Process for preparing isocyanate homopolymers containing uretdione groups

Patent metadata

Field	Value
Publication number	US-9518142-B2
Application number	US-201414907153-A
Country	US
Kind code	B2
Filing date	Mar 3, 2014
Priority date	Nov 26, 2013
Publication date	Dec 13, 2016
Grant date	Dec 13, 2016

Abstract

The present invention relates to a process for preparing isocyanate homopolymers containing uretdione groups, in which the phosphinoboron compound of formula (I) are used as catalysts to catalyze the homopolymerization reaction of raw isocyanates, thereby obtaining a solution of isocyanate homopolymers having uretdione groups, then separating the solution and thus obtaining the isocyanate homopolymers containing uretdione groups. The isocyanate homopolymers containing uretdione groups prepared by this process have a high amount of the uretdione groups, wherein the dependence of the amount on the conversion rate of raw isocyanates is significantly ameliorated, with low chromaticities.

First claim

The invention claimed is:

1. A process for preparing isocyanate homopolymers containing uretdione groups comprising:
in the presence of catalysts, homopolymerizing raw isocyanate monomers to prepare isocyanate homopolymers containing uretdione groups, wherein the catalysts comprise phosphinoboron compounds of the structure of formula (I):

wherein R 1 , R 2 and R 3 are independently selected from linear or branched C 1 -C 20 alkyl group, optionally substituted C 3 -C 20 cycloalkyl group, optionally substituted C 7 -C 15 aralkyl or optionally substituted C 6 -C 12 aryl group.

2. The process according to claim 1 , wherein the phosphinoboron compound catalysts of formula (I) are selected from the group consisting of:

3. The process according to claim 1 , wherein the raw isocyanate monomer is selected from one of the following compounds: aliphatic isocyanate, cycloaliphatic isocyanate or aromatic isocyanate; wherein the isocyanate having a NCO functionality ≧2.

4. The process according to claim 3 , wherein the isocyanates are selected from the following compounds: tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene-1,6-diisocyanate, lysine diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dicyclohexylmethane diisocyanate, norbornane dimethylene isocyanate, diphenylmethane diisocyanate, toluene diisocyanate or p-phenyl diisocyanate.

5. The process according to claim 1 , wherein the amount of phosphinoboron compound catalysts of formula (I) is 0.1-4 mol %, based on the amount of raw isocyanate monomers.

6. The process according to claim 5 , wherein the phosphinoboron compound catalysts of formula (I) are used solely or as a formulated solution, wherein the concentration of the solution is 0.5-5 mol/L.

7. The process according to claim 6 , wherein the solvents used in formulating the solution from the phosphinoboron compound catalysts are free of an active hydrogen.

8. The process according to claim 1 , wherein the temperature of homopolymerization reaction is 20-120° C.

9. The process according to claim 1 , wherein, when the conversion rate of the raw isocyanate monomers in the homopolymerization reaction reaches 20%-60% based on the mass of raw isocyanate monomers, a catalyst poison is used to terminate the homopolymerization reaction.

10. The process according to claim 9 , wherein the catalyst poisons are alkylating agents or phosphate esters, where a mole ratio of the catalyst poison to the phosphinoboron compound catalyst is 1:1-2:1.

11. The process according to claim 1 , wherein R 1 , R 2 and R 3 are independently selected from methyl, linear or branched C 3 -C 20 alkyl, alkyl-substituted C 3 -C 20 cycloalkyl group, alkyl-substituted C 7 -C 15 aralkyl group, alkyl-substituted C 6 -C 12 aryl group or alkoxyl-substituted C 6 -C 12 aryl group.

12. The process according to claim 1 , wherein R 1 , R 2 and R 3 are independently selected from methyl, n-butyl, tert-butyl, cyclopropyl, cyclohexyl, phenyl or methoxyphenyl.

13. The process according to claim 4 , wherein the isocyanate is selected from hexamethylene-1,6-diisocyanate or isophorone diisocyanate.

14. The process according to claim 5 , wherein the amount of phosphinoboron compound catalysts of formula (I) is 0.5-2 mol %, based on the amount of raw isocyanate monomers.

15. The process according to claim 6 , wherein the phosphinoboron compound catalysts of formula (I) are used solely or as a formulated solution, wherein the concentration of the solution is 2-4 mol/L.

16. The process according to claim 7 , wherein the solvents used in formulating the solution from the phosphinoboron compound catalysts are selected from the group consisting of: halogenated hydrocarbons, aromatic hydrocarbons, ethers, and combinations thereof.

17. The process according to claim 16 , wherein the solvents used in formulating the solution from the phosphinoboron compound catalysts are selected from the group consisting of: dichloromethane, tetrahydrofuran, methylbenzene, dimethylbenzene, chlorobenzene, and combinations thereof.

18. The process according to claim 8 , wherein the temperature of homopolymerization reaction is 50-100° C.

19. The process according to claim 10 , wherein the catalyst poisons are alkylating agents or phosphate esters, where a mole ratio of the catalyst poison to the phosphinoboron compound catalyst is 1:1-1.2:1.

Assignees

• Wanhua Chemical (Ningbo) Co Ltd
• Wanhua Chemical Group Co Ltd

Inventors

• Sun Lidong

Classifications

• C07F9/5414

  substituted by B, Si, P or a metal · CPC title

• C08G18/027 Primary

  the polymeric products containing urethodione groups · CPC title

• C08G18/168

  Organic compounds · CPC title

• C07D229/00 Primary

  Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms · CPC title