Hydrocarbon-based polymers bearing two alkoxysilane end groups

Patent metadata

Field	Value
Publication number	US-10400059-B2
Application number	US-201414906681-A
Country	US
Kind code	B2
Filing date	Jul 22, 2014
Priority date	Jul 23, 2013
Publication date	Sep 3, 2019
Grant date	Sep 3, 2019

Abstract

Hydrocarbon-based polymer of formula (1) bearing alkoxysilane end groups:

in which:
is a double or single bond; each of R 2 , R 3 , R 4 and R 5 is H, a halo, an alkoxycarbonyl or an alkyl, m and p are each from 0 to 5, each of R and R′ is an alkyl, Z is an alkylene, optionally interrupted with COO, q is 0 or 1, r is 0, 1 or 2, and n is an integer such that the number-average molar mass Mn of the polymer is from 400 to 50 000 g/mol, and its polydispersity index (PDI) is from 1.0 to 2.0. Preparation by ring-opening metathesis polymerization for 2 hours to 24 hours. Adhesive composition comprising polymer (1) and crosslinking catalyst. Bonding by assembly of two substrates using this adhesive composition.

First claim

The invention claimed is:

1. A hydrocarbon-based polymer comprising two alkoxysilane end groups, said hydrocarbon-based polymer being of formula (1):

in which:
each carbon-carbon bond of the chain noted as is a double bond or a single bond, in accordance with the valency rules of organic chemistry;
the groups R 2 , R 3 , R 4 and R 5 are each, independently of the other groups or otherwise, a hydrogen, a halo group, an alkoxycarbonyl group or an alkyl group, the groups R 2 to R 5 possibly being linked together as members of the same saturated or unsaturated ring or heterocycle,
m and p are integers each within a range from 0 to 5, the sum m+p itself being within a range from 0 to 10,
R and R′, which may be identical or different, each represent a linear or branched, preferably linear, alkyl group comprising from 1 to 4,
Z is a divalent alkylene group, interrupted with an ester function, and having from 1 to 22 carbon atoms,
q is 1,
r is an integer equal to 0 or 1, and
n is an integer such that the number-average molar mass Mn of the hydrocarbon-based polymer of formula (1) is within a range from 400 to 50 000 g/mol, and the polydispersity index (PDI) of the hydrocarbon-based polymer of formula (1) is within a range from 1.0 to 2.0.

2. The hydrocarbon-based polymer comprising two alkoxysilane end groups as claimed in claim 1 , said polymer being such that the group of formula —[Z] q —Si(R) r (OR′) 3-r is —CO—O—(CH 2 ) 3 Si(OCH 3 ) 3 ); or —CO—O—(CH 2 ) 3 SiCH 3 (OCH 3 ) 2 ).

3. The hydrocarbon-based polymer comprising two alkoxysilane end groups as claimed in claim 1 , said polymer being of formula (1′):

4. The hydrocarbon-based polymer comprising two alkoxysilane end groups as claimed in claim 1 , said hydrocarbon-based polymer being of formula (2) or of formula (3):

in which the bond means that the bond is geometrically oriented on one side or the other relative to the double bond (cis or trans).

5. The hydrocarbon-based polymer comprising two alkoxysilane end groups as claimed in claim 1 , said hydrocarbon-based polymer being of formula (4):

6. The hydrocarbon-based polymer comprising two alkoxysilane end groups as claimed in claim 5 , said polymer being of formula (4′):

7. The hydrocarbon-based polymer comprising two alkoxysilane end groups as claimed in claim 5 , said hydrocarbon-based polymer being of formula (5) or of formula (6):

in which the bond means that the bond is geometrically oriented on one side or the other relative to the double bond (cis or trans).

8. A process for preparing at least one hydrocarbon-based polymer as claimed claim 1 , said process comprising at least one step of ring-opening metathesis polymerization in the presence of:
at least one metathesis catalyst,
at least one chain-transfer agent (CTA) chosen from the group formed by alkenylsilanes bearing a carbon-carbon double bond, and
at least one compound comprising at least one hydrocarbon-based ring and from 6 to 16 carbon atoms per ring, said ring comprising at least one carbon-carbon double bond, or substituted derivatives of this compound, said compound being of formula (7):

in which:
each carbon-carbon bond of the chain noted as is a double bond or a single bond, in accordance with the valency rules of organic chemistry;
the groups R 2 , R 3 , R 4 and R 5 are each, independently of the other groups or otherwise, a hydrogen, a halo group, an alkoxycarbonyl group or an alkyl group, the groups R 2 to R 5 possibly being linked together as members of the same saturated or unsaturated ring or heterocycle,
m and p are integers each within a range from 0 to 5, the sum m+p itself being within a range from 0 to 10,
said step being performed for a time of between 2 hours and 24 hours, (limits inclusive).

9. The preparation process as claimed in claim 8 , such that the chain-transfer agent has the formula CH 2 ═CH—[Z] q —Si(R) r (OR′) 3-r in which:
R and R′, which may be identical or different, each represent a linear or branched alkyl group comprising from 1 to 4 carbon atom,
Z is a divalent alkylene group interrupted with an ester function, and comprising from 1 to 22 carbon atoms,
q is an integer equal to 0 or 1, and
r is an integer equal to 0 or 1.

10. The preparation process as claimed in claim 8 , such that the chain-transfer agent is: CH 2 ═CH—CO—O—(CH 2 ) 3 Si(OCH 3 ) 3 ; or CH 2 ═CH—CO—O—(CH 2 ) 3 SiCH 3 (OCH 3 ) 2 .

11. The preparation process as claimed in claim 8 , said process being such that the mole ratio of the CTA to the compound comprising at least one hydrocarbon-based ring is within a range from 1 to 10 mol %.

12. The preparation process as claimed in claim 8 , said process also comprising at least one additional hydrogenation of double bonds.

13. The preparation process as claimed in claim 12 , such that the additional hydrogenation is performed by catalytic hydrogenation, under hydrogen pressure and in the presence of a hydrogenation catalyst.

14. The process according to claim 8 , wherein the CTA is 3-(trimethoxysilyl)propyl acrylate.

15. An adhesive composition comprising at least one polymer as claimed in claim 1 and from 0.01% to 3% by weight of at least one crosslinking catalyst.

16. A process for bonding by assembly of two substrates, comprising:
the coating of an adhesive composition as claimed in claim 15 , in liquid form, optionally in the form of a layer with a thickness in a range from 0.3 to 5 mm, onto at least one of the two surfaces that belong, respectively, to the two substrates to be assembled, and which are intended to be placed in contact with each other on a tangency surface; and then
effective placing in contact of the two substrates on their tangency surface.

Assignees

• Bostik Sa

Inventors

• Michaud Guillaume
• Simon Frederic
• Fouquay Stephane
• Diallo Abdou Khadri
• Guillaume Sophie
• Carpentier Jean-Francois

Classifications

• C09J123/20

  having four to nine carbon atoms · CPC title

• C08G2261/76

  crosslinking · CPC title

• C08G2261/724

  Hydrogenation · CPC title

• C08G2261/72

  Derivatisation · CPC title

• C08G2261/418

  Ring opening metathesis polymerisation [ROMP] · CPC title