Granted Patent B2

US 8,415,496 · App. 12/816,701 · Granted Apr 9, 2013

Abstract

Claims (30)

1. A method for preparing polyalkylene terephthalate comprising

a) contacting cis,cis muconic acid and one or more isomerization catalysts, without ultraviolet radiation, in a solvent at elevated temperatures for a period of time such that the cis,cis muconic acid isomerizes to trans,trans muconic acid, wherein the one or more isomerization catalysts are selected from one or more of halides, dialkyl peroxides, alkyl peroxides, aroyl peroxides, peroxy esters and azo compounds, or a combination thereof;

b) recovering the trans,trans muconic acid; and

c) optionally, contacting the trans,trans muconic acid with one or more esterifying agents in the presence of one or more strong acids under conditions such that one or more trans, trans dihydrocarbyl muconates are formed;

d) contacting one or more of the trans,trans muconic acid or dihydrocarbyl muconates with one or more dienophiles at elevated temperatures under conditions such that the one or more of the trans,trans muconic acid or dihydrocarbyl muconates and dienophiles form one or more cyclohexene ring dicarboxylic acid containing compounds or cyclohexene ring dihydrocarbylcarboxylate containing compounds; and

e) contacting the cyclohexene ring dicarboxylic acid containing compounds or cyclohexene ring dihydrocarbylcarboxylate containing compounds in the presence of a dehydrogenation catalyst under conditions such that one or more of terephthalic acid or dihydrocarbyl terephthalates are prepared;

f) contacting the one or more of terephthalic acid or dihydrocarbyl terephthalates with one or more alkylene glycols under conditions such that one or more polyalkylene terephthalates are prepared.

2. A method for preparing polyethylene terephthalate comprising

a) contacting cis,cis muconic acid and iodine, without ultraviolet radiation, in a solvent at elevated temperatures for a period of time such that the cis,cis muconic acid isomerizes to trans,trans muconic acid;

b) recovering the trans,trans muconic acid; and

c) contacting the trans,trans muconic acid with methanol in the presence of one or more strong acids under conditions such that trans trans dimethyl muconate is formed;

d) contacting the trans,trans dimethyl muconate with ethylene at elevated temperatures under conditions such that dimethyl cyclohex-2-ene 1,4 dicarboxylate is prepared;

e) contacting the dimethyl cyclohex-2-ene 1,4 dicarboxylate with an oxidant in the presence of a dehydrogenation catalyst under conditions such that one or more dimethyl terephthalates are prepared;

f) hydrolyzing the one or more dimethyl terephthalates to form terephthalic acid; and

g) contacting the terephthalic acid with ethylene glycol under conditions such that one or more polyethylene terephthalates are prepared.

3. A method according to claim 2 wherein each monomer unit of the polyethylene terephthalates contains at least 6 carbons derived from microbial synthesis.

4. A method according to claim 2 wherein each monomer unit of the polyethylene terephthalates contains at least 6 carbons derived from muconic acid derived from microbial synthesis.

5. A method according to claim 2 wherein the cis,cis muconic acid is derived from biomass carbohydrate by microbial synthesis under fermentor controlled conditions.

6. A method according to claim 2 wherein the dienophile is ethylene derived from microbial synthesis and the total carbons in each monomer unit derived from microbial synthesis is 8 or greater.

7. A method for preparing a polyester comprising: a) contacting cis-cis muconic acid and one or more isomerization catalysts, without ultraviolet radiation, in a solvent at elevated temperatures for a period of time such that the cis-cis muconic acid isomerizes to trans-trans muconic acid, wherein the one or more isomerization catalysts are selected from one or more of halides, dialkyl peroxides, alkyl peroxides, aroyl peroxides, peroxy esters and azo compounds, or a combination thereof; b) recovering the trans-trans muconic acid; c) optionally, contacting the trans-trans muconic acid with one or more esterifying agents in the presence of one or more strong acids under conditions such that one or more trans-trans dihydrocarbyl muconates are formed; d) contacting one or more of the trans-trans muconic acid or dihydrocarbyl muconates with one or more dienophiles at elevated temperatures under conditions such that the one or more cyclohexene ring dicarboxylic acid containing compounds or cyclohexene ring dihydrocarbylcarboxylate containing compounds; and e) contacting the one or more cyclohexene ring dicarboxylic acid containing compounds or cyclohexene ring dihydrocarbylcarboxylate containing compounds with one or more alkylene glycols under conditions such that one or more polyalkylene polyesters are prepared.

8. A method for preparing a polyester comprising: a) contacting cis-cis muconic acid and one or more isomerization catalysts, without ultraviolet radiation, in a solvent at elevated temperatures for a period of time such that the cis-cis muconic acid isomerizes to trans-trans muconic acid, wherein the one or more isomerization catalysts are selected from one or more of halides, dialkyl peroxides, alkyl peroxides, aroyl peroxides, peroxy esters and azo compounds, or a combination thereof; b) recovering the trans-trans muconic acid; c) optionally, contacting the trans-trans muconic acid with one or more esterifying agents in the presence of one or more strong acids under conditions such that one or more trans-trans dihydrocarbyl muconates are formed; d) contacting one or more of the trans-trans muconic acids or dihydrocarbyl muconates with one or more dienophiles at elevated temperatures under conditions such that one or more cyclohexene ring dicarboxylic acid containing compounds or cyclohexene ring dihydrocarbylcarboxylate containing compounds; and e) contacting the cyclohexene ring containing compounds with a hydrogenation catalyst under conditions such that one or more cyclohexane compounds having carboxylic acid groups or hydrocarbylcarboxylate groups at the 1 and 4, and optionally the 2, positions are prepared; f) contacting the one or more cyclohexane compounds having carboxylic acid groups or hydrocarbylcarboxylate groups at the 1 and 4, and optionally the 2, positions with one or more alkylene glycols under conditions such that one or more polyalkylene polyesters are prepared.

9. A method according to claim 1 wherein each monomer unit of the polyalkylene terephthalates contains at least 6 carbons derived from microbial synthesis.

10. A method according to claim 8 wherein each monomer unit of the polyalkylene terephthalates contains at least 6 carbons derived from muconic acid derived from microbial synthesis.

11. A method according to claim 1 wherein the cis,cis muconic acid is derived from microbial synthesis.

12. A method according to claim 7 wherein each monomer unit of the polyalkylene polyesters contains at least 6 carbons derived from microbial synthesis.

13. A method according to claim 7 wherein each monomer unit of the polyalkylene polyesters contains at least 6 carbons derived from muconic acid derived from microbial synthesis.

14. A method according to claim 7 wherein the cis,cis muconic acid is derived from microbial synthesis.

15. A method according to claim 8 wherein each monomer unit of the polyalkylene polyesters contains at least 6 carbons derived from microbial synthesis.

16. A method according to claim 8 wherein each monomer unit of the polyalkylene polyesters contains at least 6 carbons derived from muconic acid derived from microbial synthesis.

17. A method according to claim 8 wherein the cis,cis muconic acid is derived from microbial synthesis.

Assignments (12)