Process to prepare a cyclic oligomer and a cyclic oligomer obtainable thereby and a process to polymerize it

Patent metadata

Field	Value
Publication number	US-11149111-B2
Application number	US-201816606388-A
Country	US
Kind code	B2
Filing date	Mar 23, 2018
Priority date	Apr 21, 2017
Publication date	Oct 19, 2021
Grant date	Oct 19, 2021

Abstract

A process to prepare a (iv) cyclic polyester oligomer composition includes a cyclic polyester oligomer having furanic units and two to five repeat units. The process includes (a) reacting a monomer composition including: (i) a bifunctional furan-derivative and (ii) a diol in an linear oligomerization step to produce a (iii) linear oligomer composition including a linear oligomer species, (b) reacting the (iii) linear oligomer composition in a distillation-assisted cyclization (DA-C) step to form a (iv) cyclic polyester oligomer composition and a (v) diol byproduct. The (v) diol byproduct is removed by evaporation in the distillation-assisted cyclization (DA-C) step.

First claim

The invention claimed is:

1. A process to produce a (iv) cyclic polyester oligomer composition comprising cyclic polyester oligomers having two to five repeat units and containing furanic units, the process comprising:
(a) reacting a monomer composition comprising: (i) a bifunctional furan-derivative having two functional groups selected from the group consisting of carboxylic acid, ester, acid halide and their combinations and (ii) a diol in a linear oligomerization step to produce a (iii) linear polyester oligomer composition comprising a linear oligomer species containing one or more furanic units and two to four repeat units; and
(b) reacting the (iii) linear polyester oligomer composition in a distillation-assisted cyclization (DA-C) step to form a (iv) cyclic polyester oligomer composition comprising cyclic oligomers having two to five repeat units and containing furan units and a (v) diol byproduct,
the (v) diol byproduct being removed by evaporation in the distillation-assisted cyclization (DA-C) step, and
the distillation-assisted cyclization (DA-C) step comprising a cyclization reaction in a reaction vessel that is accompanied by simultaneous removal of condensation reaction byproducts and a solvent through evaporation, followed by collection of the condensation reaction byproducts and the solvent via condensation in a separate vessel.

2. The process of claim 1 , wherein the (b) distillation-assisted cyclization (DA-C) step takes place in the presence of the solvent.

3. The process of claim 1 , wherein the viscosity during the (a) linear oligomerization step remains less than 50 centipoise.

4. The process of claim 1 , wherein the pressure during the (a) linear oligomerization step remains at least about 0.8 atm.

5. The process of claim 1 , wherein the (ii) diol or (v) diol byproduct are ethylene glycol or butylene glycol.

6. The process of claim 1 , wherein the (i) bifunctional furan-derivative having two functional groups is 2,5-furandicarboxylic acid (FDCA) or a derivative of FDCA.

7. The process of claim 6 , wherein the derivative of FDCA is a diester derivative.

8. The process of claim 1 , wherein one or more catalysts are present during the (a) linear oligomerization step or the (b) distillation-assisted cyclization (DA-C) step.

9. The process of claim 1 , wherein the (iv) cyclic polyester oligomer composition comprising cyclic polyester oligomers having two to five repeat units and containing furanic units is directly polymerized without intermediate purification to yield a polyester polymer having an Mn of at least about 5,000 Dalton.

10. The process of claim 1 , wherein the (iv) cyclic polyester oligomer composition comprising cyclic polyester oligomers having two to five repeat units and containing furan units is subsequently purified by selective precipitation to form a (iv.a) purified cyclic polyester oligomer composition by separating one or more linear oligomers or monomeric species.

11. The process of claim 10 , wherein the separated one or more linear oligomers or monomeric species are recycled to produce a (iv.b.) further cyclic polyester oligomer composition comprising cyclic polyester oligomers having two to five repeat units and containing furanic units.

12. The process of claim 10 , wherein the (iv.a) purified cyclic polyester oligomer composition or the (iv.b) further cyclic polyester oligomer composition are polymerized to yield a polyester polymer having an Mn of at least about 5,000 Dalton.

13. The process of claim 2 , wherein the viscosity during the (a) linear oligomerization step remains less than 50 centipoise.

14. The process of claim 3 , wherein the pressure during the (a) linear oligomerization step remains at least about 0.8 atm.

15. The process of claim 4 , wherein the (ii) diol or (v) diol byproduct are ethylene glycol or butylene glycol.

16. The process of claim 5 , wherein the (i) bifunctional furan-derivative having two functional groups is 2,5-furandicarboxylic acid (FDCA) or a derivative of FDCA.

17. The process of claim 7 , wherein one or more catalysts are present during the (a) linear oligomerization step or the (b) distillation-assisted cyclization (DA-C) step.

18. The process of claim 8 , wherein the (iv) cyclic polyester oligomer composition comprising cyclic polyester oligomers having two to five repeat units and containing furanic units is directly polymerized without intermediate purification to yield a polyester polymer having an Mn of at least about 5,000 Dalton.

19. The process of claim 8 , wherein the (iv) cyclic polyester oligomer composition comprising cyclic polyester oligomers having two to five repeat units and containing furan units is subsequently purified by selective precipitation to form a (iv.a) purified cyclic polyester oligomer composition by means of separating one or more linear oligomers or monomeric species.

20. The process of claim 11 , wherein the (iv.a) purified cyclic polyester oligomer composition or the (iv.b) further cyclic polyester oligomer composition are polymerized to yield a polyester polymer having an Mn of at least about 5,000 Dalton.

Assignees

• Sulzer Management Ag

Inventors

• Costa Liborio Ivano
• Fleckenstein Peter Joachim
• Rosenboom Jan-Georg
• Storti Giuseppe
• Morbidelli Massimo

Classifications

• C08G63/91

  Polymers modified by chemical after-treatment · CPC title

• C08G63/90

  Purification; Drying · CPC title

• C08G63/81

  using solvents (C08G63/79 takes precedence) · CPC title

• C08G63/181 Primary

  Acids containing aromatic rings · CPC title

• C07C69/608

  Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a ring other than a six-membered aromatic ring in the acid moiety · CPC title