Title of Invention

PROCESS OF MAKING POLYMERIZABLE POLYOL (ALLYL CARBONATE) COMPOSITIONS

Abstract

A process of making a polymerizable composition comprising: mixing (a) a major amount of a radically polymerizable first monomer represented by the following general formula, wherein R is a polyvalent residue of a polyol having at least two hydroxy groups, Ri, is an allyl group, and i is a whole number from 2 to 4; and (b) a minor amount of a radically polymerizable second monomer represented by the following general formula, wherein R2, is a polyvalent linking group that is free of urethane linkages; R3 is a residue of a material having a single hydroxy group and at least one allyl group, R3 being free of urethane linkages; and j is a number from 2 to 4.

Full Text

FORM 2 THE PATENTS ACT, 1970 (39 of 1970) COMPLETE SPECIFICATION (See Section 10, rule 13)) PROCESS OF MAKING POLYMERIZABLE POLYOL (ALLYL CARBONATE) COMPOSITIONS PPG INDUSTRIES OHIO, INC. of 3800 WEST 143RD STREET, CLEVELAND, OH 44111, U.S.A. a AMERICAN Company The following specification particularly describes the nature of the invention and the manner in which it is to be performed : - POLYMERIZABLE POIYOL (ALLYL CARBONATE) COMPOSITIONS DESCRIPTION OF THE INVENTION The present invention relator, to a polymerizable 5 composition. More particularly, the present invention relates; to a polymerizable composi t.ion comprising polyol(allyI carbonate) monomer and n ur^rlvini; having at least tv/o allyl or substituted allyl groups. The present invention relates also to polymerizar.es, e.g., lenses, obtained from the 10 polymerizable compositions. Polymerizable organic romponi ci ons baaed on polyol allyl carbonate), particularly diethylene glycol bis(allyl carbonate), and polymorizates obtained therefrom are well known in the art. Polytnerizates of polymerizable .organic 15 compositions based on homupolymerc of diethylenc glycol bis(allyl carbonate) possess excellent clarity, good flexibility and abrasion resistance. Example:-; of appl i.c:>t ionn for which such polymerisates may be used include, ophthalmic lenses, sunglasses, and iiuLumui. i ve and airur.-jft 20 trancparencien. It liar; been observed that tinting of po'lyriierizates prepared from such compositions by surface impregnation of dyes can, in certain instnncon, rem; It in an uneven tinting of the surface. Such uneven tinting is referred to as tinting failure. 25 When tinting failure occurs, it is often manitested as visually observable defects on the tinted surface(n) of the polymeri zatip, which arc commonly referred to nn "fern?;" oi. "moons." In the case of tinted ophthalmic lensen, such as tinted ophthalmic lenses having n positive diopter, i.e., plus 30 lenses, and non-corrective lenses, e.g., sunglanr.cr;, nueh tinting failure often result" in rejection and ncrapping or the tinted lens. A iirjh.n.j.rm to t i.n( ing failure if. desiable in order to avoid the economic loss that results from the scrapping of lenses having tinting defects. United States Patent No.'s 4,994,208, 5,084,529, 5,110,881, 5,221,721, 5,230,978 and 5,246,630 describe 5 polymerizable compositions composed of polyol(allyl carbonate) monomer and at least 10 weight percent of aliphatic polyurethanes, the terminal portions of which contain allyl functional groups. United States Patent No. 5,200,483 describes organic resin compositions containing polyol(allyl 0 carbonate) monomer and a mixture of aliphatic urethanes, the terminal portions of which contain allyl or acrylyl functional groups. ,, ! It has now been discovered that cured polymerizates prepared from the polymerizable compositions of the present 5 invention are substantially free of tinting defects, for example, tinting defects referred to in the art as ferns or moons. In accordance with the present invention there is provided a polymerizable composition comprising: (a) a major amount: of a radically polymei. izab.le 0 first monomer represented by the following general formula j, I R- (-O-C(O) -O-Rjj wherein R is a polyvalent residue of a polyol havinq at least two hydroxy group*;, R, is an allyl or substituted ally! group, 5 and i is a whole number from '?. to 4; and [to) a minor amount of a radically pol ymor izahl r. occond monomer roprom.uitnd by the following general formula II, wherein R3 is a polyvalent linking group that is frco of urethane linkages; R, is a residue of a material having a single hydroxy group and at least one allyl group, Rj being free of urethane linkages, acryloyl groups and methacryloyl 5 groups; and j is a number from 2 to 4, e.g., 2, 3 or 4. In an embodiment of the present invention, said r;ocond monomer (b) is present in said composition in an amount at least sufficient such that a polymorizate of said composition is, substantially free of tinting defects. 10 The features that characterize the prenent invent, ion are pointed out with particularity in the claims, which are annexed to and form a part of this disclooure. These and other features of the invention, its operating advantages and the specific Objects obtained by its use will be mote fully 15 understood from the following detailed description and the accompanying illustrative drawing. Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, etc. used in the specification and claims 20 are to be understood as modified in ail instances by the term "about." BRIEF DESCRIPTION OF THE DRAWING Figure 1 is a representation of a negative image of a 25 tinted lens having tinting defects. DETAILED DESCRIPTION OF THE INVENTION In an embodiment of the present invention, the second monomer described with reference to genera J. forinuJa XX if; 30 present in the polymerizablc compositions in an amount at least sufficient such that polymerizates prepared from such componitiong am nubfitantiall y free of tinting defect?:. As used herein and in the claims, the term "tinting defects" and similar terms refer generally to a visually observable uneven distribution of dye over the surface of a tinted polymerizate, such as a tinted lens. More particularly, tinting defects are often visually observable as lighter colored or untinted 5 surface patterns, sometimes in the form of ferns or moons. Tinting defects in the form of ferns can be Cur:t:li«r described with reference to Figure 1. The tinted pol ymeri. 7.nte. 4 of Figure 1 is a tinted plus lens 11, prepared from diethylene glycol bis(allyl carbonate) monomer, and having 10 tinting defects 15 thereon. For purposes of illustration, the tinting defects 15 of Figure 1 arc shown an a negative im.ngo. As used herein, by "plus lens" is meant a lens having a positive (+) diopter, i.e., a lenu having a positive focal length or real focal point. The tinting defects shown in the 15 lens depicted in Figure 1 were observed in a lens having a plus five (+5) diopter, I Tinting defects in the form of moons (not shown in Figure 1) are typically observed as a series of concentric circles of varying tint strength on the surface of the tinted Jens. In 20 some instances a tinted lens will exhibit a combination of: both moon and fern type tinting defects. The occurrence of tinting defects with polyiner.izator; prepared from polyoMallyl carbonate) monomers is a largely statistical phenomenon. Accordingly, in order to determine if 25 a polymerizable composition can be used to prepare polymerizates that are "substantially free of tinting defects," more than one polymerizate, e.g., several lenses, should be prepared. Optionally, a set of comparative pulymerlzatco may nlfjo be prepared under nlniilar mini i I i .MI.". , JO "■. between 10 and 100 lenne.". are prepared to determine if they are substantially free of tinting defects. Such a determination is described .in further detail in the Examples herein. Typically, a set of polymerizates, e.g., 100 ophthalmic plus lenses, prepared from a polyinerizable composition according to tho pjewent inention, is conn i tiered to be substantially free of tinting defects if 10 percent or less, preferably 5 percent or less, and more preferably 0 percent of the tinted polymerizates have tinting defects, such 10 as ferns. Second monomer (b) is present in the polymerizable composition of the present invention in a minor amount (e.g., from 0.1 percent by weight to 49 percent by weight, based on the total weight of the composition). Typically, second 15 monomer (b) is present in the composition of the instant invention in an amount of at least 0.1 percent by weight, 'preferably at least 0.2 percent by weight, and more preferably at least 0.3 percent by weight, based on the total weight of the composition. Second monomer (b) is also typically present. 20 in the composition of the present invention in an amount of less than 10 percent by weight, preferably less than 5 percent by weight and more preferably less than 3 percent by weight, based on the total weight of the composition. The amount of second monomer (b) present in the composition of the present 25 invention may range between any combination of these values, inclusive of the recited values, e.g., from 0.1 percent by weight to 10 percent by weight or from 0.3 percent by weight to 3 percent by weight, based on the total weight of the composition. 30 With reference to general formula II, second monomer (b) I is distinguishable from polyurethanes having terminal a.l lyl functional groups as described in, for example, United States Patent No.'s 4,994,208, 5,084,529, 5,110,881, 5,22.1,721, 5,236,978 and 5,246,630. In general formula II, R, and K, are each free of urethane linkages, more particularly, R3 and R, are each free of internal urethane linkages. As used herein and in the claims, the term "urethane linkage" is meant to 5 refer to the following structural linkage, -N(H) C(0)-o . In the case when R2 is a residue of a polyisocyanate, second monomer (b) can be described as a polyisocyanate that is capped with the mono-hydroxy functional material of which R, is a residue. 10 Depending on the method by which second monomer (b) i" prepared, R5 may be a residue of, for example, a polyisocyanate, i.e., a material having at least two isocyanate groups, or a polyamine, i.e., a material having at least two primary amine groups. when the second monomer is 15 prepared by capping a poly i !:ocy;uicit. functional material of which Rn is a residue, R2 is n residue of a polyisocyanate. The second monomer may also be prepared by first reacting the mono-hydroxy functional material of which R, is a residue with phosgene to form the corresponding 20 chloroformate, which is then reacted with a polyamine, in which case Rr is a residue of a polyamine. In an embodiment of the present invention, R5 is a residue of a polyisocyanate having at least two isocyanate groups, and the polyisocyanate may be selected from aromaLic 25 polyisocyanates, aliphatic polyisocyanates, cycloaliphatic polyisocyanates and mixtures thereof. As used herein and in the claims, the term "polyisocyanate" is meant to be inclusive of dimers and trimers of polyisocyanates, for example, trimers of diisocyanates containing a core isocyanurnte ring. 30 Classes of aromatic polyisocyanates of which R., may be a residue include, for example, aromatic polyisocyanntes wherein the isocyanate groups are not bonded directly t.o the ;u.UUMtie¬ring, e.g.,j a,a'-xylene diisocyanate,- and aromatic polyinocyniiatoa wheiwin Die inocyanaUo groups are bonded i directly to'the aromatic ring, e.g., benzene diisocyanate. Examples of aromatic polyisocyanates having isocyanate groups bonded directly to the aromatic ring, of which R2 may be 5 a residue include, but ar» not limited to, phenyl'"■nr- diinocyanale, eLhylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenyl one. diisocyanate, diethylphenylcne diisocyanate, diisopropylpbenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, 0 naphthalene diisocyanate, methylnaphthalene diisocyanate, biphenyl diisocyanate, ortho-t'olidine diisocyanate, 4,4'-diphenylmethane diisocyanate, bis(3-methyl-4- isocyanatophenyl)methane, bis(isocyanatophenyl)ethylene, 3,3'-dimethoxy-biphenyl-4,4'-diisocyanate, triphenylmethane 5 triisocyanate, polymeric 4,4'-diphenylmethane diisocyanate, i naphthalene triisocyanate, d.tphenylmerhano-2, 4 ,■ 4 ' -triisocyanate, 4-methyldiphenylmethane~3,5,2',4',6'-pentaisocyanate, diphenylether diisocyanate, bis(isocyanatophenylether)ethyleneglycol, 0 bin (inocynnatophcnylethor! -1,1- propylcncglycol, beu-.'.ophenone diisocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate and dichlorocarbazole diisocyanate. Examples of aromatic polyisocyanates wherein the isocyanate groups are not bonded directly to the aromatic ring, of which R3 may be a 5 residue include, but are not. limited to, bis(isocyanatoethyl)benzene, a,a,a',w -tetramethylxylene diisocyanate, 1,3-bis(1-isocyanato-l-methylethyl)benzene, bis (isocyanatobutyl) benzene , bis (isocyanatomethyl ) nnphrh.il one, bis(isocyanatomethyl)diphenyi ether, 0 bis(isocyanatoethyl)phthalate, mesitylene triisocyanate and 2,5-di(isocyanatomethyl)furan. Aliphatic polyisocyanates of which R, may be a residue may be selected from, for example, ethylene diisocyanate, hexamethylene dliaocyanatn, octomothylene diiBocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene 5 diisocyanate, 2, 4 , 4, - trimethylhexamethylene diisorryfinnto, 1,6, ll-undecanetriisocyanate, 1,3, 6-hexamethyletie triisocyanate, 1, B-di isocyanato-4- (isocyanatomethyl ) octane, 2,5,7-trimethyl-l,8-diisocyanato-5-(isocyanatomethyl)octane, bis(isocyanatoethyl)-carbonate, bis(isocyanatoethyl)ether, 2- 10 isocyanatopropyl-2 , 6-diisocyanatohexanoate, lysinedi. i pocyanafe methyl ester and lysinetriisocyanate methyl estet. In an embodiment of the present invention, I?, of general formula II is a recidue of a cyclualiphatic polyisocyanate. Examples of cycloaliphatic polyisocyanates of which R, may be a 15 residue include, but are not; limited to, isophorone • diisocyanate, cyclohexnnc di i ru-icynnate, tnethylcyc) ohexano diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexy])methane, bin(inocyanatocyclohoxyl)-2,2-propane, bis(isocyanatocyclohexyl)-1,2-ethane, 2- 20 isocyanatoinethyl-3" (3 -isocyanatopropyl) -5-isocyanatomethy.l -bicyclo[2.2.1]-heptane, 2-i socyanatomethyi-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1)-heptane, 2 -isocyanatomethyl- 2 -(3 -isocyanatopropyl)- 5-isocyanatomethyl-bicyclo12.2.1]-heptane, 2-isocyanatomethyl-2-(3- 25 isocyanatopropyl)-G-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo 12.2.1)-heptnnr? and 2 - igocynnatomothyl ■ ■?.■ (3 i . 30 isocyanatoethyl)-bicyclo[2.2.1)-heptane. In a preferred embodiment, of the present invention, R, ia a residue of a cycloalphatic diisocyanate selected from, lor example, isophorone diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, bis(isocyanatocyclohexyl)-2,2-propane, bis(isocyanatocyclohexyl)-1,2-ethane, and 5 mixtures thereof. When R3 is a residue of a diisocyanate, such as a cycloaliphatic diisocyanate, j of general formula II is 2. Classes of polyamines of which R2 may be a residue, include, aromatic polyamines, aliphatic polyamines, 10 cycloaliphatic polyamines, each having at least two primary amineE, and mixtures thereof. As is known to the skilled artisan, polyisocyanates are typically prepared from the corresponding polyamine precursors having two or more primary amine groups. Accordingly, specific examples of polyamines 15 within these recited classes include, but are not limited to, .polynmine precursors corresponding to those pol yi ruxrynii.iler: With further reference to general formula II, R, is a residue of a material having a single hydroxy group and one or 20 more allyl groups. The mono-hydroxy functional material of which R, is a residue is frnn of ncryloyl groups ant) methacryloyl groups. The allyl group may be an unsubstituted allyl group or a substituted allyl group, as represented by the following general formula III, 25 III H?C=C(R,) ~CH,-wherein R, is hydrogen, halogen or a ct to C, alkyl group. More typically, R, is hydrogen and consequently general formula III represents the unsubstituted allyl group, H2C=CH-CHS- . More 30 specifically, the ally! group of the material liavinq a sinqle hydroxy group, of which R2 is a residue, may be an allyl ether, an allyl carbonate or an allyl enter group. The material of which R, in n residue typically ban nt least one allyl et.hor group. The mono-hydroxy functional material of which K, is a residue may be selected from aromatic alcohols, aliphatic 5 alcohols, cycloaliphatic alcohols, poly(alkylene glycols), each having at least one allyl group, and combinations thereof. Examples of aromatic alcoholn having at leant: one allyl group include, but are not limited to, allyloxy phenol, e.g., 4-allyloxy phenol, allyloxybenzyl alcohol, e.g., 4- 10 allyloxybenzyl alcohol, and 4 -all yl. -2 , C, -dimethoxyphenol . Cycloaliphatic alcohols having at least one allyl group of which R, may be a residue include, for example, allyloxymethyl cyclohexylmethanols, e.g., 4-allyloxymethyl cyclohexylmethanol. 15 Examples of aliphatic alcohols having at least one allyl group, of which R, may be a residue include, but are. not limited to, allyl alcohol, substituted allyl alcohols, e.g., methallyl alcohol, allyl ethers of alkylene glycols, e.g., C, C4 alkylene glycols, sxich as, ethylene glycol allyl ether and 20 1,2- or 1,3-propylene glycol allyl ether. A preferred clacs of aliphatic alcohols, of which R, may be a residue, are poly(allyl ethers) of aliphatic polyols, e.g., trimethylol propane di(allyl ether), trimethylol ethane di(allyl ether), pentaerythritol tri(allyl ether), and'di-trimethylolprcpane 25 tri(allyl ether). Poly(alkylene glycols) of which R5 may be a residue include, for example, homopolymeric, block copolymeric, e.g., diblock and triblock copolymeric, and random copolymeric poly(alkylene glycols), such as poly(Ca-C4 alkylene glycols), 30 having a single allyl ether group and a single hydroxy group. Examples of poly(alkylene glycol) allyl ethers of which R, may be a residue include, for example, poly(ethylene glycol) allyl ether, poly(1,2-propylene glycol) allyl ether, poly(l.,2- butylene glycol) ally! ether, poly(ethylene glycol)-b- poly(1,2-propylene glycol) allyl ether, poly(1,2-propylene glycol)-b-poly(ethylene glycol) allyl ether, poly(ethylene glycol)-b-poly(l,2-butylenc glycol) allyl ether and poly(ethylene glycol)-b-poly(1,2-propylene glycol)-b-poly(1,2- butylene) allyl ether. The poly(alkylene glycol) allyl ethers of which R, may be a residue have at least 2 alkylene ether units. For example, diethylene glycol allyl ether has two (2) ethylene ether units, i.e., H,C=CHCH30- (-CH,CH,-0 -) a-H . Typically, the poly(alkylene glycol) allyl ether has less than 100 alkylene ether units, e.g., less than 50, less than 20 or less than 15 alkylene ether units. The poly(alkylene glycol) ally] ether may have a number of alkylene ether units ranging between any combination of these values, inclusive of the recited values, e.g., from 2 to 100, 2 to 50, 2 to 20 or 2 to 15 alkylene ether units. In an embodiment of the present invention, the material of which R3 is a residue is selected from a C3-C, alkylene glycol allyl ether, a poly(C2-C4 alkylene glycol) allyl ether, trimethylol propane di(allyl ether), trimethylol ethane di(allyl ether), pentaerythritol tri(allyl ether), di-trimethylolpropane tri(allyl ether) and mixtures thereof. In a preferred embodiment of the present invention, thr; material of which R3 is a residue is selected from poly(ethylene glycol) allyl ether, poly(1,2-propylene glycol) allyl ether and mixtures thereof. The polymerizable organic composition of the prenont invention includes also a radically polymerizable first monomer as described above with reference to general formula I, which may be further described as a polyol(allyl caibonate) monomer. Polyol(allyl carbonate) monomers that mny be nned in the aforedescribed polymcrizablo organic composition arc ally! carbonates of, for example, linear or branched aliphatic polyoln, o.g., aliphatic glycol bis(allyl carbonate) compounds, and cycloaliphatic polyols. The scope of the 5 present invention also includes allyl carbonates of aromatic polyols, e.g., 4,4'-isopropylidenediphenol bis(allyl carbonate). These monomers may further be described as unsaturated polycarbonates of polyols, e.g., glycoln. The polyol(allyl carbonate) monomer may be prepared by procedures 10 well known in the art, e.g., as described in U.S. Patents 2,370,567 and 2,403,113. In reference to general formula I, ^ is an allyl group, which may be described with reference to general formula II]. The allyl group Rr of general formula I may be substituted at 15 the 2-position with a halogen, most notably chlorine or bromine, or an alkyl group containing from 1 or 4, e.y., 1 to \ 2, carbon atoms, .in which case Ui is a substituted allyl group. More commonly, and with reference to general formula III, Rt is hydrogen and consequently R, of general formula I is the 20 unsubstituted allyl group, H2C=CH-CH3- . W1 r.h reference to general formula I, R in n polyvalent residue of a polyol, which can, for example, be an aliphatic or cycloaliphatic polyol, containing 2, 3 or 4 hydroxy groups. Typically, the polyol c ontains 2 hydroxy groups, i.e. , a 25 glycol. When the polyol is an aliphatic polyol, it may bo linear or branched and contain from 2 to 10 carbon atoms. Commonly, the aliphatic polyol is an alkylene glycol having from 2 to 4 carbons atoms, e.g., ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, or a 30 poly(Cj-0, alkylene glycol), e.g., diethylene glycol, triethylene glycol, etc. Specific examples of polyol(allyl carbonate) monomers that may be used in the present invention include, but are not limited to, ethylene glycol bis(2-chloroallyl carbonate), ethylene glycol blfHallyl cailiun.iln), diethylene glycol bla{2-mcthyln11yl nnrnonntn), dlfl liylni" IJ I yrnt lil«(nMyl carbonate), triethylene glycol bla(allyl carbonate), propylene 5 glycol bis(2-ethylallyl carbonate), l,3-propanediol bis(allyl carbonate), j1,3-butanediol bis(allyl carbonate), 1,4 butanediol bis(2-bromoallyl carbonate), dipropylene glycol bis(allyl carbonate), trimethylene glycol bis (2-ethylallyl carbonate), pentamethyleue glycol bis(allyl carbonate), 1,4- 10 cyclohexanediol bis(allyl carbonate) and 4,4'- isopropylidenebiscyclohexanol bis(allyl carbonate). A preferred polyol(allyl carbonate) monomer in the composition of the present invention is diethylene glycol bis(allyl carbonate). Commercially available examples of 15 diethylene glycol bis (allyl carbonate) monomers include CIJ-391" monomer and HIGH ADC CR-3 9* monomer, Chemical Abstracts (CAS) \No. 142-22-3, available from PPG Industries, Inc. A detailed description of polyol(allyl carbonate) monomers that may be used in the polyinerizable organic 20 compositions of the present invention may be found in U.S. Patent No. 4,637,698 at column 3, linn 13 through column '>, line 61. That disclosure is hereby incorporated by reference, and is summarized above. As used in the present- description with reference to the 25 radically polyinerizable monomer represented by general formula I, the term "polyol(allyl carbonate) monomer" and like names, e.g., diethylene glycol bis(allyl carbonate), is intended to mean and include the named monomers or prepolytners thereof and any related monomer or oligomer species contained therein. 30 TlKi polyol(allyl carbonate) monomer is present in the polymerizabie composition of the present invention in a wnjor amount, e.g., from 51 percent by weight to 99.9 percent by-weight, based on the total weight of the polymeriznhln composition. Typically, the polyol (al.ly.1 carbonate) monomer is present in the polymerizablo composition of the prencnt invention in an amount of at least 90 percent by weight, preferably at least 95 percent by weight, and more preferably 5 at least 97 percent by weight, based on the total weight of the polymerizable composition. Also, the polyol(allyl carbonate) monomer is typically present in the composition in an amount of not greater than 9 9.9 percent by weight, preferably not greater than 99.8 percent by weight, and more 10 preferably not greater than 99.7 percent by weight, based on the total weight of the polymerizable composition. The polyol(allyl carbonate) monomer may be present in the composition of the present invention in an amount ranging between any combination of these values, inclusive of the 15 recited values. Polymerization of the polymerizable composition of the present invention may be accomplished by adding to the composition an initiating amount of material capable of generating free radicals, such as organic peroxy compounds, 20 i.e., an initiator. Methods for polymerizing polyol(allyl carbonate) compositions are well known to the skilled artisan and any of those well known techniques may be used to polymerize the aforedescribed polymerizable compositions. Suitable examples of organic peroxy compounds, that may 25 be used as initiators include: peroxymonocarbonate esters, such as tertiarybutylperoxy isopropyl carbonate; peroxydicarbonate estertj, cuch as di(2-ethylhoxyl) peroxydicarbpnate, di(secondary butyl) peroxydicarbonate and Uiisopropylperoxydicarbonate; diacylpcroxidon, aurli an 2,1- 30 dichlorobenzoyl peroxide, isobutyryl peroxide, d«eanoyl peroxide, lauroyl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide; peroxyesters such as t-butylperoxy pivalate, t-butylperoxy octylate, and t-butylperoxyi nobutyrate,- rnethyJ.ethylker.one peroxide, acetylcyclohexane nulfonyl peroxide, and azobisisobutyronitrile. Preferred initiators are those that do not discolor the resulting polymerizate. A preferred initiator is diisopropyl peroxydicarbonate. The amount of initiator used to initiate and polymerize the polymerizable compositions of the present invention may vary and will depend on the particular initiator used. Only that amount that is required to initiate and cuntain the 10 polymerization reaction is required, i.e., an initiating amount. With respect to the preferred peroxy compound, diisopropyl peroxydicarbonate, typically between 2.0 and 5.0 parts of that initiator per 100 parts of the polymerizable organic composition (phm) may be used. More usually, between 15 2.5 and 4.0 phm is used to initiate the polymerization. The amount of initiator and the consequent cure cycle should be adequate to produce a polymerizate having a 15 second Barcol hardness of at least 1, preferably, at least 4, e.g., from 4 to 35. Typically, the cure cycle involves heating the 20 polymerizable organic composition in the presence of the initiator from room temperature to SS^C over a period of from 15 hours to 30 hours. Various conventional additives may be incorporated into the polymerizable composition of the present invention. Such 25 conventional additives may include light stabilizers, heat stabilizers, ultraviolet light abKoibers, mold release agents, > pigments and flexibilizing additives that are not radically polymerizable, e.g., alkoxylated phenol benzoates and poly(alkylene glycol) dibenzoates. Conventional additives arc 3 0 typically present in the compositions of the present invention in amounts totaling lens than 10 percent by weight, more typically less than 5 percent by weight, and commonly lens than 3 percent by weight, based on the total weight of the polymerizable composition. Polymerizates obtained from polymerization of polymerizable organic compositions of the present invention 5 will be solid, transparent and substantially free of tinting delects. Solid aiLlcleu Uml may be prepared liom t IK-polymerizable compositions of the present invention include, but are not limited to, optical lenses, such as piano and ophthalmic lenses, sun lenses or sunglasses, windows, 10 automotive transparencies, e.g., windshields, sidelights and backlights, and aircraft transparencies, etc. The present invention is more particularly described in the following examples, which are intended to be illustrative only, since numerous modifications and variations therein will 15 be apparent to those skilled in the art. Unless otherwise i i specified, all parts and percentages are by weight. Casting Composition Examples The following summarizes polymerizable casting 20 compositions that are comparative and compositions that are in accordance with the present invention. Casting composition A is a comparative composition, and Casting compositions R and C represent compositions according to the present invention. CantIng 0,'nnipori 11 ions Ingredients CR-3 9 diisopropyl peroxydicarbonate (b) Second monomer (c) Second monomer (d) Casting Composition A Casting Composition 8 Canting Compos it ion C 100 .0 99.0 99 .0 7 .G 3 . 0 3 . 2 0 1. 0 0 1 . 0 5 (a) CR-39® diethylene. glycol bis(allyl carbonate) monomer available commercially from PPG Industries, Inc. (b) In each of casting compositions B and C, the level of diisopropyl peroxydicarbonate initiator was adjusted such that 10 'tinted polymerizates obtained from thsse compositions had substantially the same percent transmission as tinted polymerizates obtained (under the same tinting conditions) from composition A, e.g., having about 35 percent transmission. The percent transmittance was determined using 15 a HunterLab Model ColorQuest II colorimeter employing the ClE Tristimulus XYZ scale, illuminant n6r. and 10°C observer. (c) Diallyl urethane monomer obtained from Sartomer Company, Inc. and having the designation NTX-4434. i 20 I (d) Tetraallyl urethnnn monomer obtained itom Salt Company, Inc. and having the designation NTX-44 ,3'J. Cast Lena Examples The casting compositions A - C were each mixed at room temperature and injected separately into glass lens molds used to prepare circular lenses having a +5 diopter and an outer rim diameter of 6.5 cm. Twenty (20) lens molds were filled at; a time and their contents polymerized using the same cuie cycle. The cure cycle used involved heating the molds in an electric forced air oven in stages from 48 °C to 85 °C over a period of 18 hours, followed by cooling to and holding at 60°C until demolding of the lenses. The cast lenses were then tinted by imbibing them with a black dye. An aqueous tinting solution of 1 part BPl" Molecular Catalytic™ Black Dye, commercially available from Brain Power Incorporated, and 10 parts deionized water was heated to and held at a temperature of 94°C - 95°C. The lenses cast from casting compositions A - C were fully immersed in the heated dye solution for a period of 5 minutes, after which they were thoroughly rinsed with deionized water. The tinted lenses were evaluated for tinting defects, the reBulte of which are summarized in Table 1. TAMI..K 1 Evaluation of TinLud Lenooa 5 Te) The lenses were evaluated for tinting defects by means of visual naked eye inspection. Tinting defects were observed as having a lighter colored vein or fern-like appearance relative to the rest of the tinted lens. 10 (f) 100 x (the number of tinted lenses observed to have tinting defects / the number of tinted lenses evaluated). example, vdth casting composition h: 100 x (57/228) - 25 percent (%). For 15 The results summarized in Table l show that articles, e.g., lenses, ca3t from polymerizable compositions according to the present invention, such as Compositions B and C, have fewer tinting defects than lenses cast from comparative compositions, such as Composition A. 20 The present invention has been described with reference to specific details of particular embodiments thereof. It is not intended that such details be regarded as limitations upon the scope of the invention except insofar as and to the extent that they are included in the accompanying claims. 25 WE CLAIM: 1. A process of making a polymerizable composition comprising: mixing (a) a major amount of a radically polymerizable first monomer represented by the following general formula, wherein R is a polyvalent residue of a polyol having at least two hydroxy groups, Ri, is an allyl group, and i is a whole number from 2 to 4; and (b) a minor amount of a radically polymerizable second monomer represented by the following general formula, wherein R2, is a polyvalent linking group that is free of urethane linkages; R3 is a residue of a material having a single hydroxy group and at least one allyl group, R3 being free of urethane linkages; and j is a number from 2 to 4. 2. A process of making a polymerizable composition of claim 1 wherein second monomer (b) is present in said composition in an amount at least sufficient such that a polymerizate of said composition is substantially free of tinting defects. 3. A process of making a polymerizable composition of claim 2 wherein said second monomer (b) is present in said composition in an amount of from 0.1 percent by weight to 10 percent by weight, based on the total weight of said polymerizable composition. 4. A process of making a polymerizable composition of claim 1 wherein R2 is a residue of a polyisocyanate selected from aromatic polyisocyanates, aliphatic polyisocyanates, cycloaliphatic polyisocyanates and mixtures thereof; and the material of which R3 is a residue is selected from, aromatic alcohols, aliphatic alcohols, cycloaliphatic alcohols, poly (alkylene glycols), each having at least one allyl group, and mixtures thereof. 5. A process of making a polymerizable composition of claim 4 wherein R2 is a residue of a cycloaliphatic diisocyanate selected from isophorone diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, bis (isocyanatomethyl) cyclohexane, bis (isocyanatocyclohexyl) methane, bis (isocyanatocyclohexyl)- 2,2-propane, bis (isocyanatocyclohexyl)-l,2-ethane, and mixtures thereof, and j is 2. 6. A process of making a polymerizable composition of claim 4 wherein the material of which R3 is a residue is selected from C2-C4 alkylene glycol allyl ether, poly (C2-C4 alkylene glycol) allyl ether, trimethylol propane di (allyl ether), trimethylol ethane di (allyl ether), pentaerythritol tri (allyl ether), di- trimethylolpropane tri (allyl ether) and mixtures thereof. 7. A process of making a polymerizable composition of claim 6 wherein the material of which R3, is a residue is selected from poly (ethylene glycol) allyl ether, poly (1, 2-propylene glycol) allyl ether and mixtures thereof. 8. A process of making a polymerizable composition of claim 1 wherein R is a residue of a poly (C2-C4 alkylene glycol), and i is 2. 9. A process of making a polymerizable composition of claim 8 wherein R is a residue of diethylene glycol. Dated this 14th day of June, 2002. HIRAL CHANDRAKANT JOSHI AGENT FOR PPG INDUSTRIES OHIO, INC.

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in-pct-2002-00802-mum-cancelled pages(22-01-2005).pdf

in-pct-2002-00802-mum-claims(granted)-(22-01-2005).doc

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