Macromonomeric stabilizer, preparation method thereof, and method for preparing polymeric polyol

Patent metadata

Field	Value
Publication number	US-11795265-B2
Application number	US-201817295581-A
Country	US
Kind code	B2
Filing date	Dec 26, 2018
Priority date	Dec 26, 2018
Publication date	Oct 24, 2023
Grant date	Oct 24, 2023

Abstract

A macromonomeric stabilizer, a preparation method thereof, a method for preparing a polymeric polyol using same, and the polymeric polyol prepared. Also disclosed are a soft polyurethane foam obtained by foaming a composition of the polymeric polyol prepared and a polyisocyanate, and a molded product comprising the soft polyurethane foam. The preparation method of the macromonomeric stabilizer comprises the following steps: reacting a polyol with a tricarboxylate not comprising a polymerizable ethylenically unsaturated double bond, or a derivative thereof, to form an adduct; and reacting the resulting adduct with an epoxide comprising a polymerizable ethylenically unsaturated double bond. The macromonomeric stabilizer of the present invention has a low viscosity, comprises a plurality of active sites, and can be directly used in subsequent reactions. The preparation method of the macromonomeric stabilizer can be carried out under normal pressure, without the need for end-blocking with ethylene oxide.

First claim

What is claimed is:

1. A method for preparing a macromonomeric stabilizer, comprising:
reacting a polyol with a tricarboxylic acid not comprising a polymerizable olefinic unsaturated double bond or a derivative thereof, to form an adduct; and
reacting the resulting adduct with an epoxide comprising a polymerizable olefinic unsaturated double bond;
wherein the structure formula of the tricarboxylic acid not comprising a polymerizable olefinic unsaturated double bond or the derivative thereof is

wherein X is a straight or branched alkane segment having 1 to 25 carbons; a cycloalkane segment having a total of 3 to 25 carbons; a straight or branched alkane segment containing cycloalkyl and having a total of 4 to 25 carbons; a cycloalkane segment substituted with straight or branched alkyl and having a total of 4 to 25 carbons; or a straight or branched alkane segment containing aryl and having a total of 7 to 25 carbons; and X does not comprise a polymerizable olefinic unsaturated double bond;
wherein the polyol is a polyether polyol.

2. The method according to claim 1 , wherein the tricarboxylic acid not comprising a polymerizable olefinic unsaturated double bond or the derivative thereof is hydrogenated maleopimaric acid.

3. The method according to claim 1 , wherein the epoxide comprising
a polymerizable olefinic unsaturated double bond is one or more of 1,2-epoxides comprising a

polymerizable olefinic unsaturated double bond, having a structure formula of
wherein R is selected from R 1 —COO—R 2 , R 3 —O—R 4 , or a straight or branched alkyl having 1 to 4carbons, wherein R 1 , R 2 , R 3 , and R 4 are each independently selected from H, or a straight or branched alkyl having 1 to 4 carbons; and
T is selected from H, cyano, or branched or straight alkyl having 1 to 4 carbons.

4. The method according to claim 1 , wherein the molar ratio of the polyol to the tricarboxylic acid not comprising a polymerizable olefinic unsaturated double bond or the derivative thereof is 0.2:1 to 4:1.

5. The method according to claim 1 , wherein the molar ratio of the tricarboxylic acid not comprising a polymerizable olefinic unsaturated double bond or the derivative thereof to the epoxide is 0.1:1 to 2:1.

6. The method according to claim 1 , wherein the reaction of forming the adduct is carried out in the presence of a catalyst.

7. The method according to claim 1 , wherein the reaction between the adduct and the epoxide comprising a polymerizable olefinic unsaturated double bond is carried out in the presence of a catalyst.

8. The method according to claim 1 , wherein the reaction between the polyol and the tricarboxylic acid not comprising a polymerizable olefinic unsaturated double bond or the derivative thereof is carried out in a solvent-containing system.

9. A macromonomeric stabilizer prepared by the method according to claim 1 .

10. A flexible polyurethane foam obtained by foaming a composition of a polyisocyanate and the polymeric polyol, wherein the polymeric polyol is prepared by a method comprising the following steps:
polymerizing at least one olefinic unsaturated monomer in the presence of a base polyether polyol, a polymerization initiator, and a macromonomeric stabilizer prepared by the method according to claim 1 .

11. The flexible polyurethane foam according to claim 10 , wherein the olefinic unsaturated monomer is one or more selected from aliphatic conjugated diene, a vinyl aromatic compound, α,β-olefinic unsaturated nitrile, α,β-olefinic unsaturated nitrile amide, α,β- olefinic unsaturated carboxylic acid, α,β-olefinic unsaturated carboxylate, vinyl ester, vinyl ether, vinyl ketone, a vinyl halide, and a vinylidene halide.

12. The flexible polyurethane foam according to claim 10 , wherein the mass of the olefinic unsaturated monomer is 20% (w/w) to 70% (w/w) of the total mass of the base polyether polyol, the olefinic unsaturated monomer, and the macromonomeric stabilizer.

13. The flexible polyurethane foam according to claim 10 , wherein the mass ratio of the olefinic unsaturated monomer to the base polyether polyol is 0.1:100 to 250:100.

14. The flexible polyurethane foam according to claim 10 , wherein the base polyether polyol is a trifunctional polyether polyol having a hydroxyl value of 10 mgKOH/g to 60 mgKOH/g.

15. The flexible polyurethane foam according to claim 10 , wherein by mass, the amount of the macromonomeric stabilizer is 0.3% to 10% of the total mass of the base polyether polyol and the olefinic unsaturated monomer.

16. The flexible polyurethane foam according to claim 10 , wherein by mass, the amount of the macromonomeric stabilizer is 2% to 5% of the total mass of the base polyether polyol and the olefinic unsaturated monomer.

17. The flexible polyurethane foam according to claim 11 , wherein the base polyether polyol is a trifunctional polyether polyol having a hydroxyl value of 10 mgKOH/g.

18. The flexible polyurethane foam according to claim 11 , wherein the base polyether polyol is a trifunctional polyether polyol having a hydroxyl value of 10 mgKOH/g to 60 mgKOH/g.

Assignees

• Wanhua Chemical Group Co Ltd

Inventors

• Li Fuguo
• Ju Changxun
• Liu Yang
• Qin Chengqun
• Liu Bin
• Wu Xunkun
• Li Jing
• Sun Ye
• Zheng Bing
• Wang Lunpeng

Classifications

• C08G18/632 Primary

  onto polyethers · CPC title

• C08G18/4829

  Polyethers containing at least three hydroxy groups (C08G18/4833 - C08G18/5096 take precedence) · CPC title

• C08G65/2615

  the other compounds containing carboxylic acid, ester or anhydride groups · CPC title

• C08G65/2696

  characterised by the process or apparatus used · CPC title

• C08J9/0061

  characterized by the use of several polymeric components · CPC title