EP3630708A1 - Liquid hydrocarbon copolymers comprising two alkoxysilane end groups, and production method thereof - Google Patents

Abstract

1) Hydrocarbon copolymer P comprising 2 alkoxysilane end groups F¹ et F² of formulae: - F¹ : (R'O)_3-tR_tSi-R"-NH-C(O)O-(CH₂)g₁- and F2 : -(CH₂)_d1—OC(O)-NH-R"-SiR_tOR')_3-t; or - F¹ : (R'O)_3-tR_tSi-R"-NR'''-C(O)-NH-(CH₂)_g1- and F² : -(CH₂)_d1-NH-C(O)-NR'''-R" -SiR_t(OR')_3-t; or - F1 : (R'O)_3-tR_tSi-R"-NR'''-C(O)-(CH₂)_g2 - and F² : -(CH₂)_d2C(O)-NR'"-R"-SiR_t(OR')_3-t; wherein t is 0, 1 or 2; g1 and d1 are 1, 2 or 3; g2 and d2 are 0, 1, 2 or 3; R and R' represent a C₁-C₄ alkyl; R" is a C₁-C₄ alkylene radical; R'" is in particular a hydrogen; the main chain comprising motifs (I) and (II) in which R⁰ is in particular the methyl radical; and the number average molecular mass Mn thereof being between 400 and 100,000 g/mol. 2) Method for producing said copolymer, comprising: (i) a step of heating a statistical bipolymer A selected from a poly(butadiene-isoprene), a poly(butadiene-myrcene) and a poly(butadiene-farnesene); and subsequently (ii) a step of heating the formed product, in the presence of a chain transfer agent of formula (C). 3) Adhesive composition comprising said copolymer and between 0.01 and 3 wt-% crosslinking catalyst.

Description

 Liquid hydrocarbon copolymers with two terminal groups

 alkoxysilanes and method of preparation

The present invention relates to hydrocarbon copolymers comprising two alkoxysilane end groups which are liquid at room temperature. The invention also relates to the preparation and use of said copolymers.

 The silane-modified polymers (MS or MS Polymers for "Modified Silane Polymers") are liquid hydrocarbon polymers having 2 alkoxysilane end groups which 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, such as, for example, tackifying resins, one or more additives with a reinforcing effect, such as a mineral filler, or one or more additives. aiming to improve the setting time (that is to say the time after which the crosslinking can be considered as completed) or other characteristics such as rheology or mechanical performance (elongation, module ...).

International application WO2016 / 1 16680 of Bostik describes hydrocarbon polymers comprising two terminal alkoxysilane groups which are obtained by a metathesis ring opening polymerization reaction, which uses, in addition to a catalyst and a transfer agent, a cycloolefin, and in particular a cyclooctene. The polymers obtained are either solid or liquid at room temperature.

 When solid, they are generally thermoplastic (that is, deformable and heat fusible). They can therefore be used as hot-melt adhesive and hot-applied on the interface of substrates to be joined at their tangency surface.

 However, it is more convenient for the adhesive industry, to have compositions that can be applied at room temperature by the end user and which can also be manufactured industrially, also at room temperature, by simply mixing the silylated polymer and additional constituents mentioned above.

 It is therefore particularly advantageous to have, for this purpose, hydrocarbon polymers with alkoxysilane end groups which are themselves liquid at room temperature.

 However, the obtaining, in WO2016 / 1 16680, liquid hydrocarbon polymers, particularly low viscosity at room temperature, generally requires the implementation of cyclooctene or substituted derivatives of cyclooctene. However, these products correspond to raw materials that are not accessible industrially or that are difficult to achieve.

 In addition, the process for the preparation of the hydrocarbon polymers that are the subject of WO2016 / 1 16680 is highly exothermic, which greatly complicates the conduct of a manufacturing process for said polymers at the industrial level.

 The object of the present invention is to propose novel polymers with two alkoxysilane end groups which remedy these disadvantages.

 Another object of the present invention is to provide liquid polymers at room temperature which can lead, after crosslinking, to the formation of an adhesive seal having improved mechanical properties.

Another object of the present invention is to provide polymers with liquid alkoxysilane terminations, in particular of lower temperature viscosity. ambient, which can also be manufactured by a process which uses industrially widely available raw materials.

 Another object of the present invention is to provide such polymers, which can, in addition, be manufactured industrially by a process whose exotherm is easier to control.

 It has now been found that these goals can be achieved, in whole or in part, by means of the hydrocarbon polymer described hereinafter.

Thus, the present invention relates to a hydrocarbon-based copolymer P comprising 2 alkoxysilane end groups F ¹ and F ² connected respectively to each of the two ends of the main chain, having the formulas:

F ¹ : (R'O) 3-tRtSi-R "-NH-C (O) O- (CH ₂ ) g- and F ² : - (CH ₂ ) di-OC (O) -NH-R" -SiR _t (OR ') _3- t; or

- F ¹ : (RO) 3-tRtSi-R "-NR ^m -C (O) -NH- (CH ₂ ) g- and F ² : - (CH 2) di-NH-C (O) -NR ^m - R "-SiRt (OR ') _3- t; or

- F ¹ : (RO) 3-tRtSi-R "-NR ^m -C (O) - (CH ₂ ) g ² - and F ² : - (CH 2) d C (O) -NR ^, " -R "- SiRt (OR ') _{3 -} t;

 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;

 R '"represents a hydrogen atom, a phenyl radical, a branched or cyclic linear alkyl radical comprising from 1 to 6 carbon atoms, or a succinate radical of formula:

R "" - O (O) C-CH ₂ --CH-C (O) O-R "" wherein R "" is a C1-C6 alkyl radical;

characterized in that the main chain of the copolymer P comprises: a unit (I) of formula (I) repeated p times, p being an integer different from 0:

 a unit (II) of formula (II repeated n times, n being an integer different from 0

 in which R ° represents the methyl radical or one of the 3 radicals of following formula:

 and, optionally, a unit (III) of formula (III) repeated m times, m being an integer greater than or equal to 0:

 in which :

- R ¹ , R ² , R ³ and R ⁴ , 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 and alkylcarbonyloxyalkyl, the hydrocarbon chain of said radical possibly being interrupted by at least one oxygen atom or one sulfur atom; ; in addition: at least one of the groups R ¹ to R ⁴ can form, together with at least one other group R ¹ to R ⁴ and with the carbon atom or atoms to which the said groups are connected, a saturated or unsaturated hydrocarbon ring or heterocycle, optionally substituted, and comprising from 3 to 10 members; and

at least one of the pairs (R ¹ , R ² ) and (R ³ , R ⁴ ) can form, with the carbon atom to which said pair is linked, 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 carrying one of the groups of the pair (R ¹ , R ² ) can be connected to the carbon atom carrying one of the groups of the pair (R ³ , R ⁴ ) by a double bond, it being understood that, according to the valence rules, only one of the groups of each of these 2 pairs is then present;

R ⁵ represents:

 an oxygen or sulfur atom, or

a divalent radical -Ch -, -C (= O) - or -NR ⁶ - in which R ⁶ is an alkyl or alkenyl radical comprising from 1 to 22 carbon atoms;

furthermore, that:

- binding == ^■ represents a single bond or a double bond;

- F ¹ and F ² are directly connected to 2 patterns (I); and

 n, p and m are such that the number-average molecular weight Mn of the copolymer P is in a range of from 400 to 100,000 g / mol and its polymolecularity index is in a range from 1.5 to 3; , 0.

The various groups, radicals and letters which are included in the formulas of F ¹ and F ² and in the definition of the main chain of the copolymer P, remain throughout this text, and, in the absence of any indication to the contrary, the same meaning.

The units (I), (II) and, optionally, (III) are divalent radicals which are randomly distributed in the main chain of the copolymer P, with the exception of 2 units (I) which are directly connected to F ¹ and F ² . The copolymer P is therefore a random copolymer. The main chain of the copolymer P therefore comprises two or three repeating units:

 a first repetition pattern (I) repeated p times of formula (I),

 a second repeating unit (II) repeated n times of formula (II); and - a third repeating unit (III) repeated m times of formula (III), which is optional;

so that the copolymer P can be a bipolymer (presence of the 2 repeating units (I) and (II)) or a terpolymer (presence of the 3 repeating units (I), (II) and (III)).

As it appears above, the terminal groups F ¹ and F ² are generally symmetrical with respect to the main chain, that is to say that they correspond substantially, with the exception of the indices 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.

 The term "copolymer" means a polymer resulting from the copolymerization of at least two comonomers, that is to say two chemically different monomers. The main chain of a copolymer comprises at least 2 chemically distinct repeating units.

 The term "terpolymer" means a copolymer resulting from the copolymerization of three comonomers, and whose main chain consists essentially of 3 distinct repeating units.

 It is meant by the term "bipolymer" a copolymer resulting from the copolymerization of two comonomers, and whose main chain consists essentially of 2 distinct 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 F ¹ and F ² : (R'O) ₃ -tRtSi becomes (R'O) ₃ Si-.

If g2 = 0 or d2 = 0, then there is no radical - (Ch) - in groups F ¹ and F ² . In other words, the radical: - (CH2) _g 2- or - (CH2) d2- is replaced by a single bond.

 The copolymer P according to the invention is particularly homogeneous and stable in temperature. It is advantageously at room temperature in the form of a viscous liquid whose Brookfield viscosity at 23 ° C is between 1 mPa.s and 150 Pa.s, preferably between 1 and 50 Pa.s.

 The copolymer P may 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 copolymer P is preferably packaged and stored protected from moisture. According to a preferred variant, the main chain of the copolymer P consists essentially of the repeating unit (I) of formula (I), the repeating unit (II) of formula (II) and, optionally, the repeating unit (III) of formula (III). Thus, the number of units (I), (II) and optionally (III) advantageously represents at least 90% of the total number of units constituting the main chain of the copolymer P, and even more advantageously at least 95%.

 According to a preferred variant, the relative proportion of units of formula (I) and units of formula (II) present in the main chain of copolymer P corresponds to an excess of units of formula (I). More particularly, the number p of units (I) and the number n of units (II) are such that:

 p / (n + p) is between 45 and 95%, and

 n / (n + p) is between 5 and 55%.

These latter parameters can be determined analytically by ¹ H and ¹³ C NMR spectroscopy.

 According to a first and more preferred embodiment of the copolymer P according to the invention, all the bonds which are represented in formulas (I),

(II) and optionally (III) as well as in the formulas giving the meaning of R ° are carbon-carbon double bonds.

 According to this first embodiment, the main chain of the copolymer P is thus such that:

 the reason (I) also has the formula (Γ):

 the reason (II) also has the formula ΙΓ):

in which R ° represents the methyl radical or one of the 3 radicals of following formula:

and, optionally, the unit (III) also has the formula (ΙΙΓ):

 it being specified that in said formulas the bond is a single bond geometrically oriented on one side or the other with respect to the double bond (cis or trans).

 The corresponding units of the main chain of the copolymer P are then themselves linked by a carbon-carbon double bond.

 According to a very particularly preferred variant of this first embodiment of the invention, the main chain of the copolymer P is such that:

 on the p units of formula (Γ), p "also correspond to formula (I"), p "being an integer different from 0, less than and such that p'Vp is greater than 0.8:

 - on the n units of formula (ΙΓ), n "also correspond to formula (II"), n "being an integer different from 0, lower than n and such that nV is greater than 0.9:

(II "). According to this embodiment, at least 80% of the units of formula (Γ) are of cis configuration, represented by formula (I "), and at least 90% of units of formula (ΙΓ) are also of cis configuration, represented by the formula (II "). The corresponding percentages can be determined by ¹ H and ¹³ C NMR.

According to another variant of this ^1st embodiment, m is equal to 0, and the main chain of P does not include a pattern of formula (ΙΙΓ).

 According to a second embodiment of the copolymer P according to the invention, all the bonds == which are represented in the formulas (I), (II) and, optionally, (III) as well as in the formulas giving the meaning of R ° , are simple carbon-carbon bonds.

 According to this second embodiment, the main chain of the copolymer P is therefore such that:

the unit (I) also has the formula (l ^H ):

the pattern (II) also has the formula (II ^H )

 in which R ° represents the methyl radical or one of the 3 radicals of following formula:

and, optionally, the unit (III) has the formula (III ^H ):

Copolymer P according to this second embodiment is for example from the hydrogenation of the copolymer P according to the embodiment ¹ described above.

 According to a still more preferred variant of each of these 2 embodiments, the radical R ° of the unit (II) represents the methyl radical.

Referring now to the alkoxysilane end groups of the copolymer P according to the invention and according to a first embodiment (called "γ-dicarbamate pathway"), F ¹ is (RO) ₃ -tRtSi-R "-NH-C ( O) O- (CH ₂ ) _g i- and F ² is - (CH ₂ ) di-OC (O) -NH-R "-SiRt (OR ') _3- t, with:

- R "= - (CH ₂ ) ₃ - and;

 or else g1 = 1 or else d1 = 1, preferably g1 = d1 = 1.

In the latter case, particularly advantageously, F ¹ and F ² are each: -CH ₂ -OC (O) -NH- (CH ₂ ) 3 -Si (OCH ₃ ) 3

According to a second embodiment (called "α-dicarbamate" pathway), F ¹ is (R'O) ₃ -tRtSi-R "-NH-C (O) O- (CH ₂ ) g- and F ² is - (CH ₂ ) di-OC (O) -NH-R "-SiRt (OR ') _3- t, with:

- R "= -CH ₂ - and;

 or else g1 = 1 or else d1 = 1, preferably g1 = d1 = 1.

In the latter case, particularly advantageously, F ¹ and F ² are each: -CH ₂ -OC (O) -NH-CH ₂ -SiCH ₃ (OCH ₃ ) ₂ .

According to a third embodiment (called "γ-diurea pathway"), F ¹ is (RO) _3-t RtSi-R "-NH-C (O) -NR"'- (CH ₂ ) g- and F ² is

- (CH ₂ ) di-NR "- C (O) -NH-R" -SiRt (OR ') _3-t , with:

- R "= - (CH ₂ ) ₃ - and;

 or else g1 = 1 or else d1 = 1, preferably g1 = d1 = 1.

In the latter case, particularly advantageously, F ¹ and F ² are each: -CH ₂ -NH-C (O) -NH- (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ . According to a fourth embodiment (called "α-diurea"), F ¹ is (RO) 3-tRtSi-R "-NR"'- C (O) -NR "" - (CH 2) g - and F ² is

- (CH 2) di-NR ^, -C (O) -NH-R "-SiRt (OR ') _3- t, with:

 - R "= -CH2- and;

 or else g1 = 1 or else d1 = 1, preferably g1 = d1 = 1.

In the latter case, particularly advantageously, F ¹ and F ² are each: -CH ₂ -NH-C (O) -NH-CH ₂ -SiCH ₃ (OCH ₃ ) 2.

According to a fifth embodiment (called "γ-diamide pathway"), F ¹ is (RO) 3-tRtSi-R "-NR"'- C (O) - (CH ₂ ) g ² - and F ² is - ( CH2) d2-C (O) -NR ^, "-R" -SiRt (OR ') _3- t, with:

- R "= - (CH ₂ ) ₃ - and;

 or else g2 = 0 or else d2 = 0, preferably g2 = d2 = 0.

In the latter case, particularly advantageously, F ¹ and F ² are each -C (O) -NH- (CH ₂ ) 3 -Si (OCH ₃ ) 3.

According to a sixth embodiment (called "a-diamide pathway"), F ¹ is

(RO) 3-tRtSi-R "-NR"'- C (O) - (CH ₂ ) g ₂ - and F ² is

- (CH2) d2-C (O) -NR ^, -R "-SiRt (OR ') _3- t, with:

 - R "= -CH2- and;

 or else g2 = 0 or else d2 = 0, preferably g2 = d2 = 0.

In the latter case, particularly advantageously, F ¹ and F ² are each -C (O) -NH-CH ₂ -SiCH ₃ (OCH ₃ ) 2.

 According to a preferred variant of the different embodiments concerned, R "'represents a hydrogen atom.

 The invention also relates to a process for preparing the hydrocarbon-based copolymer P as defined above, said process comprising:

 (i) a step of heating at a temperature ranging from 30 ° C to 80 ° C:

(a) a random bipolymer A selected from poly (butadiene-isoprene), poly (butadiene-myrcene) and poly (butadiene-farnesene); and

(b) optionally, a compound B of formula (B):

 (B); then

 (ii) a step of heating the product formed in step (i) to a temperature in a range of 20 to 60 ° C, in the presence of a chain transfer agent (also called CTA) of formula (C ) : (VS)

 in which :

- F ¹ and F ² are as defined above;

 the bond is a single bond geometrically oriented on one side or the other with respect to the double bond (cis or trans);

it being further specified that each of steps (i) and (ii) is carried out in the presence of a metathesis catalyst and a solvent.

Step (i):

 Step (i) implements a depolymerization reaction of bipolymer A and intramolecular cydization, which leads to the formation of one or more macrocyclic cooligomer O comprising:

 the unit of formula (Γ) repeated p 'times, p' ° being an integer different from 0;

the unit of formula (ΙΓ) repeated n 'times, n' ° being an integer different from 0;

and, optionally, the unit of formula (ΙΙΓ) repeated m ' ⁰ times, m' ⁰ being an integer greater than or equal to 0;

it being specified that p '°, n' ° and m ' ⁰ are such that the number-average molecular mass Mn of the cyclic cooligomer (s) O is in the range from 162 to 5000 g / mol, preferably from 1000 to 3000 g / mole.

The formation and structure of the O-macrocyclic cooligomer (s) can be characterized by size exclusion chromatography techniques (or SEC) and mass spectrometry. The distribution in the macrocycle of the units of formulas (Γ), (ΙΓ) and optionally (ΙΙΓ) is statistical.

 A preferred temperature range for heating the bipolymer A and optionally compound B according to step (i) is from 30 ° C to 60 ° C.

 The corresponding heating time is adapted to obtain a yield close to 100% relative to the molar amount of bipolymer A used, as well as that of the other reactants present. A time ranging from 1 hour to 8 hours, preferably from 1 to 3 hours, is generally suitable. Bipolymer A:

 Bipolymer A is a copolymer consisting essentially of 2 monomers and is selected from poly (butadiene-isoprene), poly (butadiene-myrcene), and poly (butadiene-farnesene).

 According to a first variant, very particularly preferred, of the process according to the invention, the bipolymer A implemented in step (i) is a poly (butadiene-isoprene). In this case, it is advantageous to obtain at the end of step (ii) a hydrocarbon-based copolymer P according to the invention, the main chain comprising:

 the repeating pattern of formula (Γ) and

 the repeating unit of formula (ΙΓ) in which R ° represents the methyl radical.

 Poly (butadiene-isoprene) are copolymers which constitute an industrially advantageous raw material, in particular because of their availability and properties in terms of industrial hygiene. Polybutadiene-isoprene is generally obtained by various polymerization processes:

- 1, 3-butadiene of the formula: H ₂ C = CH-CH = CH _2, and

 2-methylbuta-1,3-diene (or isoprene), of formula:

H ₂ C = C (CH ₃ ) -CH = CH ₂ .

The polymerization of 1,3-butadiene can be carried out in either a 1,4-trans-addition or a 1,4-cis-addition, resulting in a repeating unit in the copolymer chain (referred to as a trans-butadiene unit, respectively). 1, 4 and cis-1, 4), which is in the form of the two geometric isomers of the respective formula: butadiene trans-1,4)

 (butadiene cis-1,4)

The cis-1,4 butadiene unit is identical to the unit of formula (I ") defined previously.

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

 (butadiene vinyl-1,2)

 Thus, poly (butadiene-isoprene) generally comprises in its chain the 3 repeating units above, hereinafter referred to generically as "butadiene derived units".

 Similarly, the polymerization of isoprene can be carried out according to a trans-addition-1, 4 or a cis-addition-1, 4, resulting in a repeating unit in the copolymer chain (designated respectively by trans isoprene unit -1, 4 and cis-1, 4), which is in the form of the 2 isomers of the respective formula:

is trans-1, 4)

 (Isoprene unit cis-1, 4)

The cis-1,4 isoprene unit is identical to the unit of formula (II ") in which R ° is methyl, as defined above. The polymerization of isoprene can also be carried out in an addition-1, 2, resulting in a repeating unit in the copolymer chain (designated by isoprene vinyl-1, 2 unit) which has the formula:

 (isoprene vinyl-1 unit, 2)

 The polymerization of the isoprene can finally be carried out according to a 3,4-addition, resulting in a repeating unit in the copolymer chain (designated by 3,4-vinylisoprene unit) which has the formula:

 (isoprene vinyl-3,4 unit)

 Thus, polybutadiene-isoprene generally comprises in its chain the 4 repeating units above, hereinafter referred to generically as "isoprene derived units".

 The poly (butadiene-isoprene) used in step (i) may have a number-average molecular weight (Mn) ranging from 3,000 to 100,000 g / mol, preferably from 3,000 to 50,000 g / mol, and a glass transition temperature (Tg) of from -1 to -60 ° C.

 It preferably comprises from 45 to 95% of number of units derived from butadiene and from 5 to 55% of number of units derived from isoprene, said percentages being expressed on the basis of the total number of constituent units of the poly chain. (butadiene-isoprene).

 Preferably, the poly (butadiene-isoprene) chain implemented in step (i) comprises:

 less than 5% number of butadiene vinyl-1,2 units, on the basis of the number of units derived from butadiene, and

less than 5% of the total number of isoprene vinyl-1, 2 units and isoprene vinyl-3,4 units, based on the number of units derived from isoprene. Even more preferably, this double upper limit of 5 mol% is lowered to 2%.

 According to another variant, very particularly preferred, the poly (butadiene-isoprene) chain implemented in step (i) comprises:

 at least 80% of cis-1,4-butadiene units, based on the number of units derived from butadiene, and

 at least 90% of cis-1,4 isoprene units, based on the number of units derived from isoprene.

 According to this latter variant, such a poly (butadiene-isoprene), which is liquid at ambient temperature, is often described as "high content of butadiene cis-1,4 and isoprene cis-1,4" units and is still designated in English, by the terms "high cis poly (butadiene-isoprene)". Advantageously, at the end of step (ii), the preferred variant of the copolymer P corresponding to the presence of the units of formula (I ") and (II"), as defined above, is advantageously obtained.

 Percentages in numbers of butadiene vinyl-1,2-units, isoprene vinyl-

1, 2, isoprene vinyl-3,4, butadiene cis-1,4 and isoprene cis-1,4 defined above can be determined by NMR of ¹ H and ¹³ C.

 An example of such poly (butadiene-isoprene) is KURAPRENE® LIR-390 which is commercially available from KURARAY.

 This liquid poly (butadiene-isoprene) has a number-average molecular weight (Mn) of 48,000 g / mole. It comprises 92% number of units derived from butadiene and 8% number of units derived from isoprene, said percentages being expressed on the basis of the total number of units derived from butadiene and isoprene constituting the chain.

 It also includes:

 on the basis of the number of units derived from butadiene, about 1% of 1,2-butadiene vinyl-1 units, and

 based on the number of units derived from isoprene, about 1% number of isoprene vinyl-1,2 units and less than 1% number of isoprene vinyl-3,4 units.

He finally understands: about 85% of cis-1,4 butadiene units, based on the number of units derived from butadiene, and

 approximately 98% of cis-1,4 isoprene units, based on the number of units derived from isoprene.

 Another example of poly (butadiene-isoprene) is

KURAPRENE® LIR-340 also commercially available from KURARAY.

 This poly (butadiene-isoprene) has a number-average molecular weight (Mn) of 34,000 g / mole. It comprises 46% number of units derived from butadiene and 54% number of units derived from isoprene, said percentages being expressed on the basis of the total number of units constituting the chain. It has, moreover, the same characteristics as those indicated above for the KURAPRENE® LIR-390.

 According to a second variant of the process according to the invention, the bipolymer A is either a poly (butadiene-myrcene) or a poly (butadiene-farnesene).

 Myrcene is a naturally occurring organic compound belonging to the chemical class of monoterpenes and is an important intermediate in the perfume industry. It is produced semi-synthetic from plants of the genus Myrcia. It is in the form of two geometric isomers:

the α-m rcene, of structural formula:

l -myrcene, of structural formula:

Farnesene or β-farnesene is a natural isoprenoid compound that can be chemically synthesized by isoprene oliogomerization or by dehydration of neridol. It is used mainly as perfume or intermediate and meets the developed formula: Reference is made to application EP 2810963 for the processes for the preparation of copoly (butadiene-myrcene) and copoly (butadiene-farnesene).

 In this second variant, at the end of step (ii), a hydrocarbon-based copolymer P according to the invention, the main chain comprising:

 the repeating pattern of formula (Γ) and

 the repeating unit of formula (ΙΓ) in which R ° represents:

the radical of formula:

corres ondant with Γα-myrcene;

corresponding to β -myrcene; or

 corresponding to β-farnesene.

Compound of formula (B)

 The implementation in step (i) of the compound of formula (B) advantageously leads to obtaining copolymers P according to the invention, the main chain comprises the additional unit of formula (ΙΙΓ), as defined above.

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

Preferably: R ¹ , R ² , R ³ and R ⁴ 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 ⁶ , included in the group -NR ⁶ which is one of the meanings of R ⁵ , is a linear radical comprising from 1 to 14 carbon atoms.

 According to an even more preferred variant:

at most one of the groups selected from (R ¹ , R ² , R ² and R ⁴ ) is a C 1 -C 6 alkoxycarbonyl radical and all the others represent a hydrogen atom; and or

- R ⁵ represents a radical -Ch - or an oxygen atom.

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

norbornene, of following formula

norbornadiene, of the following formula

dic clopentadiene, of the following formula:

7-oxanorbornene, of the following formula 7-oxanorbornadiene, of the following formula: 5-Ethidene-2-norbornene, of the following formula:

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

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

in which R is an alkyl radical comprising from 1 to 22 carbon atoms, preferably from 1 to 14 carbon atoms.

 The compound of formula (B) can 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 substituted norbornenes as described in WO 201 1/038057 (norbornene dicarboxylic anhydrides and optionally 7-oxanorbornene dicarboxylic anhydrides).

 Of the various compounds of formula (B) mentioned, norbornene and dicyclopentadiene are particularly preferred.

Step (ii):

 The macrocyclic cooligomers O corresponding to the product formed in step (i) are polymerized by heating at a temperature in a range of 20 to 60 ° C., in the presence of a chain transfer agent (also called CTA) of formula (VS) :

(VS)

 in which :

- F ¹ and F ² are as defined above; the bond is a single bond oriented geometrically on one side or the other with respect to the double bond (cis or trans).

 Without being bound by any reaction mechanism, it is believed that this step implements macrocycle O opening polymerization and cross-metathesis with CTA.

 This step (ii) advantageously has a low exothermicity, so that the industrial implementation of the method according to the invention does not pose difficulties in controlling the temperature.

 The molar amount of CTA to be introduced in the present step (ii) is related to the molar amount of bipolymer A and, optionally, to the molar amount of compound B introduced in step (i).

 These molar quantities are such that the ratio r which is equal to the ratio of the number of moles of said CTA:

 at the number N (A) of moles of the bipolymer A, in the case where said bipolymer A is the only reagent implemented in step (i), or

 to the sum of N (AJ) and the number of N moles (BJ of the compound of formula (B), in the case where the compound of formula (B) is also used in step (i),

 is in the range of 0.0010 to 1.0.

 Thus, when according to a preferred variant of the process according to the invention, the bipolymer A is a poly (butadiene-isoprene), said ratio r is equal to the ratio of the number of moles of the CTA:

 at the number N (A) of moles of said polybutadiene-isoprene, in the case where said polybutadiene-isoprene is the only reagent used in step (i), or

 to the sum of N (AJ) and the number of N moles (BJ of the compound of formula (B), in the case where the compound of formula (B) is also used in step (i).

Even more preferably, the ratio r defined above is in the range of 0.0020 to 0.3. According to a first embodiment (called the "dicarbamate route"), the CTA has the formula (C) in which F ¹ is (R'O) 3-tRtSi-R "-NH-C (O) O- (CH ₂ ) and F ² is - (CH ₂ ) di-OC (O) -NH-R "-SiRt (OR ') _3- t.

 Two variants of the CTA of formula (C) are then more particularly preferred, corresponding to the two embodiments previously designated γ-dicarbamate and α-dicarbamate.

 These 2 compounds are synthesized quantitatively by reaction:

 of 2 moles of, respectively, a γ-isocyanatosilane (such as 3-isocyanatopropyltrimethoxysilane) or an α-isocyanatosilane (such as

 (isocyanatomethyl) methyldimethoxysilane), marketed under the brand name

GENIOSIL® by the company WACKER Chemie, with

 1 mole of unsaturated linear diol (for example 2-butene-1,4-diol) available from ALDRICH.

CTA of formula (C) corresponding to the γ-dicarbamate pathway, for which F ¹ and F ² are each: -CH ₂ -OC (O) -NH- (CH ₂ ) 3 -Si (OCH ₃ ) 3 is designated hereinafter by CTA ¹ .

According to a second embodiment (called "diurea pathway"), the CTA has the formula (C) in which F ¹ is (R'O) 3-tRtSi-R "-NH-C (O) -NR '" - (CH ₂ ) g- and F ² is - (CH ₂ ) di-NR " ^, -C (O) -NH-R" -SiRt (OR ') _3- t.

 Two variants of the CTA of formula (C) are then more particularly preferred, corresponding to the two embodiments previously designated γ-diurea and α-diurnal.

 These 2 compounds are synthesized quantitatively by reaction:

 of 2 moles of, respectively, a γ-isocyanatosilane (such as 3-isocyanatopropyltrimethoxysilane) or an α-isocyanatosilane (such as

(isocyanatomethyl) methyldimethoxysilane) marketed by WACKER Chemie under the trademark GENIOSIL®, with

1 mole of unsaturated linear diamine (for example 1,4-diamino-2-butene) which may be synthesized by conversion of 1,4-dibromo-2-butene according to WO 92/21235 or according to Koziara et al., Synthesis 1985, 202 or, from 1, 4-dibromo-2-butene according to LH Amundsen et al., J. Am. Chem. Soc. 1951, 73, 21 18). CTA of formula (C) corresponding to the γ-diurea pathway, for which F ¹ and F ² are each: -CH ₂ -NH-C (O) -NH- (CH ₂ ) 3 -Si (OCH ₃ ) 3 is hereinafter referred to as CTA ² .

According to a third embodiment (called the "diamide route"), the CTA has the formula (C) in which F ¹ is (RO) 3 -tRtSi-R "-NR"'- C (O) - (CH ₂ ) g2- and F ² is - (CH2) d2-C (O) -NR "'- R" -SiRt (OR') _3- t.

 Two variants of the CTA of formula (C) are then more particularly preferred, corresponding to the two embodiments previously designated γ-diamide and α-diamide route.

 These 2 compounds can be synthesized by amidification of unsaturated linear carboxylic diacids or corresponding anhydrides with 2 moles, respectively, of a γ-aminosilane (such as 3-aminopropyltrimethoxysilane) or an α-aminosilane (such as (aminomethyl) methyldimethoxysilane), marketed by WACKER Chemie under the GENIOSIL® brand. The compound obtained from maleic anhydride, which is preferred according to the invention, requires going through a step of protection / deprotection of the double bond in order to avoid undesirable side reactions.

CTA of formula (C) corresponding to the γ-diamide route, for which F ¹ and F ² are each: -C (O) -NH- (CH ₂ ) 3 -Si (OCH ₃ ) 3 is hereinafter designated by CTA ³ .

Metathesis catalyst and solvent used in steps (i) and III:

 Steps (i) and (ii) of the process according to the invention each implement a metathesis catalyst and a solvent which may be identical or different, and preferably identical in each of these two steps.

 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 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 substituted Grubbs catalysts described in US Pat. No. 5,849,851.

A Grubbs catalyst 1 ^st generation is generally of the 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 preferred catalyst is the ^2nd generation Grubbs (or G2) catalyst is generally of formula (G2):

 (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. The solvent is generally chosen from the group formed by the aqueous or organic solvents typically used in the polymerization reactions and which are inert under the conditions of the polymerization, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water or their mixtures.

 A preferred solvent is selected from the group consisting of benzene, toluene, para-xylene, methylene chloride (or dichloromethane), 1,2-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.

 It is also possible that each of the steps (i) and (ii) is carried out without solvent.

 The main chain of the hydrocarbon copolymer P according to the invention which is obtained directly after steps (i) and (ii) is unsaturated, and, more precisely, comprises - according to the first embodiment described above for said copolymer - a repeating unit (I) of formula (Γ), a repeating unit (II) of formula (ΙΓ) and, optionally, a repeating unit (III) of formula (ΙΙΓ).

 The process for the preparation of the hydrocarbon copolymer P which has just been described may also comprise, in addition to the steps (i) and (ii), an additional step of hydrogenation of the 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 obtain for the hydrocarbon copolymer P - according to the second embodiment previously described for said copolymer - a main chain which is saturated, and which therefore comprises a repeating unit (I) of formula (I ^H ), a repeating unit (II) of formula (II ^H ) n times and possibly a pattern (III) of formula (III ^H ) repeated m times.

 The invention also relates to an adhesive composition comprising a copolymer P according to the invention and from 0.01 to 3% by weight, preferably from 0.1 to 1% by weight, of a crosslinking catalyst. Said adhesive composition is advantageously in the form of a viscous liquid.

 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 include:

 organic titanium derivatives such as titanium (IV) di (acetylacetonate) diisopropylate (commercially available under the name TYZORR® AA75 from Dupont);

 organic derivatives of aluminum, such as the aluminum chelate commercially available under the name K-KAT® 5218 from King Industries;

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

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

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

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

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

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

 coating of an adhesive composition as defined above, preferably in the form of a layer of thickness in a range of 0.3 to 5 mm, preferably of 1 to 3 mm, on at least 1 one of the two surfaces which respectively belong to the two substrates to be assembled, and which are intended to be brought into contact with one another according to a tangent surface; then

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

 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 copolymer of the adhesive composition, in the presence of the catalyst and of 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. The copolymers P illustrated have a Brookfield viscosity at 23.degree.

50 Pa.s.

EXAMPLE 1 depolymerization / cyclization by heating of a liquid poly (butadiene-isoprene), followed by a hot cross metathesis in the presence of CTA ¹ :

KURAPRENE® LIR-390 as defined above is used as liquid poly (butadiene-isoprene) and CTA ¹ of the formula:

 Step (i):

Poly (butadiene-isoprene) (81, 00 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 balloon and its contents are then put under argon.

 Then the addition of a G2 catalyst previously defined (9.6 μιτιοΙ) 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 disappearance of KURAPRENE® LIR-390 and formation of a mixture of macrocyclic cooligomers O attested by steric exclusion chromatography.

 Step (ii):

The compound CTA ¹ (0.27 mmol) is added by syringe and with stirring into the mixture contained in the flask of step (i) and the temperature of 40 ° C. is maintained by heating.

 The ratio r, as defined previously, is: 0.27 / 81, 00 is 0.003

After 8 hours from the introduction of CTA ¹ , 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 liquid, after precipitation in methanol, filtration and drying at 23 ° C. under vacuum. 1 H / 13 C NMR analysis gives the following results:

1H NMR (CDCl3, 500 MHz, 298 K): δ (ppm) repetition unit 2.10 (4H ^* n), 5.43 (2H ^* n), terminal group = 0.64 (4H, m, -CH ₂ -CH ₂ -Si -), 1 .61 (4H, m, -NH-CH ₂ -CH ₂ - CH ₂ -Si), 3.16 (4H, m, -NH-CH ₂ -CH ₂ -CH ₂ -Si-), 3.57 (18H, s, -S-O-CH ₃ ), 4.52 (4H, t, -CO-O-CH ₂ -CH =), 5.73 (2H, m, -CH = CH-CH ₂ -O-CO -), 5.77 (2H, m, -CH = CH-CH ₂ -O- CO-).

¹³ C NMR (CDCIs, 100 MHz, 298 K): δ (ppm) repeat unit 27.4, 32.7, 131, 4, terminal group = 6.3 (-CH ₂ -CH ₂ -Si-), 23.2 ( -NH-CH ₂ -CH ₂ -CH ₂ -Si-), 43.3 (-NH-CH ₂ -CH ₂ -CH ₂ -Si-), 50.8 (-Si-O-CH ₃ ), 65.6 (-CO- O-CH ₂ -CH =), 130.4 (CH = CH-CH ₂ -O- CO-), 135.2 (-CH = CH-CH ₂ -O-CO-), 156.5 (-O-CO -).

 These values confirm that the product obtained is a copolymer comprising 2 alkoxysilane end groups, the main chain of which consists essentially of:

 - of the unit (I) of formula:

 - of the formula (II)

of which 2 units (I) are each connected to one of the two terminal groups of formula: -CH ₂ -OC (O) -NH- (CH ₂ ) ₃ -Si (OCH ₃ ) ₃

 The number-average molecular weight M n and the polydispersity index are respectively 17 200 g / mol and 2.7.

EXAMPLE 2 depolymerization / cyclization by heating of a poly (butadiene-isoprene) in the presence of norbornene, followed by a cross-metathesis in the presence of CTA ¹ : Example 1 is repeated, replacing in step (i) the 81.00 mmol of poly (butadiene-isoprene) with a mixture of 41.00 mmol of polybutadiene-isoprene and 40.00 mmol of norbornene of formula :

 and available from Sigma Aldrich.

 The ratio r of the reagents, as defined above, is equal to 0.27 mmol divided by 41.00 mmol + 40.00 mmol, ie 0.003.

After 8 hours from the addition of CTA ¹ , 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 ambient temperature, after precipitation in methanol, filtration and drying at 23 ° C. under vacuum.

 The 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 .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 moiety = 0.64 (4H, m, -CH ₂ -CH ₂ -Si), 1 .61 (4H, m, -NH-CH ₂ -CH ₂ - CH ₂ -Si), 3.16 (4H, m, -NH-CH ₂ -CH ₂ -CH ₂ -S-1), 3.57 (18H, s, -S 1 -O-CH 3), 4.48 (2H, t, -CO-O) -CH ₂ -CH =), 5.73 (2H, m, -CH = CH-CH ₂ -O-CO-), 5.77 (2H, m, -CH = CH-CH ₂ -O-CO-).

1 ³ C NMR (CDCl 3, 100 MHz, 298 K): δ (ppm) repeat unit: 27.4, 33.1, 42.1, 43.4, 130.3, 133.1, terminal group = 6.3 (- CH2-CH2-S1-), 23.2 (-NH-CH2-CH2-CH2-S1-), 43.3 (-NH-CH2-CH2-CH2-S1-), 50.8 (-S1-O-CH3), 65.6 ( -CO-O-CH ₂ -CH =), 124.4 (CH = CH-CH ₂ -O-CO-), 136.0 (-CH = CH-CH ₂ -O-CO-), 156.5 (-O-CO- ).

 These values confirm that the polymer obtained is a copolymer comprising 2 alkoxysilane end groups, the main chain of which consists essentially of:

- of the unit (I) of formula:

 J

 of the formula (II)

 pattern III) of formula

of which 2 units (I) are each connected to one of the two terminal groups of formula: -CH ₂ -OC (O) -NH- (CH ₂ ) 3 -Si (OCH ₃ ) 3

 The number-average molecular weight Mn and the polydispersity index are 22,800 g / mol and 2.80, respectively.

EXAMPLE 3 depolymerization / cyclization by heating of a liquid poly (butadiene-isoprene), followed by a hot cross metathesis in the presence of CTA ² :

Example 1 is repeated, replacing, as a chain transfer agent, CTA ¹ with CTA ² , of formula:

(CTA ² )

A polymer is also recovered in the form of a colorless liquid whose ¹ H / ¹³ C NMR analysis gives the following values: ¹ H NMR (CDCl 3, 500 MHz, 298 K): δ (ppm) repeat unit 2.10 (4H ^* n), 5.43 (2H ^* n), terminal group = 0.64 (4H, m, -CH ₂ -CH ₂ - Si-), 1 .61 (4H, m, -NH-CH ₂ -CH ₂ - CH ₂ -Si), 3.21 (4H, m, -NH-CH ₂ -CH ₂ -CH ₂ -Si-), 3.57 (18H, s, -S 1 -O-CH 3), 3.83 (4H, t, -CO-NH-CH ₂ -CH =), 5.73 (2H, m, -CH = CH-CH ₂ -O-CO- ), 5.77 (2H, m, -CH = CH-CH ₂ -O-CO-).

¹³ C NMR (CDCIs, 100 MHz, 298 K): δ (ppm) repeat unit 27.4, 32.7, 131, 4, terminal group = 6.3 (-CH ₂ -CH ₂ -Si-), 23.2 ( -NH-CH ₂ -CH ₂ -CH ₂ -Si-), 43.3 (-NH-CH ₂ -CH ₂ -CH ₂ -Si-), 50.8 (-S 1 -O-CH 3), 52.6 (-CH = CH- CH ₂ -NH-CO-), 130.4 (CH = CH-CH ₂ -O-CO-), 135.2 (-CH = CH-CH ₂ -O-CO-), 157.4 (-O-CO- ).

 These values confirm that the product obtained is a copolymer comprising 2 alkoxysilane end groups, the main chain of which consists essentially of:

 - of the unit (I) of formula:

 - of the formula (II)

of which 2 units (I) are each connected to one of the two terminal groups of formula: -CH ₂ -NH-C (O) -NH- (CH ₂ ) 3 -Si (OCH ₃ ) 3

 The number-average molecular weight Mn and the polydispersity index are 22,800 g / mol and 2.80, respectively.

EXAMPLE 4 depolymerization / cyclization by heating of a liquid poly (butadiene-isoprene), followed by a hot cross-metathesis in the presence of CTA ³ :

Example 1 is repeated, replacing, as a chain transfer agent, CTA ¹ with CTA ³ , of formula:

(CTA ³ )

A polymer is also recovered in the form of a colorless liquid whose ¹ H / ¹³ C NMR analysis gives the following values:

¹ H NMR (CDCl3, 500 MHz, 298 K): δ (ppm) repeat unit 2.10 (4H ^* n), 5.43 (2H ^* n), terminal group = 0.64 (4H, m, -CH2-CH2-S1- ), 1 .61 (4H, m, -NH-CH2-CH2-CH2-S1-), 3.18 (4H, m, -NH-CH 2 -CH ₂ -CH ₂ -Si -), 3.57 (18H, s, -S1-O-CH3), 6.26 (2H, m, -CH = CH-CO-), 6.62 (2H, m, -CH = CH-CO-).

¹³ C NMR (CDCl3, 100 MHz, 298 K): δ (ppm) repeat unit 27.4, 32.7, 131, 4, terminal group = 6.3 (-CH2-CH2-S1-), 23.2 (-NH -CH2-CH2-CH2-S1-), 43.3 (-NH-CH2-CH ₂ -CH ₂ -Si-), 50.8 (-S1-O-CH3), 126.2 (CH = CH-CO-NH), 148.7 (-CH = CH-CO-NH), 167.2 (-CO-NH).

 These values confirm that the product obtained is a copolymer comprising 2 alkoxysilane end groups, the main chain of which consists essentially of:

 - pattern I) of formula:

 - of the unit (II) of formula:

of which 2 units (I) are each connected to one of the two terminal groups of formula: -C (O) -NH- (CH ₂ ) 3 -Si (OCH ₃ ) 3

The number-average molecular weight Mn and the polydispersity index are respectively 17 100 g / mol and 2.7. EXAMPLE 5 depolymerization / cyclization by heating poly (butadiene-isoprene) in the presence of dicyclopentadiene, followed by cross-metathesis in the presence of CTA ¹

 Example 2 is repeated, replacing norbornene with dicyclopentadiene, of formula:

and available from Sigma Aldrich.

 A liquid polymer at room temperature is also recovered, the NMR analysis of which gives 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 (2H ^* n), 2.62 (1H ^* n), 2.85 (2H ^* n), 3.24 (1H ^* n), 5.36-5.68 (4H ^* n), terminal grouping = 0.64 (4H, m, -CH ₂ -CH ₂ -Si), 1 .61 (4H, m, -NH-CH ₂ -CH ₂ -CH ₂ -Si), 3.16 (4H, m, -NH) -CH ₂ -CH ₂ -CH ₂ -Si-), 3.57 (18H, s, -S 1 -O-CH 3), 4.48 (4H, t, -CO-O-CH ₂ -CH =), 5.73 (2H, m, -CH = CH-CH ₂ -O-CO-), 5.77 (2H, m, -CH = CH-CH ₂ -O- CO-).

¹³ C NMR (CDCIs, 100 MHz, 298 K): δ (ppm) repeat unit 27.4, 33.1, 35.1, 38.0, 42.3, 46.0, 47.1, 55.4, 130.5, terminal group = 6.3 (-CH ₂ -CH ₂ -Si-), 23.2 (- NH-CH ₂ -CH ₂ -CH ₂ -Si-), 43.3 (-NH-CH ₂ -CH ₂ -CH ₂ -Si- ), 50.8 (-S1-O-CH3), 65.6 (-CO-O-CH ₂ -CH =), 124.4 (CH = CH-CH ₂ -O-CO-), 136.0 (-CH = CH-CH ₂₎ -O-CO-), 156.5 (-O-CO-z.

 These values confirm that the polymer obtained is a copolymer comprising 2 alkoxysilane end groups, the main chain of which consists essentially of:

 pattern (I) of formula

pattern (II) of formula

 pattern (III) of formula

of which 2 units (I) are each connected to one of the two terminal groups of formula: -CH ₂ -OC (O) -NH- (CH ₂ ) 3 -Si (OCH ₃ ) 3

 The number average molecular weight Mn and the polydispersity index are 28,500 g / mol and 2.80, respectively.

Example 6 Preparation of an Adhesive Composition Comprising the Copolymer of Example 1

 An adhesive composition consisting of 0.2% by weight of a crosslinking catalyst consisting of tin dioctyl dideodecanoate (TIB KAT® 223 product from TIB Chemicals) and 99.8% by weight is prepared by simple mixing. of copolymer according to the invention obtained in Example 1.

 The mixture thus obtained is left under reduced pressure (20 mbar either

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 of:

 stretching in a tensile machine, the moving jaw of which moves at a constant speed equal to 100 mm / min, a standard specimen consisting of the crosslinked adhesive composition, then

- To record, at the moment when the test piece breaks, the tensile stress applied (expressed in MPa) and the elongation of the test piece (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 μιτι.

 In order 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 μιτι, which is left during a film, is extruded on an A4 sheet of silicone paper. 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 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

1. Hydrocarbon copolymer P comprising 2 alkoxysilane end groups F ¹ and F ² connected respectively to each of the two ends of the main chain, having the formulas:

F ¹ : (R'O) 3-tRtSi-R "-NH-C (O) O- (CH ₂ ) g- and F ² : - (CH ₂ ) di-OC (O) -NH-R" -SiR _t (OR ') _3- t; or

F ¹ : (RO) 3-tRtSi-R "-NR ^m -C (O) -NH- (CH ₂ ) g- and F ² : - (CH ₂ ) di-NH-C (O) -NR '"-R" -SiR _t (OR ') _3- t or else

- F ¹ : (RO) ₃ -tRtSi-R "-NR ^m -C (O) - (CH ₂ ) _{g 2} - and F ² : - (CH ₂ ) d C (O) -NR ^, " -R " -SiRt (OR ') _3- t;

 in which :

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

 - g 1 and d 1, 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;

 R '"represents a hydrogen atom, a phenyl radical, a branched or cyclic linear alkyl radical comprising from 1 to 6 carbon atoms, or a succinate radical of formula:

R "" - O (O) C-CH ₂ -CH- C (O) O-R "" wherein R "" is a C1-C6 alkyl radical;

characterized in that the main chain of the copolymer P comprises:

a unit (I) of formula (I) repeated p times, p being an integer different from 0 a unit (II) of formula (II) repeated n times, n being an integer different from 0:

 in which R ° represents the methyl radical or one of the 3 radicals of following formula:

 and, optionally, a unit (III) of formula (III) repeated m times, m being an integer greater than or equal to 0:

alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkylcarbonyloxyalkyl, the hydrocarbon chain of said radical possibly being interrupted by at least one oxygen atom or one sulfur atom; in addition:

at least one of the groups R ¹ to R ⁴ can form, together with at least one other group R ¹ to R ⁴ and with the carbon atom or atoms to which the said groups are connected, a saturated or unsaturated hydrocarbon ring or heterocycle, optionally substituted, and comprising from 3 to 10 members; and at least one of the pairs (R ¹ , R ² ) and (R ³ , R ⁴ ) can form, with the carbon atom to which said pair is linked, 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 carrying one of the groups of the pair (R ¹ , R ² ) can be connected to the carbon atom carrying one of the groups of the pair (R ³ , R ⁴ ) by a double bond, it being understood that, according to the valence rules, only one of the groups of each of these 2 pairs is then present; R ⁵ represents:

 an oxygen or sulfur atom, or

a divalent radical -Ch -, -C (= O) - or -NR ⁶ - in which R ⁶ is an alkyl or alkenyl radical comprising from 1 to 22 carbon atoms;

furthermore, that:

- binding == ^■ represents a single bond or a double bond;

- F ¹ and F ² are directly connected to 2 patterns (I); and

 n, p and m are such that the number-average molecular weight Mn of the copolymer P is in a range of from 400 to 100,000 g / mol and its polymolecularity index is in a range from 1.5 to 3; , 0.

2. Copolymer P according to claim 1, characterized in that its main chain consists essentially of the repeating unit (I) of formula (I), the repeating unit (II) of formula (II) and, optionally, the unit of repetition (III) of formula (III).

3. Copolymer P according to one of claims 1 or 2, characterized in that the number p of units (I) and the number n of units (II) are such that:

 p / (n + p) is between 45 and 95%, and

 n / (n + p) is between 5 and 55%.

4. Copolymer P according to one of claims 1 to 3, characterized in that its main chain is such that: the pattern (I) also has the formula (Γ):

 the reason (II) also has the formula ΙΓ):

 in which R ° represents the methyl radical or one of the 3 radicals of following formula:

 and, optionally, the unit (III) also has the formula (ΙΙΓ):

 it being specified that in said formulas the bond ***** is a single bond geometrically oriented on one side or the other with respect to the double bond (cis or trans).

5. Copolymer P according to claim 4, characterized in that its main chain is such that:

on the p units of formula (Γ), p "also correspond to formula (I"), p "being an integer different from 0, less than p and such that p" / p is greater than 0.8:

 - on the n units of formula (ΙΓ), n "also correspond to formula (II"), n "being an integer different from 0, less than n and such that vn is greater than 0.9:

6. Copolymer P according to one of claims 1 to 3, characterized in that its main chain is such that:

the unit (I) also has the formula (l ^H ):

the pattern (II) also has the formula (II ^H )

 in which R ° represents the methyl radical or one of the 3 radicals of following formula:

and, optionally, the unit (III) has the formula (III ^H )

7. Copolymer P according to one of claims 1 to 6, characterized in that the radical R ° of the unit (II) represents the methyl radical.

8. Copolymer P according to one of claims 1 to 7, characterized in that F ¹ is (R'O) 3-tRtSi-R "-NH-C (O) O- (CH ₂ ) gi- and F ² is - (CH ₂ ) di-OC (O) -NH-R "-SiRt (OR ') 3 _-tj with:

- R "= - (CH ₂ ) ₃ - and;

 - g1 = d1 = 1.

9. Process for preparing the hydrocarbon-based copolymer P as defined in one of claims 1 to 8, said process comprising:

 (i) a step of heating at a temperature ranging from 30 ° C to 80 ° C:

(a) a random bipolymer A selected from poly (butadiene-isoprene), poly (butadiene-myrcene) and poly (butadiene-farnesene); and

 (b) optionally, a compound B of formula (B):

 (ii) a step of heating the product formed in step (i) to a temperature in a range of 20 to 60 ° C, in the presence of a chain transfer agent of formula (C):

(VS) in which :

- F ¹ and F ² are as defined above;

 the bond is a single bond geometrically oriented on one side or the other with respect to the double bond (cis or trans);

it being further specified that each of steps (i) and (ii) is carried out in the presence of a metathesis catalyst and a solvent.

10. Process according to claim 9, characterized in that step (i) leads to the formation of a macrocyclic cooligomer O comprising:

 the unit of formula (Γ) repeated p 'times, p' ° being an integer different from 0;

the unit of formula (ΙΓ) repeated n 'times, n' ° being an integer different from 0;

and, optionally, the unit of formula (ΙΙΓ) repeated m ' ⁰ times, m' ⁰ being an integer greater than or equal to 0;

it being specified that p '°, n' ° and m ' ⁰ are such that the number average molecular weight Mn of the cyclic cooligomer O is in a range from 162 to 5000 g / mol, preferably from 162 to 2000 g / mol mole.

11. Method according to one of claims 9 or 10, characterized in that the bipolymer A implemented in step (i) is a poly (butadiene-isoprene), preferably comprising from 45 to 95% of the number of butadiene-derived units and 5 to 55% of number of units derived from isoprene, said percentages being expressed on the basis of the total number of units constituting the chain of poly (butadiene-isoprene).

12. Process according to claim 1, characterized in that the poly (butadiene-isoprene) chain used in step (i) comprises:

 less than 5% number of butadiene vinyl-1,2 units, on the basis of the number of units derived from butadiene, and

less than 5% of the total number of isoprene vinyl-1, 2 units and isoprene vinyl-3,4 units, based on the number of units derived from isoprene.

13. Method according to one of claims 1 1 or 12, characterized in that the poly (butadiene-isoprene) chain implemented in step (i) comprises:

 at least 80% of cis-1,4-butadiene units, based on the number of units derived from butadiene, and

 at least 90% of cis-1,4 isoprene units, based on the number of units derived from isoprene.

14. Method according to one of claims 9 to 13, characterized in that the molar amount of CTA to be introduced in step (ii), the molar amount of bipolymer A and, optionally, the molar amount of compound B introduced in step (i) are such that the ratio r which is equal to the ratio of the number of moles of said CTA:

 at the number N (A) of moles of the bipolymer A, in the case where said bipolymer A is the only reagent implemented in step (i), or

 to the sum of N (AJ) and the number of N moles (BJ of the compound of formula (B), in the case where the compound of formula (B) is also used in step (i),

 is in the range of 0.0010 to 1.0.

15. An adhesive composition comprising a copolymer P as defined in one of claims 1 to 8 and 0.01 to 3% by weight of a crosslinking catalyst.

16. A method of assembling two substrates by gluing, comprising:

- The coating of an adhesive composition as defined in claim 15, preferably in the form of a layer of thickness in a range of 0.3 to 5 mm, on at least one of the two surfaces which respectively belong to the two substrates to be assembled, and which are intended to be brought into contact with one another according to a tangent surface; then

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