WO2017198935A1 - Hydrocarbon polymers with two alkoxysilane end groups and processes for preparing same - Google Patents

Hydrocarbon polymers with two alkoxysilane end groups and processes for preparing same Download PDF

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WO2017198935A1
WO2017198935A1 PCT/FR2017/051156 FR2017051156W WO2017198935A1 WO 2017198935 A1 WO2017198935 A1 WO 2017198935A1 FR 2017051156 W FR2017051156 W FR 2017051156W WO 2017198935 A1 WO2017198935 A1 WO 2017198935A1
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formula
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radical
polymer
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Guillaume Michaud
Frédéric Simon
Stéphane Fouquay
Xiaolu MICHEL
Sophie Guillaume
Jean-François Carpentier
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Bostik Sa
Centre National De La Recherche Scientifique
Universite De Rennes 1
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Priority to FR1654356A priority Critical patent/FR3051471A1/en
Priority to FR1654356 priority
Priority to FR1659062A priority patent/FR3051472A1/en
Priority to FR1659062 priority
Application filed by Bostik Sa, Centre National De La Recherche Scientifique, Universite De Rennes 1 filed Critical Bostik Sa
Publication of WO2017198935A1 publication Critical patent/WO2017198935A1/en

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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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    • C08J11/10Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
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    • C09J165/00Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
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    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10Definition of the polymer structure
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    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10Definition of the polymer structure
    • C08G2261/16End groups
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    • C08G2261/1644End groups comprising organic end groups comprising other functional groups, e.g. OH groups, NH groups, COOH groups or boronic acid
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    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3322Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from cyclooctene
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3323Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other monocyclic systems
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    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3324Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
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    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40Polymerisation processes
    • C08G2261/41Organometallic coupling reactions
    • C08G2261/418Ring opening metathesis polymerisation [ROMP]
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    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50Physical properties
    • C08G2261/62Mechanical aspects
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    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C08G2261/72Derivatisation
    • C08G2261/724Hydrogenation
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    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70Post-treatment
    • C08G2261/76Post-treatment crosslinking

Abstract

1) Hydrocarbon polymer comprising two alkoxysilane end groups of formula (I): in which : - F1 is: (R'0)3-tRtSi-(CH2)gi- and F2 is: -(CH2)di-SiRt(OR')3-t; or else 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 equal to 1, 2 or 3; g2 and d2 are an integer equal to 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 within a range extending from 0 to 2; n1 and n2 are an integer or zero and m is an integer greater than or equal to 0; p1 and p2 are an integer or zero, the sum p1 + p2 of which is not zero and satisfies the equation: p1 + p2 = q x (z +1) in which 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 preparing this polymer from a polybutadiene with a high content of cis-1,4 units. 4) Adhesive composition comprising said polymer and from 0.01 to 3% by weight of a crosslinking catalyst.

Description

hydrocarbon polymers with two terminal groups alkoxysilanes and their methods of preparation

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

modified polymers Silane (MS or MS Polymers Polymers for "Silane Modified Polymers" in English) are known in the field of adhesives. They are used for adhesive bonding of a variety of objects (or substrates). Thus, the MS polymer-based compositions 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 placed in contact with each other to assemble. The MS polymer reacts by crosslinking in the presence of water (from the environment and / or substrates), which leads to the formation of a cohesive adhesive seal ensuring the strength of the assembly of the two substrates. This adhesive joint is mainly composed of the crosslinked polymer MS in a three-dimensional network formed by the polymer chains interconnected by siloxane bonds. The crosslinking can take place before or after contacting of the two substrates and the application, if necessary, a pressure at their tangency surface.

However, the MS polymers should most often be implemented in the form of adhesive compositions comprising other components such as tackifying resins, one or more additives to reinforcing effect, for example at least one mineral filler, or one or more additives to improve the setting time (that is to say the time at which the crosslinking can be considered completed) or other characteristics such as the rheology or the mechanical properties (elongation, modulus .. .).

CA 2242060 patent application discloses the possibility of using an adhesive seal type composition polymer base containing at least one cycloolefin, a catalyst for metathesis polymerization chain opening, a filler and a compound that comprises that one silane.

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

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

In addition, the patent application WO 201 1/038 057 discloses the ring-opening metathesis polymerisation of norbornene dicarboxylic anhydrides and optionally dicarboxylic anhydrides of 7-oxanorbornène.

Finally, patent application GB 2238791 discloses a polymerization process of 7-oxanorbornène by ring-opening metathesis polymerisation.

The present invention aims to provide novel polymers with two terminal groups alkoxysilanes. These polymers can lead, after crosslinking, to the formation of an adhesive seal having improved mechanical properties, especially a higher cohesion compared with those of the prior art.

Thus, the present invention relates to a hydrocarbon polymer comprising two alkoxysilane end groups, said hydrocarbon polymer having the formula (I):

Figure imgf000004_0001

(I)

in which :

- the link is a directed link from a geometrically side or the other with respect to the double bond (cis or trans);

- F 1 is: (R'0) 3-tRtSi- (CH 2) g i and F 2 is: - (CH 2) di-SIRT (OR ') 3 -t; or Fi is: (R'O) 3-tRtSi-R "-OOC- (CH 2) G2- and F 2 is:

- (CH 2) d2-COO-R "-SiRt (OR ') 3-t; and:

- 1 is an integer equal to 0, 1 or 2;

- g1 and d1, which are identical or different, represent an integer equal to 1, 2 or 3;

- g2 and d2, which are identical or different, represent an integer 0, 1, 2 or 3;

- R and R ', 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;

- R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8, 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 optionally being interrupted by at least one oxygen atom or a sulfur atom; in addition:

- at least one of R 1 to R 8 can form, together with at least one other of R 1 to R 8 and with one or more carbon atoms to which said groups are attached, a ring or a saturated or unsaturated hydrocarbon-based heterocycle optionally substituted, and comprising from 3 to 10 ring members; and

- at least one of the pairs (R 1, R 2) (R 3, R 4) (R 5, R 6) (R 7, R 8) may form, with the carbon atom to which said pair is connected, a carbonyl group C = O or a group of 2 carbon atoms connected by a double bond C = C, whose carbon atom other door 2 substituents selected from a hydrogen atom or a Ci-C 4 alkyl;

- x and y are integers, the same or different, within a range from 0 to 6, the sum x + y being in the range of 0 to 6;

- R 9, R 10, R 11 and R 12, identical or different, represent:

- a hydrogen or halogen atom; or - a radical comprising from 1 to 22 carbon atoms and selected from alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkylcarbonyloxyalkyl, the hydrocarbon chain of said radical optionally being interrupted by at least one oxygen atom or an atom of sulfur; in addition:

- at least one of R 9 to R 12 may form, with at least one other of R 9 to R 12 and with one or more carbon atoms to which said groups are attached, a ring or a saturated or unsaturated hydrocarbon-based heterocycle optionally substituted, and comprising from 3 to 10 ring members; and

- at least one of the pairs (R 9, R 10) and (R 1 1, R 12) may form with the carbon atom to which said pair is connected to a group of 2 carbon atoms connected by a double bond C = C, the other carbon atom has two substituents selected from a hydrogen atom or a Ci-C 4 alkyl; and

- the carbon atom bearing one of the pair of groups (R 9, R 10) can be connected to the carbon atom of one of the pair of groups (R 1 1, R 12) by a double bond, provided that, in accordance with the rules of valence, one group of each of these two pairs is then present;

- R 13 represents:

- an atom of oxygen or sulfur, or

- a divalent radical --CH -, -C (= O) - or -NR o - wherein R ° is an alkyl or alkenyl radical comprising from 1 to 22 carbon atoms;

- n1 and n2, equal or different, are each an integer or zero, the 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 zero, the 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 average molecular mass Mn of the polymer of formula (I) is within a range from 400 to 100 000 g / mol and its polydispersity index is within a range from 1, 0 to 3.0.

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

Each of the double bonds of the polymer of formula (I) is geometrically oriented cis or trans, preferably is cis orientation. Geometric isomers of the polymer of formula (I) are generally present in varying proportions, with usually a majority of double bonds oriented cis (Z), and preferably all oriented cis (Z). It is also possible according to the invention to obtain a single geometric isomers, depending on the reaction conditions and particularly depending on the nature of the catalyst used.

The following variants of the polymer of formula (I), individually or in combination, are particularly preferred:

- R and R 'included in the definition of F 1 and F 2 represent a linear alkyl, more preferably containing from 1 to 2 carbon atoms;

- the radical R "included in the definition of F 1 and F 2 represents a linear alkylene radical;

- R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 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 within a range from 0 to

2, the sum x + y being in the range of from 0 to 2;

- x is equal to 1 and y is 1;

- R 9, R 10, R 1 1 and R 12 represent a hydrogen atom or a radical in which the hydrocarbon portion contains from 1 to 14 carbon atoms, and even more preferably from 1 to 8;

- the radical R °, -NR ° included in the group which is one of the meanings of R 13 is a linear radical containing from 1 to 14 carbon atoms; - z is an integer equal to 1 or 2; and or

- average molecular weight Mn is within a range from 1000 to 50 000 g / mol, and the polydispersity index is within a range from 1, 4 2.0.

According to other particularly preferred embodiments the polymer of formula (I):

- not more than one of the groups selected from (R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8) a is Ci-Ce alkyl and all other represent a hydrogen atom ;

- not more than one of the groups selected from (R 9, R 10, R 11 and R 12) is a radical -C alkoxycarbonyl This and all other represent a hydrogen atom; and or

- R 13 represents a radical -CH2- or an oxygen atom.

The main chain of the polymer of formula (I) therefore comprises one, two or three repeat units:

- a first repeat unit repeated p1 + p2 times, - a second repeating unit, optional repeated n1 + n2 times; and

- a third repeating unit, optional repeated m times.

It is understood that the distribution of said patterns onto said main chain is statistical, and the polymer of formula (I) is thus a random polymer.

As shown above, F 1 and F 2 end groups are generally symmetrical with respect to the main chain, that is to say they substantially correspond with the exception of g1 and g2 indexes and d1 and d2.

By "heterocycle" means a hydrocarbon ring which may include an atom other than carbon in the chain of the ring, such as for example oxygen, sulfur or nitrogen.

By "terminal moiety" means a group located at one of two ends of the main polymer chain, which is constituted by one or more repeating units.

The polydispersity index (also referred to in English polydispersity index or PDI) is defined as the ratio Mw / Mn, that is to say the ratio of the weight average molecular weight to number average molecular weight of the polymer. In the present text, the two average molecular weights Mn and Mw are measured by steric exclusion chromatography (SEC or acronym of "Size Exclusion Chromatography" in English) which is also designated by the terms of gel permeation chromatography (or by the acronym corresponding GPC). The calibration used is usually a calibration PEG (polyethylene glycol) or PS (polystyrene), preferably PS.

If t = 0, then there is no R group in the groups F 1 and F 2 of the formula (I): (R'O) 3-tRtSi- becomes (R'O) 3 Si-.

If g2 = 0 or d2 = 0, then there is no radical - (CH) - in the groups F 1 and F 2 of the formula (I). In other words, the radical: - (CH2) g 2- or- (CH2) 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 hooks is zero, this means that no group within the brackets to which the index applies. Thus for example the group:

represents a single bond: ly:

Figure imgf000009_0001

represents a double bond.

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

They can form, after the presence of water crosslinking reaction and a catalyst, an adhesive joint resulting from the formation of siloxane bonds Si-O-Si bonds between the polymer chains.

Water implemented in the crosslinking reaction is the water from the environment and / or water introduced by at least one substrate, generally atmospheric moisture, for example corresponding to a relative humidity (called also humidity) usually within a range of 25 to 65%.

The formed adhesive joint exhibits high cohesion values ​​in particular greater than 2 MPa. Such coherency values ​​enable use of said polymer as an adhesive, for example as a seal on a conventional substrate (concrete, glass, marble), in the building field, or for bonding glass in the automobile industry and shipbuilding.

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

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

In a preferred embodiment of the polymer according to the invention, when m is non-zero and n1 and n2 each are 0 (corresponding to the presence in the polymer main chain of the 2 repeated only repeating units

respectively p1 + p2 times and m times), then the ratio:

m / (p1 + p2 + m)

is in the range of from 30 to 70% and, more preferably, is about 50%.

According to another alternative of this same preferred embodiment, when m is 0 and that the sum n1 + n2 is not zero (corresponding to the presence in the main chain of the polymer 2 alone repeated repeating units p1 + p2 times respectively and n1 + n2 times), then at least one of R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 is other than hydrogen, and the ratio:

(N1 + n2) / (p1 + p2 + n1 + n2)

is in the range of from 30 to 70% and, more preferably, is about 50%.

According to yet another alternative of said preferred embodiment, when m is not zero, that the sum n1 + n2 is not zero (corresponding to the presence in the polymer main chain of 3 repeating units), and each of R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 is a hydrogen atom, then the ratio:

m / (p1 + p2 + n1 + n2 + m)

is in the range of from 30 to 70% and, more preferably, is about 50%.

According to yet one more alternative of said preferred embodiment, when m is not zero, that the sum n1 + n2 is not zero (corresponding to the presence in the polymer main chain of 3 repeat units) and at least one of R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 is other than hydrogen, then the ratio:

(M + n1 + n2) / (p1 + p2 + n1 + n2 + m)

is in the range of from 30 to 70% and, more preferably, is about 50%.

According to alternative 4 of the preferred embodiment, the polymer of formula (I) is generally in the form of viscous liquid, generally having a Brookfield viscosity at 23 ° C of between 1 mPas and 500 Pa.s, preferably between 1 to 150 Pa.s and more preferably between 1 and 50 Pa.s. It is 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 non-crosslinked polymer according to the invention is solid at room temperature, it is generally thermoplastic (in an anhydrous medium), that is to say deformable and heat fusible (ie at a higher than the ambient temperature). It can therefore be used as hot melt and hot-applied adhesive on the substrate interface to be joined at their tangency surface. By solidification at room temperature, an adhesive joint interconnecting the substrates is immediately created, while giving the adhesive time advantageous properties of reduced outlet.

According to one embodiment of the polymer of formula (I) according to the invention, m is 0 é al, the polymer being of formula (II):

Figure imgf000011_0001

(he)

wherein x, y, n1, n2, p1, p2, F 1, F 2, R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R £ meanings given above.

More preferably, x is 1 and y is equal to 1 The formula (II) illustrates the case where the main chain of the polymer of formula (I) comprises only two repeating units, repeating n1 + n2 and p1 + respectively p2 times.

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

Figure imgf000012_0001
wherein m, p1, p2 F 1, F 2, R 9, R 10, R 11, R 12 and R 13 have the meanings given above.

Formula (III) illustrates the case where the main chain of the polymer of formula

(I) comprises only two repeating units, respectively repeated (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, wherein the polymer is of formula (IV):

Figure imgf000012_0002

(IV) wherein p1, p2, F 1, F 2 have the meanings given above.

The formulas (IV) illustrates the case where the main chain of the polymer of formula (I) comprises a single repeating pattern, repeated p1 + p2 once.

Regarding alkoxysilane end groups of the polymer according to the invention, when F1 is (R'O) 3-tRtSi- (CH 2) g i and F 2 is - (CH 2) di-SiR t (OR ') 3-t, then preferably g1 = 1 or d1 = 1, and, even more preferably: g1 = d1 = 1. In the latter case, F 1 and F 2 are each: -CH2-Si (OCH3) 3. When (if called "diester way"), F1

(R'O) 3-tRtSi-R "-OOC- (CH 2) G2- and F 2 is: - (CH 2) d2-COO-R" -SiRt (OR ') 3-t, then preferably g2 = 0 or d2 = 0, and, still more preferably: g2 = d2 = 0. in the latter case, particularly advantageously F 1 and F 2 are each: -COO- (CH2) 3-Si (OCH3) 3.

The invention also relates to a preparation process (P1) of a hydrocarbon polymer comprising two end groups alkoxysilanes of formula (I) according to the invention, said method comprising at least a polymerization reaction by ring-opening metathesis (also referred to as "Ring- Opening Metathesis Polymerization" or ROMP in English), in the presence:

(A) a metathesis catalyst;

(B) a chain transfer agent (also referred to hereinafter as CTA for "Chain Transfer Agent" in English) comprising two alkoxysilane groups, of formula (B):

'F 2

(B)

in which :

- F 1 and F 2 are as defined above;

- the link is a directed link from a geometrically side or the other with respect to the double bond (cis or trans);

(C) a compound of formula C) below:

Figure imgf000013_0001

wherein z is as defined above; and

(D) optionally a compound of formula (D):

Figure imgf000014_0001

wherein R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, x and y are as defined above; and

(E) optionally a compound of formula (E):

Figure imgf000014_0002

wherein R 9, R 10, R 11, R 12 and R 13 are as defined above;

said polymerization reaction being further implementation for a period ranging from 2-24 hours and at a temperature in a range of 20 to 60 ° C.

In the definition of the preparation process given above, it is understood that the indefinite article "a", as it relates to a reagent or catalyst used or the product formed, should s' interpreted to mean "at least one", that is to say "one or more".

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

The duration and temperature of the reaction generally depend on the conditions of implementation including the nature of the solvent used, and in particular the catalyst charge rate. The skilled person is able to adapt to the circumstances.

Thus, preferably, the duration of the polymerization reaction is from 2 to 10 hours. The implementation of the compound of formula (C) in the process (P1) according to the invention leads to the presence in the polymer chain of formula (I), the repeating pattern which is repeated p1 + p2 time to due to z + 1 mole of said pattern, for the implementation of one mole of the compound of formula (C). This pattern, said derivative of butadiene, answered two equivalent formulas:

Figure imgf000015_0001

or

Figure imgf000015_0002

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

Figure imgf000015_0003

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

Figure imgf000015_0004
Preferably, the molar amounts of CTA, the compound of formula (C), and optionally the compounds of formula (D) and / or (E) are implemented in the process (P1) are such that the ratio r which is the ratio of moles of said CTA:

- the number N (o 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 employed in the reaction, or

- the sum of N (o 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 within a range from 0.0010 to 1, 0.

Even more preferably, the ratio r defined above is in the range 0.0020 to 0.3. (A) A catalyst for metathesis:

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

Such a catalyst is usually a commercial product.

The metathesis catalyst is usually a transition metal catalyst including a catalyst comprising ruthenium usually in complex form (s) of ruthenium such as ruthenium carbene complex.

By Grubbs catalyst is generally defined according to the invention a Grubbs catalyst 1 st or 2 nd generation, but also any other Grubbs catalyst (such as ruthenium carbene) or Hoveyda-Grubbs accessible to the skilled person , such as for example the catalysts of Grubbs substituted disclosed in U.S. patent 5,849,851.

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

Figure imgf000016_0001
(G1) wherein Ph is phenyl, Cy is cyclohexyl, and the group P (Cy) 3 is tricyclohexylphosphine group.

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

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

Figure imgf000017_0001

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 246047-72-3 of number). This catalyst is also available from Aldrich. (B) CTA of the formula (B):

F 2

(B)

According to a first embodiment, the CTA is of 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 unsaturated mono-compounds H2C = CH- (CH2) p - SiR t (OR ') 3-t. According to this embodiment, preferably g1 = 1 or d1 = 1, and, even more preferably: g1 = d1 = 1.

According to an even more advantageous variant, t equals 0 and R 'is methyl. In the latter case, F 1 and F 2 are each: -CH2-Si (OCH3) 3 and the compound of formula (B1) becomes:

(CH 3 0) 3 SK

Si (OCH 3) 3

This compound, which is chilled, 4-bis (trimethoxysilyl) but-2-ene is referred to in the remainder of this text CTA 1.

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

Figure imgf000018_0001

(B2)

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

This compound can be synthesized by esterification of a CIC type of acid dichloride (= O) (CH 2) g 2CH = CH (CH 2) D2C (= O) CI (itself prepared starting from the commercial carboxylic diacid matching) with two moles of hydroxysilane.

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

According to an even more advantageous variant, t is 0 and R "is a n-propylene radical: - (CH2) 3-.

In the latter case, F 1 and F 2 are each -CO-O- (CH 2) 3 Si (OCH 3) 3 and the compound of formula (B2) becomes:

Figure imgf000018_0002

This compound, which is bis (propyltriméthoxysilyl) fumarate, is referred to in the remainder of this text CTA 2. According to a particularly preferred variant of the invention, the CTA of the formula (B) is selected from the group consisting of trans-1, 4-bis (trimethoxysilyl) but-2-ene (CTA1) and bis (propyltriméthoxysilyl) fumarate (CTA2).

(C) compound of formula (C:

Figure imgf000019_0001

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

Preferably, it is selected from the group consisting of:

- 1, 5-cyclooctadiene (hereinafter referred to res by COD) of the formula:

Figure imgf000019_0002

(Corresponding to z = 1)

- and the 1, 5,9-cyclododecatriene (hereinafter referred to as CDT) compound to 12 carbon atoms of formula

Figure imgf000019_0003

(Corresponding to z = 2)

These two compounds are commercially available from companies Evonik Degussa and Arkema France.

(D) compound of formula (D)

Figure imgf000020_0001

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

Preferably:

- R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 represent a hydrogen atom or an alkyl radical comprising from 1 to 14 carbon atoms, and more preferably still 1 at 8 ;

- the integers x and y are within a range from 0 to 2, the sum x + y being in the range of from 0 to 2.

According to a further preferred embodiment:

- x is equal to 1 and y is 1 and / or

- not more than one of the groups selected from (R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8) a is Ci-Ce alkyl and all other represent a hydrogen atom .

The compound of formula (D) is chosen in particular from:

- cycloheptene, cyclooctene, cyclononene, cyclodecene the cycloundécène and cyclododecene.

- 5-epoxy-cyclooctene, of formula:

Figure imgf000020_0002

(Available from Aldrich)

- 5-oxocyclooctène of the formula:

Figure imgf000020_0003
or from a 5-alkyl-cyclooctene, of formula:

Figure imgf000021_0001

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

The compounds corresponding to the last two structural formulas above may 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.

These compounds are especially preferred cyclooctene and 5-n-hexyl-cyclooctene.

(E) compound of formula (E:

Figure imgf000021_0002

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

Preferably:

- R 9, R 10, R 11 and R 12 represent a hydrogen atom or an alkyl radical or aikoxycarbonyle comprising 1 to 14 carbon atoms, and still LEMENT more preferably from 1 to 8;

- the radical R °, -NR ° included in the group which is one of the meanings of R 13 is a linear radical containing from 1 to 14 carbon atoms.

According to a further preferred embodiment:

- not more than one of the groups selected from (R 9, R 10, R 11 and R 12) is a radical -C aikoxycarbonyle This and all other represent a hydrogen atom; and or

- R 13 represents a radical -CH2- or an oxygen atom.

The compound of formula (E) is in particular selected from norbornene, of the following formula:

Figure imgf000022_0001

-l norbornadiene, of the following formula:

Figure imgf000022_0002

- the dic clopentadiène of the following formula:

Figure imgf000022_0003

- -oxanorbornène of the following formula:

Figure imgf000022_0004

- 7-oxanorbornadiène of the following formula:

Figure imgf000022_0005

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

Figure imgf000022_0006

- or, 5-norbornene-2-methylacetate, of the following formula:

Figure imgf000022_0007

The compound of formula (E) may also be selected from the following composéss:

Figure imgf000023_0001

wherein R is as defined previously for compound of formula (D).

The compound of formula (E) may also be selected from the group consisting of the addition products (adducts or English) from the Diels-Alder reaction using cyclopentadiene or furan as starting material, as well as compounds norbornene derivatives such as norbornenes connected as described in WO 2001/04173 (such as: isobornyl carboxylate norbornene, phenyl norbornene carboxylate, carboxylate ethylhexyl norbornene carboxylate phenoxyethyl norbornene and norbornene dicarboximide alkyl, the alkyl having the usually of 3 to 8 carbon atoms) and connected norbornenes such as described in WO 201 1/038057 (dicarboxylic anhydrides norbornene dicarboxylic anhydrides and optionally 7-oxanorbornène).

Among the various compounds of formula (E) mentioned, are particularly preferred norbornene, 7-oxanorbornène, 5-norbornene-2-carboxylate, of formula:

Figure imgf000023_0002

5-oxanorbornene-2-carboxylate, of formula

Figure imgf000024_0001

or dicyclopentadiene.

The step of ring-opening metathesis polymerisation (ROMP or for "Ring-Opening Metathesis Polymerization" in English) is carried out usually in the presence of at least one solvent, generally selected from the group consisting of solvents aqueous or organic typically used in polymerization reactions and which are inert under the conditions of 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 (e.g., Isopar®), methanol, ethanol, water or mixtures thereof. Even more preferably, the solvent is selected from the group consisting of benzene, toluene, xylene, methylene chloride, 1, 2- dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, hexane, heptane, methanol, ethanol or mixtures thereof. Even more preferably, the solvent is dichloromethane, 1, 2- dicholoroéthane, toluene, heptane, or a mixture of toluene and 1, 2- dichloroethane. The solubility of the polymer formed during the polymerization reaction depends generally and primarily the choice of solvent, the nature and proportion of comonomer and the number average molecular weight of the resulting polymer. It is also possible that the reaction be implemented without solvent.

The invention also relates to another process for preparing (P2) of a hydrocarbon polymer of formula (I) according to the invention, said method comprising:

(I) a step of forming one or more (co) cyclic oligobutadiène of formula (F):

Figure imgf000025_0001

(F)

in which :

- x, y, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 1 1, R 12 and R 13 have the meanings given above;

- the link is a directed link from a geometrically side or the other with respect to the double bond (cis or trans);

- a line linking the two groups -Ch - represents a single bond;

- p3 is a non-zero integer;

- n3 and m 'each are an integer number or zero;

- n3, p3 and m 'being further such that the 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 previously defined; then

(Ii) a step of polymerizing said (co) cyclic oligobutadiène of formula (F) by ring opening in the presence of a metathesis catalyst, a transfer agent (CTA) of formula (B) as defined above for a period ranging from 2-24 hours and at a temperature in a 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 a first preferred material on an industrial scale, particularly because of its availability and its properties in terms of industrial hygiene and safety, such volatility.

Step (i):

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

Figure imgf000026_0001

(Trans-1 pattern, 4) and (cis-1 pattern, 4)

Polymerization of 1, 3 - butadiene can also be made according to an addition-1, 2, resulting in a repeating unit in the polymer chain (designated pattern vinyl-1, 2) which has the formula:

Figure imgf000026_0002

(Vinyl-1 pattern 2)

Thus, polybutadiene generally comprises in its chain the repeat units 3 above, hereinafter referred to generically as "unit derived from butadiene". The molecular weight of the polybutadiene can range from 1000 to 250,000 g / mole.

Preferably, the polybutadiene chain implemented in step (i) comprises less than 5 mol% of vinyl-one repeating unit, 2, said percentage being based on the total moles of constituent units of the chain, and even more preferably less than 2%.

According to another variant, also preferably, the chain of polybutadiene implemented in step (i) comprises from 50 to 98 mol% of cis-1 units, and 4 to 48 mol% of trans-1 units, 4, said percentages being based on the total moles of constituent units of the chain. Such polybutadiene is often referred to as polybutadiene with high cis-1 pattern, 4 (in English "high cis polybutadiene") and is preferably in liquid form.

The molar percentages of vinyl-one repeating unit, 2, cis-1 units, 4 and trans-1 units, 4 defined above may be determined by 1 H NMR and 13 C

We can cite as an example, commercially available, the POLYVEST® 130 of Evonik company, which is a polybutadiene in which the percentage of cis-1 unit, 4 is about 77 mole%, the pattern of percentage trans- 1, 4 is about 22 mol%, and the percentage of vinyl-1 pattern 2 is about 1 mol%.

Heating polybutadiene in step (i) causes a depolymerization reaction of the latter and intramolecular cyclization reactions, which generally lead to the formation of several (co) polybutadiene ring of formula (F), the formation and structure can be characterized by size exclusion chromatography techniques (or SEC). The distribution of units derived from butadiene (p3 repeated times), cyclooctene (repeated n3 times) and norbornene (repeated m 'times) in a (co) oligobutadiènecyclique of formula (F) is generally random. A domain average molecular weight of 162 to 2000 g / mol is preferred for the (co) oligobutadiènes ring of formula (F).

A preferred temperature range adapted to said heating is from 30 ° C to

60 ° C.

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

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

The duration of the heating step (i) is adapted for obtaining a yield close to 100% relative to the molar amount of polybutadiene implementation, as well as other possible reagents; a period of from 1 hour to 8 hours, preferably 1 to 3 hours is generally suitable.

Step (ii) The (co) oligobutadiènes ring of formula (F) obtained at the end of step (i) are polymerised in accordance with step (ii), ring-opening in the presence of an agent transfer (CTA) of formula (B) as defined above.

The molar amount of CTA implemented 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 the ratio of moles of said CTA:

- the number N (BDJ moles of units derived from butadiene equivalent to the number of moles of polybutadiene if said polybutadiene is the only reagent used in step (i), or

- the sum of N (BDJ and the number of moles of the compounds of formula (D) and / or (E), if the compounds of formula (D) and / or (E) are implemented in step (i)

is within a range from 0.0010 to 1, 0.

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

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

A solvent may be used in said step, and in this case it is chosen from the solvents described above for the P1 process.

The invention further relates to an adhesive composition comprising a polymer according to the invention and 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), (II), (III) or (IV).

The usable crosslinking catalyst in the composition according to the invention may be any catalyst known to those skilled in the art for the silanol condensation. It Examples of such catalysts:

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

- organic tin compounds 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).

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

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

According to a particularly preferred embodiment, the adhesive composition of the invention is packaged in a sealed package to the air prior to its end use, so as to protect it from ambient moisture. Such a package may advantageously be formed of a multilayer sheet which typically comprises at least an aluminum layer and / or at least one layer of high density polyethylene. For example, the package is formed of a layer of polyethylene 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 bonding, comprising:

- coating of an adhesive composition as defined above, in liquid form, preferably in the form of a layer thickness within a range of 0.3 to 5 mm, preferably 1 to 3 mm, on at least one of the two surfaces belonging respectively 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 adhesive composition (naturally) liquid or the molten adhesive composition. The skilled person is able to proceed so that the adhesive composition used is in liquid form at the time of its use.

Naturally, coating and contacting must be performed in a suitable time interval, as is well known in the art, that is to say before the adhesive layer applied to the substrate loses its ability to fix by gluing the substrate to another substrate. In general, the crosslinking of the polymer of the adhesive composition in the presence of the catalyst and water from the environment and / or of the water supplied by at least one of the substrates, begins to occur during the coating, and then continues to occur during the contacting step of the two substrates. In practice, the water usually comes from the relative humidity of the air.

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

The following examples are given purely to illustrate the invention and should not be construed to limit its scope.

Examples 1 to 9 describe the preparation of polymers comprising two trimethoxysilyl end groups, by ring-opening metathesis polymerisation.

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

Is used 1, 5-cyclooctadiene (hereinafter referred to as COD) and commercially available as a chain transfer agent CTA 1: (CH 3 0) 3 Si

^, ^, "Si (OCH 3) 3

1, 5-cyclooctadiene (10.8 mmol) and dry CH2Cl2 (5 ml) were introduced into a flask of 20 ml in which was also placed a magnetic stirring bar coated with Teflon ®. The flask and contents are then placed under argon. The molar amount of unit derived from butadiene equivalent to the amount of COD introduced is 21, 6 mmol.

CTA compound 1 (0.27 mmol) is then added with stirring to the flask by syringe. The ratio r of the reactants, as defined above, is equal to 21 divided by 0.27 mmol, 6 mmol or 0.0125.

The flask is then immersed in an oil bath at 40 ° C and then one proceeds immediately to the addition, via cannula, the above-defined catalyst G2 (5.4 μιτιοΙ) dissolved in CH2Cl2 (2 ml ).

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

After 8 hours from the addition of the catalyst, the product in the flask is extracted after evaporation of the solvent in vacuo. The product is then recovered in the form of colorless solid powder after precipitation in methanol, filtration and drying at 20 ° C under vacuum with a yield higher than 90%.

NMR analysis 1 H / 13 C of the polymer obtained gives the following values:

1H NMR (CDCl, 500 MHz, 298 K): δ (ppm) repeating unit 2.10 (4H * n), 5.43 (2H * n), end group = 1, 78 (4H, m, = CH-CH 2 - Si-), 3.57 (18H, s, -S1-O-CH3), 13 C NMR (CDCl, 100 MHz, 298 K): δ (ppm) repeating unit 27,41, 32,72, 131, 39, group terminal = 14.03 (= CH-CH 2 -Si), 54.39 (-S1-O-CH3), 130.45 (CH = CH-CH 2 -Si), 135.16 (-CH = CH-CH 2 -Si-)

These values ​​confirm the structure below:

Figure imgf000031_0001

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

The average molecular weight Mn, measured by NMR is 4600 g / mol. The index of polymoléculahté equal to the ratio Mw / Mn (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 CTA 1, according to the method P1:

Example 1 is repeated by replacing the COD by 1, 5,9-cyclododecatriene (called CDT) which is commercially available, eg from Sigma Aldrich.

The molar amount of unit derived from butadiene equivalent to the amount of CDT introduced is 32,4 mmol. The ratio r of the reactants, as defined above, is equal to 0.27 mmol divided by 32.4 mmol, 0.008.

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

Figure imgf000032_0001

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

The average molecular weight Mn and polydispersity index are, respectively, 6,800 g / mol and 1, 80.

Example 3: Polymerization of 1, 5,9-cyclododecatriene in the presence of CTA 2 as process P1:

We repeated Example 2, replacing, as chain transfer agent, CTA CTA 1 by 2:

Figure imgf000033_0001

We also obtain a polymer in the form of colorless solid powder which NMR analysis 1 H / 13 C gives the following values:

1 H NMR (CDCl, 500 MHz, 298 K): δ (ppm) repeating unit 2.10 (4H * n), 5.43 (2H * n), end group = 0.64 (4H, m, -CH2-CH2-S1- ), 1 .61 (4H, m, -CO-CH2-CH2-CH2-S1-), 4.35 (4H, m, -O-CH2-CH2-CH2-S1-), 3.57 (18H, s, -S1-O-CH3), 5.73 (1H, m, -CH = CH-CO-), 5.77 (1H, m, -CH = CH-CO-).

13 C NMR (CDCl, 100 MHz, 298 K): δ (ppm) repeating 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-S1-), 1 19.89 (CH = CH CO-) , 135.16 (- CH = CH-CO-), 167.07 (-O-CO-).

These values ​​confirm the structure below:

Figure imgf000033_0002

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

The average molecular weight Mn and polydispersity index are respectively, 6,900 g / mol and 1, 80.

Example 4: Polymerization of CDT and norbornene (cycloolefin of formula (E)) in the presence of CTA 1, according to the method P1:

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

Figure imgf000033_0003

and available from Sigma Aldrich. The molar amount of unit derived from butadiene equivalent to the amount of CDT introduced was 16.2 mmol. The ratio r of the reactants, as defined above, is equal to 0.27 mmol divided by 16.2 + 5.4 mmol, or 0.0125.

After 8 h after addition of the catalyst, the product in the flask is extracted after evaporation of the solvent in vacuo. The product is then recovered as a liquid at room temperature, after precipitation in methanol, filtration and drying at 20 ° C under vacuum with a 90% yield.

NMR analysis of the polymer obtained gives the following values:

1 H NMR (CDCl, 500 MHz, 298 K): δ (ppm) frans: 1 .08 (2H * n), 1 .39 (4H * n), 2.07 (4H * n), 2.47 (2H * No 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 cis * n), end group = 1, 78 (4H, m, = CH-CH 2 - Si-), 3.57 (18H, s, -S \ -0-CH 3),

13 C NMR (CDCl, 100 MHz, 298 K): δ (ppm) 27.42, 33.12, 42.10, 43.43, 130.35, 133.12, end group = 14.03 (= CH-CH 2 -Si-), 54.39 (S \ -0-CH 3), 130.45 (CH = CH-CH 2 -Si), 135.16 (-CH = CH-CH 2 -Si-)

These values ​​confirm the structure below:

Figure imgf000034_0001

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

The average molecular weight Mn and polydispersity index are, respectively, 5,400 g / mol and 1, 60.

Example 5: Polymerization of CDT and 5-norbornene-2-carboxylate (cycloolefin of formula (E)) in the presence of CTA 1, according to the method P1:

Repeating Example 4 by replacing the norbornene with 5-norbornene-2-carboxylate, of formula:

Figure imgf000035_0001

and available from Sigma Aldrich.

Is also obtained a liquid copolymer at ambient temperature, of which the NMR analysis gave the following values:

1 H NMR (CDCl, 500 MHz, 298 K): δ (ppm) repeating unit 1 .08-1, 26 (1 H * n), 1, 56-1, 99 (3H * n), 2.07 (4H * n), 2.44-3,02 (3H * n), 5.13-5,29 (4H * n), end group = 1, 78 (4H, m, = CH-CH 2 -Si), 3.57 (18H, s, -S \ -0-CH 3),

13 C NMR (CDCl, 100 MHz, 298 K): δ (ppm) repeating unit: 27,42, 33,12, 36,17- 42,95, 130.35, 133.12, end group = 14.03 ( = CH-CH 2 -Si), 54.39 (CH 3 -Si-O-), 130.45 (CH = CH-CH 2 -Si), 135.16 (-CH = CH-CH 2 - Yes-)

These values ​​confirm the structure:

Figure imgf000035_0002

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

The average molecular weight Mn and polydispersity index are, respectively, 6,600 g / mol and 1, 80.

Example 6: Polymerization of CDT and 5-oxanorbornene-2-carboxylate (cycloolefin of formula (E)) in the presence of CTA 1, according to the method P1:

Repeating Example 4 by replacing the norbornene with 5-oxanorbornene-2-carboxylate, of formula:

Figure imgf000035_0003

and available from the company Boc Sciences. Is also obtained a liquid copolymer at ambient temperature, of which the NMR analysis gave the following values:

These values ​​confirm the structure:

Figure imgf000036_0001

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

The average molecular weight Mn and polydispersity index are, respectively, 6,600 g / mol and 1, 70.

Example 7: polymerization of CDT and dicyclopentadiene (cycloolefin of formula (E)) in the presence of CTA 1, according to the method P1:

Example 4 was repeated by replacing the norbornene dicyclopentadiene of the formula:

Figure imgf000036_0002

and available from Sigma Aldrich.

Is also obtained a liquid copolymer at ambient temperature, of which the NMR analysis gave the following values:

1 H NMR (CDCl, 500 MHz, 298 K): δ (ppm) repeating unit 1, 24 (1 H * n), 1 .59 (1 H * n), 2.07 (4H n *), 2 , 26 (n * 2H), 2.62 (1 H * n), 2.85 (2H * n), 3.24 (1 H * n), 5.36-5,68 (4H * n), end group = 1, 78 (4H, m, = CH-CH 2 -Si), 3.57 (18H, s, CH 3 -Si-O-).13 C NMR (CDCl, 100 MHz, 298 K): δ (ppm) repeating unit 27.42, 33.10, 35.12, 38.00, 42.34, 45.98, 47.06, 55.40, 130.48, group terminal = 14.03 (= CH-CH 2 -S \ -), 54.39 (-Si-O-CH 3), 130.45 (CH = CH-CH 2 -Si), 135.16 ( -CH = CH-CH 2 -Si-).

These values ​​confirm the structure:

Figure imgf000037_0001

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

The average molecular weight Mn and polydispersity index are, respectively, 6,200 g / mol and 2.00.

Example 8: polymerization of CDT and 5-n-hexyl-cyclooctene (cycloolefin of formula (D)) in the presence of CTA 1, according to the method P1:

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

Figure imgf000037_0002

2 (83

Γΐ, Ο No. 12 pm

Figure imgf000037_0003

S (70%) ÷ 7S%) S (87)

Raw materials (including 5,6-époxycyclooctène), reagents and solvents used in the syntheses are commercial products of 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 the reference Kobayashi et al J. Am. Chem. Soc. 201 1, 133, pp 5794-5797).

Repeating Example 4 by replacing the norbornene with 5-n-hexyl-cyclooctene.

Is also obtained a liquid copolymer at ambient temperature, of which the NMR analysis gave the following values: 1 H NMR (CDCl, 500 MHz, 298 K): δ (ppm) repeating unit 0.83 (3H * n), 1. 27 (16H * n), 2.07 (4H * n), 2.17 (5H * n), 5.37 (2H * n), end group = 1, 78 (4H, m, = CH-CH 2 -Si -), 3.57 (18H, s, -Si-O-CH 3). 13 C NMR (CDCl, 100 MHz, 298 K): δ (ppm) repeating unit 14.1, 22.7, 27.4, 29.6, 31 .8, 32.37, 33.10, 33.8, 40.65, 130.48, end group = 14.03 (= CH-CH 2 -Si), 54.39 (S \ -0-CH 3), 130.45 (CH = CH-CH 2 -Si), 135.16 (-CH = CH-CH 2 -Si -).

These values ​​confirm the structure:

Figure imgf000038_0001

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

The average molecular weight Mn and polydispersity index are, respectively, 7,400 g / mol and 1, 80.

Example 9: polymerization of CDT, cyclooctene (cycloolefin of formula (D)) and norbornene (cycloolefin of formula (E)) in the presence of CTA 1, according to the method P1:

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

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

After 8 h after addition of the catalyst, the product in the flask is extracted after evaporation of the solvent in vacuo. The product is then recovered as a liquid at room temperature, after precipitation in methanol, filtration and drying at 20 ° C under vacuum with a 90% yield.

NMR analysis of the polymer obtained gives the following values:

1 H NMR (CDCl, 500 MHz, 298 K): δ (ppm) repeating unit trans: 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 / 's), 5.24-5,44 (6H * n cis) = terminal group 1, 78 (4H, m, = CH-CH 2 -Si), 3.57 (18H, s, -Si-O-CH 3). 13 C NMR (CDCl, 100 MHz, 298 K): δ (ppm) repeating unit 27,42, 28,56, 32, 51, 33.12, 42.10, 43.43, 130.35, 133.12, group terminal = 14.03 (= CH-CH 2 -Si), 54.39 (-S1-O-CH3), 130.45 (CH = CH-CH 2 -Si), 135.16 (-CH = CH-CH 2 - Si-).

These values ​​confirm the structure:

Figure imgf000039_0001

The average molecular weight Mn and polydispersity index are, respectively, 5,200 g / mol and 1, 90.

Example 10: Heating polybutadiene, followed by ring-opening polymerization in the presence of CTA 1, according to the method P2:

Step (i):

commercial polybutadiene is used referred POLYVEST® 130 of molar mass 4600 g / mol.

This polybutadiene (0.38 mmol) and dry CH2Cl2 (9 ml) were introduced into a flask of 20 ml in which was also placed a magnetic stirring bar coated with Teflon. The flask and contents are then placed under argon.

The molar amount of unit derived from butadiene equivalent to the amount of polybutadiene is fed 32.4 mmol.

Then one proceeds to the addition, via cannula, the above-defined catalyst G2 (9.6 μιτιοΙ) dissolved in CH2Cl2 (2 mL).

This mixture was heated in an oil bath for 3 hours at 40 ° C under stirring until disappearance of POLYVEST® 130 and forming a mixture of compounds of formula (F) evidenced by size exclusion chromatography.

Step (ii):

As chain transfer agent is used CTA 1

CTA compound 1 (0.27 mmol) was added via syringe and stirring the mixture in the flask from step (i) and is maintained by heating the temperature of 40 ° C. The ratio r as defined above, is: 0.27 / 32.4 or 0.008

After 8 hours from the introduction of CTA 1, the product in the flask is extracted after evaporation of the solvent in vacuo. This product is then recovered in the form of colorless solid powder after precipitation in methanol, filtration and drying at 20 ° C under vacuum with a 90% yield.

1 H NMR (CDCl, 500 MHz, 298 K): δ (ppm) repeating unit 2.10 (4H * n), 5.43 (2H * n), end group = 1, 78 (4H, m, = CH-CH 2 -Si-), 3.57 (18H, s, -S \ -0-CH 3), 13 C NMR (CDCl, 100 MHz, 298 K): δ (ppm) repeating unit 27,41, 32,72, 131 , 39, end group = 14.03 (= CH-CH 2 -Si), 54.39 (-S1-O-CH3), 130.45 (CH = CH-CH 2 -Si), 135.16 (-CH = CH-CH 2 -Si-)

This product is identical to that of Example 2.

Example 11: Heating polybutadiene and norbornene, followed by a ring-opening polymerization in the presence of CTA 1, according to the method P2:

Repeating Example 10 by replacing in step (i) 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 reactants, as defined above, is equal to 0.27 mmol divided by 16.2 + 5.4 mmol, or 0.0125.

After 8 h after the addition of CTA1, the product in the flask is extracted after evaporation of the solvent in vacuo. The product is then recovered as a liquid at room temperature, after precipitation in methanol, filtration and drying at 20 ° C under vacuum with a 90% yield.

NMR analysis of the polymer obtained gives the following values:

1 H NMR (CDCl, 500 MHz, 298 K): δ (ppm) frans: 1 .08 (2H * n), 1 .39 (4H * n), 2.07 (4H * n), 2.47 (2H * No 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 cis * n), end group = 1, 78 (4H, m, = CH-CH 2 - Si-), 3.57 (18H, s, -S1-O-CH 3),

1 3 C NMR (CDCl, 100 MHz, 298 K): δ (ppm) 27.42, 33.12, 42.10, 43.43, 130.35, 133.12, end group = 14.03 (= CH- CH 2 -Si), 54.39 (-S1-O-CH3), 130.45 (CH = CH-CH 2 -Si), 135.16 (-CH = CH-CH 2 -Si-) This product is identical to that of example 4.

Example 12 Preparation of an adhesive composition comprising the polymer of Example 1

Is prepared by simply mixing an adhesive composition consisting of 0.2% by weight of a curing catalyst consisting of dioctyl tin dineodecanoate (product KAT® TIB 223 of the company TIB Chemicals) and 99.8% polymer according to the invention obtained in example 1.

The mixture thus obtained is left under reduced stirring (20 mbar or

2000 Pa) for 15 minutes and then conditioned in an aluminum cartridge.

Measuring the strength and elongation at break by tensile test is performed according to the protocol described below.

The measurement principle is:

- stretching in a tensile testing machine, the movable jaw moves at a constant speed 100 mm / min, a standard specimen composed of the crosslinked adhesive composition, then

- recording, when the rupture of the test piece occurs, the applied tensile stress (in MPa) and the elongation of the specimen (expressed in%).

The standard test is dumbbell-shaped, as illustrated in the international standard ISO 37. The narrow part of the dumbbell used has length 20 mm to 4 mm width and thickness to 500 μιτι.

To prepare the dumbbell, heated to 100 ° C the composition packaged as described above, then extruded on a A4 sheet of silicone paper the amount necessary to form thereon a film having a thickness of 300 μιτι which is left during 7 days at 23 ° C and 50% relative humidity for curing. The barbell is then obtained by simply cutting into the crosslinked film.

Is thus measured for said adhesive composition a stress at break of greater than 0.7 MPa and an elongation at break greater than 200%. Said adhesive composition is also subjected to bonding tests of two wooden slats (each of size 20 mm x 20 mm x 2 mm) to yield, after crosslinking of seven days at 23 ° C and forming an adhesive joint 1 mm thick on a surface of 12.5 mm X 20 mm at a stress at break of greater than 2 MPa in adhesive failure.

Claims

1. A polymer comprising two hydrocarbon alkoxysilanes end groups, said hydrocarbon polymer having the formula (I):
Figure imgf000043_0001
(I)
in which :
- the link is a directed link geometrically to one side or the other with respect to the double bond,
- F 1 is: (R'0) 3-tRtSi- (CH 2) g i and F 2 is: - (CH 2) di-SIRT (OR ') 3 -t;
or Fi is: (R'O) 3-tRtSi-R "-OOC- (CH 2) G2- and F 2 is:
- (CH 2) d2-COO-R "t -SiR (OR ') 3 -t, and:
- 1 is an integer equal to 0, 1 or 2;
- g1 and d1, which are identical or different, represent an integer equal to 1, 2 or 3;
- g2 and d2, which are identical or different, represent an integer 0, 1, 2 or 3;
- R and R ', 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; - R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8, 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 optionally being interrupted by at least one oxygen atom or a sulfur atom; in addition:
- at least one of R 1 to R 8 can form, together with at least one other of R 1 to R 8 and with one or more carbon atoms to which said groups are attached, a ring or a saturated or unsaturated hydrocarbon-based heterocycle optionally substituted, and comprising from 3 to 10 ring members; and
- at least one of the pairs (R 1, R 2) (R 3, R 4) (R 5, R 6) (R 7, R 8) may form, with the carbon atom to which said pair is connected, a carbonyl group C = O or a group of 2 carbon atoms connected by a double bond C = C, whose carbon atom other door 2 substituents selected from a hydrogen atom or a Ci-C 4 alkyl;
- x and y are integers, the same or different, within a range from 0 to 6, the sum x + y being in the range of 0 to 6; - R 9, R 10, R 11 and R 12, identical or different, represent:
- a hydrogen or halogen atom; or
- a radical comprising from 1 to 22 carbon atoms and selected from alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkylcarbonyloxyalkyl, the hydrocarbon chain of said radical optionally being interrupted by at least one oxygen atom or a sulfur atom ; in addition:
- at least one of R 9 to R 12 may form, with at least one other of R 9 to R 12 and with one or more carbon atoms to which said groups are attached, a ring or a saturated or unsaturated hydrocarbon-based heterocycle optionally substituted, and comprising from 3 to 10 ring members; and
- at least one of the pairs (R 9, R 10) (R 11, R 12) may form with the carbon atom to which said pair is connected to a group of 2 carbon atoms connected by a double bond C = C , the other carbon atom has two substituents selected from a hydrogen atom or a Ci-C 4 alkyl; and
- the carbon atom bearing one of the pair of groups (R 9, R 10) can be connected to the carbon atom of one of the pair of groups (R 11, R 12) a double bond, provided that, in accordance with the rules of valence, one group of each of these two pairs is then present;
- R 13 represents:
- an atom of oxygen or sulfur, or
- a divalent radical --CH -, -C (= 0) - or -NR o - wherein R ° is an alkyl or alkenyl radical comprising from 1 to 22 carbon atoms;
- n1 and n2, equal or different, are each an integer number or zero;
- m is an integer greater than or equal to 0;
- p1 and p2, which are identical or different, are each an integer or zero, the 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 average molecular mass Mn of the polymer of formula (I) is within a range from 400 to 100 000 g / mol and its polydispersity index is understood in a range from 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;
- R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 represent a hydrogen atom or an alkyl radical comprising from 1 to 14 carbon atoms;
- the integers x and y are within a range from 0 to 2, the sum x + y being in the range of from 0 to 2;
- R 9, R 10, R 1 1 and R 12 represent a hydrogen atom or a radical in which the hydrocarbon portion contains from 1 to 14 carbon atoms;
- the radical R ° is a linear radical containing from 1 to 14 carbon atoms;
- z is an integer equal to 1 or 2.
3. hydrocarbon polymer according to claim 1 or 2, characterized in that:
- when m is non-zero and n1 and n2 are each 0, then the ratio m / (p1 + p2 + m) is in the range of 30 to 70%; or
- when m is equal to 0 and that the sum n1 + n2 is not zero, then at least one of R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 is other that 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 each of R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 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 not zero and at least one of R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 is other that 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 m is equal to 0, wherein the polymer is of formula (II):
Figure imgf000046_0001
(he)
5. hydrocarbon polymer according to one of claims 1 to 3, wherein n1 and n2 are each 0, wherein the polymer is of formula (III):
Figure imgf000047_0001
6. hydrocarbon polymer according to one of claims 1 to 3, characterized in that n1, n2 and m are each equal to 0, wherein the polymer is of formula (IV):
Figure imgf000047_0002
(IV)
7. hydrocarbon polymer according to one of claims 1 to 6, characterized in that when F1 is (R'O) 3-tRtSi- (Ch jg-i and F2 is
- (CH 2) di-SiR t (OR ') 3-t, then g1 = d1 = 1.
8. hydrocarbon polymer according to one of claims 1 to 6, characterized in that when F1 is (R'O) 3-tRtSi-R "-OOC- (CH 2) G2- and F 2 is: - (CH 2 ) d2-COO-R "-SiRt (OR ') 3 -TJ then g2 = d2 = 0.
9. A process for preparing a hydrocarbon polymer as defined in one of claims 1 to 8, comprising at least a polymerization reaction by ring-opening metathesis, in the presence:
(A) a metathesis catalyst;
(B) a chain transfer agent (also referred to hereinafter as TAC) comprising two groupem nts alkoxysilane of the formula (B):
Figure imgf000047_0003
in which: - the link is a directed link geometrically to one side or the other with respect to the double bond;
(C) a compound of formula C) below:
Figure imgf000048_0001
d) optionally a compound of formula (D):
Figure imgf000048_0002
said polymerization reaction being further implementation for a period ranging from 2-24 hours and at a temperature in a range of 20 to 60 ° C.
10. Preparation process according to claim 9, characterized in that the molar amounts of CTA, the compound of formula (C), and optionally the compounds of formula (D) and / or (E) which are used are such that the ratio r which is the ratio of moles of said CTA:
- the number N (o 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 employed in the reaction, or - the sum N (o 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 within a range from 0.0010 to 1, 0.
January 1. A process for preparing a hydrocarbon polymer of formula (I) as defined in any of claims 1 to 8, said method comprising:
(I) a step of forming one or more (co) cyclic oligobutadiène of formula (F):
Figure imgf000049_0001
(F)
in which :
- the link is a directed link from a geometrically side or the other with respect to the double bond (cis or trans);
- a line linking the two -CH2- groups represents a single bond;
- p3 is a non-zero integer;
- n3 and m 'each are an integer number or zero;
- n3, p3 and m 'being further such that the 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 9 and,
- optionally, a compound of formula (E) as defined in claim 9; then (ii) a step of polymerizing said (co) cyclic oligobutadiène of formula (F) by ring opening in the presence of a metathesis catalyst, a transfer agent (CTA) of formula (B) as defined in claim 9, for a period ranging from 2-24 hours and at a temperature in a range of 20 to 60 ° C.
12. Preparation process according to claim 1 1, characterized in that the polybutadiene chain implemented in step (i) comprises less than 5 mol% of vinyl-one repeating unit, 2, said percentage being on based on total number of moles of constituent units of the chain.
13. A method of preparation according to one of claims 1 1 or 12, characterized in that the polybutadiene chain implemented in step (i) comprises from 50 to 98 mol% of cis-1 units, 4 and most 48 mol% of trans-1 units, 4, said percentages being based on the total moles of constituent units of the chain.
14. A method of preparation according to one of claims 1 1 to 13, characterized in that the molar amount of CTA implementation 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 the ratio of moles of said CTA:
- the number N (BDJ moles of units derived from butadiene equivalent to the number of moles of polybutadiene if said polybutadiene is the only reagent used in step (i), or
- the sum of N (BDJ and the number of moles of the compounds of formula (D) and / or (E), if the compounds of formula (D) and / or (E) are implemented in step (i)
is within a range from 0.0010 to 1, 0.
15. An adhesive composition comprising a polymer as defined in one of claims 1 to 8 and from 0.01 to 3% by weight of a catalyst
crosslinking.
16. A method of assembling two substrates by bonding, comprising:
- coating of an adhesive composition as defined in claim 15 in liquid form on at least one of the two surfaces belonging respectively to the two substrates to be assembled and which are intended to be brought into contact with each other in a tangent surface; then
- the effective contacting of the two substrates according to their tangency surface.
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