Sulfonic acid-modified polyisocyanate and preparation method therefor

Patent metadata

Field	Value
Publication number	US-12559453-B2
Application number	US-202218003965-A
Country	US
Kind code	B2
Filing date	Apr 8, 2022
Priority date	Jun 11, 2021
Publication date	Feb 24, 2026
Grant date	Feb 24, 2026

Abstract

Disclosed are a sulfonic acid-modified polyisocyanate and a preparation method thereof. By controlling a content of cyclohexylamine component in the raw material, the reaction rate of sulfamic acid and polyisocyanate is accelerated, so that the prepared product has advantages of light color and low turbidity as well as good storage stability.

First claim

What is claimed is:

1 . A sulfonic acid-modified polyisocyanate, which is a reaction product obtained from a reaction comprising the following components:
a) at least one polyisocyanate component; b) at least one organic compound with one or more of a sulfonic acid group and/or a sulfonate group, wherein the compound contains at least one of a mercapto group, a primary amino group or a secondary amino group; c) at least one tertiary amine; d) at least one cyclohexylamine with the following structure:

wherein, R 1 is one of cyclohexyl, cyclohexylmethyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl or 4-tert-butylcyclohexyl, and R 2 is hydrogen or a saturated or unsaturated, linear or branched, aliphatic or alicyclic or aromatic organic group having 1 to 18 carbon atoms
wherein based on a mass of the component a) being 1000 parts, a mass of the component d) added is 0.05-2 parts.

2 . The sulfonic acid-modified polyisocyanate according to claim 1 , wherein, based on a mass of the component a) being 1000 parts, a mass of the component b) added is 5-150 parts.

3 . The sulfonic acid-modified polyisocyanate according to claim 1 , wherein a molar ratio of the component c) to the component b) is 0.5-1.5:1.

4 . The sulfonic acid-modified polyisocyanate according to claim 1 , wherein the component a) of polyisocyanate is one or more of an aliphatic polyisocyanate, a alicyclic polyisocyanate, an araliphatic polyisocyanate and/or an aromatic polyisocyanate, or a modified polyisocyanate, which has an average isocyanate functionality of 2.0-5.0 and an NCO content of 7.0-32.0 wt %.

5 . The sulfonic acid-modified polyisocyanate according to claim 1 , wherein the polyisocyanate component is an aliphatic, alicyclic, araliphatic or aromatic diisocyanate which has a molecular mass of 100-500.

6 . The sulfonic acid-modified polyisocyanate according to claim 1 , wherein the component b) is a sulfonic acid and/or a sulfonate, which has an amino group.

7 . The sulfonic acid-modified polyisocyanate according to claim 6 , wherein the component b) is a sulfonic acid organic compound with a secondary amino group, which has the following structure:

wherein R 3 is one of cyclohexyl, cyclohexylmethyl, p-methylcyclohexyl, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl or 4-tert-butylcyclohexyl, and R 4 is a linear or branched aliphatic group having 2 to 6 carbon atoms.

8 . The sulfonic acid-modified polyisocyanate according to claim 1 , wherein the tertiary amine c) is an acyclic and/or cyclic tertiary amine substituted with an aliphatic and/or alicyclic group.

9 . The sulfonic acid-modified polyisocyanate according to claim 1 , wherein a catalyst, conventionally used in the polyurethane field, is further added in the modified polyisocyanate to mix with the tertiary amine c) for use, such as an organometallic catalyst: one or a mixture of at least two of aluminium tris (ethyl acetoacetate), tin n-octoate, zinc n-octoate, tin (II) 2-ethyl-1-hexanoate, dibutyltin (IV) dichloride, dibutyltin (IV) diacetate, dibutyltin (IV) dilaurate, dioctyltin (IV) diacetate or molybdenum glycolate.

10 . The sulfonic acid-modified polyisocyanate according to claim 1 , wherein the component d) of cyclohexylamine is one or more of cyclohexylamine, cyclohexanemethylamine, p-methylcyclohexylamine, 2-methylcyclohexylamine, 2,3-dimethylcyclohexylamine, 3,3,5-trimethylcyclohexylamine, 4-tert-butylcyclohexylamine, N-methylcyclohexylamine, N-methyl-cyclohexylmethylamine, N,4-dimethylcyclohexan-1-amine, N-methyl-2-methylcyclohexylamine, N-methyl-2,3-dimethylcyclohexylamine, N-methyl-3,3,5-trimethylcyclohexylamine, N-methyl-4-tert-butylcyclohexylamine, N-ethylcyclohexylamine, N-ethyl-methylcyclohexylamine, N-ethyl-p-methylcyclohexylamine, N-ethyl-2-methylcyclohexylamine, N-ethyl-2,3-dimethylcyclohexylamine, N-ethyl-3,3,5-trimethylcyclohexylamine and N-ethyl-4-tert-butylcyclohexylamine.

11 . A preparation method of the sulfonic acid-modified polyisocyanate according to claim 1 , comprising reacting the component a) of polyisocyanate component, the component b) and the component d) at 70-110° C. in the presence of the component c) of tertiary amine, wherein the component a) of polyisocyanate is fed in one or more steps.

12 . The preparation method according to claim 11 , wherein an antioxidant is added in the preparation method.

13 . The preparation method according to claim 11 , wherein the antioxidant is an aromatic amine, a hindered phenol, and a derivative thereof, which can scavenge free radicals, or a phosphorus-containing or sulfur-containing organic compound which can enable the decomposition of hydroperoxides, or a combination thereof.

14 . The preparation method according to claim 11 , wherein the reaction is carried out in a solvent which is inert to reacting with NCO.

15 . The preparation method according to claim 14 , wherein the solvent which is inert to reacting with NCO comprises one or a mixture of at least two of acetone, butanone, ethyl oxocyclopentylacetate, butyl acetate, N-ethylpyrrolidone, N-methylpyrrolidone, toluene, xylene, chlorobenzene, propylene glycol methyl ether acetate, 1-methoxyprop-2-yl acetate, 3-methoxy-n-butyl acetate, an aromatic compound, dimethyl carbonate, diethyl carbonate, butyrolactone, caprolactone and methyl caprolactone.

16 . The sulfonic acid-modified polyisocyanate according to claim 1 , wherein the polyisocyanate component is tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 4,4′-dicyclohexylpropane diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tetramethyl-xylylene diisocyanate and p-xylylene diisocyanate, or a mixture of the diisocyanates.

17 . The sulfonic acid-modified polyisocyanate according to claim 1 , wherein the polyisocyanate component is a modified polyisocyanate with an isocyanurate group based on one or more of 1,6-hexamethylene diisocyanate, isophorone diisocyanate and 4,4′-dicyclohexylmethane diisocyanate.

18 . The sulfonic acid-modified polyisocyanate according to claim 1 , wherein the component b) is a sulfonic acid and/or a sulfonate, which has a secondary amino group.

19 . The sulfonic acid-modified polyisocyanate according to claim 1 , wherein the tertiary amine c) is one or more of trimethylamine, triethylamine, tripropylamine, N,N-dimethylbutylamine, N,N-diethylmethylamine, N,N-diisopropylethylamine, N,N-dimethylcyclohexylamine, N-methylpiperidine, N-methylquinoline, N-ethylquinoline and/or N-ethylmorpholine.

20 . The sulfonic acid-modified polyisocyanate according to claim 1 , wherein the component d) of cyclohexylamine contains cyclohexylamine having the same group as R 3 in the component b) of organic compound.

Assignees

• Wanhua Chemical Group Co Ltd

Inventors

• Yin Xundi
• Ji Xueshun
• Jin Yunquan
• Wang Cuicui
• Shen Rubao
• Cao Yuyang

Classifications

• C08G18/3855

  having sulfur · CPC title

• C08G18/775

  sulfur · CPC title

• C08G18/244

  tin salts of carboxylic acids · CPC title

• C08G18/20

  Heterocyclic amines; Salts thereof · CPC title

• C08G18/2009

  containing one heterocyclic ring · CPC title