Process for the continuous production of polyesters

Patent metadata

Field	Value
Publication number	US-9683075-B2
Application number	US-200913056395-A
Country	US
Kind code	B2
Filing date	Jul 29, 2009
Priority date	Jul 31, 2008
Publication date	Jun 20, 2017
Grant date	Jun 20, 2017

Abstract

Continuous process of forming aliphatic polyesters The process includes continuously providing cyclic ester monomer and polymerization catalyst to a continuous mixing loop reactor (CMLR) having static mixing elements and operated at a temperature between 100 and 240° C. to form a pre-polymerized reaction mixture. The conversion is between 40 and less than 90 wt. %, wherein the cyclic ester monomer comprises lactide having a free acid content lower than 50 milli-equivalents per kg. The pre-polymerized reaction mixture is continuously provided to a plug flow reactor that is a static mixer reactor having static mixing elements and is operated at a temperature between 110-240° C., wherein the reaction mixture is polymerized to a conversion of at least 90%, to form polymer wherein the flow ratio of the CMLR and the plug flow reactor is between 1.5 an d50. The process includes continuously removing polymer from the plug flow reactor devolitizing the polymer.

First claim

The invention claimed is:

1. A continuous process for the ring-opening polymerisation of cyclic ester monomers to form aliphatic polyesters which comprises the steps of:
a) continuously providing cyclic ester monomer and polymerisation catalyst to a continuous mixing loop reactor being a static mixer reactor comprising static mixing elements, the reactor being operated at a temperature between 100-240° C. to form a pre-polymerised reaction mixture with a conversion of between 40 and less than 90 wt. %, the cyclic ester monomer comprises lactide, said lactide having a free acid content lower than 50 milli-equivalents per kg (meq/kg),
b) continuously removing pre-polymerised reaction mixture from the continuous mixing loop reactor and continuously providing pre-polymerised reaction mixture to a plug flow reactor, being a static mixer reactor comprising static mixing elements, and the plug flow reactor being operated at a temperature between 100-240° C., wherein the reaction mixture is polymerised to a conversion of at least 90%, to form polymer, and wherein the flow ratio of the continuous mixing loop reactor and the plug flow reactor is between 1.5 and 50, and
c) continuously removing polymer from the plug flow reactor, and wherein the polymer removed from the plug flow reactor is subjected to a devolatilisation step to reduce the monomer content of the polymer.

2. The process according to claim 1 wherein the flow ratio of the continuous mixing loop reactor and the plug flow reactor is between 1.5 and 15.

3. The process according to claim 1 , wherein the plug flow reactor is placed vertically or tilted.

4. The process according to claim 1 wherein the cyclic monomer is selected from the group consisting of lactide (L-lactide, D-lactide, DL-lactide, meso-lactide), glycolide, trimethylene carbonate (TMC), epsilon-caprolactone, p-dioxanone, and combinations thereof.

5. The process according to claim 1 wherein the reaction mixture is polymerised in the plug flow reactor to a degree of conversion of at least 93%.

6. The process according to claim 1 , wherein devolatilisation is carried out in a static expansion chamber.

7. The process according to claim 6 , wherein devolatilisation takes place in more than one stage.

8. The process according to claim 1 , wherein after the devolatilisation step the monomer content of the polymer is less than 2 wt. %.

9. The process according to claim 1 wherein prior to or simultaneously with the devolatilisation step, the polymer is subjected to a stabilisation step wherein the polymer is subjected to a catalyst deactivation treatment.

10. The process according to claim 1 wherein the cyclic ester monomer, the polymerisation catalyst, and optionally co-catalyst, initiator and/or additives are combined prior to feeding to the continuous mixing loop reactor.

11. The process according to claim 1 and wherein the polymerisation catalyst comprises tin octoate.

12. The process according to claim 1 and wherein the polymerisation catalyst is defined by the formula
(M)(X1,X2 . . . Xm)n
wherein M is selected from metals of Group 1, 2, 4, 8, 9, 10, 12, 13, 14, and 15 of the Periodic Table of Elements, wherein (X1, X2 . . . Xm) are selected from the group consisting of alkyls, aryls, oxides, carboxylates, halides, alkoxides, alkylesters, wherein m is an integer ranging from 1 to 6, and wherein n is an integer ranging from 1 to 6.

13. The process according to claim 1 wherein the flow ratio of the continuous mixing loop reactor and the plug flow reactor is between 1.5 and 12.

14. The process according to claim 1 and wherein the polymer exiting from the plug flow reactor has a polydispersity of between 1.4 and 1.5.

15. A continuous process for the ring-opening polymerisation of cyclic ester monomers to form aliphatic polyesters which comprises the steps of:
a) continuously providing cyclic ester monomer and polymerisation catalyst to a continuous mixing loop reactor being a static mixer reactor comprising static mixing elements, the reactor being operated at a temperature between 100-240° C. to form a re-polymerised reaction mixture with a conversion of between 40 and less than 90 wt. %, the cyclic ester monomer comprises lactide, said lactide having a free acid content lower than 50 milli-equivalents per kg (meq/kg) and a water content lower than 2000 ppm,
b) continuously removing pre-polymerised reaction mixture from the continuous mixing loop reactor and continuously providing pre-polymerised reaction mixture to a plug flow reactor, being a static mixer reactor comprising static mixing elements, and the plug flow reactor being operated at a temperature between 100-240° C., wherein the reaction mixture is polymerised to a conversion of at least 90%, to form polymer wherein the flow ratio of the continuous mixing loop reactor and the plug flow reactor is between 1.5 and 50, and
c) continuously removing polymer from the plug flow reactor.

16. A continuous process for the ring-opening polymerisation of cyclic ester monomers to form aliphatic polyesters which comprises the steps of:
a) continuously providing cyclic ester monomer and polymerisation catalyst to a continuous mixing loop reactor being a static mixer reactor comprising static mixing elements, the reactor being operated at a temperature between 100-240° C. to form a pre-polymerised reaction mixture with a conversion of between 60 and less than 90 wt. %, the cyclic ester monomer comprises lactide, said lactide having a free acid content lower than 50 milli-equivalents per kg (meq/kg),
b) continuously removing pre-polymerised reaction mixture from the continuous mixing loop reactor and continuously providing pre-polymerised reaction mixture to a plug flow reactor, being a static mixer reactor comprising static mixing elements, and the plug flow reactor being operated at a temperature between 100-240° C., wherein the reaction mixture is polymerised to a conversion of at least 90%, to form polymer wherein the flow ratio of the continuous mixing loop reactor and the plug flow reactor is between 1.5 and 15, and
c) continuously removing polymer from the plug flow reactor.

17. The process according to claim 1 wherein the cyclic ester monomer is L-lactide and wherein the polymer collected from the process is poly(L-lactide) exhibiting a D-isomer content of less than 0.4% by weight of the total amount of the lactide present in the polylactide.

18. The process according to claim 1 wherein the conversion in the continuous mixing loop reactor is between 60 and less than 90 wt. %.

Assignees

• Haan Robert Edgar
• Jansen Peter Paul
• De Vos Siebe Cornelis
• Van Breugel Jan
• Kreis Peter Willi
• Borer Sarah
• Purac Biochem Bv
• Sulzer Chemtech Ag

Inventors

• Haan Robert Edgar
• Jansen Peter Paul
• De Vos Siebe Cornelis
• Van Breugel Jan
• Kreis Peter Willi
• Borer Sarah

Classifications

• C08G63/08

  Lactones or lactides · CPC title

• C08G63/785 Primary

  characterised by the apparatus used · CPC title

• C08G63/78 Primary

  Preparation processes · CPC title

• C08G63/88

  Post-polymerisation treatment · CPC title

• C08L67/04

  Polyesters derived from hydroxycarboxylic acids, e.g. lactones (C08L67/06 takes precedence) · CPC title