Polyesters from asymetrical monomers based upon bisanhydrohexitols

Patent metadata

Field	Value
Publication number	US-9580544-B2
Application number	US-201113050304-A
Country	US
Kind code	B2
Filing date	Mar 17, 2011
Priority date	Mar 18, 2010
Publication date	Feb 28, 2017
Grant date	Feb 28, 2017

Abstract

A process for producing copolymers of a polymer and asymmetrically substituted compounds of bisanhydrohexitols, including the bisanhydrohexitol isosorbide. In a specific example, the AB monomer isosorbide 2-(4-carbomethoxybenzoate) is synthesized and copolymerized with polyester to form a copolyester. The asymmetrically substituted compounds provide a way of incorporating bisanydrohexitols that may be derived from natural sources into polymers.

First claim

We claim:

1. A process for making a copolyester, comprising the steps of:
(a) synthesizing an AB monomer comprising bisanhydrohexitol derivatives of the general type
A-X—C—Y—B

capable of self-polymerization directly to form stereoregular or regioregular condensation polymers where
A is selected from the group consisting of a carboxyl group, an ester group, and reactive carbonyl derivatives comprising acid chlorides,
Y is a bisanhydrohexitol unit derived from the group consisting of isosorbide, isoidide, and isomannide,
X is selected from the group consisting of aromatic rings, including 1,4-phenylene, 1,3-phenylene, 2,6- naphthalene or 2,7-naphthalene (or substituted derivatives thereof), and suitable heterocyclic variants, including 2,5-furan and 2,5-thiophene, both saturated and unsaturated aliphatic chains and acyclic compounds,
B is —OH, and
C is an ester carbonyl link with the carbon attached to X and the oxygen attached to Y and wherein the resulting AB monomer is either an at least about 98% pure endo-substituted bisanhydrohexitol derivative or an at least about 98% pure exo-substituted bisanhydrohexitol derivative; and

(b) reacting the AB monomer with a polyester to form a polymer, wherein the molar ratio of AB monomer to polyester is at least about 1:9.

2. The method of claim 1 , wherein the step of reacting the AB monomer with polyester is performed under melt polymerization conditions.

3. The method of claim 1 , wherein synthesizing the AB monomer further comprises the step of adding a catalyst during the synthesis of the AB monomer and removing the catalyst when the synthesis is complete.

4. The method of claim 3 , wherein the catalyst is removed prior to reacting the AB monomer with the polyester.

5. The method of claim 1 , wherein the synthesizing the AB monomer further comprises:
(a) reacting the bisanhydrohexitol unit with a protective moiety to protect one of the —OH groups of the bisanhydrohexitol unit to produce a protected bisanhydrohexitol unit;
(b) reacting the protected bisanhydrohexitol unit with X to attach X to the protected bisanhydrohexitol unit at the unprotected —OH group via C; and
(c) removing the protective moiety to create an AB monomer.

Assignees

• East Anthony
• Jaffe Michael
• Hammond Willis
• Feng Xianhong
• New Jersey Inst Technology

Inventors

• East Anthony
• Jaffe Michael
• Hammond Willis
• Feng Xianhong

Classifications

• C08G63/66

  Polyesters containing oxygen in the form of ether groups (C08G63/42, C08G63/58 take precedence) · CPC title

• C08G63/664 Primary

  derived from hydroxy carboxylic acids · CPC title

• C07D493/04 Primary

  Ortho-condensed systems · CPC title

• C07D519/00

  Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00 · CPC title

• C08G63/672

  Dicarboxylic acids and dihydroxy compounds · CPC title