# US 4,396,737 A · Polymerization of polyol allyl carbonate using polymerization initiators of short and long half lives > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,396,737 A - Document ID: US4396737A - Status: Granted - Kind: A - Application number: 06/322,823 - Filed: 1981-11-19 - Granted: 1983-08-02 - Earliest claimed: 1981-11-19 - Assignees: PPG Industries, Inc. - Inventors: Ivan R. Leatherman - Web page: https://patentgrep.com/patent/US4396737A ## CPC - C08F 18/24: Esters of carbonic or haloformic acids - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract Disclosed is a liquid composition of a polyol(allyl carbonate) monomer; a first, low initiation temperature, short half life, polymerization initiator; and, a second, high initiation temperature, long half life, polymerization initiator. Optionally, a photochromic agent may be present. Also disclosed is a method of polymerizing the composition, and the polymerizate prepared thereby. ## Claims ### Claim 1 In a method of polymerizing a polyol(allyl carbonate) having a photochromic agent incorporated therein, which method comprises adding a first organic peroxide initiator to the polyol(allyl carbonate) monomer and curing the polyol(allyl carbonate), the improvement comprising adding from about 1 to about 10 moles of a second organic peroxide initiator per mole of photochromic agent to the polyol(allyl carbonate), said second organic peroxide initiator having a half life at least five times greater than the half life of the first organic peroxide initiator. ### Claim 2 (depends on 1) The method of claim 1 wherein the first organic peroxide polymerization initiator is chosen from the group consisting of isobutyryl peroxide; di(2-ethylhexyl) peroxydicarbonate; acetyl cyclohexane sulfonyl peroxide; di(sec-butyl) peroxydicarbonate; diisopropyl peroxydicarbonate; 2,4-dichlorobenzoyl peroxide; and t-butyl peroxypivalate; and the second organic peroxide polymerization initiator is chosen from the group consisting of 2,5-dimethyl-2,5-bis(2-ethyl hexanoylproxy) hexane; acetyl peroxide; succinic acid peroxide; t-butyl peroxyoctoate; benzoyl peroxide; p-chlorobenzoyl peroxide; t-butyl peroxyisobutyrate; t-butyl peroxymaleic acid; bis(1-hydroxycyclohexyl) peroxide; 1-hydroxy-1'-hydroperoxy dicyclohexyl peroxide; t-butyl peroxyisopropyl carbonate; 2,5-dimethyl-2,5-bis(benzoylperoxy) hexane; t-butyl peroxyacetate; methyl ethyl ketone peroxides; di-t-butyl diperoxyphthalate; t-butyl peroxybenzoate; n-butyl 4,4-bis(t-butylperoxy) valerate; 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane; t-butyl hydroperoxide; 3,5-dimethyl-3,5-dihydroxy 1,2-peroxycyclopentane; di-t-butyl peroxide; 2,5-dimethyl-2,5-bis(t-butylperoxy) hexyne-3; and 1,1,3,3-tetramethylbutyl hydroperoxide. ### Claim 3 (depends on 1) The method of claim 1 wherein the photochromic agent is an organo metallic. ### Claim 4 (depends on 3) The method of claim 3 wherein the photochromic agent is a transition metal carbonyl. ### Claim 5 (depends on 4) The method of claim 4 wherein the transition metal carbonyl is tungsten hexacarbonyl. ### Claim 6 (depends on 1) The method of claim 1 wherein the polyol(allyl carbonate) is a diol bis(allyl carbonate). ### Claim 7 A liquid composition comprising a polyol bis(allyl carbonate), a photochoromic agent, a first organic peroxide initiator, and from about one to about ten moles of a second organic peroxide initiator per mole of photochromic agent, said second organic peroxide initiator having a half life at least five times longer than the half life of the first organic peroxide initiator. ### Claim 8 (depends on 7) The liquid composition of claim 7 wherein the first organic peroxide polymerization initiator is chosen from the group consisting of isobutyryl peroxide; di(2-ethylhexyl) peroxydicarbonate; acetyl cyclohexane sulfonyl peroxide; di(sec-butyl) peroxydicarbonate; diisopropyl peroxydicarbonate; 2,4-dichlorobenzoyl peroxide; and t-butyl peroxypivalate; and the second organic peroxide polymerization initiator is chosen from the group consisting of 2,5-dimethyl-2,5-bis(2-ethyl hexanoylproxy) hexane; acetyl peroxide; succinic acid peroxide; t-butyl peroxyoctoate; benzoyl peroxide; p-chlorobenzoyl peroxide; t-butyl peroxyisobutyrate; t-butyl peroxymaleic acid; bis(1-hydroxycyclohexyl) peroxide; 1-hydroxy-1'-hydroperoxy dicyclohexyl peroxide; t-butyl peroxyisopropyl carbonate; 2,5-dimethyl-2,5-bis(benzoylperoxy) hexane; t-butyl peroxyacetate; methyl ethyl ketone peroxides; di-t-butyl diperoxyphthalate; t-butyl peroxybenzoate; n-butyl 4,4-bis(t-butylperoxy) valerate; 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane; t-butyl hydroperoxide; 3,5-dimethyl-3,5-dihydroxy, 1,2-peroxycyclopentane; di-t-butyl peroxide; 2,5-dimethyl-2,5-bis(t-butylperoxy) hexyne-3; and 1,1,3,3-tetramethylbutyl hydroperoxide. ### Claim 9 (depends on 7) The liquid composition of claim 7 wherein the photochromic agent is an organo metallic. ### Claim 10 (depends on 9) The liquid composition of claim 9 wherein the photochromic agent is a transition metal carbonyl. ### Claim 11 (depends on 9) The liquid composition of claim 9 wherein the transition metal carbonyl is tungsten hexacarbonyl. ### Claim 12 (depends on 7) The liquid composition of claim 7 wherein the polyol(allyl carbonate) is a diol bis(allyl carbonate). ### Claim 13 A method of enhancing the recovery of an organic peroxide free radical initiated polyol(allyl carbonate) polymerizate having a photochromic agent incorporated therein, which method comprises adding from about one to about ten moles of a second organic peroxide free radical initiator per mole of photochromic agent to the composition of polyol(allyl carbonate) monomer, photochromic agent, and first organic peroxide free radical initiator, which second organic peroxide free radical initiator has a half life at least five times longer than the half life of the first organic peroxide free radical initiator. ### Claim 14 (depends on 13) The method of claim 13 wherein the first organic peroxide polymerization initiator is chosen from the group consisting of isobutyryl peroxide; di(2-ethylhexyl) peroxydicarbonate; acetyl cyclohexane sulfonyl peroxide; di(secbutyl) peroxydicarbonate; diisopropyl peroxydicarbonate; 2,4-dichlorobenzoyl peroxide; and t-butyl peroxypivalate; and the second organic peroxide polymerization initiator is chosen from the group consisting of 2,5-dimethyl-2,5-bis(2-ethyl hexanoylproxy) hexane; acetyl peroxide; succinic acid peroxide; t-butyl peroxyoctoate; benzoyl peroxide; p-chlorobenzoyl peroxide; t-butyl peroxyisobutyrate; t-butyl peroxymaleic acid; bis(1-hydroxyclcylohexyl) peroxide; 1-hydroxy-1'-hydroperoxy dicyclohexyl peroxide; t-butyl peroxyisopropyl carbonate; 2.5-dimethyl-2,5-bis(benzoylperoxy) hexane; t-butyl peroxyacetate; methyl ethyl ketone peroxides; di-t-butyl diperoxyphthalate; t-butyl peroxybenzoate; n-butyl 4,4-bis(t-butylperoxy) valerate; 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane; t-butyl hydroperoxide; 3,5-dimethyl-3,5-dihydroxy 1,2-peroxycyclopentane; di-t-butyl peroxide; 2,5-dimethyl-2,5-bis(t-butylperoxy) hexyne-3; and 1,1,3,3-tetramethylbutyl hydroperoxide. ### Claim 15 (depends on 13) The method of claim 13 wherein the photochromic agent is an organo metallic. ### Claim 16 (depends on 15) The method of claim 15 wherein the photochromic agent is a transition metal carbonyl. ### Claim 17 (depends on 16) The method of claim 16 wherein the transition metal carbonyl is tungsten hexacarbonyl. ### Claim 18 (depends on 13) The method of claim 13 wherein the polyol(allyl carbonate) is a diol bis(allyl carbonate). ### Claim 19 In a method of polymerizing a polyol(allyl carbonate) having a photochromic agent incorporated therein, which method comprises adding a first organic peroxide initiator to the polyol(allyl carbonate) monomer and curing the polyol(allyl carbonate), the improvement comprising adding second and third organic peroxide initiators to the polyol(allyl carbonate), said second organic peroxide initiator having a half life at least five times longer than the half life of the first organic peroxide initiator, and said third organic peroxide initiator having a half life at least five times longer than the half life of said second organic peroxide initiator and being present at a concentration of about one to about ten moles per mole of photochromic agent. ### Claim 20 (depends on 2) The method of claim 2 wherein the photochromic agent is an organo metallic. ### Claim 21 (depends on 20) The method of claim 20 wherein the photochromic agent is a transition metal carbonyl. ### Claim 22 (depends on 21) The method of claim 21 wherein the transition metal carbonyl is tungsten hexacarbonyl. ### Claim 23 (depends on 19) The method of claim 19 wherein the polyol(allyl carbonate) is a diol bis(allyl carbonate). ### Claim 24 A liquid composition comprising a polyol bis(allyl carbonate), a photochromic agent, a first peroxide initiator, a second peroxide initiator, and about one to ten moles of a third organic peroxide initiator per mole of photochromic agent, said second organic peroxide initiator having a half life at least about five times longer than the half life of the frist organic peroxide initiator, and said third organic peroxide initiator having a half life at least about five times longer than the half life of said second organic peroxide initiator. ### Claim 25 (depends on 24) The liquid composition of claim 24 wherein the photochromic agent is an organo metallic. ### Claim 26 (depends on 25) The liquid composition of claim 25 wherein the photochromic agent is a transition metal carbonyl. ### Claim 27 (depends on 25) The liquid composition of claim 25 wherein the transition metal carbonyl is tungsten hexacarbonyl. ### Claim 28 (depends on 24) The liquid composition of claim 24 wherein the polyol(allyl carbonate) is a diol bis(allyl carbonate). ### Claim 29 A method of increasing the hardness and enhancing the photochromic recovery of an organic peroxide free radical initiated polyol(allyl carbonate) polymerizate having a photochromic agent incorporated therein, which method comprises adding second and third organic peroxide free radical initiators to the composition of polyol (allyl carbonate) monomer, photochromic agent, and first organic peroxide free radical initiator, which second free radical organic peroxide initiator has a half life at least about five times longer than the half life of the first free radical organic peroxide initiator, and which third free radical organic peroxide initiator has a half life at least about five times longer than the second free radical organic peroxide initiator, said third organic peroxide free radical initiator being present at a concentration of about one to about ten mole per moles of photochromic agent. ### Claim 30 (depends on 29) The method of claim 29 wherein the photochromic agent is an organo metallic. ### Claim 31 (depends on 30) The method of claim 30 wherein the photochromic agent is a transition metal carbonyl. ### Claim 32 (depends on 31) The method of claim 31 wherein the transition metal carbonyl is tungsten hexacarbonyl. ### Claim 33 (depends on 29) The method of claim 29 wherein the polyol(allyl carbonate) is a diol bis(allyl carbonate).