FR3016362A1 - HYDROCARBON POLYMERS COMPRISING A TERMINAL GROUP WITH 2-OXO-1,3-DIOXOLAN-4-YL TERMINAL, THEIR PREPARATION AND THEIR USE - Google Patents

Abstract

A process for preparing a hydrocarbon polymer comprising a terminal moiety having a 2-oxo-1,3-dioxolan-4-yl terminus, by metathesis ring opening in the presence of metathesis catalyst, a chain transfer agent comprising a carbonate ring, and a compound of the formula comprising at least one C6-C16 carbon-carbon double bond ring. Hydrocarbon polymer obtainable by this process. Use of this polymer as an adhesion promoter or reactive plasticizer in an adhesive composition.

Description

The subject of the present invention is a process for the preparation of at least one hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl (or cyclocarbonate) end-end connected to the main chain of the polymer by an alkylene bond , and optionally a divalent carboxyl or oxy group, or a terminating terminal group: where Z is constituted by at least one alkylene group optionally directly connected to a divalent carboxyl or oxy group, the Z group comprising from 1 to 19 atoms carbon and q being an integer equal to 0 or 1. The invention also relates to the hydrocarbon polymers obtainable by this process and their use as additives, for example as adhesion promoter or plasticizer reagent. The 2-oxo-1,3-dioxolan-4-yl (CC5) -terminated end-group compounds have been the subject of numerous publications. (2-Oxo-1,3-dioxolan-4-yl) methyloxycarbonyl, glycerol carbonate esters, have interesting properties in terms of thermal stability, oxidation stability, as well as surfactant properties (Eur J. Lipid Sci.Technol 103 (2001) 216-222). The object of the present invention is to provide novel hydrocarbon polymers comprising a 2-oxo-1,3-dioxolan4-yl end-terminating group generally useful as additives, preferably as an adhesion promoter or a reactive plasticizer. , within adhesive compositions. Thus, the present invention relates to a process for the preparation of at least one hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl terminated end group, said process comprising at least one metathesis ring opening polymerization step in the presence of: - at least one metathesis catalyst, preferably a catalyst comprising ruthenium, more preferably a Grubbs catalyst; at least one chain transfer agent (CTA) compound of formula (15): the Z group being constituted by at least one alkylene group optionally connected to a divalent carboxyl or oxy group, the Z group comprising from 1 to 19 carbon atoms and q being an integer equal to 0 or 1; 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): R3 R4 (7) in which: each carbon-carbon bond of the chain noted is a double bond or a single bond, in accordance with the rules of valence of organic chemistry; one of R1 and R6 is hydrogen and the other of R1 and R6 is halo, alkoxycarbonyl or alkyl; 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 bonded to each other or to that of the groups R1 and R6 groups which are not hydrogen as members of the same ring or saturated or unsaturated heterocycle; m and p are integers each in a range of 0 to 5, the sum m + p itself being in a range of 0 to 6. When m = 0, it means that there is 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 a single carbon - carbon bond. This is the same for p = 0 or q = O.

The molar ratio of the compound comprising at least one hydrocarbon ring on CTA is generally in a range of 1 to 10,000 and preferably 1 to 100. According to the invention, at least one of R1 and R6 is not H. In this case, preferably, each of R2, R3, R4 and R5 is H.

Of course all the formulas given here are in agreement with the valence rules of organic chemistry. In general, the compound of formula (7) is such that the ring chain is preferably composed of carbon atoms, but at least one carbon atom may be replaced by another atom such as oxygen.

The compounds of formula (7) are substituted or not. By substitution, according to the invention is meant the presence of a group, generally replacing a hydrogen, the substitution being of alkyl, cyclic or acyclic, alkoxycarbonyl or halo type, and the substitution being preferably located in the alpha, beta, gamma position. or delta of the carbon - carbon double bond, even more preferably in the gamma or delta position of the carbon - carbon double bond. In a preferred embodiment of the invention, m = p = 1. Metathesis Ring Opening Polymerization (or "Ring Opening Methathesis Polymerization") is a reaction well known to those skilled in the art, which is here used in the presence of compound of formula (15).

The Z group preferably consists of either a single alkylene group optionally connected to a divalent carboxyl or oxy group or two alkylene groups, optionally connected to a divalent oxy or carboxy group. In the latter case, only one oxy or carboxy group is generally present, most often between the two alkylene groups. In the case where a single alkylene group is connected to a divalent carboxyl or oxy group, this carboxyl or oxy group is preferably located at one end of the Z group. The compound of formula (15) is preferably selected from the compounds listed below: 4-vinyl-1,3-dioxolan-2-one (or 4-ethenyl-1,3-dioxolan-2-one or vinyl carbonate or vinyl ethylene carbonate) (if q = 0) ) of formula: 4- (vinyloxymethyl) -1,3-dioxolan-2-one (if q = 1 and Z is -O-CH 2 -) of formula: 4- (acryloyloxymethyl) -1,3 -dioxolan-2-one (or 2-oxo-1,3-dioxolan-4-yl) methylpropenoate) (if q = 1 and Z is -COO-CH 2 -) of the formula: ## STR1 ## the 4- (alkenyloxymethyl) ) -1,3-dioxolan-2-one (if q = 1 and Z is - (CH2), -O-CH2- with n integer from 1 to 9) of formula: 0 020 - 4- (alkenoyloxymethyl) -1,3-dioxolan-2-one (if q = 1 and Z is - (CH2) n, _COO-CH2_ with n 'integer from 1 to 8) of formula: o JE, 0 0 n' 0 particularly preferred, the compound of Formula (15) is 4- (acryloyloxymethyl) -1,3-dioxolan-2-one of the formula: ## STR2 ## or 4-vinyl-1,3-dioxolan-2-one of the formula: ## STR2 ## 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 (DCPD) are very 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 alpha, 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 reaction zone. 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 the like. their mixtures. 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. By Grubbs catalyst is generally meant according to the invention a Grubbs 1st and 2nd generation catalyst, but also any other type of catalyst Grubbs (including ruthenium - carbene) accessible to those skilled in the art, such as for example the Substituted Grubbs catalysts described in US Pat. No. 5,849,851. A 1st generation Grubbs catalyst is generally of formula (8): P (Cy) 3 where Ph is phenyl and Cy is cyclohexyl. The group P (Cy) 3 is a tricyclohexyl phosphine group. The IUPAC name for this compound is: benzylidenebis (tricyclohexylphosphine) dichlororuthenium (CAS number 172222-30-9). A 2nd generation Grubbs catalyst is generally of formula (9): CH 3 H 3 C H 3 C CH 3 Cl s. 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 present invention also relates to any hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl terminal moiety obtainable by the process according to the invention. Preferably, this polymer comprises a terminating terminal group: Cl Ph P (Cy) 3 (8), Cl CH 3 (9) (where q = 0); or (where q = 1 and Z is a methylene connected to an oxy group); or else: C (where q = 1 and Z is methylene connected to a carboxyl group); o (or:) .- n 0 ..-. (where q = 1 and Z is an alkylene of n carbon atoms connected to a methylene via an oxy group); or: ro --Lo (where q = 1 and Z is an alkylene with n 'carbon atoms connected to a methylene via a carboxyl group). In a particularly preferred manner, this polymer has a terminating terminal group: or The preparation process according to the invention may further comprise at least one additional step of hydrogenation of carbon-carbon double bonds. Obviously this step is only carried out on an unsaturated hydrocarbon polymer. Thus, the hydrogenation of at least one carbon-carbon double bond is carried out, preferably with 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 invention also relates to a hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl-terminated end group, said hydrocarbon polymer being capable of being obtained according to the process of the invention, and being of formula ( 1) or (1a): (1) (ibis) wherein: each carbon-carbon bond of the noted chain is a double bond or a single bond, in accordance with the valence rules of organic chemistry; R 6 is hydrogen and R 1 is halo, alkoxycarbonyl or alkyl in formula (1); - R1 is hydrogen and R6 is a halo group, an alkoxycarbonyl group or an alkyl group in the formula (Ibis); 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 bonded to each other or to that of the groups R1 and R6 groups which are not hydrogen as members of the same ring or saturated or unsaturated heterocycle; the group Z is constituted by at least one alkylene group optionally connected to a divalent carboxyl or oxy group, the Z group comprising from 1 to 19 carbon atoms; q is an integer equal to 0 or 1; 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 each other, 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 in the range 600 to 20000 g / mol, and the polymolecularity (PDI) of the hydrocarbon polymer of formula (1) is in a range of 1.1 to 3.0 and preferably 1.2 to 1.6 . The polymer obtainable by the process according to the invention is preferably a polymer of formula (1) or of formula (1a).

In addition, it is polymer but it is more specifically a mixture of polymers represented by the formula (1) or (1a), as is well known to those skilled in the art. In this respect, the molar masses are "average" molar masses in number (Mn, expressed in g / mol). The polymer of formula (1) can therefore be written schematically AxByAT, where A is a monomer unit, Ax represents the sequence AAx_i, B is another monomeric unit and T is the terminal group. This formula corresponds to the case where R6 is H and R1 is different from H. The polymer of formula (1a) can therefore be written schematically BxAyBT, where B is a monomer unit, Bx represents the sequence BBx_i, A is another Monomer unit and T is the terminal group. This formula corresponds to the case where R1 is H and R6 is different from H. However, the writing of formulas (1) and (1a) is obviously for the person skilled in the art a simplified writing. In addition, the sequences of the polymers Ax_iBy or Bx_lAy are of random homogeneous structure (ie consisting of macromolecules in which the probability of finding a given monomeric unit A or B at a given point in 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 the monomeric units obeys known statistical laws). Without wishing to be limited to a theory, the inventors believe that it is highly probable that the chain of polymer Ax_iBy or Bx_lAy is randomly homogeneous structure. Excluding the ends (A and AT, or B and BT), the monomer units A and B would thus be distributed randomly along the main chain of the polymer. In such a polymer, a monomer unit is present at one end of the polymer in connection with T, and the same monomeric unit is present at the other end of the polymer.

When y = 0, this means that there is no group between the brackets to which it applies and that the two carbon-carbon bonds each overlapping one of the brackets constitute a single carbon bond - carbon. Of course all the formulas given here are in agreement with the valence rules of organic chemistry. In the particular case where y = 0 and Z is -COO-CH2-, formula (1) becomes the following formula: (101).

In the particular case where y = 0 and Z is -COO-CH 2 -, formula (1a) becomes the following formula: (101bis). In both cases, the end group is (2-oxo-1,3-dioxolan-4-yl) methyloxycarbonyl. 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. According to the invention, halogeno is understood to mean an iodo, chloro, bromo or fluoro group, 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 linear or branched divalent alkylene group, saturated or partially unsaturated, comprising from one to twenty-two, preferably from one to eight, even more preferably from one to six, carbon atoms, and such that a chain of carbon atoms that it comprises further comprises a divalent group -000-. PDI polymolecularity (or DM dispersity) is defined as the ratio Mw / Mn, i.e., 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. By terminal group is meant a group located at the end of the chain (or end) of the polymer, beyond the repeating monomeric units. If unsaturated, the polymer according to the invention most often comprises a plurality of (i.e. more than two) carbon-carbon double bonds. In a preferred embodiment, the polymers of formula (1) and (1a) comprise only one carbon-carbon double bond per repeating unit, [...] and the polymer is of the formula ) or (1'bis): (1'bis). In this case, preferably, m is equal to 1 and p is equal to 1. In the particular case where y = 0 and Z is -COO-CH 2 -, formula (1 ') becomes the following formula: 101 '). In the particular case where y = 0 and Z is -COO-CH 2 -, formula (1'bis) becomes the following formula: (101'bis). Preferably, the invention relates to a hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl-terminated end group, said hydrocarbon polymer being of formula (2) or of formula (2bis) or of formula (3). ) or of formula (3a): (2) (2a) (3) (3a) in which =, m, p, q, Z, x, y, R1, R2, R3, R4, R5 and R6 have the meanings given further and, as is known to those skilled in the art, the link -r-re means that the link is geometrically oriented on one side or the other with respect to the double bond, ie Z (for Zusammen = cis) or E (for Entgegen = trans). Particularly preferably, m is 1 and p is 1. In the particular case where y = 0 and Z is -COO-CH 2 -, formulas (2), (2bis), (3) and ( 3bis) become the following respective formulas: R5 (102) (102bis) (103) (103bis). The polymer of formula (2) or (2bis) 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. Formula (2bis) illustrates the case where the repeating units of the main chain of the polymer of formula (1a) are unsaturated and each comprise at least one carbon-carbon double bond. In a preferred embodiment, the polymer of formula (2) or (2bis) comprises only one carbon-carbon double bond per repeating unit, and the polymer is of formula (2 ') or (2'bis) : (2 ') (2'bis).

In this case, preferably, m is equal to 1 and p is equal to 1. In the particular case where y = 0 and Z is -COO-CH 2 -, formula (2 ') becomes the following formula: 102 '). In the particular case where y = 0 and Z is -COO-CH 2 -, the formula (2'bis) becomes the following formula: (102'bis). 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).

The formula (3a) illustrates the case where the main chain of the polymer of formula (1a) is saturated. The polymer of formula (3a) may for example be derived from the hydrogenation of the polymer of formula (2a). According to a preferred embodiment of the invention, the invention relates to a hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl terminated end group, said hydrocarbon polymer being of formula (4) or (4bis ): (4) (4a) in which, m, p, q, Z, R1, R6, x and y have the meanings given above.

Formula (4) corresponds to formula (1) wherein R2, R3, R4 and R5 are each hydrogen (H). The formula (4a) corresponds to the formula (1a) in which R2, R3, R4 and R5 are each a hydrogen (H). In a preferred embodiment, the polymer of formula (4) or (4bis) comprises at most only one carbon-carbon double bond per repeating unit, and the polymer is of formula (4 ') or (4) 'bis): R1 (4') 10 (4'bis). According to this embodiment, preferably, the invention relates to a hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl terminated end group, said hydrocarbon polymer being of formula (5) or of formula (5a) ) or of formula (6) or of formula (6bis): embedded image in which,, m, p, q, Z, R 1, R 6, x and y have the meanings further data.

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. Formula (5a) illustrates the case where the repeating unit of the main chain of the polymer of formula (4a) is unsaturated and has at least one carbon-carbon double bond. In a preferred embodiment, the polymer of formula (5) or (5bis) comprises only one carbon-carbon double bond per repeating unit, and the polymer is of formula (5 ') or (5'bis) . In this case, preferably, m is 1 and p is 1. (5 ') (5'bis). 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). Formula (6bis) illustrates the case where the main chain of the polymer of formula (4a) is saturated. The polymer of formula (6a) may for example be derived from the hydrogenation of the polymer of formula (5a).

Formulas (5) and (6) correspond to formulas (2) and (3) in which R2, R3, R4 and R5 are each hydrogen (H). Formulas (5a) and (6a) correspond to formulas (2a) and (3a) in which R2, R3, R4 and R5 are each hydrogen (H).

Advantageously, the hydrocarbon polymer according to the invention, ie capable of being obtained by the process of the invention and / or of formula (1) or (1a), can be used as an additive, most often: as an adhesion promoter in an adhesive composition, most often of the HMA or HMPSA type (HMA for "Hot Melt Adhesive" in English, ie hot melt adhesive, and HMPSA for "Hot Melt Pressure-Sensitive Adhesive"). in English, ie hot melt pressure sensitive adhesive) based on polyolefins or block polymers comprising styrene, or - as a reactive plasticizer in an adhesive composition, generally NIPU type (for "Non Isocyanate PolyUrethane" in English, ie polyurethane without isocyanate) especially for hot crosslinking. 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 terminal moiety end 2-oxo-1,3-dioxolan-4-y1 which advantageously constitutes a polar head located near the hydrocarbon polymer chain and lipophilic . 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 following example illustrates the invention without limiting its scope. The synthesis reaction of Example 4 according to the invention was carried out in a single step of ring-opening polymerization of 3-ethyl-1-cyclooctene in the presence of a Grubbs catalyst and the transfer agent ( CTA) (2-oxo-1,3-dioxolan-4-yl) methyl propenoate. The synthesis reaction of Example 5 according to the invention was carried out in a single step of ring-opening polymerization of 3-ethyl-1-cyclooctene in the presence of a Grubbs catalyst and the transfer agent ( CTA) 4-vinyl-1,3-dioxolan-2-one. The synthesis reaction of Example 6 according to the invention was carried out in a single step of ring-opening polymerization of 3-hexyl-1-cyclooctene in the presence of a Grubbs catalyst and the transfer agent ( CTA) 4-vinyl-1,3-dioxolan-2-one. Experimental Protocol All experiments were performed if necessary under argon atmosphere. 4- (hydroxymethyl) -1,3-dioxolan-2-one (or glycerol carbonate) was a product of ABCR Chemical. The 2nd generation Grubbs catalyst (or 2G or "Grubbs 2nd") was a product of Sigma-Aldrich. 4-Vinyl-1,3-dioxolan-2-one was also a product of Aldrich. 3-Ethyl-1-cyclootene (3-Et-COE) was synthesized as explained below (Example 1). It was degassed once, then dried on CaH2 and finally distilled 30 before use. 3-hexyl-1-cyclootene (3-Hex-COE) was synthesized as explained below (Example 2). It was degassed once, then dried on CaH2 and finally distilled before use.

2-Oxo-1,3-dioxolan-4-yl) methyl propenoate was synthesized from glycerol carbonate as explained below (Example 3). All other products were used as received. NMR spectra were recorded under AM-500 Bruker and AM-400 Bruker spectrometers at 298 K in CDCl3. The chemical shifts were referenced to tetramethylsilane (TMS) using proton (1H) carbon resonance or (13C) deuterated solvent. The number and weight average molecular weights (Mn and MW) and PDI polydispersity (MW / Mn) of the polymers were determined by size exclusion chromatography (SEC), with PolyStyrene calibration using a Polymer Laboratories PL-GPC instrument. 50. The samples were eluted with tetrahydrofuran (THF) (a product of Sigma-Aldrich) at 30 ° C and 1.0 mL / min. Mass spectra were recorded with a high resolution AutoFlex LT (Brucker) spectrometer equipped with an N2 pulsed laser source (337 nm, 4 ns pulse width). EXAMPLE 1 Synthesis of 3-ethyl-1-cyclooctene (3-Et-COE) The compound 3-ethyl-1-cyclooctene (cyclooctene substituted in the 3-position with ethyl) was synthesized according to a procedure described in the literature (Kobayashi, S. Pitet, LM, Hillmyer, MAJ Am., Chem Soc., 2011, 133, 5794-5797). Briefly, ethylmagnesium iodide was prepared by reaction of ethyl iodide (8.04mL, 0.100mol, 2 equiv) and magnesium (3.645g, 0.15mol, 3 equiv) in ether. dry ethyl. To a solution comprising 3-bromo-1-cyclooctene (9.5g, 0.050mol, 1 equiv) (Hardinger, SA, Fuchs, PLJ Org Chem 1987, 52, 27392749) and copper iodide Cul (0.101 g, 0.53mmol, 0.0106 equiv.) in dry THF, the magnesium compound in ether solution was gently added at 0 ° C for a period of 15 min under argon flow. The reaction medium was then brought to ambient temperature (approximately 20 ° C.) and stirring was continued for 3 hours. The solution was then cooled with ice. The aqueous phases were extracted three times with ether. The organic phases were then combined, dried over MgSO 4 and concentrated in vacuo. The product thus obtained was purified by fractional distillation on CaH 2 (40-50 Torr, ie 5.3-6.7kPa, boiling point = 66-68 ° C) to yield the product 3-ethyl-1-cyclooctene ( 4.3g, 62% yield). NMR analyzes of the product thus obtained gave the following values, which confirm the structural formula of the product: 1H NMR spectrum (400 MHz, CDCl3, 298 K) Eippm 5.62 (m, 1H), 5.20 (m, 1H), 2.36- 2.20 (m, 2H), 2.05 (m, 1H), 1.66-1.31 (m, 10H), 1.14 (m, 1H), 0.91 (t, 3H). Example 2 Synthesis of 3-hexy-1-cyclooctene (3-Hex-COE) The 3-hexy-1-cyclooctene compound (cyclooctene substituted at the 3-position with a hexyl) was synthesized according to a procedure described in the literature ( Kobayashi, S. Pitet, LM, Hillmyer, MAJ Am., Chem Soc., 2011, 133, 5794-5797). Briefly, hexylmagnesium iodide was prepared by reacting hexyl iodide (14.76mL, 0.100mol, 2 equiv) and magnesium (3.645g, 0.15mol, 3 equiv) in ethyl ether dry. To a solution comprising 3-bromo-1-cyclooctene (9.5g, 0.050mol, 1 equiv) (Hardinger, SA, Fuchs, PLJ Org Chem 1987, 52, 27392749) and copper iodide Cul (0.101 g, 0.53mmol, 0.0106 equiv.) in dry THF, the magnesium compound in ether solution was gently added at 0 ° C for a period of 15 min under argon flow. The reaction medium was then brought to ambient temperature (approximately 20 ° C.) and stirring was continued for 3 hours. The solution was then cooled with ice. The aqueous phases were extracted three times with ether. The organic phases were then combined, dried over MgSO4 and concentrated in vacuo. The product so obtained was purified by fractional distillation over CaH 2 (40-50 Torr, boiling point = 66-68 ° C) to afford the product 3-hexyl-1-cyclooctene (6.0 g, 62% yield). NMR analyzes of the product thus obtained gave the following values, which confirm the structural formula of the product: 1H NMR spectrum (400 MHz, CDCl3, 298 K) Eippm 5.63 (m, 1H), 5.21 (m, 1H), 2.46 ( m, 1H), 2.22 (m, 1H), 2.03 (m, 1H), 1.70-1.36 (m, 5H), 1.17 (m, 15H), 1.12 (m, 1H), 0.91 (t, 3H).

Example 3 Synthesis of (2-oxo-1,3-dioxolan-4-yl) methyl propenoate The reaction was carried out according to the following scheme 1: CH 2 Cl 2 reflux, 5 h (CTA) 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-CH 2 CO 2), 5.9 (1H, d, JHH = 10.7 Hz, CH2 = CH), 6.1 (1H, m, CH2 = CH), 6.4 (1H, d, JHH = 17.2 Hz, CH2 = CH). 13C NMR {1H} (CDCl3, 298 K): δ = 63.2, 66.2 (CH2-5CC), 74.0 (CH-5CC), 127.2 (CH2 = CH-), 132.5 (CH2 = CH-), 154.8 (0 = C00), 165.5 (0 = C0). Thus, (2-oxo-1,3-dioxolan-4-yl) methyl propenoate of formula 20 was obtained. EXAMPLE 4 Synthesis of a polymer comprising a terminal group (2-oxo-1,3-dioxolan-4- yl) methyloxycarbonyl from 3-ethyl-1-cyclooctene (3-Et-COE) synthesized in Example 1 and 2-oxo-1,3-dioxolan-4-yl) methyl propenoate (CTA) synthesized at 1 Example 3 The general reaction scheme (Scheme 2) of the polymerization of Example 4 is as follows. O C2H5 --- ° O>. (2) Scheme No. 2 Where Grubbs 2G is the catalyst of formula (9) and where x is the number of moles of CTA; n is the number of moles of 3-Et-COE, and s is the number of repeats of the monomer unit in the polymer. The polymer thus obtained is of formula (10). Grubbs 2G CH2Cl2, 40 ° C, 24h 0 (11) + x 0 The monomer 3-ethyl-1-cyclooctene (2g) and dry CH2Cl2 (5mL) were placed in a 100mL reactor with a magnetic stirrer. The reactor was placed under argon. CTA was added to the syringe. The reactor was placed in an oil bath at 40 ° C. and then the catalyst ("Ru") (5.0 mg) in solution in CH 2 Cl 2 (2 ml) was introduced using a cannula. The reaction medium was stirred at 40 ° C. After 24h reaction, the solvent was concentrated in vacuo. The polymer was precipitated in methanol, filtered and dried under vacuum at 25 ° C (94% yield). The polymer thus prepared is a colorless oil, soluble in chloroform and THF, and insoluble in methanol.

Two different tests were conducted according to this reaction. They are summarized in Table 1 below. The number average molecular weight of the polymer (MnsEc) was determined by SEC in THF at 30 ° C. Table 1 [3-Et-Mn PDI Conversion SEC COE] / [CTAV [Ru] (%) (g / mol) (mol / mol) 2,000: 100: 1,100,900 1,50 E2 2,000: 30: 1,100 17,700 1.50 NMR analyzes of the polymer obtained in the El test gave the following values, which confirm the structural formula (10) of this polymer. 1H NMR spectrum (400 MHz, CDCl3, 298 K) Einsm 1.28-1.39, 2.00, 5.08, 532, End of chain: 7.05 (m, -CH = CH-OO 2 -), 5.86 (m, -CH = CH-OO 2 -), 5.32 (m, CH2 = CH-CH-), 5.08 (m, CH2 = CH-CH-), 4.98 (m, -O-CH2-CH-), 4.53 (m, -O-CH2-CH) -), 4.31 (m, -CH-CH 2 -O-CO-O-), 1.81 (m, -CH-CH 2 -CH 3), 1.20 (m, -CH-CH 2 -CH 3), 0.85 (t, -CH 2 CH3). 13C {1H} NMR spectrum (100 MHz, CDCl3, 298 K). Δmax 134.7, 130.3, 35.3, 32.6, 29.9, 28.3, 27.2, End of chain: 165.7 (-CH = CH-CO-O-), 154.3 (-O-CO-O-), 151.8 (-CH = CH- CO-O-), 143.1 (-CH = CH-CO-O-), 119.8 (CH2 = CH-), 114.0 (CH2 = CH-), 73.8 (-O-CH2-CH-O-CO-O- ), 65.9 (-O-CH 2 -CH-O-CO-O-), 62.9 (-CH-CH 2 -O-CO-O-), 44.5 (CH 2 = CH-CH-), 35.3 (-CH-CH 2) -CH3), 11.9 (-CH2-CH3). The glass transition temperature Tg is -62 ° C as measured by DSC (10 ° C / min). Test El Example 5 Synthesis of a polymer comprising a 2-oxo-1,3-dioxolan-4-yl end group from 3-ethyl-1-cyclooctene (3-Et-COE) synthesized in Example 1 and 4-yinyl-1,3-dioxolan-2-one. The synthesis reaction was carried out by ROMP ring opening polymerization of 3-ethyl-1-cyclooctene (3-Et-COE) in the presence of a catalyst. Grubbs and 4-vinyl-1,3-dioxolan-2-one transfer agent (CTA) (12). The reaction was carried out according to Scheme 3 below: (13) Scheme No. 3 The monomer 3-ethyl-1-cyclooctene (2g) and dry CH2Cl2 (5mL) were placed in a 100mL reactor with a stirrer magnetic. The reactor was placed under argon. CTA was added to the syringe. The reactor was placed in an oil bath at 40 ° C and then the Grubbs 2G (or "Ru") catalyst (5.0 mg) in solution in CH 2 Cl 2 (2 mL) was introduced using a cannula. The reaction medium was stirred at 40 ° C. After 24h reaction, the solvent was concentrated in vacuo. The polymer was precipitated in methanol, filtered and dried under vacuum at 25 ° C (94% yield). The polymer thus prepared is a colorless oil, soluble in chloroform and THF, and insoluble in methanol.

Two different tests were conducted according to this reaction. They are summarized in Table 2 below. The number average molecular weight of the polymer (MnsEc) was determined by SEC in THF at 30 ° C. Table 2 [3-Et- Conversion Mn PDI SEC COE] / [CTAV [Ru] (%) (g / mol) (mol / mol) 2,000: 100: 1,100 6,500 1.39 E4 2,000: 30: 1,100 19,700 1,52 NMR analyzes of the polymer obtained in the E3 test gave the following values, which confirm the structural formula (13) of this polymer. Test E3 1H NMR spectrum (400 MHz, CDCl3, 298 K) δppm 1.28, 1.97, 5.00, 530, End of chain: 5.66 (m, -CH = CH-CH-), 5.52 (m, -CH = CH-CH -O-), 5.48 (m, 0-CH-), 5.44 (m, CH 2 = CH-), 5.08 (m, CH 2 = CH), 1.79 (m, -CH-CH = CH 2), 1.20 (m, -CH 2 -CH 3), 0.81 (t, -CH 2 -CH 3). 13C {1H} NMR spectrum (100 MHz, CDCl3, 298 K). Eippm 134.8, 130.3, 129.9, 38.8, 35.7, 32.6 30.0, 27.2, 11.9, End of chain: 154.9 (-O-CO-O-), 144.0 (-CH = CH-CH-), 143.3 (CH2 = CH- CH), 123.9 (-CH = CH-CH-), 113.9 (CH2 = CH-), 77.8 (-CH-O-CO-), 69.6 (-CH2-O-CO-), 44.6 (-CH- CH = CH2), 29.3 (-CH2-CH3), 11.9 (-CH2-CH3).

The glass transition temperature Tg is -62 ° C as measured by DSC (10 ° C / min). Example 6 Synthesis of a polymer comprising a 2-oxo-1,3-dioxolan-4-yl end group from 3-hexy-1-cyclooctene (3-Hex-COE) synthesized in Example 2 and The synthesis reaction was carried out by ROMP ring opening polymerization of cyclooctene (3-Hex-COE) in the presence of a Grubbs catalyst and a reaction mixture of 3-hexyl-1,3-dioxolan-2-one (12). transfer agent (CTA) 4-vinyl-1,3-dioxolan-2-one (12). The reaction was carried out according to the following scheme 4: Scheme No. 4 The monomer 3-hexyl-1-cyclooctene (2g) and dry CH 2 Cl 2 (5mL) were placed in a 100mL reactor with a magnetic stirrer. The reactor was placed under argon. CTA was added to the syringe. The reactor was placed in an oil bath at 40 ° C. and the Grubbs 2G (or "Ru") catalyst (5.0 mg) in solution in CH 2 Cl 2 (2 ml) was introduced using a cannula. . The reaction medium was stirred at 40 ° C. After 24h reaction, the solvent was concentrated in vacuo. The polymer was precipitated in methanol, filtered and dried under vacuum at 25 ° C (92% yield). The polymer thus prepared is a colorless oil, soluble in chloroform and THF, and insoluble in methanol.

A test was conducted according to this reaction. It is summarized in Table 3 below. The number average molecular weight of the polymer (MnsEc) was determined by SEC in THF at 30 ° C.

Table 3 [3-Et-Mn PDI Conversion SEC COE] / [CTAV [Ru] (%) (g / mol) (mol / mol) 2,000: 100: 1,100 7,300 1,30 NMR analyzes of the polymer obtained in test E5 gave the following values, which confirm the structural formula (10) of this polymer. 1H NMR spectrum (400 MHz, CDCl3, 298 K) δppm 5.31, 5.10, 1.99, End of chain: 5.72 (m, -CH = CH-CH-O-), 5.39 (m, CH2 = CH-), 5.34 ( m, -CH = CH-CH-O-), 5.07 (m, CH 2 = CH-), 4.92 (m, 4.53 (m, -O-CH 2 -CH-), 4.09 (m, -O-CH 2 -CH). -), 1.87 (m, -CH-CH = CH2), 1.21 (m, - (CH2) 5-CH3), 0.89 (- (CH2) 5-CH3) 13C {1H} NMR spectrum (100 MHz, CDCl3 , 298 K) Eippm 135.7, 135.0, 130.0, 129.1, 35.7, 32.0-22.1, End of chain: 154.7 (-O-CO-O-), 144.2 (-CH = CH-CH-), 143.6 (-CH = CH2), 124.0 (-CH = CH-CH-), 113.8 (CH2 = CH-), 77.9 (-CH = CH-CH-O-CO-O-), 69.3 (-CH-CH2-O-CO) -O-), 42.9 (-CH-CH = CH2), 32.7 (-CH-CH2-), 14.1 (CH3- (Cl-12) 5-) The glass transition temperature Tg is -77 ° C , measured by DSC (10 ° C / minute).

Test E5

Claims (10)

REVENDICATIONS1. Process for the preparation of at least one hydrocarbon polymer comprising a terminally terminated group 2-oxo-1,3-dioxolan-4-yl, said process comprising at least one metathesis ring opening polymerization step in the presence of: at least one metathesis catalyst, preferably a catalyst comprising ruthenium, more preferably, a Grubbs catalyst, at least one chain transfer agent (CTA) compound of formula (15): where Z is at least one alkylene group optionally connected to a group divalent carboxyl or oxy, the Z group having from 1 to 19 carbon atoms and q being an integer equal to 0 or 1; and at least one compound selected from compounds comprising at least one hydrocarbon 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): wherein each carbon-carbon bond of the noted chain is a double bond or a single bond, in accordance with the valence rules organic chemistry; one of R1 and R6 is hydrogen and the other of R1 and R6 is halo, alkoxycarbonyl or alkyl; 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 bonded to each other or to that of the groups R1 and R6 groups which are not hydrogen as members of the same ring or saturated or unsaturated heterocycle; m and p are integers each included in a range from 0 to 5, the sum m + p being itself in a range of 0 to 6. 2. Preparation process according to claim 1, said method being such that the compound of formula (15) is selected from 4-vinyl-1,3-dioxolan-2-one, 4- (vinyloxymethyl) -1,3-dioxolan-2-one, 4- (acryloyloxymethyl) 1,3-dioxolan-2-one, 4- (alkenyloxymethyl) -1,3-dioxolan-2-one and 4- (alkenoyloxymethyl) -1,3-dioxolan-2-one. 3. Preparation process according to any one of claims 1 or 2, said method further comprising at least one additional step of hydrogenation of carbon-carbon double bonds. 4. A hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl terminated end group, said hydrocarbon polymer being obtainable by the method according to any one of claims 1 to 3. 5. A hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl terminated end group according to claim 4, said hydrocarbon polymer being of formula (1) or (ibis): (1) (ibis) in which : - each carbon-carbon bond of the noted chain is a double bond or a single bond, in accordance with the valence rules of organic chemistry; R 6 is hydrogen and R 1 is halo, alkoxycarbonyl or alkyl in formula (1); - R1 is hydrogen and R6 is a halo group, an alkoxycarbonyl group or an alkyl group in the formula (Ibis); 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 bonded to each other or to that of the groups R1 and R6 groups which are not hydrogen as members of the same ring or saturated or unsaturated heterocycle; the group Z is constituted by at least one alkylene group optionally connected to a divalent carboxyl or oxy group, the Z group comprising from 1 to 19 carbon atoms; q is an integer equal to 0 or 1; 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 each other, 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 in the range of 600 to 20000 g / mol, and the polylolecularity (PDI) of the hydrocarbon polymer of formula (1) is in a range of 1.1 to 3.0 and preferably 1.2 to 1.6. 6. A hydrocarbon polymer according to claim 5, wherein said hydrocarbon polymer is of formula (2) or of formula (2a) or of formula (3) or of formula (3a): (2) (2a) (3) (3a) in which, m, p, q, Z, x, y, R1, R2, R3, R4, R5 and R6 have the meanings given in claim 5, and the bond - means that the bond is geometrically oriented on the side or on the other with respect to the double bond (cis or trans). 7. A hydrocarbon polymer according to claim 5, said hydrocarbon polymer being of formula (4) or (4a): R, (4) (4a) in which, m, p, q, Z, R1, R6, x and y have the meanings given in claim 5. 8. A hydrocarbon polymer comprising a 2-oxo-1,3-dioxolan-4-yl terminated end group according to claim 5, said hydrocarbon polymer being of formula (5) or of formula (5a) or of formula (6) or of formula (6bis): (5) (5a) (6) (6a) wherein,, m, p, q, Z, R1, R6, x and y have the meanings given in claim 5 or claim 6.20 9. Use of at least one hydrocarbon polymer according to one of claims 4 to 8, as an adhesion promoter in an adhesive composition. 10. Use of at least one hydrocarbon polymer according to one of claims 4 to 8, as a reactive plasticizer in an adhesive composition.