Process for the purification of a polycarbodiimide

Patent metadata

Field	Value
Publication number	US-9481641-B2
Application number	US-201314429151-A
Country	US
Kind code	B2
Filing date	Sep 19, 2013
Priority date	Sep 19, 2012
Publication date	Nov 1, 2016
Grant date	Nov 1, 2016

Abstract

A process for purifying a polycarbodiimide comprising (a) providing a mixture comprising a polycarbodiimide and a carbodiimidization catalyst; (b) separating carbodiimidization catalyst from the polycarbodiimide by subjecting the mixture according to (a) to a first distillation, (c) adding an entrainer to the first bottom product obtained from (b) to obtain a mixture; (d) further separating carbodiimidization catalyst from the polycarbodiimide by subjecting the mixture obtained from (c) to a second distillation.

First claim

The invention claimed is:

1. A process for purifying a polycarbodiimide, comprising:
(a) separating a carbodiimidization catalyst from an initial mixture comprising a polycarbodiimide and the carbodiimidization catalyst by subjecting the initial mixture to a first distillation, wherein a first bottom product and a first top product are obtained, wherein the first bottom product comprises the polycarbodiimide and carbodiimidization catalyst, a weight ratio of carbodiimidization catalyst relative to polycarbodiimide in the first bottom product is lower than a weight ratio of carbodiimidization catalyst relative to polycarbodiimide in the initial mixture and wherein the first top product comprises carbodiimidization catalyst;
(b) adding an entrainer to the first bottom product obtained from (a) to obtain an intermediate mixture, wherein the entrainer has a boiling point which is lower than the boiling point of the polycarbodiimide;
(c) further separating carbodiimidization catalyst from the polycarbodiimide by subjecting the intermediate mixture obtained from the adding (b) to a second distillation, wherein a second bottom product and a second top product are obtained, wherein the second bottom product comprises the polycarbodiimide and carbodiimidization catalyst, a weight ratio of carbodiimidization catalyst relative to polycarbodiimide in the second bottom product is lower than a weight ratio of carbodiimidization catalyst relative to polycarbodiimide in the first bottom product obtained from the separating (a), and wherein the second top product comprises carbodiimidization catalyst and entrainer.

2. The process according to claim 1 , wherein the weight ratio of carbodiimidization catalyst relative to polycarbodiimide in the initial mixture is from 0.02:100 to 2:100.

3. The process according to claim 1 , wherein the weight ratio of carbodiimidization catalyst relative to polycarbodiimide in the bottom product obtained from the separating (a) is at most 2:100,000.

4. The process according to claim 1 , wherein the weight ratio of carbodiimidization catalyst relative to polycarbodiimide in the bottom product obtained from the further separating (c) is at most 0.2:100,000.

5. The process according to claim 1 , wherein the entrainer added in the adding (b) has a boiling point in the range of from 150 to 350° C. at ambient pressure.

6. The process according to claim 1 , wherein the entrainer added in (b) does not comprise an aminic —NH— group, an —OH group, an —SH group and/or a —COOH group.

7. The process according to claim 1 , wherein the entrainer added in (b) is a diisocyanate.

8. The process according to claim 1 , wherein the entrainer added in (b) has the formula R(NCO) 2 , wherein R is selected from the group consisting of linear or branched aliphatic C 3 -C 15 hydrocarbon residues, cycloaliphatic C 5 -C 20 hydrocarbon residues, aryl C 6 -C 18 hydrocarbon residues, alkaryl C 6 -C 20 hydrocarbon residues, and aralkyl C 6 -C 20 hydrocarbon residues.

9. The process according to claim 1 , wherein the entrainer added in (b) is 1,3-bis(2-isocyanato-2-propyl)benzene (TMXDI).

10. The process according to claim 1 , wherein the initial mixture further comprises a diisocyanate, wherein in the separating (a) the diisocyanate is at least partially separated from the polycarbodiimide and the first top product obtained from the separating (a) further comprises diisocyanate.

11. The process according to claim 10 , wherein the diisocyanate has the formula R(NCO) 2 , wherein R is selected from the group consisting of linear or branched aliphatic C 3 -C 15 hydrocarbon residues, cycloaliphatic C 5 -C 20 hydrocarbon residues, aryl C 6 -C 18 hydrocarbon residues, alkaryl C 6 -C 20 hydrocarbon residues, and aralkyl C 6 -C 20 hydrocarbon residues.

12. The process according to claim 10 , wherein the diisocyanate is selected from the group consisting of tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, trimethylhexane diisocyanate, 2,2-bis(4-isocyanatocyclohexyl)-propane, isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (HMDI), 1,3-bis(2-isocyanato-2-propyl)benzene (TMXDI), toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI).

13. The process according to claim 10 , wherein the entrainer added in (b) is the diisocyanate further comprised in the initial mixture.

14. The process according to claim 10 , wherein in adding (b) the weight ratio of polycarbodiimide relative to added entrainer is in the range of from 10:100 to 1,000:100.

15. The process according to claim 1 , wherein the carbodiimidization catalyst comprises at least one organophosphorous compound selected from the group consisting of phospholenes, phospholene oxides, phospholidines, and phospholine oxides.

16. The process according to claim 1 , wherein the initial mixture comprising a polycarbodiimide and a carbodiimidization catalyst is obtained by a method comprising polymerizing a diisocyanate in the presence of the carbodiimidization catalyst at a temperature in the range of from 20 to 300° C. and a pressure in the range of from 10 to 800 mbar.

17. The process according to claim 16 , wherein the first top product obtained from the separating (a) comprising carbodiimidization catalyst and/or the second top product obtained from the further separating (c) comprising carbodiimidization catalyst is/are at least partially recycled as starting material for polymerizing the diisocyanate in the presence of the carbodiimidization catalyst to obtain the initial mixture.

Assignees

• Basf Se

Inventors

• Haeberle Karl
• Hechavarria Fonseca Maria Teresa
• Rehling Lars
• Schaefer Frank
• Ahmadnian Fatemeh
• Bollmann Heinrich
• Bubolz Markus
• Buschmann Carsten
• Scholz Guenter
• Thomas Maria

Classifications

• C08G69/00

  Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule (products obtained from isocyanates or isothiocyanates C08G18/00; polyamide-imides C08G73/14) · CPC title

• C08G18/6511

  compounds of group C08G18/3203 · CPC title

• C07C267/00 Primary

  Carbodiimides · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C08G18/4854

  Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group · CPC title