High molecular weight aliphatic polycarbonate copolymer and preparation method thereof

Patent metadata

Field	Value
Publication number	US-9447234-B2
Application number	US-201314440877-A
Country	US
Kind code	B2
Filing date	May 28, 2013
Priority date	Nov 9, 2012
Publication date	Sep 20, 2016
Grant date	Sep 20, 2016

Abstract

Provided is an aliphatic polycarbonate copolymer including repeating units of Formula 1 described in the specification. In Formula 1, A is a substituted or unsubstituted C 3 -C 60 alkylene or a substituted or unsubstituted C 3 -C 60 heteroalkylene and the O-A-O units in one polymer chain may be identical to or different from each other, B is a substituted or unsubstituted C 5 -C 20 arylene or a substituted or unsubstituted C 5 -C 20 heteroarylene and the —C(O)—B—C(O)— units in one polymer chain may be identical to or different from each other, and x and y are real numbers representing mole fractions.

First claim

The invention claimed is:

1. An aliphatic polycarbonate copolymer comprising repeating units of Formula 1:

wherein A is a substituted or unsubstituted C 3 -C 60 alkylene or a substituted or unsubstituted C 3 -C 60 heteroalkylene and the O-A-O units in one polymer chain are identical to or different from each other, B is a substituted or unsubstituted C 5 -C 20 arylene or a substituted or unsubstituted C 5 -C 20 heteroarylene and the —C(O)—B—C(O)— units in one polymer chain are identical to or different from each other, and x and y are real numbers representing mole fraction.

2. The aliphatic polycarbonate copolymer according to claim 1 , wherein the aliphatic polycarbonate copolymer has a weight average molecular weight of at least 50,000.

3. The aliphatic polycarbonate copolymer according to claim 1 , wherein the aliphatic polycarbonate copolymer has a weight average molecular weight of at least 100,000.

4. The aliphatic polycarbonate copolymer according to claim 1 , wherein the mole fraction of y(y/(x+y)) is from 1% to 50%.

5. The aliphatic polycarbonate copolymer according to claim 4 , wherein the aliphatic polycarbonate copolymer is prepared by condensation of HO-A-OH, as an aliphatic diol, selected from compounds of Formulae 2a to 2d:

with HO 2 C—B—CO 2 H, as a raw material for an aromatic diester, selected from the compounds of Formulae 3a to 3d:

6. The aliphatic polycarbonate copolymer according to claim 5 , wherein the HO-A-OH is 1,4-butanediol and the HO 2 C—B—CO 2 H is terephthalic acid.

7. A method for preparing an aliphatic polycarbonate, comprising:
condensing a mixture of HO-A-OH and a dialkyl carbonate in the presence of a base catalyst while removing an alcohol by-product by heating to or above the boiling point of the dialkyl carbonate (step 1); and
reacting the reaction product of step 1 while distilling off volatiles by distillation under reduced pressure at high temperature to maximize the conversion rate of the reaction (step 2),
wherein the conversion rate is maximized by controlling the molar ratio of the hydroxyl groups to the alkoxy groups in the reaction product of step 1 to 1:1-1.3 such that the molar ratio between the hydroxyl groups and the alkoxy groups is maintained close to 1:1 in the reaction of step 2 to allow the final polymer to have a weight average molecular weight of at least 50,000, and
wherein A is a substituted or unsubstituted C 3 -C 60 alkylene or a substituted or unsubstituted C 3 -C 60 heteroalkylene, the final polymer comprises repeating units having a structure represented by —[OC(O)O-A]-, and the O-A-O units in one polymer chain are identical to or different from each other.

8. The method according to claim 7 , wherein each alkyl group of the dialkyl carbonate is selected from the group consisting of methyl, ethyl, propyl, and combinations thereof.

9. The method according to claim 7 , wherein, in step 1, a mixture of the HO-A-OH, comprising HO-A-O − M + , and dimethyl carbonate (DMC) is condensed by heating to 90° C. or more while distilling off by-produced methanol and a portion of the DMC, and, in step 2, the condensation product of step 1 is condensed while removing volatiles under reduced pressure at an elevated temperature of at least 150° C. to maximize the conversion rate of the reaction, and
wherein M + is an alkali metal cation or an ammonium cation, and the molar ratio of HO-A-OH:M + is 100:0.1-1.

10. The method according to claim 9 , wherein the HO-A-OH is 1,4-butanediol, 1,6-hexanediol or a mixture thereof.

11. A method for preparing an aliphatic polycarbonate copolymer, comprising:
condensing a mixture of HO-A-OH, a dialkyl carbonate, and an aromatic diester in the presence of a base catalyst while removing alcohol by-products by heating to or above the boiling point of the dialkyl carbonate (step 1); and
reacting the reaction product of step 1 while distilling off volatiles under reduced pressure at high temperature to maximize the conversion rate of the reaction (step 2),
wherein the conversion rate is maximized by controlling the molar ratio of the hydroxyl groups to the alkoxy groups in the reaction product of step 1 to 1:≧1 such that the molar ratio between the hydroxyl groups and the alkoxy groups is maintained close to 1:1 in the reaction of step 2 to allow the final copolymer to have a weight average molecular weight of at least 50,000, and
wherein A is a substituted or unsubstituted C 3 -C 60 alkylene or a substituted or unsubstituted C 3 -C 60 heteroalkylene and the final copolymer comprises the repeating units of Formula 1 described in claim 1 .

12. The method according to claim 11 , wherein each alkyl group of the dialkyl carbonate is selected from the group consisting of methyl, ethyl, propyl, and combinations thereof.

13. The method according to claim 11 , wherein the molar ratio of the alkoxy groups to the hydroxyl groups is controlled to 1:1-1.3 in step 1.

14. The method according to claim 11 , wherein, in step 1, a mixture of HO-A-OH, comprising HO-A-O − M + , MeOC(O)—B—C(O)OMe, and dimethyl carbonate (DMC) is allowed to react by heating to or above 90° C. while distilling off by-produced methanol and a portion of the DMC to obtain a mixture in which the molar ratio of the —OH functional groups to the —OCH 3 functional groups is 1:1-1.3, and in step 2, the mixture is allowed to react while removing volatiles under reduced pressure at an elevated temperature of at least 150° C. to obtain the final polymer, and
wherein A and B are as defined in Formula 1 described in claim 1 , M − is an alkali metal cation or an ammonium cation, and the molar ratio of HO-A-OH:M + is 100:0.1-1.

15. The method according to claim 14 , wherein the HO-A-OH is 1,4-butanediol, the MeOC(O)—B—C(O)OMe is dimethyl terephthalate, and the molar ratio of HO-A-OH:MeOC(O)—B—C(O)OMe is 1:1-50.

Assignees

• Lotte Chemical Corp

Inventors

• Lee Bun Yeoul
• Jeon Jong Yeob
• Lee Jung Jae
• Park Ji Hae

Classifications

• C08G64/06 Primary

  not containing aliphatic unsaturation · CPC title

• C08G64/305

  and alcohols · CPC title

• C08G63/64 Primary

  Polyesters containing both carboxylic ester groups and carbonate groups · CPC title

• C08G64/0208

  saturated · CPC title

• C08L69/00

  Compositions of polycarbonates; Compositions of derivatives of polycarbonates · CPC title