# US 2019/0169352 A1 · Process for the synthesis of silylated polyurethanes and silylated polyurethane composition

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- Number: US 2019/0169352 A1
- Document ID: US20190169352A1
- Status: Published application
- Kind: A1
- Application number: 16/323,612
- Filed: 2017-08-01
- Published: 2019-06-06
- Earliest claimed: 2016-08-08
- Assignees: Bostik SA
- Applicants: Bostik SA
- Inventors: Olivier LAFERTE
- Web page: https://patentgrep.com/patent/US20190169352A1

## CPC

- C08G 18/3893: {containing silicon}
- C08G 18/10: Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G 18/222: {metal compounds not provided for in groups C08G18/225 - C08G18/26}
- C08G 18/227: {of antimony, bismuth or arsenic}
- C08G 18/4812: {Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups}
- C08G 18/4825: {Polyethers containing two hydroxy groups (C08G18/4833 - C08G18/5096 take precedence)}
- C08G 18/4829: {Polyethers containing at least three hydroxy groups (C08G18/4833 - C08G18/5096 take precedence)}
- C08G 18/6685: {with compounds of group C08G18/3225 or polyamines of C08G18/38}
- C08G 18/755: {and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate}
- C08G 18/7621: {being toluene diisocyanate including isomer mixtures}
- C09J 7/38: Pressure-sensitive adhesives [PSA]
- C09J 11/08: Macromolecular additives
- C09J 175/04: Polyurethanes
- C08L 75/04: Polyurethanes
- C09J 2203/334: as a label
- C09J 2301/408: additives as essential feature of the adhesive layer
- C09J 2467/006: in the substrate
- C09J 2475/00: Presence of polyurethane
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

The present invention provides a process for the synthesis of silylated polyurethanes, comprising three sequential steps, a step (i) of preparing NCO-terminated polyurethane, a step (ii) of partial grafting of the NCO functions with silane functions and a step (iii) of total grafting of the residual NCO functions with functions that react with the NCO functions by means of polyfunctional compounds. The present invention also provides a silylated polyurethane composition that can be obtained by means of the process according to the invention, an adhesive composition comprising said silylated polyurethane composition and a self-adhesive item obtained from the adhesive composition according to the invention.

## Claims

### Claim at position 1

1-15. (canceled)

### Claim 16

A process for the synthesis of a composition of silylated polyurethanes (A), said process comprising the following sequential stages:
i. polyaddition of at least one polyol (B) with at least one diisocyanate (C), in which the ratio (r1) of the number of NCO functional groups to the total number of OH functional groups, and of NH and NH2 functional groups optionally present, is strictly greater than 1;
ii. reacting the composition obtained in stage (i) with at least one silane (E) selected from the group consisting of aminosilanes (E1) and mercaptosilanes (E2), in which the ratio (r2) of the number of NCO functional groups to the number of amine and/or thiol functional groups is strictly greater than 1;
iii. reacting the composition resulting from stage (ii) with at least one compound (G) comprising at least two identical or different functional groups selected from the group consisting of alcohol, primary amine, secondary amine and thiol functional groups, in which the ratio (r3) of the number of NCO functional groups to the number of alcohol, primary amine, secondary amine and thiol functional groups is less than or equal to 1.

### Claim 17 (depends on 16)

The synthesis process as claimed in claim 16, wherein, during stage (ii), the ratio (r2) of the number of NCO functional groups to the number of amine and/or thiol functional groups ranges from 1.1 to 5, when the compound (G) comprises solely two functional groups selected from the group consisting of alcohol, primary amine, secondary amine and thiol functional groups, and in which, during stage (ii), the ratio (r2) of the number of NCO functional groups to the number of amine and/or thiol functional groups ranges from 1.1 to 2.5, when the compound (G) comprises at least three functional groups selected from the group consisting of alcohol, primary amine, secondary amine and thiol functional groups.

### Claim 18 (depends on 16)

The synthesis process as claimed in claim 16, in which, during stage (iii), the ratio (r3) of the number of NCO functional groups to the number of alcohol, primary amine, secondary amine and thiol functional groups is greater than or equal to 0.6.

### Claim 19 (depends on 16)

The synthesis process as claimed in claim 16, wherein the silane (E) exhibits the following structure:
X′—R3—Si(R4)p(OR5)3-p
wherein:
X′ represents an NH2, NHR7 and/or SH group,
R7 represents a linear, branched or cyclic alkyl radical having from 1 to 12 carbon atoms or an alkenyl radical having from 2 to 12 carbon atoms or an aryl radical having from 6 to 12 carbon atoms,
R3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms,
R4 and R5, which are identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms; two —OR5 groups can optionally be involved in one and the same ring,
p represents an integer equal to 0, 1 or 2.

### Claim 20 (depends on 16)

The synthesis process as claimed in claim 16, in which the compound (G) exhibits a number-average molecular weight ranging from 100 g/mol to 80 000 g/mol.

### Claim 21 (depends on 16)

The synthesis process as claimed in claim 16, wherein the compound (G) is selected from polyols.

### Claim 22 (depends on 16)

The synthesis process as claimed in claim 16, wherein the composition obtained on conclusion of stage (iii) is a composition of silylated polyurethanes (A) comprising a first type of silylated polyurethane (A1) of formula (I) and a second type of silylated polyurethane (A2) of formula (IIa), (IIb) or (IIc):
wherein formulae:
Jg represents a group of type:
Lg represents a group of type:
Mg represents a group of type:
Jd represents a group of type:
Ld represents a group of type:
Md represents a group of type:
R1 represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms which can be aromatic or aliphatic and linear, branched or cyclic,
R3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms,
R2 represents a divalent hydrocarbon radical optionally comprising one or more heteroatoms,
R4 and R5, which are identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms; two —OR5 groups can optionally be involved in one and the same ring,
X represents a divalent radical chosen from —NH—, —NR7— or —S—,
R7 represents a linear, branched or cyclic alkyl radical having from 1 to 12 carbon atoms or an alkenyl radical having from 2 to 12 carbon atoms or an aryl radical having from 6 to 12 carbon atoms,
R6 represents a divalent radical, a trivalent radical or a tetravalent radical chosen from polysiloxane radicals and from hydrocarbon radicals optionally comprising one or more carbonyl (C═O) functional groups and optionally one or more heteroatoms,
A, A′, A″ and A′″ represent, independently of one another, an oxygen atom, a sulfur atom, a divalent —NH— radical or a divalent —NR8— radical,
R8 represents a linear, branched or cyclic alkyl radical comprising from 1 to 18 carbon atoms,
n is an integer greater than or equal to 1 such that the polyurethane (A1) exhibits a number-average molecular weight Mn(1) ranging from 800 to 100 000 daltons,
m is an integer greater than or equal to 1 such that the polyurethane (A2) exhibits a number-average molecular weight Mn(2) such that the ratio Mn(2)/Mn(1) is greater than or equal to 2.0, and
p is an integer equal to 0, 1 or 2.

### Claim 23

A composition of silylated polyurethanes (A) comprising a first type of silylated polyurethane (A1) of formula (I) and a second type of silylated polyurethane (A2) of formula (IIa), (IIb) or (IIc):
wherein formulae:
Jg represents a group of type:
Lg represents a group of type:
Mg represents a group of type:
Jd represents a group of type:
Ld represents a group of type:
Md represents a group of type:
R1 represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms which can be aromatic or aliphatic and linear, branched or cyclic,
R3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms,
R2 represents a divalent hydrocarbon radical optionally comprising one or more heteroatoms,
R4 and R5, which are identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms; two —OR5 groups can optionally be involved in one and the same ring,
X represents a divalent radical chosen from —NH—, —NR7— or —S—,
R7 represents a linear, branched or cyclic alkyl radical having from 1 to 12 carbon atoms or an alkenyl radical having from 2 to 12 carbon atoms or an aryl radical having from 6 to 12 carbon atoms,
R6 represents a divalent radical, a trivalent radical or a tetravalent radical chosen from polysiloxane radicals and from hydrocarbon radicals optionally comprising one or more carbonyl (C═O) functional groups and optionally one or more heteroatoms,
A, A′, A″ and A′″ represent, independently of one another, an oxygen atom, a sulfur atom, a divalent —NH— radical or a divalent —NR8— radical,
R8 represents a linear, branched or cyclic alkyl radical comprising from 1 to 18 carbon atoms,
n is an integer greater than or equal to 1 such that the polyurethane (A1) exhibits a number-average molecular weight Mn(1) ranging from 800 to 100 000 daltons,
m is an integer greater than or equal to 1 such that the polyurethane (A2) exhibits a number-average molecular weight Mn(2) such that the ratio Mn(2)/Mn(1) is greater than or equal to 2.0, and
p is an integer equal to 0, 1 or 2.

### Claim 24 (depends on 23)

The composition of silylated polyurethanes as claimed in claim 23, wherein Mn(2) ranges from 1600 to 200 000 g/mol.

### Claim 25 (depends on 23)

The composition of silylated polyurethanes as claimed in claim 23, wherein the silylated polyurethane (A2) is of formula (IIb) or (IIc) and the ratio Mn(2)/Mn(1) is greater than or equal to 3.

### Claim 26 (depends on 23)

The composition of silylated polyurethanes as claimed in claim 23, exhibiting a viscosity at 23° C. ranging from 20 000 to 2 000 000 mPa·s.

### Claim 27 (depends on 23)

The composition of claim 23, further comprising at least one additional component selected from the group consisting of catalysts, fillers, tackifying resins, adhesion promoters, plasticizers or diluents, rheological agents, drying agents, UV and/or heat stabilizers, and solvents.

### Claim 28 (depends on 27)

The composition as claimed in claim 27, wherein the at least one additional component comprises at least one tackifying resin and at least one crosslinking catalyst.

### Claim 29 (depends on 28)

The composition as claimed in claim 28, wherein the composition comprises
from 17% to 85% by weight of the composition of silylated polyurethanes (A),
from 12% to 80% by weight of tackifying resin(s), and
from 0.01% to 5% by weight of crosslinking catalyst(s),
with respect to the total weight of the composition.

### Claim 30 (depends on 28)

A self-adhesive article comprising a support layer coated with a layer of the composition of claim 28, said layer being obtained by crosslinking said composition.