EP2931783A2

EP2931783A2 - Hydrocarbon polymers comprising a 2-oxo-1,3-dioxolan-4-yl end group, preparation and use thereof

Info

Publication number: EP2931783A2
Application number: EP13818302.5A
Authority: EP
Inventors: Guillaume Michaud; Frédéric Simon; Stéphane Fouquay; Liana Annunziata; Sophie Guillaume; Jean-François Carpentier
Original assignee: Bostik SA
Current assignee: Bostik SA
Priority date: 2012-12-14
Filing date: 2013-12-13
Publication date: 2015-10-21
Also published as: WO2014091174A2; FR2999578B1; US20150329666A1; FR2999578A1; WO2014091174A3

Abstract

The invention relates to a method for preparing a hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl end group, by opening the cycle by metathesis in the presence of a metathesis catalyst, a vinyl ethylene carbonate chain transfer agent, and a compound including at least one C₆-C₁₆ cycle having a double carbon-carbon bond. The invention also relates to a hydrocarbon polymer that can be obtained by said method. The invention further relates to the use of said polymer as an adhesion promoter or reactive plasticiser in an adhesive composition.

Description

Hydrocarbon polymers having a terminal group 2-oxo-1,3-dioxolan-4-yl, their preparation and their use

The present invention relates to a process for the preparation of hydrocarbon polymers comprising a terminal group 2-oxo-1,3-dioxolan-4-yl (or CC5 or 1,3-dioxolan-2-one, or cyclocarbonate), of formula :

The invention also relates to these hydrocarbon polymers and their use as additives, for example as adhesion promoter or reactive plasticizer.

Compounds having a terminal group 2-oxo-1,3-dioxolan-4-yl (CC5) have been the subject of numerous publications.

Thus, (2-oxo-1,3-dioxolan-4-yl) methyl oxycarbonyl (or glycerol carbonate esters), derivatives of glycerol carbonate, have interesting properties in terms of thermal stability, stability to oxidation, as well as surfactant properties (Eur J Lipid Sci Technol 103 (2001) 216-222).

The object of the present invention is to provide novel polymers comprising a 2-oxo-1,3-dioxolan-4-yl end group, which can generally be used as additives, preferably as adhesion promoters or reactive plasticizers. for example in hot melt adhesives.

Thus, the present invention relates to a process for preparing at least one hydrocarbon polymer, said process comprising at least one metathesis ring opening polymerization step in the presence of:

at least one metathesis catalyst, preferably a catalyst comprising ruthenium, more preferably a Grubbs catalyst, 4-ethenyl-1,3-dioxolan-2-one (or vinyl ethylene carbonate) as a chain transfer agent (CTA), and

at least one compound chosen from compounds comprising at least one hydrocarbon-based ring and generally from 6 to 16, preferably from 6 to 12, carbon atoms per ring, said ring comprising at least one carbon-carbon double bond, and the substituted derivatives of this compound, said compound being of formula (7):

(7)

in which :

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

- The groups R1 and R6 are either both hydrogen or each different from hydrogen and linked to each other as members of the same ring or saturated or unsaturated heterocycle (ie having at least one carbon-carbon double bond , including aromatics);

The groups R2, R3, R4 and R5 are each, independently or not, of the other groups, a hydrogen, a halogeno group, an alkoxycarbonyl group or an alkyl group, the groups R2 to R5 being able to be linked together as members of the same ring or saturated or unsaturated heterocycle;

m and p are integers each in the range of 0 to 5, the sum m + p being itself in a range of 0 to 6; said step being carried out for a duration less than or equal to 2 hours, preferably from 1 hour to 2 hours.

When m = 0, this means that there is no group between the brackets to which m applies and that the two carbon-carbon bonds each overlapping one of the brackets constitute one and the same carbon bond - carbon. This is the same for p = 0.

The molar ratio of the compound comprising at least one hydrocarbon-based ring on the CTA is generally in a range of from 20 to 10,000, and preferably from 40 to 1000.

The compounds of formula (7) are substituted or not. By substitution is meant according to the invention the presence of a group, generally replacing a hydrogen, the substitution being alkyl, cyclic or acyclic, alkoxycarbonyl or halo, and the substitution being preferably located in beta, gamma or delta position. the carbon-carbon double bond, even more preferably in the gamma or delta position of the carbon-carbon double bond. Thus, the substituted derivatives of the compounds of formula (7) include the compounds of formula (7) comprising at least one second ring comprising at least one carbon-carbon bond in common with the first ring.

In a preferred embodiment of the invention, these compounds are unsubstituted, i.e., R1 = R2 = R3 = R4 = R5 = R6 = H.

In a preferred embodiment of the invention, independent or not of the previous embodiment, m = p = 1.

Metathesis ring opening polymerization (or Ring Opening Methathesis Polymerization (ROMP)) is a reaction well known to those skilled in the art, which is carried out here in the presence of 4-ethenyl-1,3-dioxolamine. 2-one.

4-Ethenyl-1,3-dioxolan-2-one (or 4-vinyl-1,3-dioxolan-2-one or vinyl ethylene carbonate) is a well known compound. It is described for example in US Pat. No. 251,1942 to Dupont de Nemours (published in 1950), and in a more recent publication (US 2010/0048918 to Foosung Co). It is used in particular as an additive in the electrolytes of lithium batteries. The cyclic compounds of formula (7) are preferably according to the invention chosen from the group formed by cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, 1,5-cyclooctadiene, cyclononadiene, 1,5,9-cyclodecatriene, as well as norbornene, norbornadiene, dicyclopentadiene, 7-oxanorbornene and 7-oxanorbornadiene respectively of formulas:

Cyclooctene (COE), norbornene and dicyclopentadiene are particularly preferred.

Mention may also be made of mono- or poly-substituted derivatives of these cyclic compounds, such as, preferably, alkyl-cyclooctenes, alkyl-cyclooctadienes, halocycloalkenes and alkylcarbonylcycloalkenes. In such a case, the alkyl, halo and alkoxycarbonyl groups have the meanings given above. The alkyl groups are most often in the beta, gamma or delta position of the carbon - carbon double bond, even more preferably in the gamma or delta position of the carbon - carbon double bond.

The ring opening polymerization by metathesis is most often carried out in the presence of at least one solvent, generally chosen from the group formed by the aqueous, organic or polar solvents typically used in the polymerization reactions and which are inert in the conditions of the polymerization, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, 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, water, and the like. mixtures. Even more preferably, the solvent is selected from the group consisting of benzene, toluene, para-xylene, methylene chloride, dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane and mixtures thereof. Even more preferably, the solvent is tetrahydrofuran, toluene or a mixture of toluene and methylene chloride. The solubility of the polymer formed during the polymerization reaction depends generally and mainly on the choice of solvent and the molar weight of the polymer obtained. It is also possible that the reaction is carried out without solvent.

The metathesis catalyst, such as for example a Grubbs 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 ruthenium carbene. The Grubbs catalysts can thus be used in a particularly preferred manner. The term "Grubbs catalyst" generally means, according to the invention, a Grubbs 1 ^st and 2 ^nd generation catalyst, but also any other Grubbs type catalyst (comprising ruthenium-carbene) accessible to a person skilled in the art, such as for example substituted Grubbs catalysts described in US 5849851.

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

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

The P (Cy) 3 group and a tricyclohexyl phosphine group.

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

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

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

The preparation process according to the invention may also comprise at least one additional step of hydrogenation of carbon-carbon double bonds. Obviously this step is implemented only on an unsaturated hydrocarbon polymer. It is thus carried out the hydrogenation of at least one carbon-carbon double bond, preferably the total hydrogenation of the carbon-carbon 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).

The present invention also relates to any hydrocarbon polymer comprising a terminal group 2-oxo-1,3-dioxolan-4-yl obtainable by the process according to the invention.

The present invention also relates to a hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl end group, said hydrocarbon polymer being capable of being obtained according to the process of the invention, said hydrocarbon polymer being of formula ( 1):

(1)

in which :

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

m and p are integers each in the range of 0 to 5, the sum m + p being itself in a range of 0 to 6; and

x and y are each an integer, independently of one another, x being different from 0, the sum x + y being such that the number-average molecular weight Mn of the hydrocarbon polymer of formula (1) is comprised in a range of 400 to 50000 g / mol, preferably 600 to 20000 g / mol, and the polymolecularity (PDI) of the hydrocarbon polymer of formula (1) is in the range of 1.0 to 2.0, preferably from 1.1 to 1.7, and even more preferably from 1.4 to

1, 7.

When y = 0, this means that there is no group between the brackets to which it applies and that the two carbon-carbon bonds overlapping each one of the hooks constitute a single carbon-carbon bond.

The polymer obtainable by the process according to the invention is preferably a polymer of formula (1).

In addition, it is polymer but it is more specifically a mixture of polymers represented by the formula (1), as is well known to those skilled in the art. In this respect, the molar masses are "average" molar masses.

The polymer of formula (1) can therefore be written schematically A _x B _y AT, where A is the monomer unit present x times, B is the monomer unit present y times and T is the terminal group. However, the writing of the formula (1) is obviously for the skilled person a simplified writing. Copolymer A _x- iB _is a homogeneous random copolymer structure (ie consisting of macromolecules in which the probability of finding a given monomeric unit A or B at a given point of the chain is independent of the nature of the adjacent monomeric units) or periodic (ie consisting of macromolecules comprising two monomeric units in a regular sequential order, for example alternating) or statistical (ie consisting of macromolecules in which the distribution of monomer units obeys known statistical laws). In such a polymer, only the monomer unit A is present at both ends of the polymer, alone at one end or in connection with T at the other end. Without being limited by theory, the inventors believe that it is highly likely that the copolymer A _x- i B _is a random copolymer homogeneous structure. The monomer units A and B are therefore distributed randomly along the main chain of the polymer.

This simplification of writing is of course valid for all the polymer formulas which will be described hereinafter, including those of the examples.

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

In the particular case where y = 0, formula (1) becomes the following formula: ^RRR e (101) with n = x + 1.

By alkyl group is meant according to the invention a linear or branched hydrocarbon compound, cyclic, acyclic, heterocyclic or polycyclic, and generally comprising from one to twenty-two carbon atoms. Such an alkyl group generally comprises from 1 to 4, preferably from 1 to 2, carbon atoms.

By halo group is meant according to the invention an iodo group, chloro, bromo or fluoro, preferably chloro.

According to the invention, the term "heterocycle" means a ring which may comprise an atom other than carbon in the ring chain, such as, for example, oxygen.

By alkoxycarbonyl group is meant according to the invention a divalent alkyl group, linear or branched, saturated or partially unsaturated, comprising from one to twenty-two, preferably from one to eight, even more preferably from one to six, atoms carbon, and such that a chain of carbon atoms that it comprises further comprises a divalent group -COO-.

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

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

By terminal group means a group located at the end of the chain (or end) of the polymer.

If it is unsaturated, the polymer according to the invention most often comprises a plurality of (ie more than two) carbon-carbon double bonds. In a preferred embodiment, the polymer of formula (1) comprises only one carbon-carbon double bond per repeating unit, [...] and the polymer is of formula (1 '):

(V)

In this case, preferably, m is 1 and p is 1.

In the particular case where y = 0, the formula (1 ') becomes the following formula:

n = x + 1

Preferably, the invention relates to a hydrocarbon polymer comprising a 2-oxo-1, 3-dioxolan-4-yl end group, said hydrocarbon polymer being of formula 2) or of formula (3):

(2)

·· "·, [1 ..- Ή, j s".

(3) wherein ^'" , m, p, x, y, R 1, R 2, R 3, R 4, R 5 and R 6 have the meanings given above, and, as is known to those skilled in the art, the binding ^ means that the link is geometrically oriented on one side or on the other with respect to the double bond, either: Z (for Zusammen = cis) or E (for Entgegen = trans).

In a particularly preferred manner, m is equal to 1 and p is equal to 1.

In the particular case where y = 0, formulas (2) and (3) respectively become the following formulas:

n = x + 1.

The polymer of formula (2) is generally of trans (E) - trans (E), trans (E) - cis (Z) or cis (Z) - cis (Z) orientation. The three isomers are generally present in variable proportions, most often with a majority of trans (E) - trans (E). It is possible according to the invention for the trans (E) -trans (E) isomer to be present in a substantially majority manner.

The formula (2) illustrates the case where the repeating units of the main chain of the polymer of formula (1) are unsaturated and each comprise at least one carbon-carbon double bond. In a preferred embodiment, the polymer of formula (2) comprises only one carbon-carbon double bond per repeating unit, and the polymer is of formula (2 '):

In this case, preferably, m is 1 and p is 1. In the articular case where y = 0, the formula (2 ') becomes the following formula:

n = x + 1.

The formula (3) illustrates the case where the main chain of the polymer of formula (1) is saturated.

The polymer of formula (3) may for example be derived from the hydrogenation of the polymer of formula (2).

According to a preferred embodiment of the invention, the invention relates to a hydrocarbon polymer comprising a terminal group 2-oxo-1,3-dioxolan-4-yl, said hydrocarbon polymer being of formula (4):

n = x + 1.

Formula (4) illustrates the case where the polymer of formula (1) is such that R1, R2, R3, R4, R5 and R6 are each hydrogen (H). In a preferred embodiment, the polymer of formula (4) comprises at most only one carbon-carbon double bond per repeating unit, and the polymer is of formula (4 ').

(4 ').

In the particular case where y = 0, the formula (4 ') becomes the following formula:

n = x + 1.

According to this embodiment, the invention preferably relates to a hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl end group, said hydrocarbon polymer being of formula (5) or of formula (6):

(5)

(6) in which,, m, p, x and y have the meanings given above.

In the particular case where y = 0, formulas (5) and (6) respectively become the following formulas:

(105) with n = x + 1: and

n = x + 1.

Formula (5) illustrates the case where the repeating unit of the main chain of the polymer of formula (4) is unsaturated and has at least one carbon-carbon double bond.

In a preferred embodiment, the polymer of formula (5) comprises only one carbon-carbon double bond per repeating unit, and the polymer is of formula (5 '). In this case, preferably, m is equal to 1 and is equal to 1.

(5 ')

In the particular case where y = 0, the formula (5 ') becomes the following formula

(105 ') with n = x + 1.

Formula (6) illustrates the case where the main chain of the polymer of formula (4) is saturated.

The polymer of formula (6) may for example be derived from the hydrogenation of the polymer of formula (5).

Formulas (5) and (6) correspond to formulas (2) and (3) wherein R1, R2, R3, R4, R5 and R6 are each hydrogen (H).

Advantageously, the hydrocarbon polymer according to the invention, ie capable of being obtained by the process of the invention and optionally of formula (1), can be used as an additive, most often: - as an adhesion promoter, or

as a reactive plasticizer in an adhesive composition.

The hydrocarbon polymer according to the invention can thus be used, for example, as an adhesion promoter in an HMA or HMPSA type adhesive composition (HMA for "Hot Melt Adhesive" in English, ie hot melt adhesive, and HMPSA for "Hot Melt Pressure-Sensitive Adhesive" (English, ie hot-melt pressure-sensitive adhesive) based on polyolefins or block polymers comprising styrene.

In addition, the hydrocarbon polymers, unsaturated or saturated, according to the invention have a 2-oxo-1, 3-dioxolan-4-yl end group which advantageously constitutes a polar head located near the lipophilic polymer chain. Therefore, the addition of at least one hydrocarbon polymer, unsaturated or saturated, according to the invention makes it possible to reduce the interfacial tension of hot melt compositions based on polyolefins or block copolymers comprising styrene (type HMA and HMPSA), in their use as adhesion promoters.

The invention therefore also relates to the use of at least one hydrocarbon polymer according to the invention as adhesion promoter.

The invention therefore also relates to the use of at least one hydrocarbon polymer according to the invention as a reactive plasticizer in an adhesive composition.

The invention will be better understood from the following examples.

EXAMPLES

The examples which follow illustrate the invention without limiting its scope.

Experimental protocol

All the experiments were carried out if necessary under an argon atmosphere.

4-ethenyl-1, 3-dioxolan-2-one (or 4-vinyl-1, 3-dioxolan-2-one or vinyl ethylene carbonate) and Grubbs catalyst ^2nd generation formula (9) were products from Aldrich. Cyclooctene (COE) was a product of Aldrich, which was distilled on CaH ₂ and degassed before use.

Tetrahydrofuran (THF) was refluxed under Na / benzophenone, distilled and degassed before use. All other solvents were used as received.

FTIR (Fourier Transform Infrared) spectra were recorded on a Shimadzu IRAffinity-1 device.

NMR spectra were recorded under AM-500 Bruker and AM-400 Bruker spectrometers at 298 K in CDCl ₃ . The chemical shifts were referenced to tetramethylsilane (TMS) using resonance ( ¹ H) or ( ¹³ C) deuterated solvents. The number and weight average molecular weights (M _n and M _w ) and the PDI polydispersity (M _w / M _n ) of the polymers were determined by gel permeation chromatography (GPC) using a Polymer Laboratories PL-GPC 50 instrument. Mass spectra were recorded with a high resolution AutoFlex LT (Brucker) spectrometer equipped with a N2 pulsed laser source (337 nm, 4 ns tap width).

Example 1 Synthesis of an unsaturated polyolefin having a 2-oxo-1,3-dioxolan-4-yl end group from cyclooctene and the 4-ethenyl-1,3-dioxolan-2 chain transfer agent -one

The synthesis reaction of Example 1 was carried out by ring opening polymerization of cyclooctene (COE) in the presence of a Grubbs catalyst and the 4-ethenyl-1,3-transfer agent (CTA). dioxolan-2-one.

The reaction was carried out according to the following scheme 1:

Diagram 1 The polymerization was usually carried out according to the data below. A 100 mL flask was loaded with stirring and sequentially with THF (tetrahydrofuran) (5 mL), COE (1.4 mL) and the appropriate amount of 4-ethenyl-1,3-dioxolan transfer agent. -2-one. The resulting solution was thermostated at 40 ° C and the polymerization was started by injection of a pre-catalyst solution prepared by dissolving a Grubbs catalyst ^2nd generation ( "Ru") (5.0 mg) in THF (3 mL). After two hours of reaction, the mixture was poured into acidified cold methanol. The polymers present were recovered by filtration and dried at 25 ° C. under vacuum.

A compound of formula (10) below has thus been synthesized according to the invention:

Π

(10)

This compound (10) is a compound according to the invention of formula (105 ') in which m is equal to 1 and p is equal to 1.

Different tests were conducted according to this reaction. They are summarized in Table 1 below.

Table 1

Test [CTA] / [Ru] [COEMCTA] Conv. Mn GPC PDI

(mol / mol) (mol / mol) (%) (g / mol)

El 5 400 100 56 800 1.62

E2 10 200 100 16 800 1.48

E3 20 100 100 8 900 1.43

E4 30 66 100 6 700 1.41

E5 50 40 100 3 500 1.45

E6 20 50 100 6 500 1.43

NMR analyzes of the polymer obtained in test E4 gave the following values, which confirm the structural formula (10) of this polymer: ¹ H NMR (CDCl ₃ , 400 MHz, 298 K) δ trans unit of the main chain: 1.30, 1.97, 5.39; δ cis unit of the main chain: 1 .30, 2.03, 5.34; end of chain cyclocarbonate: 4.12, 4.56 (t, 2H, ), 5.09 (m, 1H, -CH = CH-CH-CH ₂ OCOO), 5.53 (dt, 1H, _trans = 15.0Hz, -CH = CH-CH-CH ₂ OCOO), 5.97 (m, Jtrans = 14.8 Hz, J = 7.0 Hz, 1H, -CH = CH-CH-CH ₂ OCOO), vinyl chain end: 2.14 (m, 2H, -CH ₂ CH = CH ₂ ), 4.98 (dt, J = 17.7 and 10.7 Hz, 2H, -CH ₂ -CH = CH ₂ ), 5.83 (m, 1H, -CH ₂ -CH = CH ₂ ). ¹³ C {1 H} NMR (CDCl ₃ , 125 MHz, 298 K) δ Trans unit of the main chain: 130.34, δ Cis unit of the main chain 129.88, 32.63, 29.77, 29.69, 29.24, 29.20, 29.07, 27.26 end of cyclocarbonate chain: 69.51, (-CH = CH-CH-CH ₂ OCOO), 78.24 (-CH = CH-CH-CH ₂ OCOO), 123.89 (-CH = CH-CH-CH ₂ OCOO), 140.02 (- CH = CH-CH-CH ₂ OCOO), 155.10 (O = CO), vinyl chain end: 34.20 (-CH ₂ -CH = CH ₂ ), 1 14.40 (-CH ₂ -CH = CH ₂ ), 139.6 ( -CH ₂ -CH = CH ₂ ). EXAMPLE 2 Synthesis of a Saturated Polyolefin Containing a Terminal Group 2-Oxo-1,3-dioxolan-4-yl by Catalytic Hydrogenation of the Unsaturated Polyolefin Containing a Terminal Group 2-Oxo-1,3-dioxolan-4-yl from example 1

The reaction was carried out according to Scheme 2 above.

Figure 2

In a 50 mL reactor equipped with a magnetic bar were introduced 0.500 g of polymer (10) in 20 mL of toluene and then 0.05 g of Pd / C catalyst (10% by weight). The reactor was heated to 40 bar (4 MPa) under hydrogen pressure and 100 ° C for 12 hours. The mixture was then cooled to room temperature and vented, and the suspension poured into methanol. The polymer was recovered by extraction with hot toluene. The solution was poured again into methanol and the precipitate as a white powder was collected by filtration and dried under vacuum at 40 ° C.

The hydrogenation of the double bonds was confirmed by ¹ H NMR and ¹³ C NMR.

Example 3 Use of Unsaturated Polyolefin Containing a Terminal Group 2-Oxo-1,3-dioxolan-4-yl of Example 1 as a Reactive Diluent

Example 3a Synthesis of an unsaturated polyolefin (11) comprising two end groups (2-oxo-1,3-dioxolan-4-yl) methyloxycarbonyl

The formula (1 1) is the following:

(1 1)

It was synthesized by ring opening polymerization by metathesis between a chain transfer agent of formula (12) and cyclooctene.

Synthesis of (2-oxo-1,3-dioxolan-4-yl) methyl propenoate (chain transfer agent of formula (12), used for the synthesis of the polyolefin of formula (1 1))

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

To a solution of 7 g of glycerol carbonate in dry dichloromethane (15 mL) was added, dropwise, 4.8 mL (5.7 g) of acryloyl chloride at room temperature. The resulting clear solution was slowly heated to 45 ° C and refluxed for a further 5 hours. At the end of this period, the solution was cooled to room temperature and the solvent was distilled off. The crude oily product thus obtained was purified by vacuum distillation. A clear and colorless product was obtained (yield 9.2g ie 90%). The NMR data of this product were as follows: ¹ H NMR (CDCl 3, 298 K): δ = 4.3-4.6 (4H, m, CH 2 CH-CH 2 COO), 4.9 (1H, m, CH ₂ - CH-CH2OC00), 5.9 (1H, d, J _HH = 10.7 Hz, CH ₂ = CH), 6.1 (1H, m, CH ₂ = CH), 6.4 (1H, d, J _HH = 17 , 2 Hz, CH ₂ = CH). ¹³ C NMR ^{1 H} (CDCl _3, 298 K): δ = 63.2, 66.2 (CH ₂ -5CC), 74.0 (CH-5 ° C), 127.2 (CH ₂ = CH-), 132.5 (CH ₂ = CH- ), 154.8 (O = COO), 165.5 (O = CO). The (2-oxo-1,3-dioxolan-4-yl) methyl propenoate of formula

(12).

Synthesis of an unsaturated polyolefin of formula (1 1) comprising two end groups (2-oxo-1,3-dioxolan-4-yl) methyloxycarbonyl from cyclooctene (COE) and of the chain transfer agent (CTA ) (2-oxo-1,3-dioxolan-4-yl) methyl propenoate of formula (12) synthesized above The reaction was carried out according to the following scheme 4:

Figure 4

It made it possible to obtain the polyolefin of formula (1 1).

The polymerization, the conditions of which are summarized in Table 2, was carried out according to the data below. A 100 mL flask was loaded with stirring and sequentially with THF (tetrahydrofuran) (5 mL), COE (1.4 mL) and the appropriate amount of transfer agent (2-oxo-1, 3- dioxolan-4-yl) methyl 2-propenoate. The resulting solution was thermostated at 40 ° C and the polymerization was started by injection of a pre-catalyst solution prepared by dissolving a Grubbs catalyst ^2nd generation ( "Ru") (5.0 mg) in THF (3 mL). After two hours of reaction, the mixture was poured into acidified cold methanol. The polymers present were recovered by filtration and dried at 25 ° C. under vacuum. Table 2

[CTA] / [Ru] [COEMCTA] Conv. Mn GPC PDI (mol / mol) (mol / mol) (%) (g / mol)

Test 50 40 100 12 200 1.69

The compound of formula (1 1) has thus been synthesized. Indeed, NMR analyzes of the polymer obtained gave the following values, which confirm the structural formula (1 1) of this polymer. ¹ H NMR (CDCl ₃ , 500 MHz, 298 K) - trans repeat unit: 1.30, 1.97, 5.39; cis repeat unit: 1.30, 2.03, 5.34; terminal group: 2.25 (m, 2H, -C - / 2-CH = CH-COO), 4.30, 4.63 (m, 4H, -CH 2 -CH-CH 2 COO), 4.96 (m, 1H, -CH 2 -CH) -CH2OC00), 5.87 (d, Jtrans = 15.2 Hz, 1H, -CH = CH-COO), 7.07 (m, 1H, -CH = CH-COO, Jtrans = 15.0 Hz, J = 7.0 Hz). ¹³ C NMR (CDCl3, 125 MHz, 298 K) - repeating unit: 130.34 (trans), repeat unit 129.88 (cis), 32.63, 29.77, 29.69, 29.24, 29.20, 29.07, 27.26; terminal group: 62.80, 66.0-CH2-CH-CH2OC00), 73.87 (-CH2-CH-CH2OC00), 19.50 (-CH = CH-COO-), 152.04 (-CH = CH-COO), 154.6 (0 = COO), 165.9 (OC = 0). Example 3b Use of the unsaturated polyolefin of formula (10) having a 2-oxo-1,3-dioxolan-4-yl end group of Example 1 as a reactive diluent

A 90/10 by weight mixture of unsaturated polyolefin (11) and unsaturated polyolefin (10) according to the invention comprising a single terminal group 2-oxo-1,3-dioxolane was reacted at 80 ° C. 4-yl:

not

(10)

with a primary diamine of the polyether diamine type (JEFFAMINE EDR 176, Huntsman) in a stoichiometric ratio (NH ₂ / total CC 5) and this until complete disappearance of the infrared band characteristic of the 1,3-dioxolan-2-one groups (at 1800 cm ^-1 ) and appearance of the characteristic bands of the carbamate group (1700 cm ^{-1 band} ) The reaction time was approximately 12 hours.

The compound of formula (10) according to the invention served as a reactive diluent.

The product thus synthesized led to the formation of a polyurethane, which suitably formulated two-component blend has provided adhesive properties.

Claims

CLAIMS 1. A process for preparing at least one hydrocarbon polymer, said process comprising at least one metathesis ring opening polymerization step in the presence of:

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

4-ethenyl-1,3-dioxolan-2-one (or vinyl ethylene carbonate) as a chain transfer agent (CTA), and

at least one compound chosen from compounds comprising at least one hydrocarbon-based ring and generally from 6 to 16, preferably from 6 to 12, carbon atoms per ring, said ring comprising at least one carbon-carbon double bond, and the substituted derivatives of this compound, said compound generally being of formula (7):

- The groups R1 and R6 are either both hydrogen or each different from hydrogen and linked together as members of the same ring or saturated or unsaturated heterocycle; The groups R2, R3, R4 and R5 are each, independently or not, of the other groups, a hydrogen, a halogeno group, an alkoxycarbonyl group or an alkyl group, the groups R2 to R5 being able to be linked together as members of the same ring or saturated or unsaturated heterocycle;

m and p are integers each in the range of 0 to 5, the sum m + p being itself in a range of 0 to 6;

said step being carried out for a duration less than or equal to 2 hours, preferably from 1 hour to 2 hours.

2. Process for the preparation of at least one hydrocarbon polymer according to claim 1, said process further comprising at least one additional step of hydrogenation of carbon-carbon double bonds.

3. Hydrocarbon polymer comprising a terminal group 2-oxo-1,3-dioxolan-4-yl, said polymer being obtainable by the preparation method according to any one of claims 1 and 2.

4. A hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl end group according to claim 3, said hydrocarbon polymer being of formula (1):

(1)

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

The groups R1 and R6 are either both hydrogen or each different from hydrogen and linked together as members of the same ring or saturated or unsaturated heterocycle; The groups R2, R3, R4 and R5 are each independently of the other groups hydrogen, halo, alkoxycarbonyl or alkyl, wherein R2 to R5 may be bonded together as members of the group. the same saturated or unsaturated ring or heterocycle,

x and y are each an integer, independently of one another, x being different from 0, the sum x + y being such that the number-average molar mass Mn of the hydrocarbon polymer of formula (1) is included in a range of 400 to 50000 g / mol, preferably 600 to 20000 g / mol, and the polymolecularity (PDI) of the hydrocarbon polymer of formula (1) is in the range of 1.0 to 2.0, preferably from 1.1 to 1.7, and even more preferably from 1.4 to 1.7.

Hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl end group according to claim 4, said hydrocarbon polymer being of formula 2) or of formula (3):

(2)

(3) wherein m, p, x, y, R 1, R 2, R 3, R 4, R 5 and R 6 have the meanings given in claim 4, and the bond means that the bond is geometrically oriented on one side or the other with respect to the double bond (cis or trans).

6. A hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl end group according to claim 4, said hydrocarbon polymer being of formula (4):

(4) wherein ^'" , m, p, x and y have the meanings given in claim 4.

7. A hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl end group according to claim 6, wherein said hydrocarbon polymer is of formula (5) or of formula (6):

(5)

(6) in which -, ^' , m, p, x and y have the meanings given in claim 4 or claim 5.

Use of at least one hydrocarbon polymer according to any one of claims 3 to 7 as an adhesion promoter in an adhesive composition.

Use of at least one hydrocarbon polymer according to any one of claims 3 to 7 as a reactive plasticizer in an adhesive composition.