Method for stabilizing polymers containing repeating lactic acid units, and stabilized polymers so made
View Patent ↗Metal catalyst residues in resins containing polymerized lactic acid units, such as polylactides, are deactivated by treatment with a polymer or copolymer that contain pendant acid groups and pendant ester groups, with an acid-containing PLA resin, or with a polymer or copolymer having at least one acid groups per 250 atomic mass units and which has pendant lactic acid or poly(lactic acid) groups. The deactivating agent is effective at deactivating the catalyst, and has little effect on the optical clarity of the resin.
1. A process for deactivating metal-containing catalyst residues in a PLA resin, comprising contacting PLA resin containing residues of a metal-containing catalyst with a deactivating agent that includes (1) a polymer or copolymer having pendant acid groups and pendant ester groups wherein the polymer or copolymer contains from 3 to 50 mole percent of repeating units that contain pendant ethyl ester groups, or from 2 to 25 mole percent of repeating units that contain pendant ester groups with more than 2 carbon atoms in the ester portion, (2) a polymer or copolymer having at least one acid group per 250 atomic mass units and which has pendant lactic acid or poly(lactic acid) groups, or (3) a mixture of (1) and (2).
2. The process of claim 1 , wherein the PLA resin contains from 80 to 99% by weight of repeating lactide units.
3. The process of claim 1 , wherein the deactivating agent is a polymer or copolymer having pendant acid groups and pendant ester groups, wherein the polymer or copolymer contains from 3 to 50 mole percent of repeating units that contain pendant ethyl ester groups, or from 2 to 25 mole percent of repeating units that contain pendant ester groups with more than 2 carbon atoms in the ester portion, which polymer or copolymer contains at least one pendant acid group per 250 atomic mass units.
4. The process of claim 3 , wherein the polymer or copolymer having pendant acid groups and pendant ester groups contains from 2 to 50 mole percent of ethyl carboxylic acid ester repeating units.
5. The process of claim 3 , wherein the polymer or copolymer having pendant acid groups and pendant ester groups contains from 2 to 25 mole percent of repeating alkyl or substituted alkyl carboxylic acid ester repeating units in which the alkyl or substituted alkyl group contains from 3 to 8 carbon atoms.
6. The process of claim 1 , wherein the polymer or copolymer having pendant acid groups and pendant ester groups has a refractive index from 1.35 to 1.50.
7. The process of any claim 1 , wherein the polymer or copolymer having pendant acid groups and pendant ester groups has a number average molecular weight from 1500 to 6000.
8. The process of claim 1 , wherein the metal is tin.
9. The process of claim 1 , wherein the PLA resin is contacted with from 200 to 1500 ppm of the deactivating agent.
10. A PLA resin composition comprising a) at least one PLA resin polymer having a number average molecular weight of from 25,000 to 500,000 containing residues of a metal-containing catalyst, and b) from 0.01 to 2 weight percent, based on the weight of combined weight of components a) and b), of a deactivating agent that includes (1) a polymer or copolymer having pendant acid groups and pendant ester groups, wherein the polymer or copolymer contains from 3 to 50 mole percent of repeating units that contain pendant ethyl ester groups, or from 2 to 25 mole percent of repeating units that contain pendant ester groups with more than 2 carbon atoms in the ester portion, (2) a polymer or copolymer having at least one acid group per 250 atomic mass units and which has pendant lactic acid or poly(lactic acid) groups, or (3) a mixture of (1) and (2).
11. The composition of claim 10 , wherein the PLA resin contains from 80 to 99% by weight of repeating lactide units.
12. The composition of claim 11 , wherein the polymer or copolymer has a refractive index of from 1.35 to 1.50.
13. The composition of claim 11 , wherein the polymer or copolymer has a number average molecular weight from 1500 to 6000.
14. The composition of claim 11 , wherein the metal is tin.
15. The composition of claim 11 , wherein the PLA resin contains from 200 to 1500 ppm of the polymer or copolymer.
16. The composition of claim 11 which contains up to 0.3% by weight lactide, based on the combined weight of components a), b) and the lactide.
17. The process of claim 3 wherein from 90 to 100 mole percent of the pendant acid groups are not neutralized with a counterion.