Process for organocatalytic ring-opening polymerization

Patent metadata

Field	Value
Publication number	US-9512266-B2
Application number	US-201514597618-A
Country	US
Kind code	B2
Filing date	Jan 15, 2015
Priority date	Mar 26, 2012
Publication date	Dec 6, 2016
Grant date	Dec 6, 2016

Abstract

The present invention relates to a process for organocatalytic ring-opening polymerization of at least one monomer M suitable for ring-opening polymerization, or of mixtures thereof, wherein, in a step (i), at least one N-heterocyclic compound is subjected in the presence of at least one Zerevitinov-active compound Z1 to a temperature of at least 80° C. for a period of at least 30 seconds and, in a step (ii), the monomer M is added and reacted.

First claim

The invention claimed is:

1. A process for organocatalytic ring-opening polymerization of at least one monomer M suitable for ring-opening polymerization selected from the group comprising alkylene oxides selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide, and cyclic lactones, lactides, cyclic siloxanes, or of mixtures thereof, wherein, in a step (i), at least one N-heterocyclic compound of the formula (I)

where A is selected from the group consisting of N, O and S, where no R2 radical is present when A is O or S and where R1 and R2 are each independently selected from alkyl and aryl, and where R3, R4 and R5 are each independently selected from H, alkyl, aryl, and where ring closures between R1 and R3, R3 and R4, and R4 and R2 are also possible, is subjected in the presence of at least one Zerevitinov-active compound Z1 to a temperature of at least 80° C., for a period of at least 30 seconds, and, in a step (ii), the monomer M is added and reacted.

2. The process for organocatalytic ring-opening polymerization according to claim 1 , wherein R1 and R2 are each primary alkyl groups.

3. The process for organocatalytic ring-opening polymerization according to claim 1 , wherein R1 is a primary and R2 a secondary alkyl group.

4. The process for organocatalytic ring-opening polymerization according to claim 1 , wherein the anion in the formula (I) is selected from the group consisting of formate, acetate and propionate.

5. The process for organocatalytic ring-opening polymerization according to claim 1 , wherein the anion in the formula (I) is selected from the group comprising benzoate, phthalate, terephthalate, isophthalate, succinate and glutarate.

6. The process for ring-opening polymerization according to claim 1 , wherein step (ii) is not conducted until after the end of step (i).

7. The process for ring-opening polymerization according to claim 1 , wherein step (ii) already commences during the duration of step (i).

8. The process for ring-opening polymerization according to claim 1 , wherein at least one Zerevitinov-active compound Z1 is an alcohol.

9. The process for ring-opening polymerization according to claim 1 , wherein at least one Zerevitinov-active compound Z1 is an amine.

10. The process for ring-opening polymerization according to claim 1 , wherein at least two Zerevitinov-active compounds Z1 are used, at least one Zerevitinov-active compound Z1a is an alcohol, and at least one Zerevitinov-active compound Z1b is an amine.

11. The process for ring-opening polymerization according to claim 1 , wherein the monomer M is added and reacted in the presence of at least one Zerevitinov-active compound Z2 that is selected from the group consisting of an alcohol and an amine.

12. The process for ring-opening polymerization according to claim 11 , wherein the at least one Zerevitinov-active compound Z2 is the same as the at least one Zerevitinov-active compound Z1.

13. The process for ring-opening polymerization according to claim 1 , wherein the at least one Zerevitinov-active compound Z2 is different from the at least one Zerevitinov-active compound Z1.

14. The process for ring-opening polymerization according to claim 1 , wherein step (i) does not comprise a base with a pK b (H 2 O) less than 1.

15. The process for ring-opening polymerization according to claim 1 , wherein the at least one monomer M suitable for ring-opening polymerization is an alkylene oxide-selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide.

16. The process for ring-opening polymerization according to claim 15 , wherein at least one alkylene oxide is propylene oxide.

17. The process for ring-opening polymerization according to claim 1 , wherein at least two monomers M suitable for ring-opening polymerization are used, at least one of the monomers M is an alkaline oxide selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and at least one of the second monomers M is a lactone.

18. The process for ring-opening polymerization according to claim 1 , wherein the temperature in step (i) is from 140° C. to 250° C.

19. The process for ring-opening polymerization according to claim 1 , wherein step (i) takes 5 to 30 minutes.

20. The process for ring-opening polymerization according to claim 1 , wherein a vacuum is applied during step (i).

21. The process for ring-opening polymerization according to claim 1 , wherein the at least one monomer M suitable for ring-opening polymerization is an alkaline oxide selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide, and the temperature during the reaction with the at least one monomer M in step (ii), after the end of step (i), is from 90° C. to 140° C.

22. The process for ring-opening polymerization according to claim 1 , wherein the at least one monomer M is selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide, and the at least one Zerevitinov-active compound Z1 is an alcohol, a polyol, a sugar compound,
wherein the at least one monomer M is added and reacted in the presence of at least one Zerevitinov-active compound Z2 that is an alcohol, a polyol, a sugar compound, a polyhydric phenol, and a resol,
wherein the temperature in step (i) is from 140° C. to 180° C. for a duration of 5 to 30 minutes, and wherein the temperature in step (ii), after the end of step (i), is from 90° C. to 140° C.

Assignees

• Basf Se

Inventors

• Wiss Kerstin
• Zarbakhsh Sirus
• Loeffler Achim
• Deglmann Peter
• Riebel Lothar
• Limbach Michael
• Lindner Ronald
• Lejkowski Michael Ludwik
• Grosse-Willerich Julia Frauke

Classifications

• C08G63/685 Primary

  containing nitrogen · CPC title

• C08G63/823 Primary

  for the preparation of polylactones or polylactides · CPC title

• C08G18/28

  characterised by the compounds used containing active hydrogen · CPC title

• C08G77/08

  characterised by the catalysts used · CPC title

• C08G18/48

  Polyethers · CPC title