Production methods of polyester and polyurethane

Patent metadata

Field	Value
Publication number	US-10450404-B2
Application number	US-201414560830-A
Country	US
Kind code	B2
Filing date	Dec 4, 2014
Priority date	Jun 5, 2012
Publication date	Oct 22, 2019
Grant date	Oct 22, 2019

Abstract

At the time of producing a polyester by using a dicarboxylic acid component and a biomass-resource-derived diol as raw materials, a polyester is efficiently produced with good color tone, as the raw material diol derived from biomass resources, a diol in which the content of a cyclic carbonyl compound having a carbon atom number of 5 or 6 is from 0.01 to 12 ppm by mass, is used, and by controlling the content of a cyclic carbonyl compound having a carbon atom number of 5 or 6 in the raw material diol to fall in a prescribed range, the color tone of the polyester is improved.

First claim

The invention claimed is:

1. A method for producing a polyester, comprising:
performing a reaction by using, as raw materials, a dicarboxylic acid component, and a diol produced directly from a biomass-resource-derived substance by a fermentation process,
wherein a content of a cyclic carbonyl compound having a carbon atom number of 5 or 6 in the diol is from 0.01 ppm to 12 ppm by mass, and
wherein said diol produced directly from a biomass-resource-derived substance by a fermentation process is selected from the group consisting of ethylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and isosorbide.

2. The method for producing a polyester according to claim 1 ,
wherein the cyclic carbonyl compound having a carbon atom number of 5 or 6 contains a compound having a structure represented by the following formula (I):

wherein in formula (I), each of R 1 to R 4 independently represents a hydrogen atom, a methyl group, a formyl group or an acetyl group, with the proviso that one of R 1 to R 4 is a formyl group or an acetyl group, and the total number of carbon atoms contained in respective groups of R 1 to R 4 is 2 or less.

3. The method for producing a polyester according to claim 1 ,
wherein the cyclic carbonyl compound having a carbon atom number of 5 or 6 contains a compound having a structure represented by the following formula (II):

wherein in formula (II), X represents a carbon atom or an oxygen atom, with the proviso that 1 X is an oxygen atom, each of R 5 to R 9 independently represents a methyl group or a hydrogen atom, and the total number of carbon atoms contained in respective groups of R 5 to R 9 is 1 or less.

4. The method for producing a polyester according to claim 1 ,
wherein the cyclic carbonyl compound having a carbon atom number of 5 or 6 contains a compound having a structure represented by the following formula (III) and a content of the compound having a structure represented by formula (III) in the diol is 6 ppm by mass or less:

wherein in formula (III), each of R 10 to R 13 independently represents a methyl group or a hydrogen atom, and the total number of carbon atoms contained in respective groups of R 10 to R 13 is 1 or less.

5. The method for producing a polyester according to claim 1 ,
wherein the diol is 1,4-butanediol,
the dicarboxylic acid component is at least one of a terephthalic acid and a terephthalic acid alkylate, and
the polyester is polybutylene terephthalate.

6. The method for producing a polyester according to claim 5 ,
wherein the 1,4-butanediol contains from 1 to 99 ppm by mass of 1-acetoxy-4-hydroxybutane.

7. The method for producing a polyester according to claim 1 ,
wherein a content of a nitrogen atom compound in the diol is from 0.1 to 50 ppm by mass in terms of nitrogen atom.

8. The method for producing a polyester according to claim 1 , further comprising, prior to said performing a reaction, subjecting a biomass resource to a fermentation process wherein said fermentation process comprises pretreating said biomass resource and further subjecting the biomass resource to saccharification.

9. A method for producing a polyester polyol, comprising:
performing reaction by using, as raw materials, a dicarboxylic acid component, and a diol produced directly from a biomass-resource-derived substance by a fermentation process,
wherein a content of a cyclic carbonyl compound having a carbon atom number of 5 or 6 in the diol is from 0.01 ppm to 12 ppm by mass, and
wherein said diol produced directly from a biomass-resource-derived substance by a fermentation process is selected from the group consisting of ethylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and isosorbide.

10. The method for producing a polyester polyol according to claim 9 ,
wherein the cyclic carbonyl compound having a carbon atom number of 5 or 6 contains a compound having a structure represented by the following formula (I):

wherein in formula (I), each of R 1 to R 4 independently represents a hydrogen atom, a methyl group, a formyl group or an acetyl group, with the proviso that one of R 1 to R 4 is a formyl group or an acetyl group, and the total number of carbon atoms contained in respective groups of R 1 to R 4 is 2 or less.

11. The method for producing a polyester polyol according to claim 9 ,
wherein the cyclic carbonyl compound having a carbon atom number of 5 or 6 contains a compound having a structure represented by the following formula (II):

wherein in formula (II), X represents a carbon atom or an oxygen atom, with the proviso that 1 X is an oxygen atom, each of R 5 to R 9 independently represents a methyl group or a hydrogen atom, and the total number of carbon atoms contained in respective groups of R 5 to R 9 is 1 or less.

12. The method for producing a polyester polyol according to claim 9 ,
wherein the cyclic carbonyl compound having a carbon atom number of 5 or 6 contains a compound having a structure represented by the following formula (III):

wherein in formula (III), each of R 10 to R 13 independently represents a methyl group or a hydrogen atom, and the total number of carbon atoms contained in respective groups of R 10 to R 13 is 1 or less.

13. The method for producing a polyester polyol according to claim 10 ,
wherein the diol is 1,4-butanediol,
the dicarboxylic acid component is adipic acid, and
the polyester polyol is polybutylene adipate.

14. The method for producing a polyester polyol according to claim 13 ,
wherein the 1,4-butanediol contains from 1 to 99 ppm by mass of 1-acetoxy-4-hydroxybutane.

15. The method for producing a polyester polyol according to claim 9 ,
wherein a content of a nitrogen atom compound in the diol is from 0.1 to 50 ppm by mass in terms of nitrogen atom.

16. The method for producing a polyester polyol according to claim 9 , further comprising prior to said performing reaction subjecting a biomass resource to a fermentation process wherein said fermentation process comprises pretreating said biomass resource and further subjecting the biomass resource to saccharification.

17. A method for producing a polyurethane, comprising:
reacting a polyester polyol produced by the production method of a polyester polyol according to claim 9 with an isocyanate compound.

18. A method for producing a polyurethane, comprising:
reacting a polyester polyol and an isocyanate compound,
wherein the polyester polyol is produced by an esterification and/or transesterification reaction of a dicarboxylic acid and a diol, wherein the diol is produced directly from a biomass-resource-derived substance by a fermentation process and a content of a cyclic carbonyl compound having a carb

Assignees

• Mitsubishi Chem Corp
• Genomatica Inc

Inventors

• Utsunomiya Masaru
• Izawa Yusuke
• Konishi Norikazu
• Tanaka Kota
• Matsuzono Shinichiro
• Suzuki Takayuki
• Japs Michael
• Burk Mark
• Clark Warren

Classifications

• C08G63/183

  Terephthalic acids · CPC title

• C08G63/16

  Dicarboxylic acids and dihydroxy compounds · CPC title

• C12P7/18

  polyhydric · CPC title

• C08G18/4213 Primary

  from terephthalic acid and dialcohols · CPC title

• C08G18/664

  with compounds of group C08G18/3203 · CPC title