Functional biodegradable polymers

Patent metadata

Field	Value
Publication number	US-10023689-B2
Application number	US-201615132430-A
Country	US
Kind code	B2
Filing date	Apr 19, 2016
Priority date	Jul 28, 2010
Publication date	Jul 17, 2018
Grant date	Jul 17, 2018

Abstract

Biodegradable polyesters are made by synthesizing copolymers derived from biodegradable hydroxyacid monomers as well as from hydroxyacid monomers containing a functional group such as an azide group, a halogen group, a thioacetate group, and the like. Preferably, the functionalized biodegradable polyester copolymers are derived from a functionalized hydroxyacid such as a homolog of lactic acid and/or glycolic acid with the copolyester thus containing functional groups on the backbone thereof. These biodegradable polyesters can be utilized wherever biodegradable polyesters are currently used, and also serve as a polymer to which various medical and drug delivery systems can be attached.

First claim

What is claimed is:

1. A process for synthesizing an α-halogenated copolyester comprising:
polymerizing one or more α-halogenated hydroxyacids with one or more commoners using a protonic catalyst or a Lewis acid catalyst, where the co-monomers are selected from
(i) one or more diols containing from 2 to about 10 carbon atoms and one or more dicarboxylic acids containing from 2 to about 15 carbon atoms;
(ii) one or more hydroxyacids containing from 2 to about 20 carbon atoms, or
(iii) one or more diols containing from 2 to about 10 carbon atoms, one or more dicarboxylic acids containing from 2 to about 15 carbon atoms, and one or more hydroxyacids containing from 2 to about 20 carbon atoms;

wherein the amount of the total α-halogenated hydroxyacid is from about 30 to about 80 mole % based upon the total number of moles of the α-halogenated hydroxyacid and the co-monomers.

2. The process of claim 1 , wherein at least one of the co-monomers is a hydroxyacid selected from glycolic acid, galactaric acid, hydroxypropionic acid, lactic acid, hydroxybutyric acid, hydroxyisobutyric acid, hydroxy methylbutyric acid, bis(hydroxymethyl)propionic acid, hydroxyoctadecanoic acid, di-tert-butyl hydroxybenzoic acid, benzilic acid, hydroxyl fluorenecarboxylic acid, hydroxydecanoic acid, hydroxynaphthalenecarboxylic acid, hydroxybenzenedicarboxylic acid, hydroxymethylbenzoic acid, hydroxyphenylacetic acid, mandelic acid, hydroxymethoxybenzoic acid, methoxy salicylic acid, hydroxyoctanoic acid, hydroxycinnamic acid, dihydroxycinnamic acid, dihydroxyhydrocinnamic acid, hydroxyphenylpropionic acid, dihydroxytartaric acid, hydroxymethoxycinnamic acid, salicylic acid, citrazinic acid, galacturonic acid, glucuronic acid, hydroxypropanedioic acid, hydroxyphenyl propionic acid, methoxy salicylic acid, tartaric acid or trihydroxybenzoic acid and combinations thereof.

3. The process of claim 1 , wherein the co-monomer is selected from lactic acid, glycolic acid, and a combination thereof.

4. The process of claim 1 , wherein the number average molecular weight of the α-halogenated copolyester is from about 2,000 Da to about 40,000 Da.

5. The process of claim 1 , wherein one or more of the α-halogenated hydroxyacids is a 2-halo-3-hydroxypropionic acid.

6. The process of claim 1 , wherein the 2-halo-3-hydroxypropionic acid is 2-bromo-3-hydroxypropionic acid or 2-chloro-3-hydroxypropionic acid.

7. The process of claim 1 , wherein the step of polymerizing employs a catalyst selected from p-dimethylaminopyridinium toluenesulphonate (DPTS), p-toluidine hydrochloride, dimethyl-p-phenylenediamine dihydrochloride, p-toluenesulphonic acid, or SnCl 2 , and combinations thereof.

8. The process of claim 1 , wherein the process further comprises reacting the α-halogenated copolyester with a linking agent and a protonic catalyst or a Lewis acid catalyst.

9. The process of claim 1 , wherein the α-halogenated copolyester includes an α-halogenated ester, and the process further comprises isomerizing the α-halogenated ester to a β-halogenated ester.

10. The process of claim 1 , wherein the α-halogenated copolyester includes an α-halogenated ester, and the process further comprises reacting the halogen atom of the α-halogenated ester with an amine group.

11. The process of claim 1 , wherein the α-halogenated copolyester includes an α-halogenated ester, and the process further comprises reacting the halogen atom of the α-halogenated ester with an iodo group, an azide group, or a thioacetate group.

12. The process of claim 1 , wherein the step of polymerizing is performed as a bulk process.

13. The process of claim 1 , wherein the step of polymerizing is performed under vacuum.

14. A process of functionalizing a copolyester comprising:
replacing an α-halogen atom of an α-halogenated copolyester with a functional group; wherein α-halogenated copolyester comprises:
repeat units derived one or more α-halogenated hydroxyacids, and repeat units derived from co-monomers that include:
(i) one or more diols containing from 2 to about 10 carbon atoms and one or more dicarboxylic acids containing from 2 to about 15 carbon atoms;
(ii) one or more hydroxyacids containing from 2 to about 20 carbon atoms, or
(iii) one or more diols containing from 2 to about 10 carbon atoms, one or more dicarboxylic acids containing from 2 to about 15 carbon atoms, and one or more hydroxyacids containing from 2 to about 20 carbon atoms;

where the step of replacing is performed by reacting the α-halogenated ester with an amine group, iodo group, an azide group, or a thioacetate group.

15. The process of claim 14 , wherein the step of replacing is performed by reacting the α-halogenated ester with an amine group.

16. The process of claim 14 , wherein the step of replacing is performed by reacting the α-halogenated ester with an iodo group.

17. The process of claim 14 , wherein the step of replacing is performed by reacting the α-halogenated ester with an azide group.

18. The process of claim 14 , wherein the step of replacing is performed by reacting the α-halogenated ester with a thioacetate group.

19. A process for synthesizing an α-halogenated copolyester comprising:
polymerizing one or more α-halogenated hydroxyacids with one or more commoners using a catalyst selected from p-dimethylaminopyridinium toluenesulphonate (DPTS), p-toluidine hydrochloride, dimethyl-p-phenylenediamine dihydrochloride, p-toluenesulphonic acid, or SnCl 2 , and combinations thereof,
where the co-monomers are selected from
(i) one or more diols containing from 2 to about 10 carbon atoms and one or more dicarboxylic acids containing from 2 to about 15 carbon atoms;
(ii) one or more hydroxyacids containing from 2 to about 20 carbon atoms, or
(iii) one or more diols containing from 2 to about 10 carbon atoms, one or more dicarboxylic acids containing from 2 to about 15 carbon atoms, and one or more hydroxyacids containing from 2 to about 20 carbon atoms.

20. A process for synthesizing an α-halogenated copolyester comprising:
polymerizing one or more α-halogenated hydroxyacids with one or more commoners using a protonic catalyst or a Lewis acid catalyst to form an α-halogenated copolyester, where the co-monomers are selected from
(i) one or more diols containing from 2 to about 10 carbon atoms and one or more dicarboxylic acids containing from 2 to about 15 carbon atoms;
(ii) one or more hydroxyacids containing from 2 to about 20 carbon atoms, or
(iii) one or more diols containing from 2 to about 10 carbon atoms, one or more dicarboxylic acids containing from 2 to about 15 carbon atoms, and one or more hydroxyacids containing from 2 to about 20 carbon atoms; and

reacting the α-halogenated copolyester with a linking agent and a protonic catalyst or a Lewis acid catalyst.

21. A process for synthesizing an α-halogenated copolyester comprising:
polymerizing one or more α-halogenated hydroxyacids with one or more commoners using a protonic catalyst or a Lewis acid catalyst to form an α-halogenated copolyester, where the co-monomers are selected from
(i) one or more diols containing from 2 to about 10 carbon atoms and one or more dicarboxylic acids containing from 2 to about 15 carbon atoms;
(ii) one or more hydroxyacids containing from 2 to about 20 carbon atoms, or
(iii) one or more diols containing from 2 to about 10 carbon atoms, one or more dicarboxylic acids containing from 2 to about 15 carbon atoms, and one or more hydroxyacids containing from 2 to about 20 carbon atoms; and

Assignees

• Pugh Coleen
• Banerjee Abhishek
• Storms William
• Wright Colin
• Univ Akron

Inventors

• Pugh Coleen
• Banerjee Abhishek
• Storms William
• Wright Colin

Classifications

• C08G63/06

  derived from hydroxycarboxylic acids · CPC title

• C08G63/914

  derived from polycarboxylic acids and polyhydroxy compounds · CPC title

• C08G63/6822 Primary

  derived from hydroxy carboxylic acids · CPC title

• C08G63/912

  derived from hydroxycarboxylic acids · CPC title

• C08G2230/00

  Compositions for preparing biodegradable polymers · CPC title