EP3247733A1

EP3247733A1 - Hydrocarbonated polymers with two alcoxysilane end groups

Info

Publication number: EP3247733A1
Application number: EP16702175.7A
Authority: EP
Inventors: Guillaume Michaud; Frédéric Simon; Stéphane Fouquay; Xiaolu MICHEL; Sophie Guillaume; Jean-François Carpentier
Original assignee: Centre National de la Recherche Scientifique CNRS; Universite de Rennes 1; Bostik SA
Current assignee: Centre National de la Recherche Scientifique CNRS; Universite de Rennes 1; Bostik SA
Priority date: 2015-01-22
Filing date: 2016-01-07
Publication date: 2017-11-29
Also published as: US20170369637A1; FR3031979A1; WO2016116680A1; FR3031979B1

Abstract

The invention relates to 1) a hydrocarbonated polymer comprising two alcoxysilane end groups of formula (1), and 2) a method for producing said polymer, an adhesive composition comprising said polymer and the use of said adhesive composition.

Description

Hydrocarbon polymers with two alkoxysilane end groups

The present invention relates to hydrocarbon polymers comprising two alkoxysilane end groups, their preparation and their use.

Silane-modified polymers (MS Polymers or MS Polymers for "Modified Silane Polymers") are known in the field of adhesives. They are used for bonding a wide variety of objects (or substrates). Thus, the compositions based on polymers MS are applied, in combination with a catalyst, in the form of an adhesive layer on at least one of two surfaces belonging to two substrates to be assembled and intended to be brought into contact with one another. with each other in order to assemble them. The polymer MS reacts by crosslinking with the water of the ambient medium and / or the water provided by the substrates, which leads to the formation of a cohesive adhesive seal ensuring the strength of the assembly of these two substrates. This adhesive seal consists mainly of MS polymer crosslinked in a three-dimensional network formed by the polymer chains interconnected by siloxane type bonds. The crosslinking may take place before or after contacting the two substrates and the application, if any, of a pressure at their tangency surface.

However, the MS polymers must most often be used in the form of adhesive compositions comprising other constituents, for example tackifying resins, one or more additives with a reinforcing effect, for example at least one mineral filler, or else one or more additives to improve setting time (i.e. the time after which crosslinking can be considered complete) or other characteristics such as rheology or mechanical performance (elongation, modulus). .).

CA 2242060 discloses the possibility of employing a polymer-based adhesive seal composition containing at least one cycloolefin, a catalyst for metathesis polymerization with chain opening, a charge and a compound that includes only one silane function.

It is known to prepare telechelic polymers comprising an alkoxysilane end group and a vinyl end group, by means of a transfer agent containing a single silane function.

Thus, patent application EP 2468783 describes the preparation of a polyurethane-polyether and polyurethane-polyester block polyurethane with at least two polyurethane-polyester terminal blocks connected to an alkoxysilane terminal group, as well as an adhesive composition comprising this polyurethane and a crosslinking catalyst. The silane terminal group is derived from an isocyanatosilane which comprises only one silane functional group.

It is also known to prepare telechelic polymers comprising a repeating unit derived from cyclic monomer such as, for example, norbornene.

Thus, the patent application WO 01/04173 describes the catalytic ring-opening copolymerization by metathesis of branched cycloolefins comprising the same cycloolefin. Said cycloolefin is preferably norbornene.

In addition, patent application WO 201 1/038057 describes the metathesis ring opening polymerization of dicarboxylic anhydrides of norbornene and optionally of 7-oxanorbornene dicarboxylic anhydrides.

Finally, patent application GB 2238791 describes a method for the polymerization of 7-oxanorbornene by ring opening polymerization by metathesis.

The object of the present invention is to propose novel polymers with two alkoxysilane end groups. These polymers can lead, after crosslinking, to the formation of an adhesive seal having improved mechanical properties, and in particular a higher cohesion compared with those of the state of the art. Thus, the present invention relates to a hydrocarbon polymer comprising two alkoxysilane end groups, said hydrocarbon polymer being of formula (1) below:

in which :

- Fi is (RO) ₃ -ZRzSi-R "-NH-COO- (CH ₂ ) pi- and F ₂ is

- (CH ₂₎ _q i- OOC-NH-R _"z -SiR (OR ') _3-z; or

- Fi is (R'O) _3- zRzSi-R "-NH-CO-NH- (CH2) pi- and F ₂ is

- (CH ₂ ) qi-NH-CO-NH-R "-SiRz (OR ') _3- z;

- Fi is (R'O) ₃ -z RzSi-R "-NH-CO- (CH ₂ ) p ₂ - and F ₂ is

- (CH ₂₎ _{q 2} -CONH-R _"z -SiR (OR ') _3-z;

where z is an integer equal to 0, 1, 2 or 3; p1 and q1 are independently an integer of 1, 2 or 3; p2 and q2 are independently an integer of 0, 1, 2 or 3; the groups R and R 'are independently an alkyl group, preferably linear, comprising from 1 to 4, preferably from 1 to 2, carbon atoms; the group R "is an alkylene group, preferably linear, comprising from 1 to 4 carbon atoms, and in which:

• each carbon-carbon bond of the noted chain is a double bond or a single bond, in accordance with the valence rules of organic chemistry;

The groups R1, R2, R3, R4, R5, R6, R7 and R8 are independently a hydrogen, a halogen atom, an alkyl group, a heteroalkyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, at least one of the groups R1 to R8 being part of the same ring or saturated or unsaturated heterocycle with at least one other of the groups R1 to R8, according to the valence rules of the organic chemistry and at least one of the pairs (R1, R2), (R3 R4), (R5, R6) and (R7, R8) being an oxo group; X and y are integers independently in a range from 0 to 5, preferably from 0 to 2, even more preferably x is 1 and y is 1, the sum x + y being preferably in a range of 0 to 4 and even more preferably 0 to 2;

The groups R14, R15, R16 and R17 are independently a hydrogen, a halogen atom, an alkyl group, an alkenyl group, a heteroalkyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, at least one of the groups R14 to R17 being forming part of the same ring or saturated or unsaturated heterocycle with at least one other of the groups R14 to R17, according to the valence rules of organic chemistry;

The group R20 is CH ₂ , O, S, NR ₀ or C (= O), Ro being an alkyl or alkenyl group, preferably linear, comprising from 1 to 22, preferably from 1 to 14, carbon atoms; and

N is an integer greater than or equal to 2 and m is an integer greater than or equal to 0, the molar ratio m: n being in a range from 0: 1 to 0.5: 1, preferably from 0: 1 to 0.3: 1; n and m being further such that the number average molar mass Mn of the hydrocarbon polymer of formula (1) is in the range of 400 to 50,000 g / mol, preferably 600 to 20,000 g / mol, and the The polydispersity (PDI) of the hydrocarbon polymer of formula (1) is in a range from 1.0 to 3.0, preferably from 1.0 to 2.0, more preferably from 1.45 to 1.85. .

Of course, all formulas are given here in accordance with the valence rules of organic chemistry.

The main chain of the polymer of formula (1) thus comprises one or two types of repeating units, a first type of repeat unit repeated n times and a second type of repeat unit, optional, repeated m times.

As it appears above, the terminal groups Fi and F ₂ are generally symmetrical with respect to the main chain, that is to say that they correspond substantially, with the exception of the indices p1 and p2, and q1 and q2.

The term "alkyl group" means a linear or branched, cyclic, acyclic, heterocyclic or polycyclic saturated hydrocarbon compound, and unless otherwise generally indicated from 1 to 22 carbon atoms. Such an alkyl group most often comprises from 1 to 14, preferably from 1 to 8, carbon atoms. By "heteroalkyl group" is meant according to the invention an alkyl group in which at least one of the carbon atoms is substituted with a heteroatom chosen from the group formed by O and S.

By "alkoxycarbonyl group" is meant a linear or branched, saturated or partially unsaturated (monovalent) alkyl group comprising from 1 to 22, preferably from 1 to 14, carbon atoms, as well as a divalent group - COO- . By "heteroalkoxycarbonyl group" is meant according to the invention an alkoxycarbonyl group in which at least one of the carbon atoms is substituted by a heteroatom selected from the group formed by O and S.

The term "halogen atom" means an iodo, chloro, bromo or fluoro group, preferably chloro.

By "heterocycle" is meant a hydrocarbon ring which may comprise another atom than carbon in the ring chain, such as, for example, oxygen, sulfur or nitrogen.

By "alkoxysilane group" is meant a group comprising a linear or branched, saturated or partially unsaturated alkyl group comprising from one to four, preferably from one to two, carbon atoms and, in addition, a divalent group -Si O-.

"At least one of the groups R1 to R8 which may form part of the same ring or saturated or unsaturated heterocycle with at least one other of the groups R1 to R8, according to the valence rules of organic chemistry" means according to the invention that these two groups, whether or not they are borne by the same carbon, are linked together by a hydrocarbon chain optionally comprising at least one heteroatom such as S or O. Thus, by for example, such a cycle consists of R1-O-R8. This is also applicable to groups R14 to R17.

By "pair (R1, R2) which may be an oxo group", it means according to

the invention that the pair (R1, R2) is such that , where C is the carbon that supports the two groups forming the pair (R1, R2). This is also applicable to pairs (R3, R4), (R5, R6) and (R7, R8).

By "terminal group" is meant a group located at the end of the chain (or end) of the polymer. The polymer according to the invention comprises a main chain, i.e. a longer chain, both ends of which are the terminal groups of the polymer according to the invention.

PDI polymolecularity (or D _M dispersity) is defined as the ratio Mw / Mn, that is to say the ratio of the weight average molar mass to the number average molar mass of the polymer.

The two average molar masses Mn and Mw are measured according to the invention by Size Exclusion Chromatography (SEC), usually with PEG (PolyEthyleneGlycol) or PS (Polystyrene) calibration, preferably PS.

In a particularly preferred manner, x is equal to 1 and y is 1. Preferably the R5 to R8 groups are each hydrogen.

If z = 0, then there is no group R in the formula (R'O) 3 _-z RzSi which becomes (R'O) ₃ Si-

If p2 = 0 or q2 = 0, then there is no group (CH ₂ ) in the formula- (CH ₂ ) _P 2 which becomes-or in the formula- (CH ₂ ) _q 2 which becomes -.

When the index m, x or y which applies to a set of two brackets is equal to zero, this means that it is not a group between the brackets to which this index applies. So, means fie. According to one embodiment of the invention, all the bonds of formula (1) are carbon-carbon double bonds, and formula (1) then becomes the following formula (1 '):

wherein x, y, m, n, F ₁ , F ₂ , R ₁ , R ₂ , R 3, R 4, R 5, R 6, R 7, R 8, R 14,

R15, R16, R17 and R20 have the meanings given above and the bond is a geometrically oriented bond on one side or the other with respect to the double bond (cis or trans).

According to another embodiment of the invention, all the connections ï ^"" of the formula (1) are carbon-carbon single bonds, and the formula (1) becomes the following formula (1 H) is described below -after.

Each of the double bonds of the polymer of formula (1 ') is oriented geometrically cis or trans, preferably is of cis orientation. The geometric isomers of the polymer of formula (1 ') are generally present in variable proportions, with most often a majority of cis (Z) - cis (Z) - cis (Z) - cis (Z). It is preferred according to the invention to have mixtures whose double bonds are predominantly oriented cis (Z), and preferably all oriented cis (Z). It is also possible according to the invention to obtain only one of the geometric isomers, according to the reaction conditions and in particular according to the nature of the catalyst used.

According to one embodiment of the invention, m is equal to 0, the polymer having the following formula (2):

in which x, y, n, Fi, F ₂ , R ₁ , R ₂ , R 3, R 4, R 5, R 6, R 7 and R 8 have the meanings given above.

Formula (2) illustrates the case where the main chain of the polymer of formula (1) comprises a single type of repeating unit, repeated n times.

In a particularly preferred manner, x is equal to 1 and y is 1.

The invention also relates to a polymer of formula (1 H) below:

wherein x, y, n, m, R f, F ₂ , R ₁ , R ₂ , R 3, R 4, R 5, R 6, R 7, R 8, R 14, R 15, R 16, R 17 and R 20, have the meanings given above.

The formula (1 H) illustrates the case where the main chain of the polymer of formula (1) is saturated, that is to say contains only saturated bonds.

In this case, preferably, x is 1 and y is 1.

The polymer of formula (1 H) may for example be derived from the hydrogenation of the unsaturated polymer of formula (1 ').

In one embodiment, m is 0, the polymer having the following formula (2H):

The formula (2H) illustrates the case where the main chain of the polymer of formula (1H) comprises a single type of repeating unit, repeated n times.

In this case, preferably, x is 1 and y is 1.

According to a first embodiment (called "γ-dicarbamate" pathway), Fi is (R'O) ₃ -ZRzSi-R "-NH-COO- (CH ₂ ) p 1 and F ₂ is - (CH ₂ ) qi OOC-NH-R "-SiRz (OR ') _3- z, with p1 = 1 or q1 = 1, preferably p1 = q1 = 1. In this case, preferably, R 'is methyl, R "is the group - (CH ₂ ) ₃ -, z = 0, p1 = 1 and q1 = 1.

According to a second embodiment (called "α-dicarbamate" pathway), Fi is (R'O) ₃ -ZRzSi-R "-NH-COO- (CH ₂ ) p 1 and F ₂ is - (CH ₂ ) qi OOC-NH-R "-SiRz (OR ') _3- z, with p1 = 1 or q1 = 1, preferably p1 = q1 = 1. In this case, preferably, R and R 'are each methyl, R "is the group -CH ₂ -, z = 1, p1 = 1 and q1 = 1.

According to a third embodiment (called "γ-diurea pathway"), Fi is (R'O) ₃ -ZRzSi-R "-NH-CO-NH- (CH 2) pi- and F ₂ is - (CH ₂ ) qi-NH-CO-NH-R "-SiRz (OR ') _3-z , with p1 = 1 or q1 = 1, preferably p1 = q1 = 1. In this case, preferably, R 'is methyl, R "is the group - (CH ₂ ) ₃ -, z = 0, p1 = 1 and q1 = 1.

According to a fourth embodiment (called "α-diurea route"), Fi is (RO) ₃ -Z R _z Si-R "-NH-CO-NH- (CH ₂ ) _p i- and F ₂ is - ( CH ₂ ) _q -NH-CO-NH-R "-SiRz (OR ') _3-z , with p1 = 1 or q1 = 1, preferably p1 = q1 = 1. In this case, preferably, R and R 'are each methyl, R "is the group -CH ₂ -, z = 1, p1 = 1 and q1 = 1.

According to a fifth embodiment (called "γ-diamide pathway"), Fi is (R'O) ₃ -z RzSi-R "-NH-CO- (CH ₂ ) p ₂ - and F ₂ is - (CH ₂ _q2 -CO-NH-R "-SiRz (OR ') _3-z , with p2 = 0 or q2 = 0, preferably p2 = q2 = 0. In this case, preferably, R' is a methyl, R is the group - (CH ₂ ) ₃ -, z = 0, p 2 = 0 and q 2 = 0.

According to a sixth embodiment (called "a-diamide pathway"), Fi is (R'O) ₃ -z RzSi-R "-NH-CO- (CH ₂ ) p ₂ - and F ₂ is - (CH ₂ _q2 -CO-NH-R "-SiRz (OR ') _3-z , with p2 = 0 or q2 = 0, preferably p2 = q2 = 0. In this case, preferably, R' is a methyl, R "is the group -CH ₂ -, z = 0, p2 = 0 and q2 = 0.

The polymers of formulas (1), (1 '), (1 H), (2) and (2H) according to the invention are particularly homogeneous and temperature-stable. They are preferably packaged and stored away from moisture.

The polymers of formulas (1), (1 '), (1 H), (2) and (2H) according to the invention can, after crosslinking with water of the ambient medium and / or water provided by at least one substrate, generally at atmospheric humidity, for example for a relative humidity of the air (also called the degree of hygrometry) usually in a range of 25 to 65%, and in the presence of a catalyst suitable crosslinking is an adhesive seal which exhibits high cohesion values. Such values of cohesion allow use as an adhesive, for example as a seal on a usual support (concrete, glass, marble), in the field of building, or for gluing glazing in the automotive and naval industry. .

This ability of the polymers according to the invention to crosslink in the presence of moisture is therefore particularly advantageous.

In addition, the non-crosslinked polymers of the invention are solid or liquid polymers at room temperature (i.e., about 20 ° C). Preferably, they are liquid polymers having a viscosity at 23 ° C. ranging from 1 to 500,000 mPa.s, preferably from 1 to 150,000 mPa.s and even more preferably from 1 to 50,000 mPa.s. When m is different from 0 and / or at least one of the groups R1 to R8 and / or R14 to R17 comprises an alkyl group, the non-crosslinked polymers according to the invention are preferably liquid polymers having a viscosity at 23 °. C ranging from 1 to 500,000 mPa.s.

When the uncrosslinked polymer according to the invention is solid at ambient temperature, it is generally thermoplastic (in anhydrous medium), that is to say deformable and heat fusible (i.e. at a temperature above ambient temperature). It can therefore be used as a hot-melt adhesive and hot-applied on the interface of substrates to be assembled at their tangency surface. By solidification at room temperature, an adhesive seal solidarisant the substrates is thus immediately created, giving the adhesive advantageous properties of reduced setting time.

When the non-crosslinked polymer according to the invention is a more or less viscous liquid at ambient temperature, the adhesive composition which comprises it may comprise at least one additional component such as a tackifying resin or a filler.

The invention also relates to a process for preparing at least one hydrocarbon polymer comprising two terminal groups alkoxysilanes according to the invention, said process comprising at least one metathesis ring opening polymerization step (or "Ring-Opening Metathesis Polymerization" in English), in the presence of:

at least one metathesis catalyst, preferably a catalyst comprising ruthenium, more preferably a Grubbs catalyst,

at least one alkoxysilane chain transfer agent (CTA) for the following formula (C): wherein the bond - ^R'J is a geometrically oriented bond on one side or the other with respect to the double bond (cis or trans); Fi is (R'O) ₃ zRzSi-R "-NH-COO- (CH2) pi- and F ₂ is - (CH ₂₎ _q i- OOC-NH-R" _z -SiR (OR ') ₃ z; or Fi is (R'O) ₃ -ZRzSi-R "-NH-CO-NH- (CH 2) pi- and F ₂ is

- (CH ₂ ) qi-NH-CO-NH-R "-SiRz (OR ') _{3 -} Z or else F is (R'O) _{3 -} _z RzSi-R" -NH-CO- (CH ₂ ) p2- and F ₂ is - (CH ₂ ) _q ₂ -CO-NH-R "-SiR _z (OR ') _3-z where z is an integer equal to 0, 1, 2 or 3; p1 and q1 are independently an integer equal to 1, 2 or 3; p2 and q2 are independently an integer equal to 0, 1, 2 or 3; the groups R and R 'are independently an alkyl group, preferably linear, having from 1 to 4 preferably 1 to 2 carbon atoms, the group R "is an alkylene group, preferably linear, having from 1 to 4 carbon atoms;

at least one compound of formula (A) below:

in which : The groups R1, R2, R3, R4, R5, R6, R7 and R8 are independently a hydrogen, a halogen atom, an alkyl group, a heteroalkyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, at least one of the groups R1 to R8 being part of the same ring or saturated or unsaturated heterocycle with at least one other of the groups R1 to R8, according to the valence rules of the organic chemistry and at least one of the pairs (R1, R2), (R3 R4), (R5, R6) and (R7, R8) being an oxo group;

X and y are integers independently in a range from 0 to 5, preferably from 0 to 2, even more preferably x is 1 and y is 1, the sum x + y being preferably in a range of 0 to 4 and even more preferably 0 to 2;

and

- optionally at least one compound of formula (B):

R.20

in which

The groups R14, R15, R16 and R17 are independently a hydrogen, a halogen atom, an alkyl group, an alkenyl group, a heteroalkyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, at least one of the groups R14 to R17 being forming part of the same ring or saturated or unsaturated heterocycle with at least one other of the groups R14 to R17, according to the valence rules of organic chemistry; and

The group R20 is CH ₂ , O, S, NR ₀ or C (= O), Ro being an alkyl group, preferably linear, comprising from 1 to 22, preferably from 1 to 14, carbon atoms; during a reaction time of 2 to 24 hours and at a temperature in the range of 20 to 60 ° C.

The duration and temperature for a given reaction generally depend on the reaction conditions and in particular the catalytic loading rate. The skilled person is able to adapt them depending on the circumstances.

CTA is a compound that includes two silane functions.

The molar ratio of CTA to the compound of formula (A), or to the sum of the compounds of formulas (A) and (B) if the compound of formula (B) is present, is in the range of 0.01 to 0.10, preferably 0.05 to 0.10.

The compounds of formula (A) generally comprise from 6 to 30, preferably from 6 to 22, carbon atoms.

The compounds of formula (B) generally comprise from 6 to 30, preferably from 6 to 22, carbon atoms.

In a preferred embodiment of the invention, x = y = 1.

The ring opening polymerization by metathesis is a reaction well known to those skilled in the art, which is carried out here in the presence of a particular CTA compound of formula (C).

The cyclic compounds of formula (A) are preferably, according to the invention, chosen from the group formed by cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, 1,5-cyclooctadiene and cyclonon. -cyclodécatriène.

cyclooctene 5-epoxy-cyclooctene

5-oxocyclo the 5-alkyl-cyclooctene , where R is an alkyl group comprising from 1 to 22, preferably 1 to 14, carbon atoms, are preferred according to the invention, cyclooctene being very particularly preferred. For example, R is n-hexyl.

The cyclic compounds of formula (B) are preferably according to the invention chosen from the group formed by norbornene, norbornadiene, dicyclopentadiene, 7-oxanorbornene and 7-oxanorbornadiene which are respectively of the following formulas:

Norbornene and 7-oxanorbornene are particularly preferred.

The cyclic compounds of formula (B) may also be chosen from the group formed by the compounds of formulas:

where R is an alkyl group comprising from 1 to 22, preferably 1 to 14, carbon atoms. For example, R is n-hexyl.

The cyclic compounds of formula (B) may also be chosen from the group formed by the addition products (or adducts in English) resulting from the Diels-Alder reaction using cyclopentadiene or furan as starting material, as well as the compounds derived from norbornene such as branched norbornenes as described in WO 2001/04173 (such as: isobornyl norbornene carboxylate, phenyl norbornene carboxylate, ethylhexyl norbornene carboxylate, phenoxyethyl norbornene carboxylate and alkyl dicarboxymide norbornene, the alkyl comprising most often from 3 to 8 carbon atoms) and branched norbornenes as described in WO 201 1/038057 (norbornene dicarboxylic anhydrides and optionally 7-oxanorbornene dicarboxylic anhydrides).

According to a first and second embodiment (called "dicarbamate route"), the CTA has the following formula (C1):

C ^: ROH-R s-R ^" -

in which z, R, R ', p1, q1 and have the meanings given above.

In this case, preferably:

R 'is methyl and R "is propylene - (CH ₂ ) 3 with z = 0, p1 = 1 and q1 = 1, or

R and R 'are each methyl and R "is methylene -CH ₂ - with z = 1, p1 = 1 and q1 = 1. This compound is synthesized quantitatively by reaction of 2 moles of an α-isocyanatosilane (such as r (isocyanatomethyl) methyldimethoxysilane), or

2 moles of a γ-isocyanatosilane (such as 3-isocyanatopropyltrimethoxysilane)

®

marketed under the trademark GENIOSIL by the company WACKER Chemie on 1 mole of unsaturated linear diol (for example 2-butene-1,4-diol, CAS: 1 10-64-5) available from ALDRICH.

According to a third and fourth embodiment (called "diurea pathway"), the CTA has the following formula (C2):

• R 'h .RS> ^■ · NH --- C ------ ™ - CH- ₇ W

II

0 ·

^; H _" " C - _™ NH _™ - R ^

in which z, R, R ', p1, q1 and - ^rJ have the meanings given above.

In this case, preferably:

R and R 'are each methyl and R "is methylene -CH ₂ - with z = 1, p1 = 1 and ql = 1.

This compound is synthesized quantitatively by reaction of 2 moles of an α-isocyanatosilane (such as (isocyanatomethyl) methyldimethoxysilane), or 2 moles of a γ-isocyanatosilane (such as 3-isocyanatopropyltrimethoxysilane) sold by the company Wacker.

®

Chemie under the trademark GENIOSIL on 1 mole of unsaturated linear diamine (for example 1,4-diamino-2-butene which can be synthesized by conversion of 1,4-dibromo-2-butene according to WO 92/21235 or according to Koziara et al., Synthesis 1985, 202 or from 1, 4-dibromo-2-butene according to LH Amundsen et al., J. Am Chem Soc 1951, 73, 21 18).

According to a fifth and sixth embodiment (called "diamide route"), the CTA has the following formula (C3):

in which z, R, R ', R ", p2, q2 and - ^ ^' have the meanings given above.

In this case, preferably:

R 'is methyl and R "is propylene - (CH ₂ ) 3 with z and q2 = 0, or

R and R 'are each methyl and R "is methylene -CH ₂ - with z = 1, p2 = 0 and q2 = 0.

This compound can be synthesized by amidification of unsaturated linear carboxylic diacids or corresponding anhydrides with 2 moles of an α-aminosilane (such as r (aminomethyl) methyldimethoxysilane), or 2 moles of a γ-isocyanatosilane (such as 3- aminopropyltrimethoxysilane)

® marketed by WACKER Chemie under the GENIOSIL brand. The compound obtained from maleic anhydride, which is preferred according to the invention, requires going through a step of protection / deprotection of the double bond in order to avoid undesirable side reactions.

The metathesis ring opening polymerization step (or ROMP for "Ring-Opening Methathesis Polymerization" in English) is most often carried out in the presence of at least one solvent, generally chosen from the group formed by the solvents. aqueous or organic compounds typically used in polymerization reactions and which are inert under the conditions of the polymerization, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water or mixtures thereof. A preferred solvent is selected from the group consisting of benzene, toluene, para-xylene, methylene chloride, dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, hexane heptane, methanol, ethanol, water or mixtures thereof. Even more preferably, the solvent is chosen from a group formed by benzene, toluene, para-xylene, methylene chloride, dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, hexane, heptane, methanol, ethanol or their mixtures. Even more preferably, the solvent is toluene, heptane, or a mixture of toluene and methylene chloride. The solubility of the polymer formed during the polymerization reaction depends generally and mainly on the choice of solvent and the molar mass of the polymer obtained. It is also possible that the reaction is carried out without solvent.

The metathesis catalyst, such as, for example, a catalyst for

Grubbs, is usually a commercial product.

The metathesis catalyst is most often a transition metal catalyst including a catalyst comprising ruthenium most often in the form of complex (s) of ruthenium such as a ruthenium-carbene complex. The Grubbs catalysts can thus be used in a particularly preferred manner. The term "Grubbs catalyst" generally means, according to the invention, a Grubbs 1 ^st or 2 ^nd generation catalyst, but also any other Grubbs type catalyst (ruthenium-carbene type) accessible to a person skilled in the art, such as for example the substituted Grubbs catalysts described in US Pat. No. 5,849,851.

A Grubbs catalyst 1 ^st generation is generally of the formula (8):

(8), wherein Ph is phenyl and Cy is cyclohexyl.

The P (Cy) 3 group and a tricyclohexylphosphine group.

The IUPAC name for this compound is: benzylidenebis (tricyclohexylphosphine) dichlororuthenium (CAS number 172222-30-9). A Grubbs 2 ^nd generation catalyst (or G2) is generally of the formula (9):

(9), wherein Ph is phenyl and Cy is cyclohexyl.

The IUPAC name of the second generation of this catalyst is benzylidene [1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (tricyclohexylphosphine) ruthenium (CAS number 246047-72-3).

The method for preparing a hydrocarbon polymer according to the invention may further comprise at least one additional step of hydrogenation of double bonds.

This step is generally carried out by catalytic hydrogenation, most often under hydrogen pressure and in the presence of a hydrogenation catalyst such as a palladium catalyst supported by carbon (Pd / C). It more particularly makes it possible to form a compound of formula (1H) or (2H) from an unsaturated compound of formula (1 ') or (2).

The invention also relates to an adhesive composition comprising a polymer according to the invention and from 0.01 to 3% by weight, preferably from 0.1 to 1% by weight, of a crosslinking catalyst, relative to the weight of the adhesive composition. The polymer according to the invention is a polymer of formula (1), (1 '), (1 H), (2) or (2H).

The crosslinking catalyst can be used in the composition according to the invention and can be any catalyst known to those skilled in the art for the silanol condensation. Examples of such catalysts include:

organic titanium derivatives, such as titanium (IV) di (acetylacetonate) diisopropylate (commercially available under the name TYZORR® AA75 from Dupont); organic derivatives of aluminum, such as the aluminum chelate commercially available under the name K-KAT® 5218 from King Industries;

organic tin derivatives such as dibutyltin dilaurate (DBTL); and

amines, such as 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 1,5-diazabicyclo [4.3.0] non-5-ene (DBN).

UV stabilizers such as amines or antioxidants may also be included in the composition according to the invention.

Antioxidants may include primary antioxidants that scavenge free radicals and are generally substituted phenols like Irganox ^® 1010 from Ciba. Primary antioxidants may be used alone or in combination with other antioxidants such as phosphites such as Ciba Irgafos ^® 168.

According to a particularly preferred embodiment, the adhesive composition according to the invention is packaged in an airtight package prior to its final use, so as to protect it from ambient humidity. Such a package may advantageously be formed of a multilayer sheet which typically comprises at least one aluminum layer and / or at least one layer of high density polyethylene. For example, the package is formed of a polyethylene layer coated with aluminum foil. Such a package may in particular take the form of a cylindrical cartridge.

The invention finally relates to a method of bonding by assembling two substrates comprising:

- Coating an adhesive composition as defined above, in liquid form, preferably in the form of a thick layer in a range of 0.3 to 5 mm, preferably 1 to 3 mm, on at least one of the two surfaces which respectively belong to the two substrates to be joined, and which are intended to be brought into contact with each other along a tangent surface; then the effective contacting of the two substrates according to their tangency surface.

The adhesive composition in liquid form is either the (naturally) liquid adhesive composition or the melted adhesive composition. The skilled person is able to proceed so that the adhesive composition used is in liquid form at the time of use.

Of course, the coating and the contacting must be carried out within a compatible time interval, as is well known to those skilled in the art, that is to say before the adhesive layer applied to the substrate loses its ability to bond this substrate to another substrate. In general, the crosslinking of the polymer of the adhesive composition, in the presence of the catalyst and the water of the ambient medium and / or the water provided by at least one of the substrates, begins to occur during the coating, then continues to occur during the step of contacting the two substrates. In practice, water usually results from the relative humidity of the air.

Suitable substrates are, for example, inorganic substrates such as glass, ceramics, concrete, metals or alloys (such as aluminum alloys, steel, non-ferrous metals and galvanized metals); or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; metal substrates and paint-coated composites (as in the automotive field).

The invention will be better understood from the following examples, which illustrate the invention without limiting its scope.

EXAMPLES

The synthesis reactions of the examples were carried out in two or three stages, with a step of synthesis of the cycloolefin, a step of synthesis of the transfer agent (CTA) of formula (C) and a stage of polymerization by ring opening. by metathesis of cycloolefin of formula (A) and optionally of compound of formula (B) in the presence of a Grubbs catalyst and the transfer agent.

The general scheme 1 of the polymerization reactions used in Examples 1 to 8 is given below, and will be explained case by case in the detailed examples.

(A) (B) (C)

(1 ')

In this diagram 1:

- DCM stands for dichloromethane

the bond is a geometrically oriented bond on one side or the other with respect to the double bond (cis or trans); CTA is the chain transfer agent of formula (C), the cycloolefins are of formulas (A) and (B),

G2 is the metathesis catalyst of formula (9): (9), wherein Ph is phenyl and Cy is cyclohexyl;

the groups F1 and F ₂ are symmetrical and correspond respectively to the group -CH ₂ -OOC-NH- (CH ₂ ) 3 -Si (OCH ₃ ) 3 (in case the CTA is a γ-dicarbamate), to the group -CH 2- NH-CO-NH- (CH ₂ ) 3 -Si (OCH ₃ ) 3 (where CTA is a γ-diurea), and -CO-NH- (CH ₂ ) 3-Si (OCH ₃ ) 3 (where CTA is a γ-diamide);

n is the number of moles of cycloolefins of formula (A);

m is the number of moles of cycloolefins of formula (B);

x is the number of moles of CTA of formula (C).

The number of monomer units in the polymer is equal to n + m.

In each of Examples 1 to 8 described below using Scheme 1, the reaction lasts 24 hours at a temperature of 40 ° C.

All polymerizations were performed in a similar manner. The only differences are in the nature and initial concentration of the chain transfer agent (s) (CTA). The γ-dicarbamate (CTA ¹ ), the γ-diurea (CTA ² ) and the γ-diamide (CTA ³ ), illustrating the invention, which are used in Examples 1 to 8 have the following respective formulas:

(which corresponds to the case where F1 is (R'O) _3-z zIf-R "-NH-COO- (CH2) pi- and F ₂ is - (CH ₂₎ _q i- OOC-NH-R" -SiR _z (OR ') ₃ , with R' = methyl, R "= - (CH ₂ ) ₃ -, z = 0, p1 = 1 and q1 = 1);

(which corresponds to the case where F 1 is (R'O) ₃ zSi-R "-NH-CO-NH- (CH 2) p 1 and F ₂ is - (CH ₂ ) qi-NH-CO-NH-R "-SiR _z (OR ') _3j with R' = methyl, R" = - (CH ₂ ) ₃ -, z = 0, p1 = 1 and q1 = 1);

(which corresponds to the case where Fi is (R'O) ₃ -ZRzSi-R "-NH-CO- (CH 2) p ₂ - and F ₂ is - (CH ₂ ) q ₂ -CO-NH-R" -SiR _z (OR ') _3j with R' = methyl, R "= - (CH ₂ ) ₃ - z = 0, p2 = 0 and q2 = 0).

Two reaction possibilities exist, depending on whether the cycloolefin of formula (A) alone (examples 1 to 6) or according to whether the cycloolefins of formulas (A) and (B) in mixture are used (examples 7 and 7). 8).

Examples 1 to 6: Polymerization of the cycloolefins of formula (A)

The polymerization process described below corresponds to Examples 1 to 4 (the results of which are indicated in Table 1 below), to Examples 5 (cf. Table 2) and 6 (cf. Table 3).

The cycloolefins of formula (A) used in these examples are as follows: (5-hexyl COE).

Cyclooctene (COE) and 5,6 epoxycyclooctene (5-epoxyCOE) were commercial products of Sigma Aldrich.

5-oxocyclooctene (5-O = COE) and 5-n-hexyl-cyclooctene (5-hexyl-COE) were synthesized from 5,6-epoxycyclooctene (5-epoxyCOE) according to the route shown in the diagram. next reaction 2:

9 ¾ ^■

EQ rt 1.2 h

S (70%) 4 (78%) 5-oxocyclooctene (5-O = COE, referenced 2 in the above scheme) was synthesized according to the procedure indicated in the publication of A. Diallo et al., Polymer Chemistry , Vol 5, Issue 7, 7 April 2014, pp 2583-2591 (which referred to Hillmyer et al, Macromolecules, 1995, 28, 631 1-6316).

The 5-hexyl-cyclooctene (5-hexyl-COE referenced in the above scheme) was synthesized according to the procedure indicated in the publication of A. Diallo et al., Polymer Chemistry, supra (which referred to Kobayashi et al., J. Am Chem Soc 201 1, 133, pp 5794-5797).

The raw materials, reagents and solvents used in these syntheses were commercial products from Sigma Aldrich.

A cycloolefin of formula (A) described above (10.8 mmol) and

Dry CH2Cl2 (5 mL) were placed in a 100 mL flask in which was also placed a magnetic stirring bar coated with Teflon ^®. The flask and its contents were then put under argon. The compound of formula CTA ¹ (0.54 mmol) was then introduced into the flask by syringe. The flask was then immersed in an oil bath at 40 ° C., then G2 catalyst (5.4 μmol) dissolved in CH 2 Cl 2 (2 ml) was immediately added by means of a cannula. . The reaction mixture then became very viscous within two minutes. The viscosity then decreased slowly over the next 10 minutes. After 24 hours from the addition of the catalyst, the product in the flask was removed after the solvent was concentrated in vacuo. A product was then recovered after precipitation in methanol, filtration and drying at 20 ° C under vacuum (yield greater than 90% for each of Examples 1 to 6). ¹ H / ¹³ C NMR analysis showed that the product was indeed a polymer having the expected formula.

All the polymers prepared in the examples were recovered as a solid powder or as a liquid depending on the nature of the cycloolefin, colorless, easily soluble in chloroform and insoluble in methanol.

The different tests of Examples 1 to 6 are summarized in the

Tables 1, 2 and 3 detailed below. Table 1

Test »* I & MCTA * | / pial {œ fm® This» s «toe ¾ _{$ c} 2000 ;! O 1 4500 153

2 i mm im 5200 1.47

3 ^2§eS:: IOO D0il 1.50 4800

4 2§0Oi! DOil ¾S 5000 1,51

Where CTA ¹ = γ-dicarbamate Table 2

Corners »» Ogç-ç F

§. 2 OO & iOO / i 100 900 1.49

CTA ² = γ-diurea

Table 3

Test **

2 eooi.soi 100 53Q0 1.52

CTA ³ = γ-diamide

Example 1 Synthesis of a Polymer Comprising Two Alkoxysilane End-groups from Cyclooctene (COE) and CTA ¹

The reaction was carried out according to the following scheme 3:

(CTA ¹ )

The polymer obtained was solid at room temperature.

The NMR analyzes of the polymer obtained for this test gave the following values, which confirmed the structure of the polymer:

1H NMR (CDCl3, 500 MHz, 298 K): δ (ppm) repetition unit 1 .29 (8H ^* n), 1 .96 (4H ^* n), 5.37 (2H ^* n), terminal group = 0.64 (4H) , m, -CH ₂ -CH-Si-), 1 .61 (4H, m, -NH-CH ₂ -CH ₂ -CH ₂ -S ₁ -), 3.16 (4H, m, -NH-CH-CH ₂ -CH ₂ -Si-), 3.57 (18H, s, -S 1 -O-CH 3), 4.48 (4H, t, -CO-O-CH-CH =), 5.73 (2H, m, -CH = CH- CH ₂ -O-CO-), 5.77 (2H, m, -CH = CH-CH ₂ -O-CO-).

1 ³ C NMR (CDCl ₃ , 100 MHz, 298 K): δ (ppm) repetition unit 29.17, 29.54, 29.78, 32.37, 33.10, 130.48, terminal group = 6.28 (-CH ₂ -CH -Si-), 23.17 (-NH-CH ₂ -CH ₂ -CH ₂ -Si-), 43.34 (-NH-CH ₂ -CH ₂ -Si-), 50.77 (-S 1 -O-CH 3), 65.57 (-CO- O-CH ₂ -CH =), 124.41 (CH = CH-CH ₂ -O-CO-), 136.05 (-CH = CH-CH ₂ -O-CO-), 156.50 (-O-CO-).

Example 2 Synthesis of a Polymer Comprising Two Alkoxysilane Ending Groups from Cyclooctene Monoepoxide (5-EpoxyCOE) and CTA ¹

The reaction was carried out according to the following scheme 4:

5 * f KîK¾ CQiE)

The resulting polymer was liquid at room temperature.

1 H NMR (CDCl 3, 500 MHz, 298 K): δ (ppm) repeat unit 1 .29 (4H * n), 1 .96 (4H * n), 2.72 (2H * n), 5.37 (2H * n) ), terminal moiety = 0.64 (4H, m, -CH2-CH2-S1-), 1.61 (4H, m, -NH-CH2-CH2-CH2-S1-), 3.16 (4H, m, -NH- CH ₂ -CH ₂ -CH ₂ -S ₁ -), 3.57 (18H, s, -S 1 -O-CH 3), 4.48 (4H, t, -CO-O-CH ₂ -CH =), 5.73 (2H, m, - CH = CH-CH ₂ -O-CO-), 5.77 (2H, m, -CH = CH-CH ₂ -O-CO-).

1 ³ C NMR (CDCl3, 100 MHz, 298 K): δ (ppm) repeat unit 29.17, 29.54, 29.78, 32.37, 33.10, 56.72, 130.48, terminal group = 6.28 (-CH ₂ -CH ₂ -Si-) , 23.17 (-NH-CH2-CH2-CH2-S1-), 43.34 (-NH-CH2-CH2-CH2-S1-), 50.77 (-Si-O- CH _3), 65.57 (-CO-O-CH ₂ -CH =), 124.41 (CH = CH-CH ₂ -O-CO-), 136.05 (-CH = CH-CH ₂ -O-CO-), 156.50 (-O-CO-).

Example 3 Synthesis of a Polymer Comprising Two Alkoxysilane Terminal Groups from 5-Oxocyclooctene (5-0 = COE) and CTA ¹

The reaction was carried out according to the following scheme:

(5-0 = COE) (CTA ¹ )

From € 48

2: 4 hours

The polymer obtained was solid at room temperature. The NMR analyzes of the polymer obtained for this test gave the following values, which confirmed the structure of the polymer:

¹ H NMR (CDCl 3, 500 MHz, 298 K): δ (ppm) repetition unit 1 .56 (2H * n), 1.91 (2H * n), 2.17-2.53 (6H * n), terminal group = 0.64 (4H, m, -CH ₂ -CH- Si-), 1.61 (4H, m, -NH-CH ₂ -CH-CH ₂ -Si-), 3.16 (4H, m, -NH-CH - CH ₂ -CH ₂ -Si-), 3.57 (18H, s, -S 1 -O-CH 3), 4.48 (4H, t, -CO-O-CH-CH =), 5.73 (2H, m, -CH = CH-CH ₂ -O-CO-), 5.77 (2H, m, -CH = CH-CH ₂ -O-CO-).

¹³ C NMR (CDCl3, 100 MHz, 298 K): δ (ppm) repeat unit 21.51, 23.31, 26.53, 31.82, 42.17, 130.48, terminal group = 6.28 (-CH ₂ -CH ₂ -Si) ), 23.17 (-NH-CH ₂ -CH ₂ -CH ₂ -Si-), 43.34 (-NH-CH ₂ -CH ₂ CH ₂ CH 2 Si), 50.77 (-S 1 -O-CH 3), 65.57 (-CO -O-CH ₂ -CH =), 124.41 (CH = CH-CH ₂ -O-CO-), 136.05 (-CH = CH-CH ₂ -O-CO-), 156.50 (-O-CO-).

EXAMPLE 4 Synthesis of a Polymer Comprising Two Alkoxysilane End-groups from 5-Hexyl-cyclooctene (5-Hexyl-COE) and CTA ¹

The reaction was carried out according to the following scheme 6:

(5-hex¾l COE)

G2 24 hours

The resulting polymer was liquid at room temperature. The NMR analyzes of the polymer obtained for this test gave the following values, which confirmed the structure of the polymer:

1H NMR (CDCl 3, 500 MHz, 298 K): δ (ppm) repeat unit 0.83 (3H * n), 1 .19 (2H * n), 1.27 (8H * n), 1.75 (2H *) n), 1.96 (4H * n), 5.37 (2H * n), terminal group = 0.64 (4H, m, -CH ₂ -CH-Si), 1 .61 (4H, m, -NH-CH). ₂ -CH-CH ₂ -SiI), 3.16 (4H, m, -NH-CH-CH ₂ -CH ₂ -Si), 3.57 (18H, s, -S 1 -O-CH 3), 4.48 (4H, t, -CO-O-CH-CH =), 5.73 (2H, m, -CH = CH-CH ₂ -O-CO-), 5.77 (2H, m, -CH = CH-CH ₂ -O- CO -).

¹³ C NMR (CDCl3, 100 MHz, 298 K): δ (ppm) repeat unit 14.1, 22.7, 27.4, 29.6, 31.8, 32.37, 33.10, 33.8, 40.65, 130.48, terminal group = 6.28 (-CH ₂ -CH ₂ -Si-), 23.17 (-NH-CH ₂ -CH ₂ -CH ₂ -Si), 43.34 (-NH-CH 2 -CH 2 CH 2 Si), 50.77 (-S 1 -O-CH 3) ), 65.57 (-CO-O-CH ₂ -CH =), 124.41 (CH = CH-CH ₂ -O-CO-), 136.05 (-CH = CH-CH ₂ -O-CO-), 156.50 (- O-CO-).

Example 5 Synthesis of a Polymer Comprising Two Alkoxysilane End-groups from Cyclooctene (COE) and CTA ²

The reaction was carried out according to the following scheme 7:

¹ H NMR (CDCl 3, 500 MHz, 298 K): δ (ppm) repetition unit 1 .29 (8H ^* n), 1 .96 (4H ^* n), 5.37 (2H ^* n), terminal group = 0.64 ( 4H, m, -CH ₂ -CH ₂ -Si-), 1 .61 (4H, m, -NH-CH ₂ -CH 2 -CH ₂ -S1-), 3.21 (4H, m, -NH-CH ₂ - CH ₂ -CH ₂ -Si-), 3.57 (18H, s, -S 1 -O-CH 3), 3.83 (4H, t, -CO-NH-CH ₂ -CH =).

1 ³ C NMR (CDCl3, 100 MHz, 298 K): δ (ppm) repetition unit 29.17, 29.54, 29.78, 32.37, 33.10, 130.48, terminal group = 6.28 (-CH ₂ -CH ₂ -Si-), 23.17 (-NH-CH2-CH2-CH2-S1-), 43.34 (-NH-CH2-CH2-CH2-S1-), 50.77 (-S1-O-CH3), 52.57 (-CH = CH-CH2-NH- CO-), 124.41 (-CH = CH-CH2-NH-CO-), 136.05 (-CH = CH-CH2-NH-CO-), 157.45 (-O-CO-).

Example 6 Synthesis of a Polymer Comprising Two Alkoxysilane End-groups from Cyclooctene (COE) and CTA ³

The reaction was carried out according to the following scheme 8:

OC

24 ftmt

¹ H NMR (CDCl3, 500 MHz, 298 K): δ (ppm) repetition unit 1 .29 (8H ^* n), 1 .96 (4H ^* n), 5.37 (2H ^* n), terminal group = 0.64 ( 4H, m, -CH ₂ -CH ₂ -Si-), 1 .61 (4H, m, -NH-CH ₂ -CH ₂ -CH ₂ -S-1), 3.18 (4H, m, -NH-CH ₂ -CH ₂ -CH ₂ -Si -), 3.57 (18H, s, -S 1 -O-CH 3), 6.26 (2H, m, -CH = CH-CO-), 6.62 (2H, m, -CH = CH-CO- ).

¹³ C NMR (CDCl3, 100 MHz, 298 K): δ (ppm) repetition unit 29.17, 29.54, 29.78, 32.37, 33.10, 130.48, terminal group = 6.28 (-CH ₂ -CH ₂ -Si-), 23.17 ( -NH-CH2-CH2-CH2-S1-), 43.34 (-NH-CH2-CH2-CH2-S1-), 50.77 (-S1-O-CH3), 126.20 (CH = CH-CO-NH), 148.7 (-CH = CH-CO-NH), 167.18 (-CO-NH).

Examples 7 and 8: Polymerization of a mixture of cycloolefins of formulas (A) and (B):

(B) The polymerization process described below corresponds to Examples 7 and 8, the results of which are given in Tables 4 and 5 below. The cycloolefins of formula (A) and (B) used in Examples 7 and 8 are respectively the following:

Cyclooctene (COE) of greater than 95% purity and norbornene (NBN) of greater than 99% purity were commercial products of Sigma Aldrich. They were previously distilled on CaH ₂ .

The cycloolefins of formulas (A) and (B), respectively COE (5.4 mmol) and NBN (5.4 mmol) described above, and dry CH2Cl2 (5 mL) were placed in a 100 mL flask. in which was also placed a magnetic stir bar coated Teflon ^® . The flask and its contents were then put under argon. The compound of formula CTA ¹ (for example 7) or CTA ³ (for example 8) (0.54 mmol) was then introduced into the flask by syringe. The flask was then immersed in an oil bath at 40 ° C., then G2 catalyst (5.4 μmol) dissolved in CH2Cl2 (2 mL) was immediately added by means of a cannula. . The reaction mixture then became very viscous in two minutes. The viscosity then decreased slowly over the next 10 minutes. After 24 hours from the addition of the catalyst, the product in the flask was removed after the solvent was concentrated in vacuo. A product was then recovered after precipitation in methanol, filtration and drying at 20 ° C under vacuum (yield 94% in this case). ¹ H / ¹³ C NMR analysis showed that the product was indeed a polymer having the expected formula.

All the polymers prepared in the examples were recovered as a solid powder or as a liquid in the molar ratio NBN / COE, colorless, easily soluble in chloroform and insoluble in methanol.

The various tests of Examples 7 and 8 are summarized in Tables 4 and 5 and detailed below.

Table 4

Test No. [AJ / IB1 / ICTA ^ / IRu] (mol / mol) Conversion Mn SEC PDI

( ^% ) (g / mol)

1000/1000/100/1 100 4900 1.60

Where CTA = β-dicarbamate

Table 5

Test No. [A] / [B] / [CTA ³ ] / [Ru] (mol / mol) Conversion Mn SEC PDI

( ^% ) (g / mol)

8 1 000/1000/100/1 100 4800 1.58 Where CTA ³ = β-diamide

Example 7 Synthesis of a Polymer Comprising Two Alkoxysilane End-groups from Cyclooctene (COE), Norbornene (NBN) and CTA ¹

The reaction was carried out according to the following scheme 9, in a molar ratio m: n equal to 0.3: 1, 0

ICOE) (m (CTA ¹ )

24 hours

The resulting polymer was liquid at room temperature. The NMR analyzes of the polymer obtained for this test gave the following values, which confirmed the structure of the polymer: ¹ H NMR (CDCl3, 500 MHz, 298 K): δ (ppm) trans unit of rep: 1 .23 (12H ^* n), 1 .72-1 .89 (6H ^* n), 2.37 (2H ^* n trans ), 5.31 (2H ^* n trans), cis: 1.23 (12H ^* n), 1.72-1 .89 (6H ^* n), 2.72 (2H ^* n cis), 5.13 (2H ^* n cis), terminal moiety = 0.64 (4H, m, -CH ₂ -CH-Si), 1 .61 (4H, m, -NH-CH ₂ -CH-CH ₂ -Si-), 3.16 (4H, m, -NH) -CH-CH ₂ -CH ₂ -Si-), 3.57 (18H, s, -S 1 -O-CH 3), 4.48 (2H, t, -CO-O-CH-CH =), 5.73 (2H, m, -CH = CH-CH ₂ -O-CO-), 5.77 (2H, m, -CH = CH-CH ₂ -O- CO-).

¹³ C NMR (CDCl3, 100 MHz, 298 K): δ (ppm) repetition unit: 29.17, 29.54, 29.78, 32.37, 33.10, 38.02, 38.67, 41.35, 42.77, 43.13, 43.52, 130.35, 134.89, grouping terminal = 6.28 (-CH ₂ -CH ₂ -Si-), 23.17 (-NH-CH ₂ -CH ₂ -CH ₂ -Si), 43.34 (-NH-CH ₂ -CH ₂ CH ₂ Si), 50.77 (-S 1 -O-CH 3), 65.57 (-CO-O-CH ₂ -CH =), 124.41 (CH = CH-CH ₂ -O-CO-), 136.05 (-CH = CH-CH ₂ -O- CO-), 156.50 (-O- CO-). EXAMPLE 8 Synthesis of a Polymer Comprising Two Alkoxysilane End-groups from Cyclooctene (COE), Norbornene (NBN) and CTA ³

The reaction was carried out according to the following scheme, in a molar ratio m: n equal to 0.3: 1, 0:

COE) (NBN) (0ΤΆ)

40 ° C.

G2 24 hours

The resulting polymer was liquid at room temperature.

¹ H NMR (CDCl3, 500 MHz, 298 K): δ (ppm) trans unit of rep: 1 .23 (12H ^* n), 1 .72-1 .89 (6H ^* n), 2.37 (2H ^* n trans ), 5.31 (2H ^* n trans), cis: 1.23 (12H * n), 1.72-1.89 (6H * n), 2.72 (2H * n cis), 5.13 (2H * n cis), terminal group = 0.64 (4H, m, -CH ₂ -CH - Si-), 1 .61 (4H, m, -NH-CH ₂ -CH-CH ₂ -Si), 3.18 (4H, m, -NH-CH-CH ₂ -CH ₂ -Si), 3.57 ( 18H, s, -Si-O-CH ₃ ), 6.26 (2H, m, -CH = CH-CO-), 6.62 (2H, m, -CH = CH-CO-).

1 ³ C NMR (CDCl3, 100 MHz, 298 K): δ (ppm) repetition unit: 29.17, 29.54, 29.78, 32.37, 33.10, 38.02, 38.67, 41.35, 42.77, 43.13, 43.52, 130.35, 134.89, terminal group = 6.28 (-CH ₂ -CH-Si), 23.17 (-NH-CH ₂ -CH ₂ -CH ₂ -Si), 43.34 (-NH-CH ₂ -CH ₂ -Si) , 50.77 (-S1-O-CH3), 126.20 (CH = CH-CO-NH), 148.7 (-CH = CH-CO-NH), 167.18 (-CO-NH).

Example 9 Preparation of an Adhesive Composition from a Polymer Comprising Two Alkoxysilane End-groups

By simple mixing, 8 adhesive compositions each comprising 0.2% by weight of a crosslinking catalyst consisting of tin dioctyl dideodecanoate (Tib kat product 223 from Tib Chemicals) and a polymer according to US Pat. invention obtained in Examples 1 to 8.

Each mixture thus obtained was left under reduced agitation (20 mbar or 2000 Pa) for 15 minutes, before the composition thus obtained is packaged in an aluminum cartridge.

Measurement of tensile strength and elongation at break was performed for each of the 8 adhesive compositions according to the protocol described hereinafter.

The principle of the measurement consists in stretching in a tensile machine, whose moving jaw moves at a constant speed equal to 100 mm / min, a standard specimen consisting of the crosslinked adhesive composition and recording, at the moment when the rupture of the specimen, the tensile stress applied (in MPa) and the elongation of the specimen (in%).

The standard test piece is dumbbell-shaped, as shown in International Standard ISO 37. The narrow part of the dumbbell used has a length of 20 mm, a width of 4 mm and a thickness of 500 μιτι. To prepare the dumbbell, the composition packaged as described above was heated to 100 ° C., then the amount necessary to form a film having a thickness of 300 μιτι which was left on a sheet of silicone paper was extruded on a sheet of silicone paper. during 7 days at 23 ° C. and 50% relative humidity for crosslinking. The dumbbell is then obtained by simple cutting in the crosslinked film.

The dumbbell of each of the 8 adhesive compositions tested then has a tensile strength greater than 0.7 MPa with an elongation at break greater than 200%.

Each adhesive composition was then subjected to bonding tests of two wooden strips (each size 20 mm × 20 mm × 2 mm) to conduct after crosslinking for seven days at 23 ° C. at a breaking force greater than 2. MPa in adhesive rupture.

Claims

claims

A hydrocarbon polymer comprising two termi- (alkoxysilane) groups, said hydrocarbon polymer being of formula (1) below:

in which :

- Fi is (RO) ₃ -ZRzSi-R "-NH-COO- (CH ₂ ) pi- and F ₂ is

- (CH ₂₎ _q i- OOC-NH-R _"z -SiR (OR ') _3-z; or

- Fi is (RO) ₃ -ZRzSi-R "-NH-CO-NH- (CH ₂ ) pi- and F ₂ is

- (CH ₂₎ _q i-NH-CO-NH-R _"z -SiR (OR ') _3-z; or

- Fi is (R'O) ₃ -z RzSi-R "-NH-CO- (CH ₂ ) _p ₂ - and F ₂ is

- (CH ₂₎ _{q 2} -CONH-R _"z -SiR (OR ') _3-z;

where z is an integer equal to 0, 1, 2 or 3; p1 and q1 are independently an integer of 1, 2 or 3; p2 and q2 are independently an integer of 0, 1, 2 or 3; the groups R and R 'are independently an alkyl group, preferably linear, comprising from 1 to 4 carbon atoms; the group R "is an alkylene group having from 1 to 4 carbon atoms, and in which:

The groups R1, R2, R3, R4, R5, R6, R7 and R8 are independently a hydrogen, a halogen atom, an alkyl group, a heteroalkyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, at least one of the groups R1 to R8 being part of the same ring or saturated or unsaturated heterocycle with at least one other group R1 to R8, according to the rules of valence organic chemistry and at least one of the pairs (R1, R2), (R3, R4), (R5, R6) and (R7, R8) may be an oxo group;

X and y are integers independently within a range of 0 to 5, the sum x + y being preferably in a range of 0 to 4;

The group R20 is CH ₂ , O, S, NR ₀ or C (= O), Ro being an alkyl or alkenyl group containing from 1 to 22 carbon atoms; and

N is an integer greater than or equal to 2 and m is an integer greater than or equal to 0, the molar ratio m: n being in a range of 0: 1 to 0.5: 1, n and m being in the range of in addition, such that the number-average molar mass Mn of the hydrocarbon polymer of formula (1) is in a range of 400 to 50,000 g / mol, and the polydispersity (PDI) of the hydrocarbon polymer of formula (1) is included in a range from 1.0 to 3.0.

2. Hydrocarbon polymer according to claim 1, characterized in that: x = y = 1.

3. Hydrocarbon polymer according to one of claims 1 or 2, characterized in that m is equal to 0, the polymer having the following formula (2):

4. Hydrocarbon polymer according to one of claims 1 to 3, characterized in that it has for formula (1 '):

5. Hydrocarbon polymer according to one of claims 1 to 4, characterized in that Fi is (R'O) _3- z z Si-R "-NH-COO- (CH 2) p 1 and F ₂ is - (CH ₂ ) _q i- OOC-NH-R _"z -SiR (oR ') _3-z, with p1 = 1 and q1 = 1.

6. Hydrocarbon polymer according to claim 5, characterized in that R 'is a methyl, R "is a group -CH ₂ - or - (CH ₂ ) ₃ -, z = 0, p1 = 1 and q1 = 1.

7. A hydrocarbon polymer according to one of claims 1 to 4, characterized in that Fi is (RO) ₃ -ZRzSi-R "-NH-CO-NH- (CH ₂ ) _p i- and F ₂ is - (CH ₂₎ _q i NH-CO-NH-R _"z -SiR (oR ') _3-z, with p1 = 1 and q1 = 1.

8. Hydrocarbon polymer according to claim 7, characterized in that R 'is a methyl, R "is a group -CH ₂ - or - (CH ₂ ) ₃ -, z = 0, p1 = 1 and q1 = 1.

9. hydrocarbon polymer according to any of claims 1 to 4, characterized in that access is (RO) _3-z R _z Si-R "-NH-CO- (CH ₂₎ _p2 - and F ₂ is

- (CH ₂₎ _{q 2} -CONH-R _"z -SiR (OR ') _3-z, with p2 = 0 or q2 = 0.

10. A hydrocarbon polymer according to claim 9, characterized in that R 'is a methyl, R "is a group -CH ₂ - or - (CH ₂ ) ₃ -, z = 0, p 2 = 0 and q 2 = 0.

11. Process for the preparation of at least one hydrocarbon polymer as defined in one of claims 1 to 10, said process comprising at least one metathesis ring opening polymerization step, in the presence of:

at least one metathesis catalyst, preferably a catalyst comprising ruthenium, more preferably a Grubbs catalyst, at least one alkoxysilane chain transfer agent (CTA) for the following formula (C): wherein the bond - is a geometrically oriented bond on one side or the other with respect to the double bond (cis or trans); Fi is (R'O) _3- _z R _z Si-R "-NH-COO- (CH ₂ ) _P i- and F ₂ is

- (CH ₂₎ _q i- OOC-NH-R _"z -SiR (OR ') _3-z, or access is (R'O) ₃ zRzSi-R" -NH-CO-NH- (CH2) pi- and F ₂ is

- (CH ₂₎ qi-NH-CO-NH-R _"z -SiR (OR ') _3-z, or access is (R'O) _{_3-z} R _z Si-R" -NH-CO- ( CH ₂ ) _p ₂ - and F ₂ is - (CH ₂ ) _q ₂ -CO-NH-R "-SiR _z (OR ') _3-z where z is an integer equal to 0, 1, 2 or 3; q1 are independently an integer equal to 1, 2 or 3; p2 and q2 are independently an integer of 0, 1, 2 or 3; the groups R and R 'are independently an alkyl group, preferably a linear one, comprising 1 to 4, preferably 1 to 2 carbon atoms, the group R "is an alkylene group, preferably linear, having 1 to 4 carbon atoms;

at least one compound of formula (A) below:

x and y are integers independently in a range from 0 to 5, preferably from 0 to 2, even more preferably x is 1 and y is 1, the sum x + y being preferably ranging from 0 to 4 and even more preferably from 0 to 2;

and

- optionally at least one compound of formula (B):

in which

The group R20 is CH ₂ , O, S, NR ₀ or C (= O), Ro being an alkyl group, preferably linear, comprising from 1 to 22, preferably from

1 to 14, carbon atoms;

during a reaction time of 2 to 24 hours and at a temperature in the range of 20 to 60 ° C.

12. Preparation process according to claim 1 1, characterized in that the molar ratio of CTA to the compound of formula (A), or the sum of the compounds of formulas (A) and (B) if the compound of formula ( B) is present, is in a range of 0.01 to 0.10, preferably 0.05 to 0.10.

13. Preparation process according to one of claims 1 1 or 12, characterized in that the CTA is selected from the group consisting of:

14. Adhesive composition comprising at least one polymer according to one of claims 1 to 10 and from 0.01 to 3% by weight of at least one crosslinking catalyst, relative to the weight of the adhesive composition.

15. A method of bonding by assembling two substrates comprising:

- The coating of an adhesive composition according to claim 14, in liquid form, preferably in the form of a thick layer in a range of 0.3 to 5 mm, on at least one of the two surfaces which respectively belong to the two substrates to be assembled, and which are intended to be brought into contact with one another according to a tangent surface; then

the effective contacting of the two substrates according to their tangency surface.