# US 9,752,013 B2 · Composition comprising silylated polymers

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 9,752,013 B2
- Document ID: US9752013B2
- Status: Granted
- Kind: B2
- Application number: 14/782,342
- Filed: 2014-04-01
- Published: 2016-02-18
- Granted: 2017-09-05
- Earliest claimed: 2013-04-25
- Assignees: Huntsman International LLC
- Applicants: Huntsman International LLC
- Inventors: Christopher Phanopoulos; Servaas Holvoet; Fabrice Desesquelles; Alexander Rene Klein
- Web page: https://patentgrep.com/patent/US9752013B2

## CPC

- C08K 5/56: Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08G 18/289: {containing silicon}
- C08G 18/4825: {Polyethers containing two hydroxy groups (C08G18/4833 - C08G18/5096 take precedence)}
- C08G 18/7671: {containing only one alkylene bisphenyl group}
- C08K 5/549: containing silicon in a ring
- C09D 175/04: Polyurethanes
- C09J 175/04: Polyurethanes
- C08G 77/08: characterised by the catalysts used
- C08G 77/16: to hydroxy groups
- C08G 77/18: to alkoxy or aryloxy groups
- C08G 77/485: {containing less than 25 silicon atoms}
- C08G 77/58: Metal-containing linkages
- C08G 2110/0008: flexible
- C08G 2110/0016: semi-rigid
- C08G 2110/0025: rigid
- C08G 2190/00: Compositions for sealing or packing joints
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)

## 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.

## Claims

### Claim 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.

### Claim 2 (depends on 1)

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
X1, X2, and X3 are each independently selected from Si or M1, wherein M1 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;
Z1, Z2 and Z3 are each independently selected from L2, R5, R6, or R7; wherein L2 is selected from —OH or —O—C1-10 alkyl;
Y1 and Y2 are each independently —O-M2-L3; or Y1 and Y2 are linked together and form —O-M2(L3)-O— or —O—; wherein L3 is selected from OH or —O—C1-10 alkyl; and M2 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;
R1, R2, R3, R4, R5, R6, and R7 are each independently selected from substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C3-6 cycloalkyl, substituted or unsubstituted C2-20 alkenyl, or substituted or unsubstituted C6-10 aryl;
and
X4 is -M3L1, or M3, and Q1 and Q2 are each a single bond linked to M3; wherein L1 is selected from —OH or —O—C1-10 alkyl, and M3 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
X4 is -M3L1; and Q2 is a single bond linked to M3; and Q1 is -M4L4 or —SiR38; wherein M4 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 L4 is selected from —OH or alkyl, and R38 is selected from substituted or unsubstituted O1-20 alkyl, substituted or unsubstituted O3-6 cycloalkyl, substituted or unsubstituted O2-20 alkenyl, or substituted or unsubstituted O6-10 aryl;
or
X4, Q1 and Q2 are each independently -M3L1;
or
X4 is —Si(R38)—O-M3L1; Q2 is a single bond linked to the Si of X4; and Q1 is -M4L4;
or
X4 is —Si(R38)—O-M3L1; Q2 is a single bond linked to the Si of X4; and Q1 is a single bond linked to the M3 of X4.

### Claim 3 (depends on 2)

The composition according to claim 2, wherein X1, X2, X3 are each independently Si;
X4 is -M3L1; and Q1 and Q2 are each a single bond linked to M3; wherein M3 is Ti and L1 is O-i-propyl;
Z1, Z2 and Z3 are each independently C1-6 alkyl;
R1, R2, R3, R4 are each independently C1-6 alkyl;
Y1 and Y2 are linked together and form —O—.

### Claim 4 (depends on 2)

The composition according to claim 2, wherein M1, M2, M3 and M4 each independently are selected from the group consisting of Ti, Zr and Hf.

### Claim 5 (depends on 1)

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 X1, X2, and X3 are each independently selected from Si or M1, wherein M1 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;
Z1, Z2 and Z3 are each independently selected from L2, R5, R6, or R7; wherein L2 is selected from —OH or —O—C1-10 alkyl;
Y1 and Y2 are each independently —O-M2-L3; or Y1 and Y2 are linked together and form faun —O-M2(L3)-O— or —O—; wherein L3 is selected from OH or —O—C1-10 alkyl; and M2 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;
R1, R2, R3, R4, R5, R6, and R7 are each independently selected from substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C3-6 cycloalkyl, substituted or unsubstituted C2-20 alkenyl, or substituted or unsubstituted C6-10 aryl;
and X4 is -M3L1, or M3, and Q1 and Q2 are each a single bond linked to M3; wherein L1 is selected from OH or —O—C1-10 alkyl, and M3 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
X4 is -M3L1; and Q2 is a single bond linked to M3; and Q1 is -M4L4 or —SiR38; wherein M4 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 L4 is selected from —OH or —O—C1-10 alkyl, and R38 is selected from substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C3-6 cycloalkyl, substituted or unsubstituted C2-20 alkenyl, or substituted or unsubstituted C6-10 aryl;
or
X4, Q1 and Q2 are each independently -M3L1;
or
X4 is —Si(R38)—O-M3L1; Q2 is a single bond linked to the Si of X4; and Q1 is -M4L4;
or
X4 is —Si(R38)—O-M3L1; Q2 is a single bond linked to the Si of X4; and Q1 is a single bond linked to the M3 of X4.

### Claim 6 (depends on 1)

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;
R8 and R9 are each independently C1-20 alkyl;
R10 and R11 are each independently C1-20 alkyl;
and R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, and R25 are each independently selected from substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C3-6 cycloalkyl, substituted or unsubstituted C2-20 alkenyl, or substituted or unsubstituted C6-10 aryl.

### Claim 7 (depends on 6)

The composition according to claim 6, wherein x and y are each 0; M is Ti; R8, R9, R10 and R11 are each independently C1-6 alkyl; and R12 to R25 are each independently C1-6 alkyl.

### Claim 8 (depends on 7)

The composition according to claim 7, wherein R8 and R9 are each i-propyl; and R12 to R25 are each i-butyl.

### Claim 9 (depends on 7)

The composition according to claim 7, wherein R8 and R9 are each i-propyl; and R12 to R25 are each i-octyl.

### Claim 10 (depends on 1)

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 copolymers thereof.

### Claim 11 (depends on 1)

The composition according to claim 1, wherein said silylated polyurethane compound is obtained by reaction of at least one isocyanate with at least one isocyanate reactive compound and with at least one alkoxysilane compound and/or silanol compound.

### Claim 12 (depends on 11)

The composition according to claim 11, wherein the alkoxysilane compound is an aminoalkoxysilane.

### Claim 13 (depends on 1)

The composition according to claim 1, wherein the amount of said tin-free polyhedral oligomeric metallo silsesquioxane compound ranges from 0.001 wt % to 5 wt %, based on total weight of the composition.

### Claim 14 (depends on 1)

The composition according to claim 1, wherein said composition further comprises one or more additives selected from the group consisting of fillers, adhesion promoters, moisture scavengers, plasticizers, UV stabilizers, thixotropic agents, or combinations thereof.

### Claim 15 (depends on 1)

The composition according to claim 1, wherein said composition contains less than 0.001 wt % of tin.

### Claim 16 (depends on 1)

A process of curing a composition according to claim 1, comprising the step of: contacting at least one silylated polyurethane compound comprising an alkoxysilyl group, a silanol group, or combinations thereof with at least one tin-free polyhedral oligomeric metallo silsesquioxane curing agent thereby obtaining a cured composition.

### Claim 17 (depends on 1)

The composition according to claim 1, wherein the amount of said tin-free polyhedral oligomeric metallo silsesquioxane curing agent is ranging from 0.01 to 2 wt %, based on total weight of the composition.

### Claim 18 (depends on 1)

The composition according to claim 1, wherein the amount of said tin-free polyhedral oligomeric metallo silsesquioxane curing agent is ranging from 0.1 to 2 wt %, based on total weight of the composition.

### Claim 19 (depends on 1)

The composition according to claim 1, wherein the curing agent increases the hydrolysis and condensation rate of said alkoxysilyl and silanol groups of the silylated polyurethane compound.

### Claim 20 (depends on 16)

The process according to claim 16, wherein the curing agent increases the hydrolysis and condensation rate of said alkoxysilyl and silanol groups of the silylated polyurethane compound.