Process for producing polycarbodiimide

Patent metadata

Field	Value
Publication number	US-9416213-B2
Application number	US-201314429227-A
Country	US
Kind code	B2
Filing date	Sep 19, 2013
Priority date	Sep 19, 2012
Publication date	Aug 16, 2016
Grant date	Aug 16, 2016

Abstract

A process for producing a polycarbodiimide, comprising polymerizing a diisocyanate in the presence of a carbodiimidization catalyst in a reaction vessel in liquid phase at a temperature in the range of from 20 to 250° C., at a pressure in the range of from 20 to 800 mbar and in the presence of at least one inert gas, wherein the at least one inert gas is introduced into the liquid phase in the reaction vessel with a flow rate in the range of from 0.1 x/h to 100 x/h, x being the volume of the reaction vessel.

First claim

The invention claimed is:

1. A process for producing a polycarbodiimide, the process comprising:
(a) polymerizing a diisocyanate in the presence of a carbodiimidization catalyst in a reaction vessel in liquid phase at a temperature in the range of from 20 to 250° C., at a pressure in the range of from 20 to 800 mbar and in the presence of at least one inert gas,
wherein the at least one inert gas is introduced into the liquid phase in the reaction vessel with a flow rate in the range of from 1 x/h to 20 x/h, x being the volume of the reaction vessel, and
wherein the at least one inert gas is selected from the group consisting of nitrogen, helium, neon, argon, and a mixture of two or more thereof.

2. The process according to claim 1 , wherein the diisocyanate is polymerized at a temperature in the range of from 130 to 200° C.

3. The process according to claim 1 , wherein the diisocyanate is polymerized at a pressure in the range of from 200 to 500 mbar.

4. The process according to claim 1 , wherein the diisocyanate has formula R(NCO) 2 , wherein R is selected from the group consisting of a linear or branched aliphatic C 3 -C 15 hydrocarbon residue, a cycloaliphatic C 5 -C 20 hydrocarbon residue, an aryl C 6 -C 18 hydrocarbon residue, an alkaryl C 6 -C 20 hydrocarbon residue, and an aralkyl C 6 -C 20 hydrocarbon residue.

5. The process according to claim 1 , 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).

6. The process according to claim 1 , wherein the diisocyanate is 1,3-bis(2-isocyanato-2-propyl)benzene (TMXDI).

7. The process according to claim 1 , wherein at the beginning of said polymerizing, the carbodiimidization catalyst is present, relative to the diisocyanate, in an amount in the range of from 100 to 20,000 wppm.

8. The process according to claim 1 , wherein the carbodiimidization catalyst comprises an organophosphorous compound selected from the group consisting of a phospholene, a phospholene oxide, a phospholidine, a phospholine oxide and a mixture of two or more thereof.

9. The process according to claim 1 , wherein the carbodiimidization catalyst comprises 1-methyl-2-phospholene-1-oxide (MPO).

10. The process according to claim 1 , wherein the inert gas is nitrogen.

11. The process according to claim 1 , wherein the diisocyanate is polymerized in the absence of a solvent.

12. The process according to claim 1 , wherein the polycarbodiimide obtained from (a) has a degree of polymerization in the range of from 1 to 20.

13. The process according to claim 1 , wherein the polycarbodiimide obtained from (a) has an NCO content in the range of from 0 to 25% by weight based on a total weight of the polycarbodiimide.

14. The process according to claim 13 , wherein the NCO content is achieved after a polymerization time in the range of from 1 to 30 hours.

15. The process according to claim 1 , wherein the polycarbodiimide obtained from (a) has a color index of at most 20 as determined according to DIN 6162.

16. The process according to claim 1 , further comprising:
(b) separating the carbodiimidization catalyst from the polycarbodiimide by subjecting a reaction mixture obtained from (a) 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 the carbodiimidization catalyst, wherein a weight ratio of the carbodiimidization catalyst relative to the polycarbodiimide in the first bottom product is lower than a weight ratio of the carbodiimidization catalyst relative to the polycarbodiimide in the mixture according to (a), and wherein the first top product comprises the carbodiimidization catalyst;
(c) adding an entrainer to the first bottom product obtained from (b) to obtain a mixture, wherein the entrainer has a boiling point which is lower than a boiling point of the polycarbodiimide;
(d) further separating the carbodiimidization catalyst from the polycarbodiimide by subjecting the mixture obtained from (c) 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 the carbodiimidization catalyst, wherein a weight ratio of the carbodiimidization catalyst relative to the polycarbodiimide in the second bottom product is lower than a weight ratio of the carbodiimidization catalyst relative to the polycarbodiimide in the first bottom product obtained from (b), and wherein the second top product comprises the carbodiimidization catalyst and the entrainer;
(e) optionally at least partially recycling the first top product obtained from (b) and/or the second top product obtained from (d) into (a) as starting material for polymerizing the diisocyanate in the presence of the carbodiimidization catalyst.

17. The process according to claim 1 , wherein the polycarbodiimide is further reacted with a compound selected from the group consisting of a monool, a diol, a polyoxyalkylene alcohol, a monoamine, a polyethylene glycol, and a polypropylene glycol.

Assignees

• Basf Se

Inventors

• Bubolz Markus
• Haeberle Karl
• Henke Kai
• Kempfert Dirk
• Kraemer Markus
• Lawrenz Sven
• Schaefer Frank
• Thomas Maria
• Treuling Ulrich

Classifications

• C08G18/025 Primary

  the polymeric products containing carbodiimide groups · CPC title

• C08G18/095

  oligomerisation to carbodiimide or uretone-imine groups · CPC title

• C08G18/0838

  Manufacture of polymers in the presence of non-reactive compounds (preparation of compositions C08L75/00) · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C08G2115/06

  to carbodiimide or uretone-imine groups · CPC title