Process to prepare a cyclic oligomer and a cyclic oligomer obtainable thereby

Patent metadata

Field	Value
Publication number	US-9725558-B2
Application number	US-201314773480-A
Country	US
Kind code	B2
Filing date	Nov 27, 2013
Priority date	Mar 15, 2013
Publication date	Aug 8, 2017
Grant date	Aug 8, 2017

Abstract

A process to prepare a cyclic polyester oligomer composition having a cyclic polyester oligomer having furanic units, includes the step of reacting a monomer component, for example, 2,5-furan dicarboxylic acid and, for example, ethylene glycol, in a ring closing oligomerization at a reaction temperature and reaction time, for example, at 100° C. to 350° C. for 30 to 600 minutes to obtain a cyclic polyester oligomer having furanic units. The process yields a cyclic polyester oligomer composition which can be used in further ring-opening polymerization reactions to produce a polyester polymer. The cyclic polyester oligomer composition has a cyclic polyester oligomer having furanic units and less than 5% linear oligomeric polyester species in the composition.

First claim

The invention claimed is:

1. A process to prepare a cyclic polyester oligomer composition comprising a cyclic polyester oligomer having furanic units, wherein the process comprises:
a step of either:

(I) reacting a monomer component C 1 or D 1 in the presence of an optional catalyst and/or optional organic base in a ring closing oligomerization step under conditions of a reaction temperature and reaction time sufficient to yield a cyclic polyester oligomer having furanic units and of structure Y 1 , wherein the monomer component C 1 comprises the structure

and wherein each of the groups A is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, and wherein l is an integer from 1 to 100,
and wherein
R 1 =OH, OR, halogen, or O-A-OH,
R=optionally substituted linear, branched or cyclic alkyl, phenyl, aryl or alkylaryl,
R 2 =H or

wherein the monomer component D 1 comprises the structure

and wherein A is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, and wherein each of the groups X is an OH, a halogen, or an optionally-substituted alkyloxy, phenoxy, or aryloxy, and wherein the groups X are not OH when A is n-butyl, and wherein the structure Y 1 of the cyclic polyester oligomer having furanic units is

wherein m is an integer from 1 to 20,
OR

(II) reacting a monomer component C 2 or D 2 in the presence of an optional catalyst and/or optional organic base in a ring closing oligomerization step under conditions of a reaction temperature and reaction time sufficient to yield a cyclic polyester oligomer having furanic units and of structure Y 2 , wherein the monomer component C 2 comprises the structure

and wherein each of the groups B is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, wherein l is an integer as defined above, and wherein n′ is an integer from 1 to 20, and wherein
R 3 =OH, OR, halogen, or O—(B—O) n —H,
R=optionally substituted linear, branched or cyclic alkyl, phenyl, aryl or alkylaryl,
R 4 =H or

the monomer component D 2 comprises the structures

and wherein each of the groups X is an OH, a halogen, or an optionally-substituted alkyloxy, phenoxy, or aryloxy, each of the groups B is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, and n′ is an integer as defined above,
and wherein the structure Y 2 of the cyclic polyester oligomer having furanic units is

wherein each of the groups B is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, n′ is an integer as defined above, and m is an integer from 1 to 20, AND
a subsequent step (III) in which linear oligomeric polyester species having furanic units are separated and removed from the cyclic oligomeric composition.

2. The process of claim 1 , wherein either:
(I)—the monomer component is C 1 and A is an optionally-substituted linear, branched or cyclic alkyl, l is an integer from 3 to 25,
OR
the monomer component is D 1 and A is an optionally-substituted linear, branched or cyclic alkyl, X is a halogen, or optionally-substituted alkyloxy or phenoxy, and m is as defined previously in this claim, and wherein the structure of the cyclic polyester oligomer having furanic units is one of Y 1 ,
OR

(II)—the monomer component is C 2 and wherein B is an optionally-substituted linear, branched or cyclic alkyl, l and m are integers as defined above, and n′ is an integer from 2 to 10,
OR
the monomer component is D 2 , and wherein X is an OH, a halogen, or optionally-substituted alkyloxy, phenoxy, or aryloxy, B is an optionally-substituted linear, branched or cyclic alkyl, or phenyl, and n′ and m are integers as defined previously in this claim, and wherein the structure of the cyclic polyester oligomer having furanic units is one of Y 2 .

3. The process of claim 1 , wherein either
the monomer component is C 1 and A is an optionally-substituted linear, branched or cyclic C 1 to C 6 alkyl, and l is an integer from 3 to 25, and m is an integer from 3 to 10,
the monomer component is D 1 and A is an optionally-substituted linear, branched or cyclic C 1 to C 6 alkyl, X is a halogen, or optionally-substituted alkyloxy or phenoxy, and m is an integer as defined above,
the monomer component is C 2 and wherein B is an optionally-substituted linear, branched or cyclic C 1 to C 6 alkyl, l and m are integers as defined above and n′ is an integer from 2 to 10,

OR
the monomer component is D 2 , X is a halogen, or an optionally-substituted alkyloxy, phenoxy, or aryloxy, B is an optionally-substituted linear, branched or cyclic C 1 to C 6 alkyl, or phenyl, and n′ and m are integers as defined in claim 2 .

4. The process of claim 1 , wherein the monomer component is C 1 or C 2 and the reaction temperature is from 100 to 350° C., and wherein the reaction time is from 30 to 600 minutes,
OR
wherein the monomer component is D 1 or D 2 and the reaction temperature is from −10 to 150° C., and wherein the reaction time is from 5 to 240 minutes.

5. The process of claim 1 , wherein either the monomer component C 1 comprises the specific structure

or the monomer component D 1 comprises the specific structure

and the structure Y 1 of the cyclic polyester oligomer having furanic units is the specific structure

wherein
R 5 =OH, OR, halogen, or O—CH 2 CH 2 —OH,
R=optionally substituted linear, branched or cyclic alkyl, phenyl, aryl or alkylaryl,
R 6 =H or

and X, l, and m are defined as indicated in the previous claim on which this claim depends.

6. The process of claim 1 , wherein either the monomer component C 1 comprises the specific structure C 1″

or the monomer component D 1 comprises the specific structure D 1″

and the structure Y 1 of the cyclic polyester oligomer having furanic units is the specific structure Y 1″

R 7 =OH, OR, halogen, or O—CH 2 CH 2 CH 2 CH 2 —OH,
R=optionally substituted linear, branched or cyclic alkyl, phenyl, ar

Assignees

• Sulzer Chemtech Ag

Inventors

• Costa Liborio Ivano
• Nising Philip
• Tancini Francesca
• Pfister David
• Storti Giuseppe
• Morbidelli Massimo

Classifications

• C08G63/78 Primary

  Preparation processes · CPC title

• C08G63/916 Primary

  Dicarboxylic acids and dihydroxy compounds · CPC title

• C08G63/181

  Acids containing aromatic rings · CPC title

• C08G63/16

  Dicarboxylic acids and dihydroxy compounds · CPC title

• C08L67/02

  Polyesters derived from dicarboxylic acids and dihydroxy compounds (C08L67/06 takes precedence) · CPC title