Silyl terminated polyurethanes and intermediates for the preparation thereof

Patent metadata

Field	Value
Publication number	US-2023057382-A1
Application number	US-202017785591-A
Country	US
Kind code	A1
Filing date	Dec 17, 2020
Priority date	Dec 23, 2019
Publication date	Feb 23, 2023
Grant date	—

Abstract

The present invention relates to silyl terminated polyurethanes and to intermediates for the preparation thereof. In particular to an allyl-monool-containing initiator, allyl-terminated polyurethane prepolymer and to processes for their preparation. According to another of its aspect, the invention relates to a product obtainable by curing the silyl terminated polyurethane of the invention and to uses thereof.

First claim

1 . An allyl-monool-containing initiator for the preparation of a Silyl terminated polyurethane, which initiator has the general formula

wherein
R 1 is selected from the group consisting of C 1-24 alkyl, hetero C 1-24 alkyl, C 3-24 cycloalkyl, C 6-24 aryl, C 6-24 heteroaryl and a group of formula II

wherein * represents where L 2 is bound to the compound of formula I; and wherein said C 1-24 alkyl, hetero C 1-24 alkyl, C 3-24 cycloalkyl, C 6-24 aryl, or C 6-24 heteroaryl can be unsubstituted or substituted with one or more Z 1 ; and wherein,
L 2 is selected from the group consisting of C 1-6 alkylene, a single bond, C 3-8 cycloalkylene, O, and S; and wherein said C 1-6 alkylene, or C 3-8 cycloalkylene can be unsubstituted or substituted with one or more Z 2 ; R 3 is selected from the group consisting of C 1-6 alkyl, hetero C 1-6 alkyl, C 3-10 cycloalkyl, and C 6-10 aryl; and wherein said C 1-6 alkyl, hetero C 1-6 alkyl, C 3-10 cycloalkyl, and C 6-10 aryl can be unsubstituted or substituted with one or more Z 3 ; R 4 is selected from the group consisting of C 1-6 alkyl, hetero C 1-6 alkyl, C 3-10 cycloalkyl, and C 6-10 aryl; and wherein said C 1-6 alkyl, hetero C 1-6 alkyl, C 3-10 cycloalkyl, and C 6-10 aryl can be unsubstituted or substituted with one or more Z 4 ; or R 3 and R 4 together with the carbon atom to which they are attached form a saturated or unsaturated 3, 4, 5, 6 or 7 membered ring; and
R 2 is selected from the group consisting of C 1-24 alkyl, hetero C 1-24 alkyl, C 3-24 cycloalkyl, C 6-24 aryl, C 6-24 heteroaryl and a group of formula III

wherein * represents where L 3 is bound to the compound of formula I; and wherein said C 1-24 alkyl, hetero C 1-24 alkyl, C 3-24 cycloalkyl, C 6-24 aryl, or C 6-24 heteroaryl can be unsubstituted or substituted with one or more Z 5 ; and wherein,
L 3 is selected from the group consisting of C 1-6 alkylene, a single bond, C 3-8 cycloalkylene, O, and S; and wherein said C 1-6 alkylene, or C 3-8 cycloalkylene can be unsubstituted or substituted with one or more Z 6 ; R 5 is selected from the group consisting of C 1-6 alkyl, hetero C 1-6 alkyl, C 3-10 cycloalkyl, and C 6-10 aryl; and wherein said C 1-6 alkyl, hetero C 1-6 alkyl, C 3-10 cycloalkyl, and C 6-10 aryl can be unsubstituted or substituted with one or more Z 7 ; R 6 is selected from the group consisting of C 1-6 alkyl, hetero C 1-6 alkyl, C 3-10 cycloalkyl, and C 6-10 aryl; and wherein said C 1-6 alkyl, hetero C 1-6 alkyl, C 3-10 cycloalkyl, and C 6-10 aryl can be unsubstituted or substituted with one or more Z 8 ; or R 5 and R 6 together with the carbon atom to which they are attached form a saturated or unsaturated 3, 4, 5, 6 or 7 membered ring; and
Y is selected from the group consisting of C 1-24 alkylene, hetero C 1-24 alkylene, C 3-24 cycloalkylene, C 6-24 arylene, and oxygen or sulfur atom;

and
wherein,
X is selected from the group consisting of C 1-24 hydrocarbon chain, C 1-24 alkylene, hetero C 1-24 alkylene, C 3-24 cycloalkylene, C 6-24 arylene, poly C 1-6 alkyleneoxide, poly C 6-10 aryleneoxide, heterocyclylene, and heteroarylene, wherein said C 1-24 alkylene, hetero C 1-24 alkylene, C 3-24 cycloalkylene, C 6-24 arylene, poly C 1-6 alkyleneoxide, poly C 6-10 aryleneoxide, heterocyclylene, and heteroarylene, can be unsubstituted or substituted with one or more Z 9 with n equal to 1;
n is an integer from 1 to 24; and
W and the terminal OH group form together a primary or a secondary alcohol
each of Z 1 to Z 9 is independently selected from the group consisting of C 1-6 alkoxy, halo C 1-6 alkoxy, halo, C 1-6 alkyl, halo C 1-6 alkyl, C 3-12 cycloalkyl, C 6-12 aryl, C 6-12 aryl C 1-6 alkyl, C 3-12 heterocyclyl, and C 4-12 heteroaryl.

2 . The allyl-monool-containing initiator according to claim 1 , wherein:
R 1 and R 2 are both C 1-3 alkyl, Y is selected from the group consisting of C 1-24 alkyl, hetero C 1-24 alkyl, C 3-24 cycloalkyl, C 6-24 aryl, O and S; X is selected from the group consisting of C 1-24 hydrocarbon chain, C 1-24 alkylene, hetero C 1-24 alkylene, C 3-24 cycloalkylene, C 6-24 arylene, poly C 1-6 alkyleneoxide, poly C 6-10 aryleneoxide, heterocyclylene, and heteroarylene, wherein said C 1-24 alkylene, hetero C 1-24 alkylene, C 3-24 cycloalkylene, C 6-24 arylene, poly C 1-6 alkyleneoxide, poly C 6-10 aryleneoxide, heterocyclylene or heteroarylene, can be unsubstituted or substituted with one or more Z 9 , with n equal to 1; and W and the terminal OH group form together an alcohol.

3 . The allyl-monool-containing initiator according to claim 1 , wherein:
R 1 and R 2 are both C 1-3 alkyl, Y is —CH 2 ; X is selected from the group consisting of C 1-24 hydrocarbon chain, C 1-24 alkylene, hetero C 1-24 alkylene, C 3-24 cycloalkylene, C 6-24 arylene, poly C 1-6 alkyleneoxide, poly C 6-10 aryleneoxide, heterocyclylene, and heteroarylene, wherein said C 1-24 alkylene, hetero C 1-24 alkylene, C 3-24 cycloalkylene, C 6-24 arylene, poly C 1-6 alkyleneoxide, poly C 6-10 aryleneoxide, heterocyclylene, or heteroarylene, can be unsubstituted or substituted with one or more Z 9 , with n equal to 1; and W and the terminal OH group form together a primary or a secondary alcohol.

4 . The allyl-monool-containing initiator according to claim 1 , wherein:
R 1 and R 2 are both C 1-3 alkyl, when Y is O or S; X is selected from the group consisting of C 1-24 hydrocarbon chain, C 1-24 alkylene, hetero C 1-24 alkylene, C 3-24 cycloalkylene, C 6-24 arylene, poly C 1-6 alkyleneoxide, poly C 6-10 aryleneoxide, heterocyclylene, and heteroarylene, wherein said C 1-24 alkylene, hetero C 1-24 alkylene, C 3-24 cycloalkylene, C 6-24 arylene, poly C 1-6 alkyleneoxide, poly C 6-10 aryleneoxide, heterocyclylene, or heteroarylene, can be unsubstituted or substituted with one or more Z 9 , with n equal to 1; and R 3 and the terminal OH group form together a primary or a secondary alcohol.

5 . The allyl-monool-containing initiator according to claim 1 , wherein the initiator is aliphatic.

6 . An allyl terminated polyurethane prepolymer obtained by a process comprising the following steps:
(i) reacting the allyl-monool-containing initiator as defined in claim 1 with at least one alkylene oxide having from 2 to 6 carbon atoms; and (ii) directly reacting the reaction product obtained in step (i) with an isocyanate-containing compound with the formation of an allyl terminated polyurethane prepolymer.

7 . The allyl terminated polyurethane prepolymer according to claim 6 , wherein step (i) is performed in the presence of a catalyst selected from the list consisting of basic catalysts, and a double metal cyanide catalysts.

8 . The allyl terminated polyurethane prepolymer according to claim 7 , wherein said catalyst is totally or partly removed before step (ii) and is present in an amount of at most 0.500% by weight based on the total weight of the reaction mixture.

9 . The allyl terminated polyurethane prepolymer according to claim 6 , wherein said at least one alkylene oxide having from 2 to 6 carbon atoms is selected from propylene oxide, ethylene oxide and mixtures thereof.

10 . The allyl terminated polyurethane prepolymer according to claim 6 , wherein the allyl terminated prepolymer has a mole

Assignees

• Huntsman Int Llc

Inventors

• Chuang Ya-Mi
• Martini Giulio
• Phanopoulos Christopher

Classifications

• C09D175/08

  from polyethers · CPC title

• C08G2190/00

  Compositions for sealing or packing joints · CPC title

• C08G18/7671 Primary

  containing only one alkylene bisphenyl group · CPC title

• C08G18/283

  Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds · CPC title

• C08G18/3893

  containing silicon · CPC title