. However, when doing so, it is generally desirable that the photochromic substance does not interact with, for example, initiators that may be present and/or the isocyanate, isothiocyanate and amine groups of the first and second components, which may be undesirable. Such adverse interactions can lead to deactivation of the photochromic substances, for example, by trapping them in an open or closed form. Photochromic substances may also include photochromic pigments and organic photochromic substances encapsulated in metal oxides, the latter being described in US patents 4,166,043 and 4,367,170. Organic photochromic materials that are sufficiently encapsulated within an organic polyurethane/polymer matrix, as described in U.S. Pat. No. 4,931,220, can also be incorporated into the multi-component compositions of the present invention and then cured. If photochromic substances are added to the multi-component organic compositions of the present invention prior to curing, they are typically incorporated into the second component and the first and second components are then mixed together.

Examples

In each of the following examples, the NCO concentration of component A was determined according to ASTM-D-2572-91 using the following titrimetric procedure. The titrimetric analysis method consists of the following steps: a sample of 2 grams of component a was added to an Erlenmeyer flask. The sample was purged with nitrogen and then several glass beads (5mm) were added. To this mixture was added 20mL of 1N dibutylamine (in toluene) with a pipette. The mixture was spun and capped. The flask was then placed on a heating source and the flask was heated to slight reflux, held at this temperature for 15 minutes, and then cooled to room temperature. Note that a piece of Teflon was placed between the plug and the fitting to prevent pressure build-up upon heating. During the heating cycle, the contents are frequently swirled in an attempt to completely dissolve and react. Blank values were obtained by direct titration of 20mL of pipetted 1N Dibutylamine (DBA) plus 50mL of methanol and 1N hydrochloric acid (HCl) using a Titrino 751 dynamic autotitrator. The average of HCl standard concentration and DBA blank was calculated and then the values were input into an auto-titrator. After the sample had cooled, the contents were transferred to a beaker containing approximately 50-60mL of methanol. A magnetic stir bar was added and the sample was titrated with 1N HCl using a pre-entered Titrino 751 autotitrator. Percent NCO and IEW (isocyanate equivalent weight) were automatically calculated according to the following formula:

The "standard HCl" value was determined as follows. To a pre-weighed beaker was added 0.4 g of Na₂CO₃Primary standard and record weight. To this was added 50mL of deionized water and the Na was magnetically stirred₂CO₃And (4) dissolving. Using an autotitrator (i.e., Metrohm GPD Titrino 751 dynamic autotitrator with a 50mL burette) equipped with a combination pH electrode (i.e., Metrohm combination glass electrode number 6.0222.100), a primary standard was titrated with 1N HCl and the volume was recorded. This procedure was repeated two additional times, three titrations in total, and the average was used as the standard concentration according to the following formula:

standard concentration HCl ═ standard wt., g/(mLs HCl) (0.053).

Further, in each of the following examples, six semi-finished lenses were produced from the component a prepolymer using the following lens casting method. Component A and DETDA (referred to as component B) were injected into a specially designed molding machine (from Max Machinery). DETDA is available from Albemarle corporation. The molding machine was a polyurethane processing processor, model 601-000-232, available from Max Machinery, Healdsburg, Calif. Components a and B were added to the machine and high shear mixed for a short time. Component B and component a are present in a molar ratio of 0.95 to 1.0. The blended mixture is then injected into a lens mold. The mold was placed in a convection oven and allowed to stand at 130 ℃ for six hours. The cast semi-finished lens is then removed from the oven and allowed to cool. The front of the lens was coated with a commercially available hard coating available from SDC Incorporated under the trade name SDC 1154. The coating was applied by spin coating the lens at 1100rpm for 13 seconds using a spin coater, followed by 3 hours of curing at 120 ℃. The lenses were then sent to 20/20 optical laboratories where the lenses were cut into 55mm diameter circles and the surface processed to a flat light (Plano power) with a central thickness of 2.1 mm. The back of each lens was coated with a hard coat layer using a commercially available UV curable coating manufactured by UltraOptics under the trade name UVX. These lenses were then fed into Essilor and coated with Essilor's Reflection Free anti-reflective coating using Essilor's Reflection Free Process.

The cast lenses were then subjected to an impact strength test by a high speed impact test procedure. The "High-speed Impact Test procedure" refers to the following procedures conducted in accordance with Z87.1-200X, Committee balloon Draft replacement of ANSI Z87.1-1989(R1998), section 7.5.2.1 "High Velocity Impact" and section 14.3 "Test for High Impact Prescription stresses" on 2002, 12.9.2002. A Universal lens tester (ULT-II) manufactured by international certification Services Laboratories, Incorporated was used in this process. Plano power lenses with a maximum base curve of 6.25 were edge rounded with industrial safety bevel gears to 55mm +0.04mm/-0.25mm diameter. Each lens was tested once and each additional impact was performed using a new lens. Each lens is mounted in the test holder such that the test lens is held firmly in the bevel gear of the lens holder. The high speed impact test involved projecting a projectile at a velocity of 150 feet per second into the middle of each lens. The projectile consisted of a 6.35mm (0.25 inch) steel ball, weighing 1.06g (0.037 ounce). If there is any rearward movement of the lens as a whole in the test holder; any breakage of the lens; a lens having any portion detached from its inner surface or having any full thickness penetration of the lens is considered to have failed the test. As used herein, "fracture" means that the entire thickness of the lens is broken into two or more separate pieces or detached from the inner surface of any lens material, as visible to the naked eye. Failure of any one lens means failure.

Example 1

In a reaction vessel containing a nitrogen blanket, 4.5 equivalents of 400MW polycaprolactone, 0.58 equivalent of 750MW polycaprolactone, 3.387 equivalents of trimethylolpropane, 1.695 equivalents of Pluracol P2000, and 27.44 equivalents of Desmodur W were mixed together at room temperature. Desmodur W represents 4, 4' methylenebis (cyclohexyl isocyanate) containing 20% by weight of the trans-, trans-isomer and 80% by weight of the cis-cis and cis-trans isomers. Desmodur W was obtained from Bayer Corporation and Pluracol P2000 was obtained from BASF. The reaction mixture was heated to 78 ℃ to obtain a substantially clear mixture. To this mixture was added 20ppm dibutyltin laurate catalyst and the heating was removed. The addition of the catalyst produced an exothermic reaction and the temperature started to rise and reached a peak of 123 ℃. The reaction was completed by continuous stirring and allowed to cool at ambient conditions. At about 116 ℃, the following materials were added: 0.5 wt% Irganox1010 (obtained from Ciba Geigy), 2 wt% UV absorber Cyasorb5411 (obtained from American Cyanamid/Cytec) and 1.5ppm Exalite Blue 78-13 (obtained from Exciton). The mixture was stirred at 100 ℃ for another 1 hour and then cooled to room temperature. This mixture is referred to as component A prepolymer. The isocyanate (NCO) concentration in the prepolymer of component A was determined as described above. The theoretical% NCO was determined to be 10.3 and the experimental% NCO was determined to be 10.1. This component a prepolymer was then used in the lens casting process described above, and the resulting lenses were subjected to high speed impact test using the treatment method described above. The lens is capable of withstanding a maximum speed of 150 feet per second.

Example 2

The same procedure as described in example 1 was used except that 1.695 of Pluronic L62D was used instead of Pluracol P2000. The theoretical% NCO was determined to be 10.3 and the experimental% NCO was determined to be 10.1. Then, the component a prepolymer was used in the above-mentioned lens casting process, and the resulting lens was subjected to a high-speed impact test using the above-mentioned treatment method. The lens did not fail and/or break at a speed of 300 feet per second.

Example 3

The same procedure as described in example 1 was used for example 3, except that a blend of 1.356 equivalents of Pluracol P2000 and 0.338 equivalents of Pluracol E2000 was used instead of Pluracol P2000. It was determined that the theoretical% NCO was 10.3 and the experimental% NCO was 9.02. Then, the component a prepolymer was used in the above-mentioned lens casting process, and the resulting lens was subjected to a high-speed impact test using the above-mentioned treatment method. The lens is capable of withstanding a maximum speed of 137 feet per second.

EXAMPLE 4

The same procedure as in example 1 was used for example 4, except that 1.695 equivalents of Tone were used^TMPolyol 0241 replaces Pluracol P2000. The component A prepolymer was used in the above-described lens casting process, and the resulting lens was subjected to a high-speed impact test using the above-described treatment method. The lens is able to withstand a maximum speed of 146 feet per second.

Claims

1. A polyether-containing polyureaurethane comprising the reaction product of:

a. a prepolymer comprising a polyisocyanate and at least one polyether-containing polyol material; and

b. an amine-containing curing agent is included in the curing agent,

wherein said prepolymer has an NCO/OH equivalent ratio of 2.0 to less than 4.5, said polyether-containing polyureaurethane comprising segmented portions derived from a polyether polyol, said polyether polyol comprising the formula:

HO-(CRRCRR-Y_n-O)_a-(CRRCRR-Y_n-O)_b-(CRRCRR-Y_n-O)_c--H

wherein R represents hydrogen or C₁-C₆An alkyl group; y represents CH₂(ii) a n is an integer of 0 to 6; a. b and c are each an integer from 0 to 300, wherein a, b and c are selected such that the polyol has a weight average molecular weight of no more than 32,000, said polyureaurethane when at least partially cured and when tested in the form of a lens having an impact resistance of at least 148 feet per second, wherein both surfaces of said lens have a hard coating layer in a planar configuration having a maximum central thickness of 2.2mm, said impact resistance being determined by a high speed impact test.

2. The polyether-containing polyureaurethane of claim 1 having an NCO/OH equivalent ratio of from 2.1 to 4.0.

3. The polyether-containing polyureaurethane of claim 1 having a viscosity of less than 2,000cPs at 73 ℃.

4. The polyether-containing polyureaurethane of claim 1 wherein said polyether-containing polyureaurethane comprises a prepolymer and an amine-containing curing agent.

5. The polyether-containing polyureaurethane of claim 4 wherein said prepolymer comprises a polyisocyanate and at least one polyether-containing polyol material.

6. The polyether-containing polyureaurethane of claim 5 wherein said polyisocyanate is selected from the group consisting of aliphatic polyisocyanates, cycloaliphatic polyisocyanates, aromatic polyisocyanates, and mixtures thereof.

7. The polyether polyureaurethane of claim 6 wherein said polyisocyanate is selected from aliphatic diisocyanates, cycloaliphatic diisocyanates, and mixtures thereof.

8. The polyether-containing polyureaurethane of claim 5 wherein said polyisocyanate is selected from cyclohexylmethane and isomeric mixtures thereof.

9. The polyether-containing polyureaurethane of claim 5 wherein said polyisocyanate is selected from the trans-trans isomer of 4, 4' -methylenebis (cyclohexyl isocyanate).

10. The polyether-containing polyureaurethane of claim 5 wherein said polyisocyanate is selected from the group consisting of 3-isocyanato-methyl-3, 5, 5-trimethylcyclohexyl-isocyanate; meta-tetramethylxylene diisocyanate (1, 3-bis (1-isocyanato-1-methylethyl) -benzene) and mixtures thereof.

11. The polyether-containing polyureaurethane of claim 4 wherein said prepolymer has an NCO/OH equivalent ratio of from 2.0 to less than 4.5.

12. The polyether-containing polyureaurethane of claim 5 wherein said polyether-containing polyol material is selected from polyether polyols and mixtures thereof.

13. The polyether-containing polyureaurethane of claim 5 wherein said polyether-containing polyol material has a weight average molecular weight of from 200 to 32,000.

14. The polyether-containing polyureaurethane of claim 8 wherein said polyether-containing polyol material has a number average molecular weight of from 2,000 to 15,000.

15. The polyether-containing polyureaurethane of claim 4 wherein said amine-containing curing agent is selected from materials having the formula:

wherein R is₁And R₂Each independently selected from methyl, ethyl, propyl and isopropyl and R₃Selected from hydrogen and chlorine.

16. The polyether-containing polyureaurethane of claim 4 wherein said amine-containing curing agent is 4, 4' -methylenebis (3-chloro-2, 6-diethylaniline).

17. The polyether-containing polyureaurethane of claim 4 wherein said amine-containing curing agent is selected from the group consisting of 2, 4-diamino-3, 5-diethyl-toluene; 2, 6-diamino-3, 5-diethyl-toluene and mixtures thereof.

18. The polyether-containing polyureaurethane of claim 4 wherein said amine-containing curing agent has NCO/NH₂The equivalent ratio is 1.0NCO/0.60 NH₂To 1.0NCO/1.20NH₂。

19. The polyether-containing polyureaurethane of any of claims 1-18 wherein said polyureaurethane when at least partially cured and when tested in the form of a lens, has an impact resistance of at least 170 feet per second wherein both surfaces of said lens have a hard coating in a planar configuration having a maximum central thickness of 2.2mm, said impact resistance being determined by the high speed impact test.

20. A process for preparing a polyether-containing polyureaurethane comprising the steps of:

a. reacting a polyisocyanate with at least one polyether-containing polyol to form a polyether-containing polyurea prepolymer; and is

b. Reacting said prepolymer with an amine-containing curing agent,

HO-(CRRCRR-Y_n-O)_a-(CRRCRR-Y_n-O)_b-(CRRCRR-Y_n-O)_c-H

21. The process for preparing a polyether-containing polyureaurethane of claim 20 having a viscosity of less than 2,000 cPs.

22. The method for preparing a polyether-containing polyureaurethane of claim 20 wherein said polyether-containing polyureaurethane comprises a prepolymer and an amine-containing curing agent.

23. A process for preparing a polyether-containing polyureaurethane as defined in claim 22 wherein said prepolymer comprises a polyisocyanate and at least one polyether-containing polyol material.

24. The process for preparing a polyether-containing polyureaurethane of claim 23 wherein said polyisocyanate is selected from the group consisting of aliphatic polyisocyanates, cycloaliphatic polyisocyanates, aromatic polyisocyanates, and mixtures thereof.

25. The process for preparing a polyether-containing polyureaurethane of claim 24 wherein said polyisocyanate is selected from the group consisting of aliphatic diisocyanates, cycloaliphatic diisocyanates, and mixtures thereof.

26. A process for preparing a polyether-containing polyureaurethane as set forth in claim 23 wherein said polyisocyanate is selected from cyclohexylmethane and isomeric mixtures thereof.

27. The process for preparing a polyether-containing polyureaurethane of claim 23 wherein said polyisocyanate is selected from the trans-trans isomer of 4, 4' -methylenebis (cyclohexyl isocyanate).

28. The process for preparing a polyether-containing polyureaurethane of claim 23 wherein said polyisocyanate is selected from 3-isocyanato-methyl-3, 5, 5-trimethylcyclohexyl-isocyanate; meta-tetramethylxylene diisocyanate (1, 3-bis (1-isocyanato-1-methylethyl) -benzene) and mixtures thereof.

29. The process for preparing a polyether-containing polyureaurethane of claim 22 wherein said prepolymer has an NCO/OH equivalent ratio of from 2.1 to less than 4.0.

30. A process for preparing a polyether-containing polyureaurethane as set forth in claim 23 wherein said polyether-containing polyol material is selected from polyether polyols and mixtures thereof.

31. The process for preparing a polyether-containing polyureaurethane of claim 23 wherein said polyether-containing polyol material has a number average molecular weight of from 200 to 32,000.

32. The process for preparing a polyether-containing polyureaurethane of claim 26 wherein said polyether-containing polyol material has a number average molecular weight of from 2,000 to 15,000.

33. The process for preparing a polyether-containing polyureaurethane of claim 22 wherein said amine-containing curing agent is selected from materials having the formula:

34. The method for preparing a polyether-containing polyureaurethane of claim 22 wherein said amine-containing curing agent is 4, 4' -methylenebis (3-chloro-2, 6-diethylaniline).

35. The process for preparing a polyether-containing polyureaurethane of claim 22 wherein said amine-containing curing agent is selected from the group consisting of 2, 4-diamino-3, 5-diethyl-toluene; 2, 6-diamino-3, 5-diethyl-toluene and mixtures thereof.

36. The method for preparing a polyether-containing polyureaurethane of claim 22 wherein said amine-containing curing agent has NCO/NH₂The equivalent ratio is 1.0NCO/0.60 NH₂To 1.0NCO/1.20NH₂。

37. An optical article comprising the polyether-containing polyureaurethane of any of claims 1-19 wherein said polyether-containing polyureaurethane comprises the reaction product of:

a. a prepolymer comprising a polyisocyanate and at least one polyether-containing polyol; and

b. an amine-containing curing agent is included in the curing agent,

wherein said prepolymer has an NCO/OH equivalent ratio of 2.0 to 4.5, said polyether-containing polyureaurethane comprising segmented portions derived from a polyether polyol, said polyether polyol comprising the formula:

HO-(CRRCRR-Y_n-O)_a-(CRRCRR-Y_n-O)_b-(CRRCRR-Y_n-O)_c-H

38. The optical article of claim 37, said polyether-containing polyureaurethane when at least partially cured and when tested in the form of a lens having a hard coating on both surfaces in a planar configuration having a maximum central thickness of 2.2mm, said impact resistance being determined by the high speed impact test, having an impact resistance of at least 170 feet per second.

39. A photochromic article comprising the polyether-containing polyureaurethane of any of of claims 1-19 wherein said polyether-containing polyureaurethane comprises the reaction product of:

b. an amine-containing curing agent is included in the curing agent,

HO-(CRRCRR-Y_n-O)_a-(CRRCRR-Y_n-O)_b-(CRRCRR-Y_n-O)_c-H

wherein R represents hydrogen or C₁-C₆An alkyl group; y represents CH₂(ii) a n is an integer of 0 to 6; a. b and c are each integers from 0 to 300, where a, b and c are selected such that the weight average molecular weight of the polyolNo more than 32,000, said polyureaurethane when at least partially cured and when tested in the form of a lens, having an impact resistance of at least 148 feet per second, wherein both surfaces of said lens have a hard coating in a planar configuration having a maximum central thickness of 2.2mm, said impact resistance being determined by a high speed impact test.

40. The photochromic article of claim 39, said polyether-containing polyureaurethane when at least partially cured and when tested in the form of a lens having a hard coating on both surfaces thereof in a planar configuration having a maximum central thickness of 2.2mm, said impact resistance being determined by the high speed impact test, having an impact resistance of at least 170 feet per second.