Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/38—Esters containing sulfur
  • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements

Definitions

• the present invention relates to polymerizabie compositions that include ethy!enicaily unsaturated monomers having episulfide functional groups such as ⁇ -epithiopropy! functional groups in the monomer, and to methods of reducing the yellowness index of a sulfur-containing poiymerizate prepared by addition polymerization.
• Polymeric materials such as plastics
• plastics have been developed as alternatives and replacements for silica based inorganic glass in applications such as, optical lenses, fiber optics, windows and automotive, nautical and aviation transparencies.
• These polymeric materiais can provide advantages relative to glass, including, shatter resistance, lighter weight for a given application, ease of molding and ease of dyeing.
• Representative examples of such polymeric materiais include, poiy(methyi methacrylate), polycarbonate and poly(diethylene glycol bis(al!ylcarbonate)).
• the refractive indices of many polymeric materiais are generally lower than that of high index glass.
• the refractive index of poly(diethy!ene glycol bis(allylcarbonate)) is about 1.50, compared to that of high index glass, which can range, for example, from 1.60 to 180.
• Polymeric materials (polymerizates) prepared from the polymerization of monomers containing aromatic rings and/or sulfur typically have high refractive indices.
• Polymeric materials having a combination of high refractive indices, such as at least 1.57, and low ieve!s of chromatic dispersion can be prepared from monomers containing certain heteroatoms, such as sulfur atoms.
• Such polymerizates are very useful in the making of optical elements requiring superior optical properties.
• yellowing is often a problem in polymerizates that contain sulfur.
• polymerization initiators that are conventionally used in such compositions can have safety risks associated with them. For example, peroxides are ignitable and present explosion hazards. Certain initiators, including peroxides and azo initiators, can generate gases during polymerization, causing safety concerns and potentially affecting the appearance of the final polymerizaie product.
• a polymerizable composition comprising, (a) a monomer composition comprising at least one ethytenically unsaturated monomer having a ⁇ -epithiopropy! functional group; (b) optionally, a compound having two or more ⁇ -epithiopropyf functional groups but no polymerizable ethyienicaliy unsaturated groups; (c) an isourea functional polymerization initiator; and (d) a catalyst that effects reaction between the ⁇ -epithiopropy! functional groups.
• a method of reducing the yellowness index of a sulfur-containing poiymerlzate prepared by addition polymerization comprises reacting in the presence of an isourea functional polymerization initiator and a catalyst that effects reaction between ⁇ -epithiopropyl functional groups, a polymerizable composition comprising: (a) a monomer composition comprising at least one ethylenica ' fly unsaturated monomer having a ⁇ -epithiopropyl functional group; and, optionally, (b) a compound having two or more ⁇ -ep!thiopropyl functional groups but no polymerizable ethylenica!iy unsaturated groups,
• molecular weight values of polymers such as weight average molecular weights (Mw) and number average molecular weights (Mn), are determined by gel permeation chromatography using polystyrene standards.
• po!ydispersity index (PDI) values represent a ratio of the weight average molecular weight (fvw) to the number average molecular weight (Mn) of the polymer (i.e., Mw/Mn).
• polymer means homopolymers (e.g., prepared from a single monomer species), and copolymers (e.g., prepared from at least two monomer species ⁇ .
• (meth)acrySate and similar terms, such as (meth)acryloyi and (meth)acrylic acid ester, means methacrylate and acrylate, Either or both may be present In a composition.
• thio ⁇ meth)acryia ⁇ e° and similar terms such as thto(me ⁇ h)acryloyl and thio ⁇ rneth)acrylic acid ester, means thiomethacryiate and thioacryiate, as above.
• linear or branched groups such as linear or branched a!kyi
• linear or branched a!kyi are understood to include: a methylene group or a methyl group; groups thai are linear, such as linear C 2 -C 25 alky] groups; and groups that are appropriately branched, such as branched C 3 -C 25 alkyi groups.
• halo and similar terms, such as haio group, halogen, halogen group, halide, and ftalide group means F, CI, Br and/or I, such as f!uoro, chioro, bromo and/or iodo.
• the polymerizabie compositions of the present invention include (a) a monomer composition comprising at least one ethylenicaf!y unsaturated monomer having a ⁇ - epithiopropyl functional group.
• the monomer composition (a) may comprise a compound having one or more (meth)acryloyl, aliyl, and/or vinyl groups and one or more ⁇ - epithiop-ropyi functional groups in a molecule. Mixtures of such compounds may also be used.
• Suitable monomers include, but are not limited to, thioglycidy!rrtethacryiate (2,3-epithiopropyf methacrylate), ally!thsogiycidyi ether, and the Sike.
• the ethyienicafly unsaturated monomer having a ⁇ -epithiopropyl functional group may be prepared ahead of time and added to the poiymerizable composition, or alternatively may be prepared within the polymenzable composition from "precursor" reactants present in the polymenzable composition.
• thiog!ycidylmethacryiate may be formed within the poiymerizable composition as a reaction product of a reaction composition comprising g!ycidy! methacrylate and thiourea.
• the ethylenically unsaturated monomer having a ⁇ -epithlopropyi functional group may constitute up to 100 percent by weight of the monomer composition (a), based on the total weight of resin solids in the monomer composition.
• the monomer may be present In an amount ranging from 5 to 100 percent by weight, such as from 25 to 100 percent by weight, or from 25 to 85 percent by weight, or from 25 to 80 percent by weight
• the monomer composition (a) may further comprise at least one different poiymerizable ethylenically unsaturated monomer.
• Ethylenically unsaturated groups include (rneth)acryioyl, ally!, and/or vinyl groups.
• Useful alky! esters of acrylic acid or methacryiic acid include aliphatic alkyl esters containing from 1 to 30, and preferably 4 to 18 carbon atoms in the alkyl group, which may be miiear, branched, cyclic, and/or substituted.
• Representative alkyl groups include but are not limited to methyl, ethyl, propyl, isopropyi, butyl, isobutyl, sec-butyl, tert-butyi pentyi, neopentyf, hexyl, heptyl, octyi, nonyl, decyi, and structural Isomers thereof.
• Representative cycloalkyi groups include but are not limited to cyciopropyl, cyclobutyi, cyciopentyf, cyciohexyl, and cyclooetyl substituents.
• Representative po!y-fused-ring cycloalkyi groups include but are not limited to decahydronaphthalenyi, tetradecahydroanthraceny), and tetradecahydrophenanthrenyl.
• Representative polycycllcaikyl groups include but are not limited to, bicycio[2.2.1]heptanyl (norbornyl), and bicydo[2.2.2]octanyl.
• Representative heterocydoalkyl groups include but are not limited to tetrahydrofuranyl, ietrahydropyranyi and piperidiny!, including but not limited to piperidin-4-yi
• Representative pofycyciicheterocycloaikyf groups include but are not limited to, 7-fhiabicyclo[2.2.1]heptanyi, ljheptanyl, and 7 ⁇ azabicyclo[2.2,1]heptanyL
• Representative aralkyl groups include but are not limited to benzyl, and phenethyl.
• Examples of monomers having a single ethylenically unsaturated radically poiymerizable group that can be present, in the monomer composition (a) of the poiymerizable compositions of the present invention include, but are not limited to: acrylic acid; methacrylic acid; esters of acrylic acid such as methyl or ethyl acryiate and 2-hydroxyethy! acryiate; esters of methacrylic acid, such as methyl or ethyl methacrylate, phenoxyethy! methacrylate, isobomyl methacrylate, cyciohexyl methacrylate and 2-hydroxyethy I mefhacryiate; ally!
• the monoethylenieaHy unsaturated monomers include methyl methacrylate, isobornyl methacrylate, phenoxyethyl methacrylate, cyc!ohexyl methacryiafe. styrene and mixtures, thereof.
• Monomers having more than one ethylenicaily unsaturated group, such as divinyi benzene, may also be used in the monomer composition (a).
• the ethylenicaily unsaturated monomer(s), when used, can be present in an amount of from 1 percent by weigh! to 60 percent by weight, based on the total monomer weight of the polymerizable composition, such as from 3 percent by weight to 55 percent by weight, or from 20 to 45 percent by weight, based on the total monomer weight of the polymerizable composition.
• the monomer composition (a) can be present In the polymerizable composition of the present invention in an amount ranging from 5 to 100 percent by weight, such as from 25 to 100 percent by weight, or from 25 to 75 percent by weight, or from 50 to 60 percent by weight based on the total weight of resin solids in the polymerizable composition.
• the polymerizable compositions of the present invention can further include a compound (b) having two or more ⁇ -epithtopropyl functional groups but no polymerizable ethylenicaily unsaturated groups.
• a compound (b) having two or more ⁇ -epithtopropyl functional groups but no polymerizable ethylenicaily unsaturated groups examples include bis(
• the compound (b) may be prepared ahead of time and added to the polymerizable composition, or alternatively may be prepared within the polymerizable composition from "precursor" reactants present in the polymerizable composition.
• bts(p-epithiopropyloxyphenyi)propane may be formed within the polymerizable composition as a reaction product of a reaction composition comprising 2,2- bis(4 ⁇ giycidyioxyphenyi)propane and thiourea.
• the 2,2-bis(4-glycidyloxyphenyi ⁇ propane may be formed as a reaction product of a reaction composition comprising 2,2 ⁇ .bis ⁇ 4- hydroxyphenyi)propane (Bisphenoi A) and epichlorohydrin.
• the compound (b) can be present in the polymerizable composition of the present invention in an amount of 0.5 to 75 percent by weight, such as 25 to 55 percent by weight, or 30 to 55 percent by weight, based on the total weight of resin solids in the polymerizable composition.
• the weight ratio of the monomer composition (a) to the compound (b) in the polymerizable compositions of the present invention may range from 1 :3 to 3:1.
• the ratio of (a) to (b) generally is 3:2.
• the poiymerizable compositions of the present invention further include an isourea functional polymerization initiator (c) that is capable of initiating free radical polymerization of and amongst the ethylenicalfy unsaturated groups of the monomers.
• an initiator is thermally activated.
• thermally activated means the free radical initiator becomes active at elevated temperature, such as at temperatures greater than ambient room temperature, such as greater than 25° C, as will be described In further detail herein.
• the thermally activated free radical initiator can be selected from O-imino-isourea compounds, O-dialkyiamino-isourea compounds, and combinations thereof.
• Suitable O- dialkylamsno-isourea compounds are disclosed in WO 2010/079102 A1, incorporated herein by reference in its entirety.
• Such O-diaikylamino-isoureas compounds have the general formula I:
• R 100 and R 101 are each independently of one another C C 20 alkyl or C 6 -C 10 aryi; or R f oo and 101 form together a mono or poiycyclic heterocyclic ring, said heterocyclic ring optionally contains further heteroatoms O, S, N and P; 10 2 and R 10 3 are Independently Ci- C ig alky), C 6 -Ci 2 cyc!oalkyi, C 3 -Ci 0 aryl, C 7 -C 10 araikyl, (CH 3 ) 3 Si- , said C1-C19 alkyl, C 5 -Ci 2 cycloaikyi, C 6 -C 1a aryi, C- C 10 araikyl group is optionally interrupted by O or N atoms or substituted by C1 -C19 alkyl groups or substituted by N containing groups selected from C- r Ci9 aikyiamino, bis(C r C 1g alkyl )
• the structure of (I) can be such (e.g. dimeric, trimeric, oligomeric or polymeric) that the molecule (I) contains the isourea fragment more than once, for example 2 to 10 times.
• Suitable O-imino-isourea compounds are disdosed in WO 2010/128062 A1 , incorporated herein by reference in its entirety, Such O-imino-isourea compounds have the general formula II:
• n 1 , 2, 3 or 4,
• R 200 and f3 ⁇ 4oi are independently H, C 8 alkyl, C3-C 12 cycioaikyi, C 6 -Ci 4 aryf, Ct-C 14 heteroaryi, C7-C15 aralkyi, C 2 -C 14 heteroaraikyl, cyano, or R 20 o and R 2 o font! together with the carbon to which they are attached a mono or poiycyciic C3-C1 8 carbocycfic or CT-C-JS heterocyclic ring;
• R202 and R203 are independently C r C 18 alkyl, C3-C1 2 cycioa!kyl, C 6 -Ci 4 ary!, C 6 -C 14 aryl once or more than once substituted by C C e aikyi; C 7 --C 15 aralkyi, f CH 3 ) 3 Si-; or R 202 and R 2 03 are Ci-C 18 alkyi, C3-C 12 cycioaikyi, Ce-C ⁇ aryi, C 7 ⁇ C 15 aralkyi or
• R 202 and R203 are C C1 ⁇ 2 aikyl, C3-C 12 cycioaikyi which are interrupted or substituted by O or by containing groups selected from Ci-Ci 8 alkyiamino, bis(CrC 58 aikyl)amino or trisiC Cn aikyi)ammonium;
• R204 if n is 1 is H, C C 13 - alkyl, C3-C12 cycioaikyi, C C 14 aralkyi, C 6 ⁇ G 14 aryl or acyl selected from the group consisting of the following acyls
• alkenyl-C 6 -Ci 4 aryl, aikyi, - C ⁇ 0)-NH-C 6 -C aryl and -C ⁇ O)- ⁇ C r C 18 alky1) 2 ; or
• R204 if n is more than 1 is dl-, tri-, tetra-C-i-C-lsalkylidene, diacyis, triacyis or ietraacyls and salts thereof.
• rings R are: pyrrolidine, piperidine, rnorphoiine, piperazine, N-methyl-piperazine, hexamethyleneimine.
• the structure of (11) can be such (e.g. dimeric, trimeric, oligomeric or polymeric) that the molecule (If) contains the isourea fragment more than once, for example 2 to 10 times.
• Preferred is a monomeric structure (n is 1 ); a dimeric structure (n« 2), or a trimeric structure n ⁇ 3.
• the isourea functional polymerization initiator is present an amount at least sufficient to initiate polymerization of the components in the monomer composition (a). Typically, only that amount that is required to initiate and sustain the polymerization reactson is required, which can be referred to as an "initiating amount”. With some embodiments, the initiator is present in an amount of from 0,01 and ? parts of Initiator, or from 0.1 to 3.5 parts initiator, or from 0.5 to 2.5 parts initiator, in each case the parts initiator being per 100 parts of monomer(s) (phm) present in the po!yrnerlzab!e composition.
• the pofymerizabie compositions of the present invention further include a catalyst (d) that effects or promotes reaction between the ⁇ -epithiopropyl functional groups.
• the catalyst is present in an amount at least sufficient to effect reaction among the ⁇ - epithiopropyi functional groups in the polymerizable composition, such that the ⁇ - epithiopropyl functional groups react with each other in a chemical reaction, such as a polymerization reaction,
• Suitable catalysts for use as the catalyst (d) can include, but are not limited to, one or more of: phosphines; quaternary phosphonium saits; 1 ,4 ⁇ diazabicycio[2.2.2]ocfane, also known as 1 ,4-diazabicyclo[2.2.2]octane or triethylenediamine; other amine catalysts such as amines having a heterocyclic ring; quaternary ammonium salts; tertiary sulfonium salts; secondary sodonium salts; boron trihaiides and complexes thereof; organic acids and esters thereof; and metal halides.
• Non-limiting examples of suitable amines having a heterocyclic ring can include imidazoles such as imidazole, N-methyiimidazole, N-methyl-2-mercaptoimidazole, 2- methylimidazole, 4-methylirmdazole., N-eihyiimidazo!e, 2-ethylimidazole, 4-ethylimidazoie, N- butylimidazole, 2-butylimidazoie, N-undecylimidazoie, 2-undecyllmidazole, N- phenyiimidazoie, 2-pheny!imidazoie, N-benzylirnidazole, 2-benzylimidazole, 1-benzyl-2- methylimidazole, N-(2'-cyanoethy!-2-methyJlmidazo!e, N-(2'-cyanoethyl)-2-undecylimi
• Suitable phosphines can include
• iricyc!ohexylphosphine trioctylphosphine, triphenylphosphine, tribenzylphosphine, tris(2- methy!pheny!phosphine, iris ⁇ 3-methy!phenyi)phosphine, tris ⁇ 4-methylpheny!phosphine, iris(diethytamino ⁇ phosphine, dimethyipheny!phosphine, diethyiphenylphosphine,
• Suitable non-iimiting examples of quaternary ammonium salts that may be used as a catalyst can include tetramethyfammoniumchloride, tetramethy!ammontumbromide, tetramethyiammoniumacetate, tetraethyiammonlumchloride, tetraethyiammonlumbromide, tetraethylammoniumacetate, tetra-n-butyiammoniumfluoride, tetra-n ⁇
• butyiammoniumchloride tetra-n-butylammoniumbromide, tetra-n-birtylammoniumiodide, tetra-n-butylammoniumacetate, tetra-n-butylammoniumborohydride, tetra-n- butylammoniumhexafluorophosphite, tetra-n butyiammoniumhydrogensuiphite, tetra-n- butyiammoniumtetrafluoroborate, tetra-n-butyfammonlumtetraphenylborate, tetra-n- butyiamrnoniumparaioiuenesuifonate, tetra-n-hexylammoniumchloride., tetra-n- hexylammoniumbromide, tetra-n-hexylammoriiurnacetate, ietra-
• triethy!benzylammoniumchioride trieihylbenzylammoniumbromide, tri-n-butyl-n- octylammoniumchloride, tri-n-butylbenzylammoniumfluoride, iri-n- buiylbenzy!ammontumcriionde, tri-n-butylbenzylammoniumbromide, tri-n- butyibenzylammonium iodide, methyl triphenylammoniumchloride,
• ethyitriphenylammoniumbromide n-butyliriphenylammonitimchloride, n- butyltriphenylammoniumbromide, 1 -methyipyridiniumbromide, 1 -ethylpyridinlumbromide, 1 - n-butyfpyridiniumbromide, l-n-hexylpyridiniumbromide, 1-n-octylpyridiniumbromide, 1 ⁇ n- dodecylpyridiniumbromide, 1 -phenyipyridiniumbromide, 1 -methylplcolinlumbromide, 1- eihylpicollniumbromide, i-n-buty!picoliniumbromide, 1-n-hexyiprcoliniumbromide, 1-n- octylptcoiiniumbromide, 1 -n-dodecylpicolini umbrom
• tetraethylphosphoniumchioride tetraethyiphosphoniumbromide, tetra-n- butylphosphoniurnch!oride, tetra-n-butylphospnoniumbromide, tetra-n- biftyiphosphoniumiodtde, tetra-n-hexylphosphoniumbromide, tetra-n- ociyiphosphoniumbromide, meihy!triphenylphosphoniumbromide,
• ethyitriphenylphosphoniumiodide n-buiyltriphenylphosphoniumbromide, n- butyltriphenylphosphoniumiodide, n-hexyitriphenyiphosphoniumbromrde, n- octyitriphenylphospboniumbromtde, teiraphenyiphosphoniumbromide,
• tertiary sulfonium salts include
• triphenylsulfontumbromide triphenylsulfoniumiodide, and the like.
• Suitable secondary iodonium salts can include dipheny!iodoniumchforide, diphenyliodoniumbromide, diphenyliodoniumiodide, and the like.
• boron trihaiides and complexes thereof can include boron irifluoride, boron trifluoride-ethyiether complex, boron trifiuoride-n-butylether complex, boron trifiuoride-pheno! complex, boron trifluoride-ethyiamine complex, boron trifluoride-ptperidine complex, boron irifluoride -acetic acid complex, boron trifluoride-triethanolamine. complex, boron trrfluoride-ammonia complex, and the like.
• Examples of catalytic organic acids and esters thereof can include sulfonic acid, carboxyiic acid, and esters thereof. Specific examples thereof include methanesulfonic acid, trifluoromethanesurfonic acid, benzenesulfonic acid, p-to!uenesulfonic acid, 10-cbamfer sulfonic acid, and methyls and ethylesters thereof.
• metal halides can include zinc chloride, iron chloride, aluminum chloride, tin chloride, titanium chloride, methy!aluminum dichloride, ethyis!uminum dichloride. dimethyla!urninurn chloride, and diethylaluminum chloride.
• the amount of catalyst (d) present in the poiymerizable composition is an amount sufficient to effect reaction between the ⁇ -epithiopropy! functional groups in the poiymerizable composition.
• the amount of the catalyst can range, for example, from 0.001 to 3% by weight, such as 0.005 to 2% by weight, based on the total weight of resin sol ds in the poiymerizable composition.
• the poiymerizable composition can be essentially free of inorganic compounds having sulfur and/or selenium atoms.
• essentially free of is meant that the composition does not contain these compounds in any essentia! amounts such that they would be available to participate in any chemical reactions to an appreciable (measurable) degree, if they are present at all, it is only in trace amounts.
• the thermal cure cycle used fo cure the poiymerizable compositions of the present invention generally involves heating the poiymerizable composition in the presence of the initiator at room temperature (e.g., 25°C) up to a temperature ranging from 50°C to 150 °C, over a period of from 2 hours to 48 hours, or from 55°C up to 90°C or 100°C over a period of from 12 fo 24 hours, or from 65°C up to 1 15°C or 125°C over a period of from 12 to 24 hours.
• room temperature e.g. 25°C
• a temperature ranging from 50°C to 150 °C over a period of from 2 hours to 48 hours, or from 55°C up to 90°C or 100°C over a period of from 12 fo 24 hours, or from 65°C up to 1 15°C or 125°C over a period of from 12 to 24 hours.
• Polymerization of the poiymerizable compositions of the present invention results in the formation of a polymerizate, which can be in the form of a shaped article.
• Polymerizates obtained from polymerization of the poiymerizable compositions of the present invention are solid, and with some embodiments, transparent.
• Transparent polymerizates prepared from the poiymerizable compositions of the present invention can be used in optical or ophthalmic applications, e.g., the polymerizates can be used to prepare Senses.
• the polymerizate Upon polymerization of the composition of the present invention and formation of a polymerizate, the polymerizate demonstrates reduced yellowing compared to a similar poiymerizable composition that does not contain an isourea functional polymerization initiator and a catalyst for reaction of ⁇ -epithiopropyi functional groups as described above.
• Polymerizates prepared using the composition of the present invention demonstrate significantly lower yellowness indices compared to similar poiymerizable compositions that are polymerized using conventional Initiators such as peroxides or azo compounds.
• the present Invention also provides a method of reducing the yellowness index of a sulfur-containing polymerizate prepared b addition polymerization, comprising reacting: (a) a monomer composition comprising at least one ethylenically unsaturated monomer having a ⁇ -epithiopropyl functional group; and, optionally, (b) a compound having two or more ⁇ - epithiopropyi functional groups but no poiymerizable ethylenically unsaturated groups in the presence of an isourea functional polymerization initiator and a catalyst to effect reaction between the B-epifhlopropyl functional groups.
• the ethylenically unsaturated monomer having a ⁇ -epithiopropyl functional group (a), and the compound (b) having two or more ⁇ - epithiopropyi functional groups but no po!ymerizab!e ethy!enicaily unsaturated groups, respectively, are any of those described previously.
• yellowness Index is measured in accordance with AST E313-1Q as described below in the Examples.
• an isourea functional polymerization initiator and catalyst as in the composition of the present invention can reduce gas evolution during polymerization as compared to conventional initiators such as peroxides. Ignition and combustion risks often associated with the use of peroxide initiators can be avoided with the use of isourea functional polymerization initiators and the catalysts as described above,
• Polymerizates prepared from the pa!ymerizabie compositions of the present invention typically have a refractive index of at least 1.57, or at least 1.58,. or at least 1 ,59; an ABBE number of at least 30, or at least 33, or at least 35; and a Fischer microhardness value of at least 50 N/mm 2 , or at least 70 N/mm 2 , or at least 90 N/mm 2 .
• po!ymerizates prepared from the polymerizable compositions of the present invention have an initial (zero second) Barcol hardness of at least 1, or at least 10, or at least 20.
• the refractive Index, ABBE number, and Fischer Hardness values can be determined in accordance with art-recognized methods.
• Refractive index values (n ⁇ 0 ) and ABBE numbers may be determined using a etricon Mode! 2010 Prism Coupler, Thin Film Thickness / Refractive Index Measurement System, in accordance with the manufacturer's Operation and Maintenance Guide; and Fischer Hardness values are determined in accordance with ISO 14577 using a Fischer Technologies H100C Microhardness Measurement System.
• Po!ymerizates prepared from the poiymerizable compositions of the present inventio can be used to form solid articles such as optica! element(s) or device(s).
• optic means pertaining to or associated with light and/or vision.
• the optical element or device can comprise ophthalmic elements and devices, display elements and devices, windows, mirrors, and/or active and passive liquid crystal ceil elements and devices.
• ophthalmic means pertaining to or associated with the eye and vision.
• Non-limiting examples of ophthalmic elements include corrective and non-corrective lenses, including single vision or multi-vision lenses, which may be either segmented or non-segmented multi-vision lenses (such as, but not limited to, bifocal lenses, trifocal lenses and progressive lenses), as well as other elements used to correct, protect, or enhance (cosmetically or otherwise) vision, including without limitation, contact lenses, Infra-ocular lenses, magnifying lenses, and protective lenses or visors.
• display means the visible or machine-readable representation of information in words, numbers, symbols, designs or drawings.
• Non-limiting examples of display elements and devices include screens, monitors, and security elements, such as security marks.
• window means an aperture adapted to permit the transmission of radiation there-through.
• windows include automotive and aircraft transparencies, filters, shutters, and optical switches.
• mirror means a surface that specularly reflects a large fraction of incident light.
• Example 1-6 and Comparative Examples (CE) 1-13 is described in Part 1.
• Part II describes the preparation of poiymerizate sheets of Examples 1-6 and CE 1 -7 and viscous liquid polymerizates of CE 8-13.
• Table 1 shows that Examples 1-6 demonstrated yellowness indexes that were lower than CE 1-7.
• Table 2 showed that the isourea functional initiators did not show the unexpected result of reduced yellowness when thiirane was not present in the monomer compositions of CE 9, 1 and"! 3 as compared to the peroxy functional initiators in the monomer compositions of CE 8, 0 and 12.
• Step B into a 20 ml giass scintillation vial was added 100 parts by weight of thiogiycidyi methacrylate which was filtered through a 0.45 pm syringe filter, 1 part N-methylirnidazoie and 1 part of the product of Step A.
• the components were mixed and/or placed in an ultrasonic bath at ambient temperature until a homogeneous solution was obtained.
• the mixture was injected into a glass sheet mold having a thickness of 3 mm and diameter appropriate for the amount injected.
• the mixture in the mold was cured by raising the temperature from 30°C to 1 10°C at a uniform rate over 22 hours in an oven, followed by cooling to 85°C at a uniform rate over 2 hours and demoiding.
• Step B of Example 1 The procedure from Step B of Example 1 was followed except that 1 part of tetrabutyiphosphonium bromide was used in place of 1 part of N-methyiimidazo!e and 1.5 parts of 1 ,3 ⁇ diisopropyl-0-(N-cyciohexy!ideneaniino)-isourea was used in place of 1.0 part.
• Step B of Example 1 The procedure from Step B of Example 1 was followed except that the following was used: 90 parts of filtered thiogiycidyi methacrylate, 10 parts of bis-(p- epithiopropyi)suifide, 1 part of boron trifluoride diethyl etherate and 1 part of 1,3 ⁇ diisopropyl- 0-(N-cyclohexylideneamino)-isourea,
• Example 4 The procedure from Example 3 was followed except that 1 part of TRIGONOX® 421 was used in place of 1 part of 1 ,3-diisopropyl-0 ⁇ (N-cycl0hexylldeneamino)-isourea.
• TRIGONOX® 421 1 part of TRIGONOX® 421 was used in place of 1 part of 1 ,3-diisopropyl-0 ⁇ (N-cycl0hexylldeneamino)-isourea.
• Example 4 The procedure from Example 4 was followed except that 1 part of TRIGONOX® 421 was used in place of 1 part of I jS-diisopropyl-O ⁇ -cydohexylideneaminoJ-isourea.
• Example 5 The procedure from Example 5 was followed except that 0.6 part of TRIGONOX® 421 was used in place of 1 part of 1 ,3-diisopropyl-0-(N-cyclohexy1ideneamino)-tsourea.
• Example 5 The procedure from Example 5 was followed except that 0.8 part of TRIGONOX® 421 was used in place of 1 pari of 1 ,3-difsopropyi-0-(N-cyclohexy(ideneamino)-isourea.
• Example 5 The procedure from Example 5 was followed except that 0.8 part of LUPERGX® 256 polymerization initiator, reported to be 2,5-dimeihyi-2 s 5-di ⁇ (2 ⁇ eihyihexanoylperoxy)hexane. was used in place of 1 part of 1 ,3-ditsopropyl-0 ⁇ N ⁇ cycfohexylideneamino)-isourea. Comparative Example 8 (CE-8)
• Polymerizate sheet samples of Examples 1-6 and CE 1-7 were tested for Fischer microhardness (FMH), refractive index and yellowness index and the results are reported in Table 1.
• the viscous liquid polymerizate samples of CE-8- 13 were tested for molecular weight and yellowness index and the results are reported in Table 2.
• Fischer microhardness was tested according to ISO 14577-07 and was measured using a F SCHERSCOPE® H-100S C available from Fischer Technology, Inc.
• the Fischer microhardness (FMH) of the po!ymerizates, ⁇ 3 Newtons/mm2 was measured at a load of 300 roiillNewion (mN), following a load application of 0-300 mN In 15 seconds.
• the results are an arithmetic average of 5 measurements.
• the yellowness index was measured using a HunterLab ULTRASCAN® PRO according to ASTM E313-10.
• the path length for the sheet samples of Examples 1-6 and CE 1-7 was equal to the sample thickness (3 mm) and the path length for the liquid samples of CE-8-13 was 2 cm.
• the viscous polymerizates of CE-8-13 were dissolved in teirahydrofuran and the weight average molecular weight (Mw) was determined by gel permeation chromatography, also referred to as size exclusion chromatography, using the appropriate polystyrene standards.

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