FR3051472A1 - HYDROCARBON POLYMERS WITH TWO ALCOXYSILANE TERMINAL GROUPS AND PROCESSES FOR PREPARING THE SAME - Google Patents

Abstract

1) hydrocarbon polymer comprising two alkoxysilane end groups of formula (I): in which: F1 is: (R'O) 3-tRtSi- (CH2) g1- and F2 is: - (CH2) d1-SiRt (OR ' ) 3-t; or F1 is: (R'O) 3-tRtSi-R '' - OOC- (CH2) g2- and F2 is: - (CH2) d2-COO-R '' - SiRt (OR ') 3-t; where t is an integer equal to 0, 1 or 2; g1 and d1 are an integer of 1, 2 or 3; g2 and d2 are an integer of 0, 1, 2 or 3; R and R 'represent a linear alkyl radical; R "represents a linear alkylene radical; - R1 to R12 represent a hydrogen atom or an alkyl radical comprising from 1 to 14 carbon atoms; - x and y are integers such that the sum x + y is included in a range ranging from 0 to 2, n1 and n2 are an integer or nil and m is an integer greater than or equal to 0; p1 and p2 are an integer or nil whose sum p1 + p2 is non-zero and satisfies the equation: p1 + p2 = qx (z + 1) where q is an integer greater than 0 and z is an integer equal to 1 or 2. 2) Process for preparing this polymer from cyclooctadiene or cyclododecatriene 3) Process for the preparation of this polymer from a cis-1,4 high content polybutadiene. 4) An adhesive composition comprising said polymer and from 0.01 to 3% by weight of a crosslinking catalyst.

Description

Hydrocarbon polymers with two alkoxysilane end groups and methods for their preparation

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 in the presence of water (from the ambient medium and / or 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, such as 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 chain-opening metathesis polymerization, a charge and a compound which comprises only a single silane function.

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, the patent application WO 2011/038057 describes the ring-opening polymerization by metathesis 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 having the formula (I):

(I) in which:

-1 is an integer equal to 0, 1 or 2; - g1 and d1, identical or different, represent an integer equal to 1, 2 or 3; - g2 and d2, identical or different, represent an integer equal to 0, 1, 2 or 3; R and R ', which may be identical or different, represent an alkyl radical comprising from 1 to 4 carbon atoms; R "is an alkylene radical comprising from 1 to 4 carbon atoms; each carbon-carbon bond of the main chain of the polymer, denoted by ------ represents a double bond or a single bond, in accordance with the valence rules of organic chemistry; - R1, R2, R3, R4, R5, R6, R7 and R8, identical or different, represent: - a hydrogen or halogen atom; or a radical comprising from 1 to 22 carbon atoms selected from alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, the hydrocarbon chain of said radical possibly being interrupted by at least one oxygen atom or a sulfur atom; in addition: at least one of the groups R1 to R8 may form, with at least one other of the groups R1 to R8 and with the carbon atom or atoms to which the said groups are connected, a saturated or unsaturated or optionally substituted hydrocarbon or hydrocarbon heterocycle; and comprising from 3 to 10 members; and - at least one of the pairs (R1, R2), (R3, R4), (R5, R6) and (R7, R8) can form, with the carbon atom to which said pair is connected, a carbonyl group C = 0 or a group of 2 carbon atoms connected by a double bond: C = C, the other carbon atom carries 2 substituents chosen from a hydrogen atom or a C1-C4 alkyl radical; x and y are integers, identical or different, in a range from 0 to 6, the sum x + y being in the range 0 to 6; - R9, R10, R11 and R12, identical or different, represent: - a hydrogen or halogen atom; or - a radical comprising from 1 to 22 carbon atoms and chosen from alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkylcarbonyloxyalkyl, the hydrocarbon chain of said radical possibly being interrupted by at least one oxygen atom or one atom of sulfur; in addition: at least one of the groups R9 to R12 may form, with at least one other of the groups R9 to R12 and with the carbon atom (s) to which the said groups are connected, a saturated or unsaturated, optionally substituted hydrocarbon or hydrocarbon ring. and comprising from 3 to 10 members; and - at least one of the pairs (R9, R10) and (R11, R12) can form with the carbon atom to which said pair is connected a group of 2 carbon atoms connected by a double bond: C = C, of which another carbon atom carries 2 substituents chosen from a hydrogen atom or a C1-C4 alkyl radical; and the carbon atom carrying one of the groups of the pair (R9, R10) can be connected to the carbon atom bearing one of the groups of the pair (R11, R12) by a double bond , it being understood that, in accordance with the valence rules, only one of the groups of each of these 2 pairs is then present; - R13 represents: - an oxygen or sulfur atom, or - a divalent radical -CH2-, -C (= O) - or -NR ° - in which R ° is an alkyl or alkenyl radical comprising from 1 to 22 carbon atoms; n1 and n2, which are identical or different, are each an integer or nil whose sum is denoted by n; m is an integer greater than or equal to 0; p1 and p2, which are identical or different, are each an integer or nil whose sum p1 + p2 is non-zero and satisfies the equation: p1 + p2 = qx (z + 1) in which: q is an integer greater than 0; and - z is an integer from 1 to 5; and - n1, n2, m, p1 and p2 being further such that the number-average molecular weight Mn of the polymer of formula (I) is in the range of 400 to 100,000 g / mol and its polymolecularity index is within a range of 1.0 to 3.0.

The various groups, radicals and letters which are included in the formula (I) and which are defined above, retain throughout the present text, and, in the absence of indication to the contrary, the same definition.

The following variants of the polymer of formula (I), taken individually or in combination, are particularly preferred: the radicals R and R 'included in the definition of F1 and F2 represent a linear alkyl radical, more preferably still comprising from 1 to 2 carbon atoms; the radical R "included in the definition of F1 and F2 represents a linear alkylene radical; R1, R2, R3, R4, R5, R6, R7 and R8 represent a hydrogen atom or an alkyl radical comprising from 1 to 14; carbon atoms, and even more preferably from 1 to 8, the integers x and y are in a range from 0 to 2, the sum x + y being in the range from 0 to 2; is equal to 1 and y is 1; R9, R10, R11 and R12 represent a hydrogen atom or a radical whose hydrocarbon portion comprises from 1 to 14 carbon atoms, and even more preferably from 1 to 8; the radical R °, included in the group -NR ° which is one of the meanings of R13, is a linear radical comprising from 1 to 14 carbon atoms; z is an integer equal to 1 or 2; and or - the number-average molecular weight Mn is in a range of from 1000 to 50,000 g / mol, and the polymo index the uniformity is in a range from 1.4 to 2.0.

According to other more particularly preferred variants of the polymer of formula (I): at most one of the groups (R1, R2, R3, R4, R5, R6, R7 and R8) is a C1-C6 alkyl radical and all the others represent a hydrogen atom; at most one of the groups (R 9, R 10, R 11 and R 12) is a C 1 -C 6 alkoxycarbonyl radical and all the others represent a hydrogen atom; and / or - R13 represents a -CH2- radical or an oxygen atom.

The main chain of the polymer of formula (I) thus comprises one, two or three repeating units: a first repetition pattern repeated p1 + p2 times, a second repeating unit, optional, repeated n1 + n2 times; and a third repeating pattern, optional, repeated m times.

As appears above, the terminal groups F1 and F2 are generally symmetrical with respect to the main chain, that is to say that they correspond substantially, with the exception of the indices g1 and g2, and d1 and d2.

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 atoms.

By "terminal group" is meant a group located at one of the two ends of the main chain of the polymer, which is constituted by one or more repeating units. Polymolecularity index (also referred to as polydispersity index or PDI) is defined as the Mw / Mn ratio, that is to say the ratio of the weight average molecular weight to the number average molecular weight of the polymer.

In the present text, the two average molecular weights Mn and Mw are measured by Size Exclusion Chromatography (SEC), which is also referred to as gel permeation chromatography (or the term "Size Exclusion Chromatography"). by the corresponding English acronym GPC). The calibration implemented is usually a PEG (PolyEthyleneGlycol) or PS (Polystyrene) calibration, preferably PS.

If t = 0, then there is no group R in the groups F1 and F2 of the formula (I): (R'0) 3-tRtSi becomes (R'0) 3Si.

If g2 = 0 or d2 = 0, then there is no radical - (CH2) - in groups F1 and F2 of formula (I). In other words, the radical: - (Chl2) g2- or - (Ch12) d2- is replaced by a single bond.

When one of the indices n1, n2, m, x or y that applies to a set of two brackets is equal to zero, this means that there is no group between the brackets to which this index applies. For example, the grouping:

represents a simple link: -, and the grouping:

represents a double bond:

The polymers of formula (I) according to the invention are particularly homogeneous and temperature-stable. They are preferably packaged and stored away from moisture.

They can form, after a crosslinking reaction in the presence of water and a catalyst, an adhesive seal resulting from the formation of Si-O-Si siloxane bonds between the polymer chains. The water used in the crosslinking reaction is the water of the ambient medium and / or the water supplied by at least one substrate, generally the atmospheric humidity, corresponding for example to a relative humidity of the air (called also degree of hygrometry) usually in a range of 25 to 65%.

The formed adhesive seal exhibits high cohesion values, in particular greater than 2 MPa. Such cohesive values allow a use of said polymer 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 industry and naval.

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

The polymers of formula (I) according to the invention are solid or liquid at room temperature (i.e. about 20 ° C.).

According to a preferred variant of the polymer according to the invention, when m is non-zero and n1 and n2 are each equal to 0 (corresponding to the presence in the main chain of the polymer of the only two repeating units repeated p1 + p2 times respectively and m times), then the ratio: m / (p1 + p2 + m) is in the range of 30 to 70%, and more preferably is about 50%.

According to another alternative of this same preferred variant, when m is equal to 0 and the sum n1 + n2 is non-zero (corresponding to the presence in the main chain of the polymer of the only two repeating units repeated p1 + p2 times respectively and n1 + n2 times), then at least one of the groups R1, R2, R3, R4, R5, R6, R7 and R8 is other than a hydrogen atom, and the ratio: (n1 + n2) / (p1 + p2 + n1 + n2) is in the range of 30 to 70%, and more preferably is about 50%.

According to yet another alternative of said preferred variant, when m is non-zero, the sum n1 + n2 is non-zero (corresponding to the presence in the main chain of the polymer of the 3 repeating units) and each of the groups R1, R2 R3, R4, R5, R6, R7 and R8 is a hydrogen atom, then the ratio: m / (p1 + p2 + n1 + n2 + m) is in the range of 30 to 70%, and more preferably is about 50%.

According to another last alternative of said preferred variant, when m is non-zero, the sum n1 + n2 is non-zero (corresponding to the presence in the main chain of the polymer of the 3 repeating units) and that at least one of the groups R1 , R2, R3, R4, R5, R6, R7 and R8 is other than a hydrogen atom, then the ratio: (m + n1 + n2) / (p1 + p2 + n1 + n2 + m) is included in the range from 30 to 70%, and more preferably, is about 50%.

In accordance with the 4 alternatives of said preferred variant, the polymer of formula (I) is generally in the form of a viscous liquid, generally having a Brookfield viscosity at 23 ° C. of between 1 mPa.s and 500 Pa.s, preferably between 1 to 150 Pa.s and even more preferably from 1 to 50 Pa.s. It is then advantageously easy to implement and can be combined with an additional component such as a tackifying resin or a filler, to form an adhesive composition.

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.

According to one embodiment of the invention, all the bonds ===== of the formula (I) are carbon-carbon double bonds, and the formula (I) then becomes the following formula (Γ):

(I) wherein x, y, n1, n2, m, p1, p2, F1, F2, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 and R13 have the same 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).

Each of the double bonds of the polymer of formula (Γ) is oriented geometrically cis or trans, preferably is of cis orientation. The geometric isomers of the polymer of formula (Γ) are generally present in variable proportions, with most often a majority of cis (Z) oriented double bonds, and preferably all cis (Z) oriented. 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 another embodiment of the invention, all the bonds ...... of the formula (I) are carbon-carbon single bonds, and the formula (I) then becomes the formula (IH) below :

(IH) wherein x, y, n1, n2, m, p1, p2, F1, F2, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 and R13 have the same meanings previously given.

The formula (IH) illustrates the case where the main chain of the polymer of formula (I) 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 (IH) may for example be derived from the hydrogenation of the unsaturated polymer of formula (Γ).

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

(II) wherein x, y, n1, n2, p1, p2, F1, F2, R1, R2, R3, R4, R5, R6, R7 and R8 have the meanings given above.

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

According to a particularly preferred form of this embodiment, all the bonds of the formula (II) are carbon-carbon double bonds, and the formula (II) then becomes the following formula (ΙΓ):

(He')

Formulas (II) and (ΙΓ) illustrate the case where the main chain of the polymer of formula (1) comprises only two repeating units, repeated respectively n1 + n2 and p1 + p2 times.

According to another embodiment of the polymer of formula (I) according to the invention, n1 and n2 are each equal to 0, the polymer having the following formula (III):

(III) wherein m, p1, p2 F1, F2, R9, R10, R11, R12 and R13 have the meanings given above.

According to a particularly preferred form of this embodiment, all the bonds ...... of the formula (III) are carbon-carbon double bonds, and the formula (III) then becomes the following formula (ΙΙΓ):

(III1)

Formulas (III) and (ΙΙΓ) illustrate cases where the main chain of the polymer of formula (I) comprises only two repeating units, repeated respectively (p1 + p2) times and m times.

According to yet another embodiment of the polymer of formula (I) according to the invention, n1, n2 and m are each equal to 0, the polymer having the following formula (IV):

(IV) wherein p1, p2, F1, F2 have the meanings given above.

According to a particularly preferred form of this embodiment, all the bonds == of the formula (IV) are carbon-carbon double bonds, and the formula (IV) then becomes the following formula (IV):

(IV)

Formulas (IV) and (IV) illustrate the case where the main chain of the polymer of formula (I) comprises a single repeating unit, repeated p1 + p2 times. With regard to the alkoxysilane end groups of the polymer according to the invention, when F1 is (R'O) 3-tRtSi (CFhJgi- and Fz is - (CFhJcn-SiRt (OR ') 3 -t, then preferably g1 = 1 or d1 = 1, and even more preferably: g1 = d1 = 1. In the latter case, F1 and F2 are each: -CH2-Si (OCH3) 3.

When (so-called "diester route"), F1 is (RO) s-tRtSi-R "-OOC- (CH2) g2- and Fz is: - (CH2) d2-COO-R" -SiRt (OR ') 3 t, then preferably g2 = 0 or d2 = 0, and even more preferably: g2 = d2 = 0. In the latter case, particularly advantageously F1 and F2 are each: -COO- (CH2) 3 -Si (OCH3) 3. The invention also relates to a process for preparing (P1) a hydrocarbon polymer comprising two alkoxysilane end groups of formula (I) according to the invention, said process comprising at least one metathesis ring opening polymerization reaction (also called "Ring-Opening Metathesis Polymerization" or ROMP in the presence of: (a) a metathesis catalyst; (b) a chain transfer agent (hereinafter also referred to as CTA for "chain transfer agent" in English) comprising 2 alkoxysilane groups, of formula (B) below:

in which: F1 and F2 are as defined above; the bond is a geometrically oriented bond on one side or the other with respect to the double bond (cis or trans); (c) a compound of formula (C) below:

wherein z is as previously defined; and (d) optionally a compound of formula (D):

wherein R1, R2, R3, R4, R5, R6, R7, R8, x and y are as previously defined; and (e) optionally a compound of formula (E):

wherein R9, R10, R11, R12 and R13 are as previously defined; said polymerization reaction being further carried out for a period of from 2 to 24 hours and at a temperature in the range of 20 to 60 ° C.

In the definition of the preparation method given above, it is understood that the indefinite article "a", as it relates to a reagent or to the catalyst used or to the product formed, must be interpret as meaning "at least one", that is, "one or more".

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 (B).

The duration and the temperature of the reaction generally depend on its operating conditions, in particular the nature of the solvent used, and in particular the catalytic loading rate. The skilled person is able to adapt them depending on the circumstances.

Thus, preferably, the duration of the polymerization reaction is from 2 to 10 hours.

The use of the compound of formula (C) in the process (P1) according to the invention leads to the presence, in the chain of the polymer of formula (I), of the repeating unit which is repeated p1 + p2 times, to reason of z + 1 mole of said pattern, for the implementation of 1 mole of the compound of formula (C). This so-called butadiene-derived unit responds to the following two equivalent formulas:

or

The optional implementation of the compound of formula (D) in the process (P1) according to the invention leads to the presence, in the chain of the polymer of formula (I), of the repeating unit which is repeated n1 + n2 times, at a rate of 1 mole of said unit, for the implementation of 1 mole of the compound of formula (D). This so-called cyclooctene derivative thus corresponds to the following formula:

Finally, the optional implementation of the compound of formula (E) in the process (P1) according to the invention results in the presence, in the chain of the polymer of formula (I), of the repeating unit which is repeated m times, at a rate of 1 mole of said unit, for the implementation of 1 mole of the compound of formula (E). This reason, called norbornene derivative, therefore corresponds to the following formula:

Preferably, the molar amounts of the CTA, the compound of formula (C), and optionally compounds of formula (D) and / or (E) which are used in the process (P1) are such that the ratio r which is equal to the ratio of the number of moles of said CTA: to the number N (c) of moles of the unit derived from butadiene, equivalent to the number of moles of the compound of formula (C), if said compound is the only reagent other than CTA used in the reaction, or - the sum of N (c> and the number of moles of the compounds of formula (D) and / or (E), if the compounds of formula (D) and / or (E) are also implemented in the reaction, is in the range of 0.0010 to 1.0.

Even more preferably, the ratio r defined above is in the range of 0.0020 to 0.3. (a) Metathesis catalyst:

The metathesis catalyst is preferably a catalyst comprising ruthenium, and even more preferably a Grubbs catalyst,

Such a catalyst is generally 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.

By Grubbs catalyst is generally meant according to the invention a Grubbs catalyst of 1st or 2nd generation, but also any other catalyst type Grubbs (ruthenium-carbene type) or Hoveyda-Grubbs accessible to the skilled person, such as as for example the substituted Grubbs catalysts described in US Pat. No. 5,849,851.

A Grubbs 1st generation catalyst is generally of formula (G1):

wherein Ph is phenyl, Cy is cyclohexyl, and P (Cy) 3 is a tricyclohexylphosphine group.

The IUPAC name for this compound is: benzylidene-bis (tricyclohexylphosphine) dichlororuthenium (CAS number 172222-30-9). Such a catalyst is available in particular from Aldrich.

A 2nd generation Grubbs (or G2) catalyst is generally of formula (G2):

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). This catalyst is also available from Aldrich. (b) CTA of formula (B):

According to a first embodiment, the CTA has the following formula (B1):

(B1) wherein R, R ', t, g1, d1 and have the meanings given above.

This compound can be manufactured according to the procedure described in WO 01/83097 by cross metathesis of mono-unsaturated compounds H2C = CH- (CH2) p-SiRt (OR ') 3-t.

According to this embodiment, preferably g1 = 1 or d1 = 1, and even more preferably: g1 = d1 = 1.

According to a still more advantageous variant, t is 0 and R 'is methyl. In the latter case, F1 and F2 are each: -CH2-Si (OCH3) 3 and the compound of formula (B1) becomes:

This compound, which is frans-1,4-bis (trimethoxysilyl) but-2-ene is hereinafter referred to as CTA1.

According to a second embodiment (called "ester route"), the CTA of formula (B) has the following formula (B2):

(B2) wherein R, R ', R ", t, g2, d2 and have the meanings given above.

This compound can be synthesized by esterification of a CIC (= O) (CH 2) g 2 CH = CH (CH 2) d 2 C (= O) CI type acid dichloride (itself prepared from the corresponding commercial dicarboxylic acid) with two moles of hydroxysilane.

According to this embodiment, preferably g2 = 0 or d2 = 0, and even more preferably: g2 = d2 = 0.

According to a still more advantageous variant, t equals 0 and R "is an n-propylene radical: ## STR2 ##

In the latter case, F1 and F2 are each: -C0-O- (CH2) 3- Si (OCH3) 3 and the compound of formula (B2) becomes:

This compound, which is bis (propyltrimethoxysilyl) fumarate, is hereinafter referred to as CTA2.

According to a very particularly preferred variant of the invention, the CTA of formula (B) is chosen from the group formed by frans-1,4-bis (trimethoxysilyl) but-2-ene (CTA1) and bis (propyltrimethoxysilyl). fumarate (CTA2). (c) compound of formula (C):

(VS)

The cyclic compound of formula (C) generally comprises from 8 to 32 carbon atoms.

Preferably, it is chosen from the group formed by: 1,5-cyclooctadiene (hereinafter referred to as COD) of formula:

(corresponding to z = 1) - and 1,5,9-cyclododecatriene (hereinafter referred to as CDT) composed of 12 carbon atoms of formula:

(corresponding to z = 2) these 2 compounds being commercially available from Evonik Degussa and Arkema France. (d) compound of formula (D):

The compound of formula (D) generally comprises from 6 to 30, preferably from 6 to 22, carbon atoms.

Preferably: R1, R2, R3, R4, R5, R6, R7 and R8 represent a hydrogen atom or an alkyl radical comprising from 1 to 14 carbon atoms, and even more preferably from 1 to 8; the integers x and y are in a range from 0 to 2, the sum x + y being in a range from 0 to 2.

According to a still more preferred variant: x is equal to 1 and y is equal to 1 and / or at most one of the groups taken from R1, R2, R3, R4, R5, R6, R7 and R8 is a radical C 1 -C 6 alkyl and all others represent a hydrogen atom.

The compound of formula (D) is especially chosen from: cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene and cyclododecene. 5-epoxy-cyclooctene, of formula:

(available from Aldrich), 5-oxocyclooctene, of formula:

or from a 5-alkyl-cyclooctene, of formula:

wherein R is an alkyl radical having 1 to 22 carbon atoms, preferably 1 to 14; R being for example the n-hexyl radical.

The compounds corresponding to the last two formulas developed above can be prepared by a process generalizing the reaction scheme of Example 8, in particular by carrying out the alkylation of intermediate 2 with a suitable Grignard reagent.

Among these compounds, cyclooctene and 5-n-hexylcyclooctene are very particularly preferred. (e) compound of formula (E):

The compound of formula (E) generally comprises from 6 to 30, preferably from 6 to 22, carbon atoms.

Preferably: R 9, R 10, R 11 and R 12 represent a hydrogen atom or an alkyl or alkoxycarbonyl radical comprising from 1 to 14 carbon atoms, and even more preferably from 1 to 8; the radical R °, included in the group -NR ° which is one of the meanings of R13, is a linear radical comprising from 1 to 14 carbon atoms.

According to an even more preferred variant: at most one of the groups (R 9, R 10, R 11 and R 12) is a C 1 -C 6 alkoxycarbonyl radical and all the others represent a hydrogen atom; and / or - R13 represents a -Chh- radical or an oxygen atom.

The compound of formula (E) is especially chosen from: - norbornene, of following formula:

norbornadiene, of the following formula:

dicyclopentadiene, of the following formula:

7-oxanorbornene, of the following formula:

7-oxanorbornadiene, of the following formula:

5-ethylidene-2-norbornene, of the following formula:

or else 5-norbonene-2-methylacetate, of the following formula:

The compound of formula (E) may also be chosen from compounds of the following formulas:

in which R is as defined above for the compound of formula (D).

The compound of formula (E) 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 norbornene derivatives 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 having the more often 3 to 8 carbon atoms) and branched norbornenes as described in WO 2011/038057 (norbornene dicarboxylic anhydrides and optionally 7-oxanorbornene dicarboxylic anhydrides).

Among the various compounds of formula (E) mentioned, methyl norbornene, 7-oxanorbornene, 5-norbornene-2-carboxylate, of formula:

methyl 5-oxanorbornene-2-carboxylate, of formula:

or else dicyclopentadiene. The step of polymerization by ring opening metathesis (or ROMP for "Ring-Opening Metathesis Polymerization" in English) is implemented most often 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, a mixture of liquid isoparaffins (for example Isopar®), methanol, ethanol, water or their mixtures. Even more preferably, the solvent is selected from the group consisting of benzene, toluene, paraxylene, methylene chloride, 1,2-dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, hexane, heptane, methanol, ethanol or mixtures thereof. Even more particularly preferably, the solvent is dichloromethane, 1,2-dicholoroethane, toluene, heptane, or a mixture of toluene and 1,2-dichloroethane. The solubility of the polymer formed during the polymerization reaction depends generally and mainly on the choice of solvent, the nature and the proportion of comonomers and the number average molecular weight of the polymer obtained. It is also possible that the reaction is carried out without solvent.

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 saturated compound of formula (IH) from an unsaturated compound of formula (Γ), and in particular the saturated compounds corresponding to the unsaturated compounds of formula (ΙΓ), (ΙΙΓ) and (IV) to from said unsaturated compounds. The invention also relates to another process for the preparation (P2) of a hydrocarbon polymer of formula (I) according to the invention, said process comprising: (i) a step of forming one or more cyclic (co) oligobutadiene of formula (F):

(F) wherein: - x, y, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12 and R 13 have the meanings given above; the bond is a geometrically oriented bond on one side or the other with respect to the double bond (cis or trans); the line connecting the two -CH 2 groups represents a single bond; p3 is a non-zero integer; n3 and m 'are each an integer or nil; - n3, p3 and m 'being further such that the number average molecular weight of the compound of formula (F) is between 162 and 5000 g / mol; said step being carried out by heating, at a temperature ranging from 30 ° C to 80 ° C, a polybutadiene, in the presence of a metathesis catalyst, a solvent, and: - optionally, a compound of formula (D) as defined above and, optionally, a compound of formula (E) as defined above; and then (ii) a step of polymerizing said cyclic (co) oligobutadiene of formula (F) by ring opening, in the presence of a metathesis catalyst, of a transfer agent (CTA) of formula (B) as defined previously, for a period of from 2 to 24 hours and at a temperature in the range of 20 to 60 ° C.

This process allows the preparation of the polymer of formula (I) according to the invention from polybutadiene which is an industrially advantageous raw material, in particular because of its availability and properties in terms of industrial hygiene and safety, for example, its volatility.

Step (i):

Polybutadiene is, as is well known, generally obtained by various methods of polymerizing 1,3-butadiene, which can be carried out in a trans-1,4-addition or a 1,4-cis-addition, resulting in a repeating unit in the polymer chain (designated respectively by trans-1,4 and cis-1,4-unit), which is in the form of the two geometric isomers of the respective formula:

The polymerization of 1,3-butadiene can also be carried out according to a 1,2-addition, resulting in a repeating unit in the polymer chain (designated 1,2-vinyl unit) which has the formula:

Thus, the polybutadiene generally comprises in its chain the 3 repeating units above, hereinafter referred to generically as "butadiene derived unit". The molar mass of the polybutadiene can vary from 1000 to 250000 g / mol.

Preferably, the polybutadiene chain implemented in step (i) comprises less than 5 mol% of the 1,2-vinyl repeat unit, said percentage being expressed on the basis of the total number of moles of units constituting the chain, and even more preferably less than 2%.

According to another variant, also preferred, the polybutadiene chain implemented in step (i) comprises from 50 to 98 mol% of cis-1,4 units and at most 48 mol% of trans-1,4 units, said percentages being expressed on the basis of the total number of moles of constituent units of the chain. Such a polybutadiene is often referred to as polybutadiene with a high content of cis-1,4 ("high cis polybutadiene") unit and is advantageously in the liquid form.

As an example, the commercially available POLYVEST® 130 from Evonik, which is a polybutadiene for which the percentage of cis-1,4 unit is about 77 mol%, the percentage of trans-1 unit, 4 is about 22 mol%, and the percentage of 1,2-vinyl moiety is about 1 mol%.

The heating of the polybutadiene in step (i) results in a depolymerization reaction of the latter and intramolecular cyclization reactions, which generally lead to the formation of several cyclic (co) polybutadienes of formula (F), the formation and structure can be characterized by size exclusion chromatography (SEC) techniques. The distribution of the units derived from butadiene (repeated 3 times), cyclooctene (repeated 3 times) and norbornene (repeated once) in a (co) oligobutadienecyclic of formula (F) is generally statistical. A number average molecular weight range of 162-2000 g / mol is preferred for cyclic (co) oligobutadienes of formula (F).

A preferred temperature range suitable for said heating is from 30 ° C to 60 ° C.

The metathesis catalyst used in step (i) may be chosen from the metathesis catalysts (a) previously described for process P1. However, a Grubbs catalyst of formula (G2) is preferred.

The solvent used in step (i) is advantageously chosen from the solvents described above for process P1.

The duration of the heating of step (i) is adapted to obtain a yield close to 100% relative to the molar amount of polybutadiene used, as well as that of other possible reactants; a time ranging from 1 hour to 8 hours, preferably from 1 to 3 hours, is generally appropriate.

Step (ii):

The cyclic (co) oligobutadienes of formula (F) obtained after step (i) are polymerized, according to step (ii), by ring opening, in the presence of a transfer agent (CTA ) of formula (B) as defined above.

The molar amount of CTA used in step (ii) as well as the molar amount of polybutadiene and, optionally, of compounds of formula (D) and / or (E)) implemented in step (i) are preferably such that the ratio r which is equal to the ratio of the number of moles of said CTA: - to the number N (bd) of moles of units derived from butadiene equivalent to the number of moles of the polybutadiene, if said polybutadiene is the only reagent set in step (i), or - to the sum of N (bd> and the number of moles of the compounds of formula (D) and / or (E), if the compounds of formula (D) and / or (E) are also implemented in step (i), is in the range of 0.0010 to 1.0.

Even more preferably, the ratio r defined above is in the range of 0.0020 to 0.3.

The metathesis catalyst used in step (ii) may be chosen from the metathesis catalysts (a) described above for process P1.

A solvent may be used in said step, and in this case it is selected from the solvents described above for the method P1. 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. The polymer according to the invention is a polymer of formula (I), (Γ), (III), (II), (Ν '), (III), (NI'), (IV) or (IV).

The crosslinking catalyst that may be used in the composition according to the invention may be any catalyst known to those skilled in the art for the condensation of silanols. Examples of such catalysts are: 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 trap free radicals and are generally substituted phenols such as Ciba Irganox® 1010. 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 assembling two substrates by gluing, comprising: - coating an adhesive composition as defined above, in liquid form, preferably in the form of a layer of thickness included 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 assembled, and which are intended to be brought into contact with each other. another according to a surface of tangency; then - the effective contact 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 does not lose its ability to fix by bonding 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 comes 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 following examples are given purely by way of illustration of the invention, and can not be interpreted to limit its scope.

Examples 1 to 9 describe the preparation of polymers comprising 2 trimethoxysilyl end groups, by ring opening polymerization by metathesis.

Example 1: Polymerization of 1,5-cyclooctadiene (cycloolefin of formula (C)) in the presence of CTA1, according to the method P1:

Commercially available 1,5-cyclooctadiene (hereinafter COD) is used and CTA1 is the chain transfer agent:

1,5-Cyclooctadiene (10.8 mmol) and dry CH 2 Cl 2 (5 ml) are added to a 20 ml flask in which a Teflon®-coated magnetic stir bar is also placed. The balloon and its contents are then put under argon. The molar amount of butadiene derived unit equivalent to the amount of DOC introduced is 21.6 mmol.

Compound C7A1 (0.27 mmol) is then added with stirring to the flask by syringe. The ratio r of the reagents, as defined above, is equal to 0.27 mmol divided by 21.6 mmol, ie 0.0125.

The flask is then immersed in an oil bath at 40 ° C., and then the cannulated catalyst G2 (5.4 pmol) in solution in CH2Cl2 (2 ml) is immediately added by means of a cannula. ).

The reaction mixture becomes very viscous in the course of 10 minutes. The viscosity then decreases slowly during the following hours.

After 8 hours from the addition of the catalyst, the product present in the flask is removed after evaporation of the solvent in vacuo. The product is then recovered in the form of a colorless solid powder, after precipitation in methanol, filtration and drying at 20 ° C. under vacuum, with a yield greater than 90%. The 1 H / 13 C NMR analysis of the polymer obtained gives the following values: 1 H NMR (CDCl 3, 500 MHz, 298 K): δ (ppm) repetition unit 2.10 (4H * n), 5.43 (2H * n), terminal group = 1.78 (4H, m, = CH-CH2-Si-), 3.57 (18H, s, -Si-O-CH3), 13C NMR (CDCl3, 100 MHz, 298 K): δ (ppm) unit of repeat 27.41, 32.72, 131.39, terminal group = 14.03 (= CH-CH2-Si-), 54.39 (-Si-O-CH3), 130.45 (CH = CH-CH2) -Si-), 135.16 (CH = CH-CH2-Si-)

These values confirm the structure below:

This structure is well covered by the formula (IV) defined above.

The number average molecular weight Mn, measured by NMR, is 4600 g / mol. The polymolecularity index equal to the Mw / Mn ratio (measured by steric exclusion chromatography with polystyrene standard) is 1.60.

EXAMPLE 2 Polymerization of 1,5,9-cyclododecatriene (cycloolefin of formula (C)) in the presence of CTA1, according to the method P1

Example 1 is repeated replacing the COD with 1,5,9-cyclododecatriene (known as CDT) which is commercially available, for example from Sigma Aldrich.

The molar amount of butadiene-derived unit equivalent to the amount of CDT introduced is 32.4 mmol. The ratio r of the reagents, as defined above, is equal to 0.27 mmol divided by 32.4 mmol, ie 0.008.

A polymer is also recovered in the form of a colorless solid powder whose 1 H / 13 C NMR analysis is identical to the polymer of Example 1, thus confirming the structure below:

which is also covered by formula (IV) defined above.

The number-average molecular weight Mn and the polydispersity index are 6800 g / mol and 1.80, respectively.

Example 3: Polymerization of 1,5,9-Cyclododecatriene in the Presence of CTA2, According to Method P1

Example 2 is repeated, replacing CTA1 by CTA2 as a chain transfer agent:

A polymer is also recovered in the form of a colorless solid powder whose 1H / 13C NMR analysis gives the following values: 1H NMR (CDCl 3, 500 MHz, 298 K): δ (ppm) repetition unit 2.10 (4H * n) 5.43 (2H * n), terminal moiety = 0.64 (4H, m, -CH2-C21-S1-), 1.61 (4H, m, -CO-CH2-CH2-CH2-S1-), 4, (4H, m, -O-CH2-CH2-CH2-Si-), 3.57 (18H, s, -Si-O-CH3), 5.73 (1H, m, -CH = CH-CO-), 5.77 ( 1H, m, -CH = CH-CO-). 13C NMR (CDCl3, 100 MHz, 298 K): δ (ppm) repeat unit 27.41, 32.72, 131.39, terminal group = 6.28 (-CH2-CH2-S1-), 23.17 (-CO- CH2-CH2-CH2-S1-), 50.77 (-S1-O-CH3), 68.10 (-CO-CH2-CH2-CH2-Si-), 119.89 (CH = CH-CO-), 135 , 16 (-CH = CH-CO-), 167.07 (-O-CO-).

These values confirm the structure below:

This structure is well covered by the formula (IV) defined above.

The number average molecular weight Mn and the polydispersity index are 6900 g / mol and 1.80, respectively.

EXAMPLE 4 Polymerization of CDT and Norbornene (Cycloolefin of Formula (E)) in the Presence of CTA1, According to Method P1

Example 1 is repeated, replacing the 10.8 mmol of COD with a mixture of 5.4 mmol of CDT and 5.4 mmol of norbornene, of formula:

and available from Sigma Aldrich.

The molar amount of butadiene-derived unit equivalent to the amount of CDT introduced is 16.2 mmol. The ratio r of the reagents, as defined above, is equal to 0.27 mmol divided by 16.2 + 5.4 mmol, ie 0.0125.

After 8 hours from the addition of the catalyst, the product in the flask is removed after evaporation of the solvent in vacuo. The product is then recovered in the form of a liquid at room temperature, after precipitation in methanol, filtration and drying at 20 ° C. under vacuum, with a yield greater than 90%. The NMR analysis of the polymer obtained gives the following values: 1 H NMR (CDCl 3, 500 MHz, 298 K): δ (ppm) trans: 1.08 (2H * n), 1.39 (4H * n), 2.07 (4H *) n), 2.47 (2H * n trans), 5.24-5.44 (4H * n trans), cis: 1.82-1.91 (6H * n), 2.07 (4H * n), 2.82 (2H * n); cis), 5.24-5.44 (4H * n cis), terminal group = 1.78 (4H, m, = CH-CH2-Si-), 3.57 (18H, s, -Si-O-CH3), 13C NMR (CDCl3, 100 MHz, 298 K): δ (ppm) 27.42, 33.12, 42.10, 43.43, 130.35, 133.12, terminal group = 14.03 (= CH-CH2-Si -), 54.39 (-Si-O-CH3), 130.45 (CH = CH-CH2-Si-), 135.16 (-CH = CH-CH2-S1-)

These values confirm the structure below:

This structure is well covered by the formula (ΙΙΓ) defined previously.

The number-average molecular weight Mn and the polydispersity index are, respectively, 5400 g / mol and 1.60.

EXAMPLE 5 Polymerization of CDT and methyl 5-norbornene-2-carboxylate (cycloolefin of formula (E)) in the presence of CTA1, according to method P1

Example 4 is repeated replacing norbornene by methyl 5-norbornene-2-carboxylate, of formula:

and available from Sigma Aldrich.

A copolymer which is liquid at room temperature is also obtained, NMR analysis of which gives the following values: 1H NMR (CDCl 3, 500 MHz, 298 K): δ (ppm) repetition unit 1.08-1.26 (1H * n) , 1.56-1.99 (3H * n), 2.07 (4H * n), 2.44-3.02 (3H * n), 5.13-5.29 (4H * n), terminal group = 1, 78 (4H, m, = CH-CW2-Si-), 3.57 (18H, s, -S1-O-CH3), 13C NMR (CDCl3, 100MHz, 298K): δ (ppm) repetition unit: 27 , 42, 33.12, 36.17-42.95, 130.35, 133.12, terminal moiety = 14.03 (= CH-CH2-Si-), 54.39 (-Si-O-CH3), 130 , 45 (CH = CH-CH2-Si-), 135.16 (CH = CH-CH2-S1-)

These values confirm the structure:

This structure is well covered by the formula (III ') defined above.

The number-average molecular weight Mn and the polydispersity index are, respectively, 6600 g / mol and 1.80.

EXAMPLE 6 Polymerization of CDT and methyl 5-oxanorbornene-2-carboxylate (cycloolefin of formula (E)) in the presence of CTA1, according to the method P1

Example 4 is repeated replacing norbornene by methyl 5-oxanorbornene-2-carboxylate, of formula:

and available from Boc Sciences.

A liquid copolymer at room temperature is also obtained, the NMR analysis of which gives the following values:

These values confirm the structure:

which is well covered by the formula (IIΓ) defined above.

The number-average molecular weight Mn and the polydispersity index are, respectively, 6600 g / mol and 1.70.

EXAMPLE 7 Polymerization of CDT and of Dicyclopentadiene (Cycloolefin of Formula (E)) in the Presence of CTA1, According to Process P1

Example 4 is repeated, replacing norbornene with dicyclopentadiene, of formula:

and available from Sigma Aldrich.

A copolymer which is liquid at room temperature and whose NMR analysis gives the following values is also obtained: 1H NMR (CDCl 3, 500 MHz, 298 K): δ (ppm) repetition unit 1.24 (1H * n), 1.59 (1H * n), 2.07 (4H * n), 2.26 (2H * n), 2.62 (1H * n), 2.85 (2H * n), 3.24 (1H * n) , 5.36-5.68 (4H * n), terminal group = 1.78 (4H, m, = CH-CW2-Si-), 3.57 (18H, s, -Si-O-CW3) .13C NMR (CDCb , 100 MHz, 298 K): δ (ppm) repeat unit 27.42, 33.10, 35.12, 38.00, 42.34, 45.98, 47.06, 55.40, 130.48, terminal group = 14, 03 (= CH-CH2-Si-), 54.39 (-S1-O-CH3), 130.45 (CH = CH-CH2-Si-), 135.16 (CH = CH-CH2-Si-) .

These values confirm the structure:

This structure is well covered by the formula (ΙΙΓ) defined previously.

The number-average molecular weight Mn and the polydispersity index are respectively 6200 g / mol and 2.00.

Example 8: Polymerization of CDT and 5-n-hexylcyclooctene (cycloolefin of formula (D)) in the presence of CTA1, according to the method P1:

The 5-n-hexyl-cyclooctene used in this example was synthesized according to the route indicated in the reaction scheme below (see compound No. 5):

The raw materials (in particular the 5,6-epoxycyclooctene), reactants and solvents used in these syntheses are commercial products from Sigma Aldrich. Reference is made for further details to the publication of A. Diallo et al. (Polymer Chemistry, Vol 5, Issue 7, April 7, 2014, pp 2583-2591), or at Kobayashi et al., J. J. Chem. Soc. 2011, 133, pp 5794-5797).

Example 4 is repeated substituting 5-n-hexylcyclooctene for norbornene.

A copolymer which is liquid at room temperature and whose NMR analysis gives the following values: 1H NMR (CDCl 3, 500 MHz, 298 K): δ (ppm) repetition unit 0.83 (3H * n), 1.27 (16H) * n), 2.07 (4H * n), 2.17 (5H * n), 5.37 (2H * n), terminal group = 1.78 (4H, m, = CH-CH2-Si-), 3.57 (18H, s, -Si-O-CH3) .13C 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 moiety = 14.03 (= CH-CH2-Si-), 54.39 (-Si-O-CH3), 130.45 (CH = CH-CH2-Si-), 135.16 (-CH = CH-CH2-Si-).

These values confirm the structure:

which is well covered by the formula (ΙΓ) defined above.

The number average molecular weight Mn and the polydispersity index are 7400 g / mol and 1.80, respectively.

EXAMPLE 9 Polymerization of CDT, Cyclooctene (Cycloolefin of Formula (D)) and Norbornene (Cycloolefin of Formula (E)) in the Presence of CTA1, According to Process P1

Example 1 is repeated, replacing the 10.8 mmol of COD with a mixture of 3.6 mmol of CDT, 3.6 mmol of cyclooctene and 3.6 mmol of norbornene.

The molar amount of butadiene-derived unit equivalent to the amount of CDT introduced is 10.8 mmol. The ratio r of the reagents, as defined above, is equal to 0.27 mmol divided by 10.8 + 3.6 + 3.6, ie 0.015.

After 8 hours from the addition of the catalyst, the product in the flask is removed after evaporation of the solvent in vacuo. The product is then recovered in the form of a liquid at room temperature, after precipitation in methanol, filtration and drying at 20 ° C. under vacuum, with a yield greater than 90%. The NMR analysis of the polymer obtained gives the following values: 1 H NMR (CDCl 3, 500 MHz, 298 K): δ (ppm) trans repeat unit: 1.08 (2H * n), 1.26 (8H * n), 1.39 (4H * n), 2.00 (4H * n), 2.07 (4H * n), 2.47 (2H * n trans), 5.24-5.44 (6H * n trans), cis: 1.26 ( 8H * n), 1.82-1.91 (6H * n), 2.00 (4H * n), 2.07 (4H * n), 2.82 (2H * n cis), 5.24-5.44 (6H *), n cis), terminal group = 1.78 (4H, m, = CH-CH2-Si-), 3.57 (18H, s, -Si-O-CH3) .13C NMR (CDCh, 100MHz, 298K): δ (ppm) repeat unit 27.42, 28.56, 32, 51, 33.12, 42.10, 43.43, 130.35, 133.12, terminal group = 14.03 (= CH-CH2-Si -), 54.39 (-Si-O-CH3), 130.45 (CH = CH-CH2-Si-), 135.16 (-C "= CH-CH2-Si-).

These values confirm the structure:

The number-average molecular weight Mn and the polydispersity index are, respectively, 5200 g / mol and 1.90.

EXAMPLE 10 Heating of polybutadiene, followed by ring opening polymerization in the presence of CTA1, according to process P2: step (i)

Commercial polybutadiene called POLYVEST® 130 with a molar mass of 4600 g / mol is used.

This polybutadiene (0.38 mmol) and dry CH 2 Cl 2 (9 ml) are introduced into a 20 ml flask in which a Teflon®-coated magnetic stirring bar was also placed. The balloon and its contents are then put under argon.

The molar amount of butadiene-derived unit equivalent to the amount of polybutadiene introduced is 32.4 mmol.

Then the addition of the catalyst G2 defined previously (9.6 pmol) in solution in CH 2 Cl 2 (2 ml) is carried out by means of a cannula.

This mixture is heated in an oil bath for 3 hours at 40 ° C. with stirring until the disappearance of POLYVEST® 130 and formation of a mixture of compounds of formula (F) attested by steric exclusion chromatography, step ( ii):

CTA1 (0.27 mmol) is added by syringe and with stirring into the mixture contained in the flask of step (i) and the temperature of the mixture is maintained by heating. 40 ° C.

The ratio r, as defined above, is: 0.27 / 32.4 is: 0.008 After 8 hours from the introduction of CTA1, the product present in the flask is removed after evaporation of the solvent in vacuo. This product is then recovered in the form of a colorless solid powder, after precipitation in methanol, filtration and drying at 20 ° C. under vacuum, with a yield greater than 90%. 1H NMR (CDCl 3, 500 MHz, 298 K): δ (ppm) repeat unit 2.10 (4H * n), 5.43 (2H * n), terminal group = 1.78 (4H, m, = CH-CH 2 -Si) -), 3.57 (18H, s, -Si-O-CHa), 13C NMR (CDCl3, 100 MHz, 298 K): δ (ppm) repeat unit 27.41, 32.72, 131.39, terminal group = 14.03 (= CH-CW2-Si-), 54.39 (-Si-O-CHe), 130.45 (CH = CH-CH2-Si-), 135.16-CH = CH-CH2 -S1-)

This product is identical to that of Example 2.

EXAMPLE 11 Heating of polybutadiene and norbornene, followed by ring opening polymerization in the presence of CTA1, according to process P2:

Example 10 is repeated, replacing in step (i) the 0.38 mmol of polybutadiene with a mixture of 0.19 mmol of polybutadiene (corresponding to 16.2 mmol of units derived from butadiene) and 5.4 mmol of norbornene. .

The ratio r of the reagents, as defined above, is equal to 0.27 mmol divided by 16.2 + 5.4 mmol, ie 0.0125.

After 8 hours from the addition of CTA1, the product in the flask is removed after evaporation of the solvent in vacuo. The product is then recovered in the form of a liquid at room temperature, after precipitation in methanol, filtration and drying at 20 ° C. under vacuum, with a yield greater than 90%. The NMR analysis of the polymer obtained gives the following values: 1 H NMR (CDCl 3, 500 MHz, 298 K): δ (ppm) trans: 1.08 (2H * n), 1.39 (4H * n), 2.07 (4H *) n), 2.47 (2H * n trans), 5.24-5.44 (4H * n trans), cis: 1.82-1.91 (6H * n), 2.07 (4H * n), 2.82 (2H * n cis) , 5.24-5.44 (4H * n cis), terminal group = 1.78 (4H, m, = CH-CH2-Si-), 3.57 (18H, s, -Si-O-CH3), 13C NMR ( CDCl3, 100 MHz, 298 K): δ (ppm) 27.42, 33.12, 42.10, 43.43, 130.35, 133.12, terminal group = 14.03 (= CH-CH2-Si-) , 54.39 (-S₁-CH-), 130.45 (CH = CH-CH₂-Si-), 135.16 (CH = CH-CH₂-Si-)

This product is identical to that of Example 4.

Example 12 Preparation of an Adhesive Composition Comprising the Polymer of Example 1

An adhesive composition comprising 0.2% by weight of a crosslinking catalyst consisting of tin dioctyl dideodecanoate (TIB KAT® 223 product from TIB Chemicals) is prepared by simple mixing, and the polymer according to the invention obtained from Example 1

The mixture thus obtained is left under reduced stirring (20 mbar or 2000 Pa) for 15 minutes and then packaged in an aluminum cartridge.

The measurement of the tensile strength and elongation at break is carried out according to the protocol described below.

The principle of measurement consists in: stretching a standard test specimen made of the reticulated adhesive composition into a traction machine, whose moving jaw moves at a constant speed equal to 100 mm / min, and then recording it at the moment where the rupture of the specimen occurs, the tensile stress applied (expressed in MPa) and the elongation of the specimen (expressed 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 μm.

To prepare the dumbbell, the composition conditioned as described above is heated to 100 ° C., then the amount necessary to form a film having a thickness of 300 μm which is left 7 days at 23 ° C and 50% relative humidity for crosslinking. The dumbbell is then obtained by simple cutting in the crosslinked film.

Thus, for said adhesive composition, a tensile stress greater than 0.7 MPa and an elongation at break greater than 200% are measured.

Said adhesive composition is also subjected to bonding tests of two wooden strips (each of size 20 mm × 20 mm × 2 mm) to conduct, after crosslinking for seven days at 23 ° C. and forming an adhesive seal of 1 mm thick on a surface of 12.5 mm X 20 mm, with a breaking stress greater than 2 MPa in adhesive breaking.

Claims (20)

A hydrocarbon polymer comprising two alkoxysilane end groups, said hydrocarbon polymer having the formula (I): in which : -1 is an integer equal to 0, 1 or 2; - g1 and d1, identical or different, represent an integer equal to 1, 2 or 3; - g2 and d2, identical or different, represent an integer equal to 0, 1, 2 or 3; R and R ', which may be identical or different, represent an alkyl radical comprising from 1 to 4 carbon atoms; R "is an alkylene radical comprising from 1 to 4 carbon atoms; each carbon-carbon bond of the main chain of the polymer, denoted by ------ represents a double bond or a single bond, in accordance with the valence rules of organic chemistry; - R1, R2, R3, R4, R5, R6, R7 and R8, identical or different, represent: - a hydrogen or halogen atom; or a radical comprising from 1 to 22 carbon atoms selected from alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, the hydrocarbon chain of said radical possibly being interrupted by at least one oxygen atom or a sulfur atom; in addition: at least one of the groups R1 to R8 may form, with at least one other of the groups R1 to R8 and with the carbon atom or atoms to which the said groups are connected, a saturated or unsaturated or optionally substituted hydrocarbon or hydrocarbon heterocycle; and comprising from 3 to 10 members; and - at least one of the pairs (R1, R2), (R3, R4), (R5, R6) and (R7, R8) can form, with the carbon atom to which said pair is connected, a carbonyl group C = 0 or a group of 2 carbon atoms connected by a double bond: C = C, the other carbon atom carries 2 substituents chosen from a hydrogen atom or a C1-C4 alkyl radical; x and y are integers, identical or different, in a range from 0 to 6, the sum x + y being in the range 0 to 6; - R9, R10, R11 and R12, identical or different, represent: - a hydrogen or halogen atom; or - a radical comprising from 1 to 22 carbon atoms and chosen from alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkylcarbonyloxyalkyl, the hydrocarbon chain of said radical possibly being interrupted by at least one oxygen atom or one atom of sulfur; in addition: at least one of the groups R9 to R12 may form, with at least one other of the groups R9 to R12 and with the carbon atom (s) to which the said groups are connected, a saturated or unsaturated, optionally substituted hydrocarbon or hydrocarbon ring. and comprising from 3 to 10 members; and - at least one of the pairs (R9, R10) and (R11, R12) can form with the carbon atom to which said pair is connected a group of 2 carbon atoms connected by a double bond: C = C, of which another carbon atom carries 2 substituents chosen from a hydrogen atom or a C1-C4 alkyl radical; and the carbon atom carrying one of the groups of the pair (R9, R10) can be connected to the carbon atom bearing one of the groups of the pair (R11, R12) by a double bond , it being understood that, in accordance with the valence rules, only one of the groups of each of these 2 pairs is then present; - R13 represents: - an oxygen or sulfur atom, or - a divalent radical -CH2-, -C (= O) - or -NR ° - in which R ° is an alkyl or alkenyl radical comprising from 1 to 22 carbon atoms; n1 and n2, which are identical or different, are each an integer or nil; m is an integer greater than or equal to 0; p1 and p2, which are identical or different, are each an integer or nil whose sum p1 + p2 is non-zero and satisfies the equation: p1 + p2 = qx (z + 1) in which: q is an integer greater than 0; and - z is an integer from 1 to 5; and - n1, n2, m, p1 and p2 being further such that the number-average molecular weight Mn of the polymer of formula (I) is in the range of 400 to 100,000 g / mol and its polymolecularity index is within a range of 1.0 to 3.0. 2. Hydrocarbon polymer according to claim 1, characterized in that: the radicals R and R 'represent a linear alkyl radical; the radical R "represents a linear alkylene radical; R1, R2, R3, R4, R5, R6, R7 and R8 represent a hydrogen atom or an alkyl radical comprising from 1 to 14 carbon atoms; x and y are in a range from 0 to 2, the sum x + y being in a range from 0 to 2; R9, R10, R11 and R12 represent a hydrogen atom or a radical whose the hydrocarbon portion comprises 1 to 14 carbon atoms; the radical R 0 is a linear radical comprising from 1 to 14 carbon atoms; z is an integer equal to 1 or 2. 3. Hydrocarbon polymer according to one of claims 1 or 2, characterized in that: - when m is not zero and n1 and n2 are each equal to 0, then the ratio: m / (p1 + p2 + m) is ranging from 30 to 70%; or - when m is equal to 0 and the sum n1 + n2 is non-zero, then at least one of R1, R2, R3, R4, R5, R6, R7 and R8 is other than a hydrogen atom, and the ratio: (n1 + n2) / (p1 + p2 + n1 + n2) is in the range of 30 to 70%; or - when m is not zero, that the sum n1 + n2 is not zero and that each of the groups R1, R2, R3, R4, R5, R6, R7 and R8 is a hydrogen atom, then the ratio: m / (p1 + p2 + n1 + n2 + m) is in the range of 30 to 70%; or - when m is not zero, that the sum n1 + n2 is non-zero and that at least one of the groups R1, R2, R3, R4, R5, R6, R7 and R8 is other than a hydrogen atom, then the ratio: (m + n1 + n2) / (p1 + p2 + n1 + n2 + m) is in the range of 30 to 70%. 4. Hydrocarbon polymer according to one of claims 1 to 3, characterized in that it has the following formula (Γ): (Γ) wherein the bond is a geometrically oriented bond on one side or the other with respect to the double bond. 5. Hydrocarbon polymer according to one of claims 1 to 4, characterized in that m is equal to 0, the polymer having the following formula (II): (He) 6. Hydrocarbon polymer according to claim 5, characterized in that it has the following formula (ΙΓ): (ΙΓ) 7. Hydrocarbon polymer according to one of claims 1 to 4, characterized in that n1 and n2 are each equal to 0, the polymer having the following formula (III): (OR) 8. Hydrocarbon polymer according to claim 7, characterized in that it has the following formula (IIΓ): (ΙΙΓ) 9. Hydrocarbon polymer according to one of claims 1 to 4, characterized in that n1, n2 and m are each equal to 0, the polymer having the following formula (IV): (IV) 10. Hydrocarbon polymer according to claim 9, characterized in that it has the following formula (IV): (IV) 11. Hydrocarbon polymer according to one of claims 1 to 10, characterized in that when F1 is (R'0) 3-tRtSi- (CH2) gi- and F2 is - (CH2) di-SiRt (OR ') 3 -t, then g1 = d1 = 1. 12. hydrocarbon polymer according to one of claims 1 to 10, characterized in that when F1 is and F2 is: 13. Process for the preparation of a hydrocarbon polymer as defined in one of claims 1 to 12, comprising at least one metathesis ring opening polymerization reaction, in the presence of: (a) a metathesis catalyst; (b) a chain transfer agent (hereinafter also referred to as CTA) comprising 2 alkoxysilane groups of the following formula (B): wherein: the bond is a geometrically oriented bond on one side or the other with respect to the double bond; (c) a compound of formula (C) below: (d) optionally a compound of formula (D): ; and (e) optionally a compound of formula (E): said polymerization reaction being further carried out for a time ranging from 2 to 24 hours and at a temperature in the range of 20 to 60 ° C. 14. Preparation process according to claim 13, characterized in that the molar amounts of the CTA, the compound of formula (C), and optionally compounds of formula (D) and / or (E) which are used are such that that the ratio r which is equal to the ratio of the number of moles of said CTA: - to the number N (o of moles of the unit derived from butadiene, equivalent to the number of moles of the compound of formula (C), if said compound is the only reagent other than the CTA used in the reaction, or - the sum of N (c) and the number of moles of the compounds of formula (D) and / or (E), if the compounds of formula (D) and / or (E) are also used in the reaction, is in the range of 0.0010 to 1.0. 15. Process for the preparation of a hydrocarbon polymer of formula (I) as defined in one of claims 1 to 12, said process comprising: (i) a step of forming one or more cyclic (co) oligobutadiene of formula (F): (F) wherein: the bond is a geometrically oriented bond on one side or the other with respect to the double bond (cis or trans); the line connecting the two -CH 2 groups represents a single bond; p3 is a non-zero integer; n3 and m 'are each an integer or nil; - n3, p3 and m 'being further such that the number average molecular weight of the compound of formula (F) is between 162 and 5000 g / mol; said step being carried out by heating, at a temperature ranging from 30 ° C to 80 ° C, a polybutadiene, in the presence of a metathesis catalyst, a solvent, and: - optionally, a compound of formula (D) as defined in claim 13 and, optionally, a compound of formula (E) as defined in claim 13; and then (ii) a step of polymerizing said cyclic (co) oligobutadiene of formula (F) by ring opening, in the presence of a metathesis catalyst, of a transfer agent (CTA) of formula (B) as defined in claim 13 for a period of from 2 to 24 hours and at a temperature in the range of 20 to 60 ° C. 16. Preparation process according to claim 15, characterized in that the polybutadiene chain used in step (i) comprises less than 5 mol% of the 1,2-vinyl repeat unit, said percentage being expressed on the basis of the total number of moles of constituent units of the chain. 17. Preparation process according to one of claims 15 or 16, characterized in that the polybutadiene chain used in step (i) comprises from 50 to 98 mol% of cis-1,4 units and at most 48 mol% of trans-1,4 units, said percentages being expressed on the basis of the total number of moles of units constituting the chain. 18. Preparation process according to one of claims 15 to 17, characterized in that the molar amount of CTA used in step (ii) and the molar amount of polybutadiene and, optionally, compounds of formula ( D) and / or (E)) implemented in step (i) are preferably such that the ratio r which is equal to the ratio of the number of moles of said CTA: - to the number N (bd) of moles of units butadiene derivatives equivalent to the number of moles of polybutadiene, if said polybutadiene is the only reagent used in step (i), or - to the sum of N (bd) and the number of moles of compounds of formula (D ) and / or (E), if the compounds of formula (D) and / or (E) are also used in step (i), is in the range of 0.0010 to 1.0. 19. Adhesive composition comprising a polymer as defined in one of claims 1 to 12 and 0.01 to 3% by weight of a crosslinking catalyst. 20. A method of assembling two substrates by gluing, comprising: - coating an adhesive composition as defined in claim 19, in liquid form on at least one of the two surfaces which belong respectively to the two substrates to to assemble, and which are intended to be brought into contact with each other according to a surface of tangency; then - the effective contact of the two substrates according to their tangency surface.