Lewis acid-base pair catalytic initiator and application thereof

Patent metadata

Field	Value
Publication number	US-11247199-B2
Application number	US-202117356509-A
Country	US
Kind code	B2
Filing date	Jun 24, 2021
Priority date	Dec 25, 2018
Publication date	Feb 15, 2022
Grant date	Feb 15, 2022

Abstract

The present disclosure provides a Lewis acid-base pair catalytic initiator and an application thereof. The Lewis acid-base pair catalytic initiator includes a Lewis acid and a Lewis base, the Lewis acid having a structural general formula as shown in formula (I) and the Lewis base having a structural general formula as shown in formula (II); wherein: the A is selected from element Baron or element Aluminum; the R1, R2, R3, R4 are independently selected from alkyl, alkoxy, aryl or halogen groups; the alkyl or alkoxy have a carbon number being equal to or greater than 1 to equal to or less than 16; the aryl contains substituents with the number being equal to or less than 5, the substituents being selected from methyl, methoxy or halogen; n is selected from an integer from 1 to 16.

First claim

What is claimed is:

1. A Lewis acid-base pair catalytic initiator, comprising a Lewis acid and a Lewis base, the Lewis acid having a structural general formula as shown in formula (I) and the Lewis base having a structural general formula as shown in formula (II);

wherein:
the A is selected from element Boron or element Aluminum;
the R 1 , R 2 , R 3 , R 4 are independently selected from alkyl, alkoxy, aryl or halogen groups;
the alkyl or alkoxy have a carbon number being equal to or greater than 1 to equal to or less than 16;
the aryl contains substituents with the number being equal to or less than 5, the substituents being selected from methyl, methoxy or halogen;
n is selected from an integer from 1 to 16.

2. The Lewis acid-base pair catalytic initiator according to claim 1 , wherein the Lewis acid is selected from at least one of triethylborane, tripropylborane, tributylborane, tri-sec-butylborane, triphenylborane, tris(pentafluorophenyl)borane, diethylmethoxyborane, di(trimethylphenyl)borane fluoride, trimethylaluminum, triethylaluminum, triisobutylaluminum, triphenylaluminum, and tris(pentafluorophenyl)aluminum;
the Lewis base is selected from at least one of N,N,N′,N′-tetramethylmethanediamine, N,N,N′,N′-tetramethylethylenediamine, N,N,N′,N′-tetraethylmethanediamine, N,N,N′,N′-tetraethylethylenediamine, and N,N,N′,N′-tetraethyl-1,3-propanediamine.

3. An application of a Lewis acid-base pair catalytic initiator in a preparation of an epoxide homopolymer,
wherein the Lewis acid-base pair catalytic initiator comprises a Lewis acid and a Lewis base, the Lewis acid having a structural general formula as shown in formula (I) and the Lewis base having a structural general formula as shown in formula (II);

wherein:
the A is selected from element Boron or element Aluminum;
the R 1 , R 2 , R 3 , R 4 are independently selected from alkyl, alkoxy, aryl or halogen groups;
the alkyl or alkoxy have a carbon number being equal to or greater than 1 to equal to or less than 16;
the aryl contains substituents with the number being equal to or less than 5, the substituents being selected from methyl, methoxy or halogen;
n is selected from an integer from 1 to 16;
wherein a molar ratio of the Lewis acid to the Lewis base is from 0.125:1 to 8:1.

4. The application of the Lewis acid-base pair catalytic initiator in the preparation of the epoxide homopolymer according to claim 3 , wherein:
the epoxide is selected from at least one of ethylene oxide, propylene oxide, epichlorohydrin, allyl glycidyl ether, 1,2-butylene oxide, isobutylene oxide, cyclohexene oxide, 4-vinyl cyclohexene oxide, styrene oxide, limonene oxide, cyclopentene oxide and alpha-alkene oxide from C5 to C20;
the molar ratio of the Lewis acid to the Lewis base is from 0.5:1 to 4:1; a molar ratio of the Lewis base to the epoxide is from 1:50 to 1:4000; a homopolymerization reaction is carried out under a native or solution condition, the homopolymerization reaction being carried out at a temperature of 0 to 100 ° C.

5. The application of the Lewis acid-base pair catalytic initiator in the preparation of the epoxide homopolymer according to claim 3 , wherein the epoxide homopolymer is prepared with an addition of a chain transfer agent;
the chain transfer agent is selected from at least one of an alcoholic small molecule, a terminal hydroxyl group polymer, a carboxylic acid small molecule, and a terminal carboxyl group polymer.

6. An application of a Lewis acid-base pair catalytic initiator in a preparation of an epoxide copolymer,
wherein the Lewis acid-base pair catalytic initiator comprises a Lewis acid and a Lewis base, the Lewis acid having a structural general formula as shown in formula (I) and the Lewis base having a structural general formula as shown in formula (II);

wherein:
the A is selected from element Boron or element Aluminum;
the R 1 , R 2 , R 3 , R 4 are independently selected from alkyl, alkoxy, aryl or halogen groups;
the alkyl or alkoxy have a carbon number being equal to or greater than 1 to equal to or less than 16;
the aryl contains substituents with the number being equal to or less than 5, the substituents being selected from methyl, methoxy or halogen;

n is selected from an integer from 1 to 16;
wherein a molar ratio of the Lewis acid to the Lewis base is from 0.125:1 to 8:1.

7. The application of the Lewis acid-base pair catalytic initiator in the preparation of the epoxide copolymer according to claim 6 , wherein:
the epoxide is selected from at least one of ethylene oxide, propylene oxide, epichlorohydrin, allyl glycidyl ether, 1,2-butylene oxide, isobutylene oxide, cyclohexene oxide, 4-vinyl cyclohexene oxide, styrene oxide, limonene oxide, cyclopentene oxide and alpha-alkene oxide from C5 to C20;
the molar ratio of the Lewis acid to the Lewis base is from 0.2:1 to 8:1; a molar ratio of the Lewis base to the epoxide is from 1:50 to 1:4000; a molar ratio of the epoxide to a comonomer is from 1:1 to 1:10;
the comonomer is selected from at least one of C1 monomer, cyclic anhydride, and cyclic lactone;
a copolymerization reaction is carried out under a native or solution condition, the copolymerization reaction being carried out at a temperature of 0 to 100 ° C. and at an autogenous pressure for 0.01 to 150 h.

8. The application of the Lewis acid-base pair catalytic initiator in the preparation of the epoxide copolymer according to claim 7 , wherein:
the C1 monomer is selected from at least one of carbon dioxide, carbonyl sulfide, and carbon disulfide;
the cyclic anhydride is selected from at least one of maleic anhydride, glutaric anhydride, succinic anhydride, diglycolic anhydride, and phthalic anhydride;
the cyclic lactone is selected from at least one of propiolactone, butyrolactone, valerolactone, caprolactone, enantolactone, glycolide, lactide, and dimethyl trimethylene ester.

9. The application of the Lewis acid-base pair catalytic initiator in the preparation of the epoxide copolymer according to claim 6 , wherein a comonomer is carbonyl sulfide; the Lewis base is N,N,N′,N′-tetraethyl ethylenediamine, and the Lewis acid is triethylborane.

10. The application of the Lewis acid-base pair catalytic initiator in the preparation of the epoxide copolymer according to claim 6 , wherein the epoxide copolymer is prepared with an addition of a chain transfer agent;
the chain transfer agent is selected from at least one of an alcoholic small molecule, a terminal hydroxyl group polymer, a carboxylic acid small molecule, and a terminal carboxyl group polymer.

Assignees

• Univ Zhejiang

Inventors

• Zhang Xinghong
• Yang Jialiang
• Hu Lanfang

Classifications

• C08G63/58

  Cyclic ethers (C08G59/00 takes precedence); Cyclic carbonates; Cyclic sulfites {; Cyclic orthoesters} · CPC title

• B01J31/0238 Primary

  with a primary amino group · CPC title

• C08G63/87

  Non-metals or inter-compounds thereof (boron C08G63/84) · CPC title

• C08G2650/22

  characterised by the initiator used in polymerisation · CPC title

• C08G59/686

  containing nitrogen · CPC title