Imine-type quaternary ammonium salt catalyst, preparation method thereof and use thereof for preparation of polyisocyanate composition

Patent metadata

Field	Value
Publication number	US-11059772-B2
Application number	US-201816762265-A
Country	US
Kind code	B2
Filing date	Feb 13, 2018
Priority date	Nov 30, 2017
Publication date	Jul 13, 2021
Grant date	Jul 13, 2021

Abstract

Disclosed is an imine-type quaternary ammonium salt catalyst, wherein the catalyst has a general structure formula shown by formula I below; in the formula, R1 and R2, respectively, are independently selected from a C1-C20 linear alkyl or a branched C3-C20 alkyl, and a C1-C20 hydroxylalkyl, a C3-C8 cycloalkyl, and arylated alkyl; R3 is a linear or branched alkyl, cycloalkyl or aryl; and R4 is hydrogen, aryl, a linear C1-C15 alkyl or branched C3-C15 alkyl. Also disclosed are a method for preparing the catalyst and a polyisocyanate composition prepared therefrom. The catalyst, by introducing an imine structure, on the basis of ensuring high catalytic activity thereof, is allowed to have properties of high temperature decomposition and inactivation, and when applied to the synthesis of polyisocyanate, can effectively prevent the risk of explosive polymerization caused by an uncontrolled reaction.

First claim

The invention claimed is:

1. A polyisocyanate composition, characterized in that, the polyisocyanate composition has isocyanurate, urethane, allophanate, and iminooxadiazinedione groups, wherein the molar ratio of allophanate group/(isocyanurate group+allophanate group) is 0.1-0.8; the molar ratio of allophanate group/(allophanate group+urethane group) is 0.1-0.7; the molar ratio of iminooxadiazinedione group/isocyanurate group is 0.005-0.15.

2. A polyisocyanate composition according to claim 1 , characterized in that, the polyisocyanate composition is prepared by the oligomerization of at least one kind of isocyanate monomer having a NCO functionality>1 in the presence of a quaternary ammonium salt catalyst which has a general structural formula as shown in the following formula I:

in the formula, R 1 and R 2 are independently selected from a linear C1-C20 alkyl or a branched C3-C20 alkyl and a C1-C20 hydroxyalkyl, a C3-C8 cycloalkyl, and an arylated alkyl;
R3 is a linear or branched alkyl, cycloalkyl or aryl;
R4 is hydrogen, aryl, a linear C1-C15 alkyl or a branched C3-C15 alkyl.

3. A polyisocyanate composition according to claim 2 , characterized in that, the isocyanate monomer is selected from aliphatic diisocyanate.

4. A polyisocyanate composition according to claim 2 , characterized in that, the catalyst is added in the form of an alcohol solution during the preparation process;
the amount of the catalyst used is 0.001-5% of the mass of the isocyanate monomer.

5. A polyisocyanate composition according to claim 2 , characterized in that, the oligomerization is reacted at a temperature of 0° C.-100° C..

6. A polyisocyanate composition according to claim 2 , characterized in that, the oligomerization is terminated after converting 5-80 wt% of the isocyanate monomer.

7. A polyisocyanate composition according to claim 1 , characterized in that, the polyisocyanate composition is prepared by the oligomerization of at least one kind of isocyanate monomer having a NCO functionality>1 in the presence of a quaternary ammonium salt catalyst which is prepared by a preparation method comprising the following steps:
(1) adding trimethylchlorosilane gradually into a di-substituted secondary amine under ice-water bath condition, after the addition, returning to room temperature and continuing the reaction, after the reaction, adding ice water into the reaction solution to quench the reaction, and separating to obtain an intermediate product a;
(2) adding trimethylchlorosilane gradually into a carboxylic acid under ice-water bath condition, after the addition, returning to room temperature and continuing the reaction, after the reaction, adding ice water into the reaction solution to quench the reaction, and separating to obtain an intermediate product b;
(3) dissolving the separated intermediate product a, intermediate product b and a dimethyl acetal in an alcohol solvent, and reacting at 50-80° C., after the reaction, optionally removing part of the alcohol solvent, and obtaining an alcohol solution containing the quaternary ammonium salt catalyst at a target concentration.

8. A polyisocyanate composition according to claim 1 , characterized in that, the molar ratio of allophanate group/(isocyanurate group+allophanate group) is 0.2-0.6; the molar ratio of allophanate group/(allophanate group+urethane group) is 0.2-0.5; the molar ratio of iminooxadiazinedione group/isocyanurate group is 0.01-0.1.

9. A polyisocyanate composition according to claim 3 , characterized in that, the isocyanate monomer is selected from is one or more of hexamethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 2,4,4-trimethyl-1,6-hexane diisocyanate, 2,2,4-trimethyl-1,6-hexane diisocyanate, 4-isocyanatomethyl-1,8-octane diisocyanate, 3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate, isophorone diisocyanate, 1,3- and 1,4-bis(isocyanatomethyl)benzene, and 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane.

10. A polyisocyanate composition according to claim 4 , characterized in that, the mass concentration of the catalyst in the alcohol is 0.25%-50%;
the amount of the catalyst used is 0.002-2% of the mass of the isocyanate monomer.

11. A polyisocyanate composition according to claim 5 , characterized in that, the oligomerization is reacted at a temperature of 20-90° C..

12. A polyisocyanate composition according to claim 6 , characterized in that, the oligomerization is terminated after converting 10-70 wt% of the isocyanate monomer;
the oligomerization is terminated by deactivating the catalyst.

Assignees

• Wanhua Chemical Group Co Ltd

Inventors

• Wang Nuancheng
• Shang Yonghua
• Wang Yuqi
• Shi Bin
• Zhu Zhicheng
• Li Hefu
• Li Yuan
• Hua Weiqi

Classifications

• B01J31/04

  containing carboxylic acids or their salts {(B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226)} · CPC title

• C07F7/12

  Organo silicon halides · CPC title

• C08G18/7837

  containing allophanate groups · CPC title

• C08G18/1875

  containing ammonium salts or mixtures of secondary of tertiary amines and acids · CPC title

• C08G18/1858

  having carbon-to-nitrogen double bonds · CPC title