# US 5,352,757 A · Sulfur compounds and new polymers obtained from these sulfur compounds > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,352,757 A - Document ID: US5352757A - Status: Granted - Kind: A - Application number: 07/920,363 - Filed: 1992-09-16 - Granted: 1994-10-04 - Earliest claimed: 1990-12-14 - Assignees: Rhone-Poulenc Chimie - Inventors: Sylvie Lavault; Gerard Velleret - Web page: https://patentgrep.com/patent/US5352757A ## CPC - G02B 1/041: {Lenses} - C07C 323/52: the carbon skeleton being acyclic and saturated - C08G 18/3876: {containing mercapto groups} - G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS ## Abstract The present invention relates to new sulfur compounds which are polyol esters of mercaptocarboxylic acids. It also relates to the use of these sulfur esters for preparing polymers exhibiting a refractive index higher than 1.50. The manufacture of optical discs and of waveguides may be mentioned among the optical applications of these polymers. ## Claims ### Claim 1 Sulfur compounds of general formula (I): ##STR10## in which: R.sub.1 denotes a linear or branched alkylene radical containing 1 to 3 carbon atoms, A denotes a hydrocarbon residue of valency n, chosen from the radicals of formulae: ##STR11## n denotes 2, 3 or 5. ### Claim 2 (depends on 1) Compounds of formula (I) according to claim 1, characterized in that R.sub.1 denotes a methylene radical, an ethylene radical or an ethylidene radical. ### Claim 3 (depends on 1, 2) Compounds of formula (I) according to either claim 1 or 2, characterized in that they are 1,4-benzenedimethylene di(thioglycolate), 4,4'-thiodiphenylene-1,1'-oxyethyl di(thioglycolate), 1,1,1-tris(4-phenylene-1-oxyethyl)ethane tri(thioglycolate), 2,2,6,6-tetramethylenecyclohexyl penta(thioglycolate), 1,4-benzenedimethylene di(2-mercaptopropionate), 4,4'-thiophenylene-1,1'-oxyethyl di(2-mercaptopropionate), 1,1,1-tris-(4-phenylene-1-oxyethyl)ethane tri(2-mercaptopropionate) or 2,2,6,6-tetramethylenecyclohexyl penta(2-mercaptopropionate). ### Claim 4 (depends on 3) Polythiourethanes characterized in that they are prepared by a reaction between at least one of the sulfur compounds of the formula (I) according to claim 3 and at least one polyisocyanate chosen from those in whose formula the --NCO groups are not bonded directly to an aromatic ring. ### Claim 5 (depends on 4) Polythiourethanes according to claim 4, characterized in that said at least one polyisocyanate is hexamethylene diisocyanate, 2-methyl-1,5-diisocyanatopentane, 2-ethyl-1,4diisocyanatobutane, isophorone diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, hydrogenated xylylene diisocyanate, a trimer containing an isocyanurate ring or a biuret of such polyisocyanates. ### Claim 6 (depends on 4) Polythiourethanes according to claim 4, characterized in that the polyisocyanate is chosen from those which have a refractive index equal to or higher than 1.53. ### Claim 7 (depends on 1) Polythioethers characterized in that they are prepared by reaction between the sulfur compounds of formula (I) according to one of claim 1 and at least one compound containing at least two ethylenic unsaturations. ### Claim 8 (depends on 7) Polythioethers according to claim 7, characterized in that the compound containing ethylenic unsaturation is triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, divinylbenzene, trimethallyl thiocyanurate, 2-hydroxyethyl cyanurate triacrylate, 2-hydroxyethyl cyanurate trimethacrylate, 2-hydroxyethyl cyanurate tri(allylcarbonate), 2-hydroxyethyl cyanurate tri(methallylcarbonate) or 2,2-bis(4-hydroxyphenyl)propane diacrylate. ### Claim 9 (depends on 7) Polythioethers according to claim 7, characterized in that a ternary mixture of polythiol/diunsaturated compound/acrylate or methacrylate compound selected from trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate or dipentaerythritol hexamethacrylate is used. ### Claim 10 (depends on 8) Polythioethers according to claim 8, characterized in that the reaction between the sulfur compounds of formula (I) and the compounds containing ethylenic unsaturations takes place with an excess of ethylenic unsaturations relative to the thiol functional groups. ### Claim 11 (depends on 7) Polythioethers according to claim 7, characterized in that their preparation takes place in the presence of a peroxide or radical generator catalyst. ### Claim 12 (depends on 7) Polythioethers according to claim 7, characterized in that during their preparation from 0.1% to 10% by weight of catalyst is employed relative to the weight of the reaction mixture. ### Claim 13 (depends on 4) Material useful for optical application comprising a polythiourethane of claim 4. ### Claim 14 (depends on 5) Polythiourethanes according to claim 5, characterized in that the polyisocyanate is chosen from those which have a refractive index equal to or higher than 1.53. ### Claim 15 (depends on 8) Polythioethers according to claim 8, characterized in that a ternary mixture of polythiol/diunsaturated compound/acrylate or methacrylate compound selected from trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate or dipentaerythritol hexamethacrylate is used. ### Claim 16 (depends on 8) Polythioethers according to claim 8 characterized in that the reaction between the sulfur compounds of formula (1) and the compounds containing ethylenic unsaturations takes place with an excess of ethylenic unsaturations relative to the thiol functional groups. ### Claim 17 (depends on 9) Polythioethers according to claim 9 characterized in that the reaction between the sulfur compounds of formula (1) and the compounds containing ethylenic unsaturations takes place with an excess of ethylenic unsaturations relative to the thiol functional groups. ### Claim 18 (depends on 8) Polythioethers according to claim 8, characterized in that their preparation takes place in the presence of a peroxide or radical generator catalyst. ### Claim 19 (depends on 9) Polythioethers according to claim 9, characterized in that their preparation takes place in the presence of a peroxide or radical generator catalyst. ### Claim 20 (depends on 10) Polythioethers according to claim 10, characterized in that their preparation takes place in the presence of a peroxide or radical generator catalyst. ### Claim 21 (depends on 8) Polythioethers according to claim 8, characterized in that, during their preparation, from 0.1% to 10% by weight of catalyst is employed relative to the weight of the reaction mixture. ### Claim 22 (depends on 9) Polythioethers according to claim 9, characterized in that, during their preparation, from 0.1% to 10% by weight of catalyst is employed relative to the weight of the reaction mixture. ### Claim 23 (depends on 10) Polythioethers according to claim 10, characterized in that, during their preparation, from 0.1% to 10% by weight of catalyst is employed relative to the weight of the reaction mixture. ### Claim 24 (depends on 11) Polythioethers according to claim 11, characterized in that, during their preparation, from 0.1% to 10% by weight of catalyst is employed relative to the weight of the reaction mixture. ### Claim 25 (depends on 5) Material useful for optical application comprising a polythiourethane of claim 5. ### Claim 26 (depends on 7) Material useful for optical application comprising a polythioether of claim 7. ### Claim 27 (depends on 8) Material useful for optical application comprising a polythioether of claim 8. ### Claim 28 (depends on 9) Material useful for optical application comprising a polythioether of claim 9. ### Claim 29 (depends on 1) A polythiourethane formed by the reaction of a sulfur compound of one of claim 1 and xylylene diisocyanate, toluene diisocyanate, 4,4'-diisocyanatodiphenylmethane, or polymeric 4,4'-diisocyanatodiphenylmethane. ### Claim 30 (depends on 1, 9) A polythiourethane according to claim 9 formed by the reaction of a sulfur compound of one of claim 1 and xylylene diisocyanate. ### Claim 31 (depends on 4) A polythiourethane according to claim 4 further comprising at least one additional monomer bearing at least three functional groups that react with isocyanates to give carbamate functional groups, at least 40% of said functional groups being mercaptan groups and the mass of said mercaptan groups being at least 45% of the mass of the said additional monomer. ### Claim 32 (depends on 5) A polythiourethane according to claim 5 further comprising at least one additional monomer bearing at least three functional groups that react with isocyanates to give carbamate functional groups, at least 40% of said functional groups being mercaptan groups and the mass of said mercaptan groups being at least 45% of the mass of the said additional monomer. ### Claim 33 (depends on 29) A polythiourethane according to claim 29 further comprising at least one additional monomer bearing at least three functional groups that react with isocyanates to give carbamate functional groups, at least 40% of said functional groups being mercaptan groups and the mass of said mercaptan groups being at least 45% of the mass of the said additional monomer.