Composition comprising silylated polymers

Patent metadata

Field	Value
Publication number	US-9752013-B2
Application number	US-201414782342-A
Country	US
Kind code	B2
Filing date	Apr 1, 2014
Priority date	Apr 25, 2013
Publication date	Sep 5, 2017
Grant date	Sep 5, 2017

Abstract

The present invention relates to a tin-free composition comprising at least one silylated polymer and at least one tin-free polyhedral oligomeric metallo silsesquioxane. The present invention also relates to a process of curing a composition comprising a silylated polymer comprising the step of: contacting a silylated polymer with a tin-free polyhedral oligomeric metallo silsesquioxane.

First claim

The invention claimed is:

1. A composition comprising at least one silylated polyurethane compound comprising an alkoxysilyl group, a silanol group, or combinations thereof and at least one tin-free polyhedral oligomeric metallo silsesquioxane curing agent.

2. The composition according claim 1 , wherein said at least one tin-free polyhedral oligomeric metallo silsesquioxane curing agent is a compound of formula (I):

wherein
X 1 , X 2 , and X 3 are each independently selected from Si or M 1 , wherein M 1 is selected from the group consisting of s and p block metals with the exclusion of tin and d and f block transition metals, lanthanide and actinide metals, and metalloids;
Z 1 , Z 2 and Z 3 are each independently selected from L 2 , R 5 , R 6 , or R 7 ; wherein L 2 is selected from —OH or —O—C 1-10 alkyl;
Y 1 and Y 2 are each independently —O-M 2 -L 3 ; or Y 1 and Y 2 are linked together and form —O-M 2 (L 3 )-O— or —O—; wherein L 3 is selected from OH or —O—C 1-10 alkyl; and M 2 is selected from the group consisting of s and p block metals with the exclusion of tin and d and f block transition metals, lanthanide and actinide metals, and metalloids;
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each independently selected from substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-6 cycloalkyl, substituted or unsubstituted C 2-20 alkenyl, or substituted or unsubstituted C 6-10 aryl;
and
X 4 is -M 3 L 1 , or M 3 , and Q 1 and Q 2 are each a single bond linked to M 3 ; wherein L 1 is selected from —OH or —O—C 1-10 alkyl, and M 3 is selected from the group consisting of s and p block metals with the exclusion of tin and d and f block transition metals, lanthanide and actinide metals, and metalloids;
or
X 4 is -M 3 L 1 ; and Q 2 is a single bond linked to M 3 ; and Q 1 is -M 4 L 4 or —SiR 38 ; wherein M 4 is selected from the group consisting of s and p block metals with the exclusion of tin and d and f block transition metals, lanthanide and actinide metals, and metalloids; wherein L 4 is selected from —OH or alkyl, and R 38 is selected from substituted or unsubstituted O 1-20 alkyl, substituted or unsubstituted O 3-6 cycloalkyl, substituted or unsubstituted O 2-20 alkenyl, or substituted or unsubstituted O 6-10 aryl;
or
X 4 , Q 1 and Q 2 are each independently -M 3 L 1 ;
or
X 4 is —Si(R 38 )—O-M 3 L 1 ; Q 2 is a single bond linked to the Si of X 4 ; and Q 1 is -M 4 L 4 ;
or
X 4 is —Si(R 38 )—O-M 3 L 1 ; Q 2 is a single bond linked to the Si of X 4 ; and Q 1 is a single bond linked to the M 3 of X 4 .

3. The composition according to claim 2 , wherein X 1 , X 2 , X 3 are each independently Si;
X 4 is -M 3 L 1 ; and Q 1 and Q 2 are each a single bond linked to M 3 ; wherein M 3 is Ti and L 1 is O-i-propyl;
Z 1 , Z 2 and Z 3 are each independently C 1-6 alkyl;
R 1 , R 2 , R 3 , R 4 are each independently C 1-6 alkyl;
Y 1 and Y 2 are linked together and form —O—.

4. The composition according to claim 2 , wherein M 1 , M 2 , M 3 and M 4 each independently are selected from the group consisting of Ti, Zr and Hf.

5. The composition according to claim 1 , wherein said at least one tin-free polyhedral oligomeric metallo silsesquioxane curing agent is a compound of formula (II):

wherein X 1 , X 2 , and X 3 are each independently selected from Si or M 1 , wherein M 1 is selected from the group consisting of s and p block metals with the exclusion of tin and d and f block transition metals, lanthanide and actinide metals, and metalloids;
Z 1 , Z 2 and Z 3 are each independently selected from L 2 , R 5 , R 6 , or R 7 ; wherein L 2 is selected from —OH or —O—C 1-10 alkyl;
Y 1 and Y 2 are each independently —O-M 2 -L 3 ; or Y 1 and Y 2 are linked together and form faun —O-M 2 (L 3 )-O— or —O—; wherein L 3 is selected from OH or —O—C 1-10 alkyl; and M 2 is selected from the group consisting of s and p block metals with the exclusion of tin and d and f block transition metals, lanthanide and actinide metals, and metalloids;
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each independently selected from substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-6 cycloalkyl, substituted or unsubstituted C 2-20 alkenyl, or substituted or unsubstituted C 6-10 aryl;
and X 4 is -M 3 L 1 , or M 3 , and Q 1 and Q 2 are each a single bond linked to M 3 ; wherein L 1 is selected from OH or —O—C 1-10 alkyl, and M 3 is selected from the group consisting of s and p block metals with the exclusion of tin and d and f block transition metals, lanthanide and actinide metals, and metalloids;
or
X 4 is -M 3 L 1 ; and Q 2 is a single bond linked to M 3 ; and Q 1 is -M 4 L 4 or —SiR 38 ; wherein M 4 is selected from the group consisting of s and p block metals with the exclusion of tin and d and f block transition metals, lanthanide and actinide metals, and metalloids; wherein L 4 is selected from —OH or —O—C 1-10 alkyl, and R 38 is selected from substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-6 cycloalkyl, substituted or unsubstituted C 2-20 alkenyl, or substituted or unsubstituted C 6-10 aryl;
or
X 4 , Q 1 and Q 2 are each independently -M 3 L 1 ;
or
X 4 is —Si(R 38 )—O-M 3 L 1 ; Q 2 is a single bond linked to the Si of X 4 ; and Q 1 is -M 4 L 4 ;
or
X 4 is —Si(R 38 )—O-M 3 L 1 ; Q 2 is a single bond linked to the Si of X 4 ; and Q 1 is a single bond linked to the M 3 of X 4 .

6. The composition according to claim 1 , wherein said at least one tin-free polyhedral oligomeric metallo silsesquioxane curing agent is a compound of formula (III):

wherein M is selected from the group consisting of s and p block metals with the exclusion of tin and d and f block transition metals, lanthanide and actinide metals, and metalloids;
x is an integer selected from 0 or 1;
y is an integer selected from 0 or 1;
R 8 and R 9 are each independently C 1-20 alkyl;
R 10 and R 11 are each independently C 1-20 alkyl;
and R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , and R 25 are each independently selected from substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-6 cycloalkyl, substituted or unsubstituted C 2-20 alkenyl, or substituted or unsubstituted C 6-10 aryl.

7. The composition according to claim 6 , wherein x and y are each 0; M is Ti; R 8 , R 9 , R 10 and R 11 are each independently C 1-6 alkyl; and R 12 to R 25 are each independently C 1-6 alkyl.

8. The composition according to claim 7 , wherein R 8 and R 9 are each i-propyl; and R 12 to R 25 are each i-butyl.

9. The composition according to claim 7 , wherein R 8 and R 9 are each i-propyl; and R 12 to R 25 are each i-octyl.

10. The composition according to claim 1 , further comprising a silylated polymer selected from the group consisting of silylated silicones, silylated polyethers (MS polymers), silylated polycarbonates, silylated polyolefins, silylated polyesters, silylated polyacrylates, silylated polyvinyl acetates, mixtures thereof and c

Assignees

• Huntsman Int Llc

Inventors

• Phanopoulos Christopher
• Holvoet Servaas
• Desesquelles Fabrice
• Klein Alexander Rene

Classifications

• C08G18/289

  containing silicon · CPC title

• C09J175/04

  Polyurethanes · CPC title

• C08K5/549 Primary

  containing silicon in a ring · CPC title

• C08G18/4825

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

• C08G77/16

  to hydroxy groups · CPC title