Polyisocyanate modified with sulphamic acid, preparation method thereof and use thereof

Patent metadata

Field	Value
Publication number	US-9975985-B2
Application number	US-201314914223-A
Country	US
Kind code	B2
Filing date	Sep 26, 2013
Priority date	Sep 13, 2013
Publication date	May 22, 2018
Grant date	May 22, 2018

Abstract

A polyisocyanate modified with sulphamic acid and a mixture thereof, the preparation method thereof, and the use thereof in the production of polyurethane, especially as a cross-linking ingredient in the field of aqueous coatings and adhesives containing groups that are capable of reacting with isocyanate groups.

First claim

The invention claimed is:

1. A polyisocyanate modified with sulphamic acid, which is prepared by a reaction of a polyisocyanate and a sulphamic acid with the formula of

wherein in the reaction, the polyisocyanate is added through a two-step adding process, wherein a first portion of the polyisocyanate is mixed with the sulphamic acid, a tertiary amine and optionally a polyether, and the reaction lasts 3-5 h at 95-110° C., then the rest of the polyisocyanate is added, after cooling to room temperature, the polyisocyanate modified with sulphamic acid is obtained; wherein the first portion of the polyisocyanate represents 30-90 wt % of the total weight of the polyisocyanate,
wherein R 1 is one of cyclohexyl, methyl cyclohexyl, p-methyl cyclohexyl, 2-methyl cyclohexyl, 2,3-dimethyl cyclohexyl, 3,3,5-trimethyl cyclohexyl, 4-tertbutyl cyclohexyl, cycloheptyl, methyl cyclooctyl, 2-norcamphanyl, 2-adamantyl and 3,5-dimethyl-1-adamantyl, R 2 is butyl;
or R 1 is one of methyl cyclohexyl, p-methyl cyclohexyl, 2-methyl cyclohexyl, 2,3-dimethyl cyclohexyl, 3,3,5-trimethyl cyclohexyl, 4-tertbutyl cyclohexyl, cycloheptyl, methyl cyclooctyl, 2-norcamphanyl, 2-adamantyl and 3,5-dimethyl-1-adamantyl, R 2 is propyl;
or R 1 is one of cyclohexyl, methyl cyclohexyl, p-methyl cyclohexyl, 2-methyl cyclohexyl, 2,3-dimethyl cyclohexyl, 3,3,5-trimethyl cyclohexyl, 4-tertbutyl cyclohexyl, cycloheptyl, methyl cyclooctyl, 2-norcamphanyl, 2-adamantyl and 3,5-dimethyl-1-adamantyl, R 2 is isobutyl; and
wherein the amount of said sulphamic acid is 0.5-20 wt % of the total weight of the polyisocyanate and the sulphamic acid.

2. The polyisocyanate modified with sulphamic acid according to claim 1 , characterized in that:
a) the average functionality of isocyanate is at least 1.8,
b) the content of isocyanate groups is 4.0-35.0 wt %,
c) the content of SO 3 − is 0.1-6.8 wt %, and
d) the polyisocyanate modified with sulphamic acid optionally comprises a polyether with a molecular chain comprising average ethoxy units of 5-30, wherein the content of ethoxy units bonded to the molecular chain of the polyether is 0-15 wt % based on the total weight of the polyisocyanate, the sulphamic acid and the polyether.

3. The polyisocyanate modified with sulphamic acid according to claim 1 , characterized in that said polyisocyanate applied in the reaction is one or more of aliphatic, alicyclic, aromatic, araliphatic polyisocyanates and modified polyisocyanates with average isocyanate functionality of 2.0-5.0 and isocyanate groups content of 7.0-32.0 wt %.

4. A preparation method of the polyisocyanate modified with sulphamic acid according to claim 1 , characterized in that the polyisocyanate reacts with the sulphamic acid with the formula of

at the presence of a tertiary amine,
wherein in the reaction, the polyisocyanate is added through a two-step adding process, wherein a first portion of the polyisocyanate is mixed with the sulphamic acid, the tertiary amine and optionally a polyether, and the reaction lasts 3-5 h at 95-110° C., then the rest of the polyisocyanate is added, after cooling to room temperature, the polyisocyanate modified with sulphamic acid is obtained; wherein the first portion of the polyisocyanate represents 30-90 wt % of the total weight of the polyisocyanate,
wherein R 1 is one of cyclohexyl, methyl cyclohexyl, p-methyl cyclohexyl, 2-methyl cyclohexyl, 2,3-dimethyl cyclohexyl, 3,3,5-trimethyl cyclohexyl, 4-tertbutyl cyclohexyl, cycloheptyl, methyl cyclooctyl, 2-norcamphanyl, 2-adamantyl and 3,5-dimethyl-1-adamantyl, R 2 is butyl;
or R 1 is one of methyl cyclohexyl, p-methyl cyclohexyl, 2-methyl cyclohexyl, 2,3-dimethyl cyclohexyl, 3,3,5-trimethyl cyclohexyl, 4-tertbutyl cyclohexyl, cycloheptyl, methyl cyclooctyl, 2-norcamphanyl, 2-adamantyl and 3,5-dimethyl-1-adamantyl, R 2 is propyl;
or R 1 is one of cyclohexyl, methyl cyclohexyl, p-methyl cyclohexyl, 2-methyl cyclohexyl, 2,3-dimethyl cyclohexyl, 3,3,5-trimethyl cyclohexyl, 4-tertbutyl cyclohexyl, cycloheptyl, methyl cyclooctyl, 2-norcamphanyl, 2-adamantyl and 3,5-dimethyl-1-adamantyl, R 2 is isobutyl; and
wherein the amount of the sulphamic acid is 0.5-20 wt % of the total weight of the polyisocyanate and the sulphamic acid.

5. The method according to claim 4 , characterized in that said reaction is carried out under the presence of a polyether comprising ethoxy units, and/or the polyisocyanate used already comprises ethoxy polyether units.

6. The method according to claim 4 , characterized in that said polyisocyanate is one or more of aliphatic, alicyclic, aromatic, araliphatic polyisocyanates and modified polyisocyanates with average isocyanate groups functionality of 2.0-5.0, and isocyanate groups content of 7.0-32.0 wt %.

7. The method according to claim 5 , characterized in that the content of the ethoxy units bonded to the molecular chain of the polyether is 0-15 wt % 7 based on the total weight of the polyisocyanate, the sulphamic acid and the polyether, the polyether is monohydric, the number-average molecular weight is 300-1000, and the average number of the ethoxy units in the molecular chain of the polyether is 5-30.

8. The method according to claim 4 , characterized in that said tertiary amine is aliphatic and/or alicyclic substituted, non-cyclic and/or cyclic tertiary amine; and
the molar ratio of said tertiary amine to the SO 3 − group of the sulphamic acid is 0.2-2.0:1, and the molar ratio of isocyanate groups and groups which are reactive towards isocyanate groups is kept to 4-300:1.

9. The polyisocyanate modified with sulphamic acid according to claim 1 , characterized in that,
R 1 is one of cyclohexyl, methyl cyclohexyl, p-methyl cyclohexyl and cycloheptyl, R 2 is butyl;
or R 1 is methyl cyclohexyl, p-methyl cyclohexyl and 3,3,5-trimethyl cyclohexyl, R 2 is propyl;
or R 1 is cyclohexyl and methyl cyclohexyl, R 2 is isobutyl; and
the amount of said sulphamic acid is 1-10 wt % of the total weight of the polyisocyanate and the sulphamic acid.

10. The polyisocyanate modified with sulphamic acid according to claim 2 , characterized in that,
a) the average functionality of isocyanate is 2.0-4.8,
b) the content of isocyanate groups is 6.0-31.0 wt %,
c) the content of SO 3 − is 0.2-4.8 wt %, and
d) the polyisocyanate modified sulphamic acid comprises the polyether with the molecular chain comprising average ethoxy units of 10-20, wherein the content of ethoxy units bonded to the molecular chain of the polyether is 4-12 wt % based on the total weight of the polyisocyanate, the sulphamic acid and the polyether.

11. The polyisocyanate modified with sulphamic acid according to claim 3 , characterized in that, said polyisocyanate applied in the reaction is one or more of the aliphatic, alicyclic polyisocyanates and modified polyisocyanates with average isocyanate functionality of 2.0-4.0, and the isocyanate groups content of 12.0-25.0 wt %.

12. The polyisocyanate modified with sulphamic acid according to claim 3 , characterized in that, said polyisocyanate applied in the reaction is isocyanurate modified groups-comprising polyisocyanates that are based on one or more of 1,6-hexamethylene diisocyanate, isophorone diisocyanate and 4,4′-dicyclohexyl methane diisocyanate.

13. The polyisocyanate modified with sulphamic acid according to claim 4 , characterized in that,
R 1 is one of cyclohexyl, methyl cyclohexyl, p-methyl cyclohexyl

Assignees

• Wanhua Chemical Group Co Ltd
• Wanhua Chemical Guangdong Co Ltd
• Wanhua Chemical Ningbo Co Ltd

Inventors

• Ji Xueshun
• Jin Yunquan
• Lin Zhengchao
• Wang Zhen
• Qi Ruiquan

Classifications

• C08G18/622

  Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids · CPC title

• C08G18/755

  and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate · CPC title

• C08G18/0828 Primary

  containing sulfonate groups or groups forming them · CPC title

• C09D175/04

  Polyurethanes · CPC title

• C08G18/771

  oxygen · CPC title