# US 2009/0275706 A1 · Lactic Acid Based Compositions with Enhanced Properties > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2009/0275706 A1 - Document ID: US20090275706A1 - Status: Published application - Kind: A1 - Application number: 12/355,033 - Filed: 2009-01-16 - Published: 2009-11-05 - Earliest claimed: 2008-01-23 - Assignees: Tate & Lyle Ingredients Americas LLC - Inventors: Anders Södergard; Mikael Stolt; Geoffrey A.R. Nobes - Web page: https://patentgrep.com/patent/US20090275706A1 ## CPC - C08G 63/60: derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds - C08G 63/06: derived from hydroxycarboxylic acids - C08J 3/246: {Intercrosslinking of at least two polymers} - C08J 2367/04: Polyesters derived from hydroxy carboxylic acids, e.g. lactones (C08J2367/06 takes precedence) - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) ## Abstract A crosslinked lactic acid polymer composition containing (i) a macromer comprising (i-a) a flexible segment produced by the condensation of two or more compounds selected from the group consisting of lactones, furans, epoxies, isocyanates, anhydrides, dianhydrides, alcohols, diols, triols, carboxylic acids, dicarboxylic acids, tricarboxylic acids, esters, diesters, triesters, ethers, diethers, and triethers; and (ii) a lactic acid polymer produced by the condensation of a lactic acid monomer or dimer selected from the group consisting of D-lactic acid, L-lactic acid, D,L-lactic acid, L,L-lactide, D,D-lactide, and D,L-lactide; wherein the macromer and the lactic acid polymer contain carbon-carbon single-bond crosslinks. The macromer may further contain (i-b) a lactic acid segment produced by the condensation of a lactic acid monomer or dimer selected from the group consisting of D-lactic acid, L-lactic acid, D,L-lactic acid, L,L-lactide, D,D-lactide, and D,L-lactide with a polyfunctional monomer selected from the group consisting of dianhydrides, diols, triols, dicarboxylic acids, and tricarboxylic acids. Also, a method of producing the crosslinked lactic acid polymer composition by (a) condensing two or more compounds selected from the group consisting of lactones, furans, epoxies, isocyanates, anhydrides, dianhydrides, alcohols, diols, triols, carboxylic acids, dicarboxylic acids, tricarboxylic acids, esters, diesters, triesters, ethers, diethers, and triethers, to yield a flexible segment of a macromer; and (b) melt blending the macromer with a lactic acid polymer, to yield the crosslinked lactic acid polymer. The method may further involve (c) condensing a lactic acid monomer or dimer selected from the group consisting of D-lactic acid, L-lactic acid, D,L-lactic acid, L,L-lactide, D,D-lactide, and D,L-lactide with a polyfunctional monomer selected from the group consisting of dianhydrides, diols, triols, dicarboxylic acids, and tricarboxylic acids, to yield a lactic acid segment; and (d) condensing the lactic acid segment and the flexible segment, to yield the macromer. ## Claims ### Claim 1 A crosslinked lactic acid polymer composition, comprising: (i) a macromer comprising (i-a) a flexible segment produced by the condensation of two or more compounds selected from the group consisting of lactones, furans, epoxies, isocyanates, anhydrides, dianhydrides, alcohols, diols, triols, carboxylic acids, dicarboxylic acids, tricarboxylic acids, esters, diesters, triesters, ethers, diethers, and triethers; and (ii) a lactic acid polymer produced by the condensation of a lactic acid monomer or dimer selected from the group consisting of D-lactic acid, L-lactic acid, D,L-lactic acid, L,L-lactide, D,D-lactide, and D,L-lactide; wherein the macromer and the lactic acid polymer contain carbon-carbon single-bond crosslinks. ### Claim 2 (depends on 1) The crosslinked lactic acid polymer composition of claim 1, wherein the macromer further comprises (i-b) a lactic acid segment produced by the condensation of a lactic acid monomer or dimer selected from the group consisting of D-lactic acid, L-lactic acid, D,L-lactic acid, L,L-lactide, D,D-lactide, and D,L-lactide with a polyfunctional monomer selected from the group consisting of dianhydrides, diols, triols, dicarboxylic acids, and tricarboxylic acids. ### Claim 3 (depends on 2) The crosslinked lactic acid polymer composition of claim 2, wherein the lactic acid segment (i-b) is produced by the condensation of from about 50 weight parts to about 100 weight parts D-lactic acid, L-lactic acid, D,L-lactic acid, or lactide with about 1 weight part polyfunctional monomer. ### Claim 4 (depends on 3) The crosslinked lactic acid polymer composition of claim 3, wherein the polyfunctional monomer is maleic anhydride. ### Claim 5 (depends on 1) The crosslinked lactic acid polymer composition of claim 1, wherein the flexible segment (i-a) is produced by the condensation of reactants selected from the group consisting of (i-a-1) adipic acid and 1,4-butanediol; (i-a-2) adipic acid, 1,4-butanediol, and maleic anhydride; (i-a-3) tetrahydrofuran and maleic anhydride; and (i-a-4) ε-caprolactone and maleic anhydride. ### Claim 6 (depends on 5) The crosslinked lactic acid polymer composition of claim 5, wherein the flexible segment (i-a) is produced by the condensation of from about 25 weight parts to about 75 weight parts adipic acid, from about 20 weight parts to about 60 weight parts 1,4-butanediol, and from about 5 weight parts to about 15 weight parts maleic anhydride. ### Claim 7 (depends on 2) The crosslinked lactic acid polymer composition of claim 2, wherein the macromer is the condensation product of from about 20 weight parts to about 80 weight parts lactic acid segment with about 20 weight parts to about 80 weight parts flexible segment. ### Claim 8 (depends on 1) The crosslinked lactic acid polymer composition of claim 1, wherein the composition comprises from about 10 weight parts to about 90 weight parts lactic acid polymer (ii) and from about 10 weight parts to about 90 weight parts macromer (i) and the macromer (i) and the lactic acid polymer (ii) together comprise 100 weight parts. ### Claim 9 (depends on 8) The crosslinked lactic acid polymer composition of claim 8, wherein the composition comprises from about 60 weight parts to about 80 weight parts lactic acid polymer (ii) and from about 20 weight parts to about 40 weight parts macromer (i) and the macromer (i) and the lactic acid polymer (ii) together comprise 100 weight parts. ### Claim 10 (depends on 1) The crosslinked lactic acid polymer composition of claim 1, wherein the dispersion index (Mw/Mn) of the crosslinked lactic acid polymer is from about 10 to about 70. ### Claim 11 A method of producing a crosslinked lactic acid polymer composition, comprising: (a) condensing two or more compounds selected from the group consisting of lactones, furans, epoxies, isocyanates, anhydrides, dianhydrides, alcohols, diols, triols, carboxylic acids, dicarboxylic acids, tricarboxylic acids, esters, diesters, triesters, ethers, diethers, and triethers, to yield a flexible segment of a macromer; and (b) melt blending the macromer with a lactic acid polymer, to yield the crosslinked lactic acid polymer. ### Claim 12 (depends on 11) The method of claim 11, wherein step (a) comprises condensing from about 25 weight parts to about 75 weight parts adipic acid, from about 20 weight parts to about 60 weight parts 1,4-butanediol, and from about 5 weight parts to about 15 weight parts maleic anhydride. ### Claim 13 (depends on 12) The method of claim 12, wherein step (a) comprises: contacting the 1,4-butanediol and the maleic anhydride with a stabilizer and a catalyst at a temperature from about 90° C. to about 130° C.; contacting the 1,4-butanediol, the maleic anhydride, the stabilizer, and the catalyst with the adipic acid at a temperature from about 180° C. to about 240° C. and ambient pressure; reducing the pressure from ambient pressure to from about 5 mbar to about 50 mbar over from about 1 hr to about 8 hr; and maintaining the temperature at from about 180° C. to about 240° C. and the pressure from about 5 mbar to about 50 mbar for about 3 hr to about 24 hr. ### Claim 14 (depends on 13) The method of claim 13, wherein the catalyst is dibutyl tin oxide in an amount from about 0.002 weight parts to about 0.05 weight parts and the stabilizer is trinonyl phenyl phosphate in an amount from about 0.005 weight parts to about 0.1 weight parts. ### Claim 15 (depends on 11) The method of claim 11, wherein step (b) comprises: melting from about 10 weight parts to about 90 weight parts lactic acid polymer at a temperature from about 200° C. to about 240° C., to yield a melted lactic acid polymer; adding from about 10 weight parts to about 90 weight parts macromer and a free radical initiator to the melted lactic acid polymer, to yield a melted blend; maintaining the melted blend at a temperature from about 200° C. to about 240° C. for about 30 sec to about 10 min, to yield a mixture of the crosslinked lactic acid polymer, water, and residual free lactide; removing the residual free lactide from the mixture, to yield a mixture of the crosslinked lactic acid polymer and water; and removing the water from the mixture, to yield the crosslinked lactic acid polymer. ### Claim 16 (depends on 15) The method of claim 15, wherein the free radical initiator is a peroxide in an amount from about 0.1 weight parts to about 1 weight part. ### Claim 17 (depends on 11) The method of claim 11, further comprising: (c) condensing a lactic acid monomer or dimer selected from the group consisting of D-lactic acid, L-lactic acid, D,L-lactic acid, L,L-lactide, D,D-lactide, and D,L-lactide with a polyfunctional monomer selected from the group consisting of dianhydrides, diols, triols, dicarboxylic acids, and tricarboxylic acids, to yield a lactic acid segment; and (d) condensing the lactic acid segment and the flexible segment, to yield the macromer. ### Claim 18 (depends on 17) The method of claim 17, wherein step (c) comprises condensing from about 50 weight parts to about 100 weight parts D-lactic acid, L-lactic acid, D,L-lactic acid, or lactide with about 1 weight part maleic anhydride. ### Claim 19 (depends on 18) The method of claim 18, wherein step (c) comprises: contacting the D-lactic acid, L-lactic acid, D,L-lactic acid, or lactide with from about 0.02 weight parts to about 0.2 weight parts of a tin catalyst at a temperature from about 90° C. to about 130° C.; contacting the D-lactic acid, L-lactic acid, D,L-lactic acid, or lactide and the catalyst with the maleic anhydride at a temperature from about 160° C. to about 220° C. and ambient pressure; reducing the pressure from ambient pressure to from about 50 mbar to about 200 mbar over from about 1 hr to about 6 hr; and maintaining the pressure at from about 50 mbar to about 200 mbar for about 30 min to about 5 hr. ### Claim 20 (depends on 17) The method of claim 17, wherein step (d) comprises condensing from about 20 weight parts to about 80 weight parts lactic acid segment with about 20 weight parts to about 80 weight parts flexible segment. ### Claim 21 (depends on 20) The method of claim 20, wherein step (d) comprises: contacting the lactic acid segment with the flexible segment and a stabilizer at a temperature from about 160° C. to about 220° C. and ambient pressure; reducing the pressure from ambient pressure to from about 5 mbar to about 25 mbar over from about 1 hr to about 6 hr; and maintaining the temperature from about 160° C. to about 220° C. and the pressure from about 5 mbar to about 25 mbar for about 8 hr to about 72 hr. ### Claim 22 (depends on 21) The method of claim 21, wherein the stabilizer is phosphoric acid in an amount from about 0.1 weight parts to about 0.75 weight parts.