• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    The present invention relates to a method for grafting carboxylic acid ester functionality onto an unsaturated polymer which comprises reacting a 1,3-dipolar compound on at least one unsaturated unsaturated polymer, which compound comprises a Q group and a group B linked together by a group A in which: Q comprises a dipole containing at least and preferably a nitrogen atom, B represents a carboxylic acid ester function, A, preferably divalent, is an atom or a group of atoms connecting Q to B.
    公开号:FR3021320A1
    申请号:FR1454660
    申请日:2014-05-23
    公开日:2015-11-27
    发明作者:Anne-Frédérique Salit
    申请人:Michelin Recherche et Technique SA Switzerland ；Compagnie Generale des Etablissements Michelin SCA；Michelin Recherche et Technique SA France；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a process for the synthesis of a polymer comprising an unsaturated carbon chain and carboxylic acid ester functions along the polymer chain. The synthesis of polymers having both an unsaturated carbon chain and carboxylic acid ester functions along the polymer chain can be achieved by the radical copolymerization of 1,3-diene and methacrylate. Reference can be made to patent EP 1 451 246 B1 which describes such a method. This synthetic process is very widely known. The success of this process stems in part from the availability of many methacrylate monomers on the market. However, it is still of interest to have alternative synthesis methods to those already known, to give the opportunity to use the process that will prove most appropriate to the case. The Applicants have discovered a new process for the synthesis of a polymer having an unsaturated carbon chain and carboxylic acid ester functions along the polymer chain. This discovery was made possible by the development of a new compound. Thus, a first object of the invention is a method for synthesizing an unsaturated polymer comprising at least one carboxylic acid ester function along the polymer chain, which process comprises reacting a 1,3-dipolar compound on at least one an unsaturation of the unsaturated polymer, which 1,3-dipolar compound comprises a group Q and a group B connected to each other by a group A in which: Q comprises a dipole containing at least and preferably a nitrogen atom, B represents a carboxylic acid ester function, A, preferably divalent, is an atom or a group of atoms connecting Q to B.
    [0002] The invention also relates to a polymer which can be obtained by the process according to the invention. Another object of the invention is a composition which comprises a filler and a polymer according to the invention. I. DETAILED DESCRIPTION OF THE INVENTION In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are% by weight. The abbreviation "pce" means parts by weight per hundred parts of elastomer (of the total elastomers if several elastomers are present).
    [0003] On the other hand, any range of values designated by the expression "between a and h" represents the range of values greater than "a" and less than "h" (i.e., terminals a and b excluded). while any range of values designated by the expression "from a to h" means the range of values from "a" to "h" (i.e. including the strict limits a and b).
    [0004] By unsaturated polymer is meant a polymer having an unsaturated carbon chain. The 1,3-dipolar compound has the essential characteristic of comprising a group Q and a group B linked together by a group A in which: Q comprises a dipole containing at least and preferably a nitrogen atom, B represents a functional group carboxylic acid ester, A, preferably divalent, is an atom or a group of atoms connecting Q to B. The term 1,3-dipolar compound is included as defined by IUPAC.
    [0005] According to one embodiment of the invention, the group B corresponds to the formula (I) -C (OR) = O (I) in which R is a carbon group which may contain at least one heteroatom. The carbon group which may contain a heteroatom preferably contains 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms. According to any embodiment of the invention, those having 1 to 3 carbon atoms, such as the methyl group or the ethyl group, are suitable as the carbon group.
    [0006] A may be a group containing up to 20 carbon atoms, which group may contain at least one heteroatom. A may be an aliphatic or aromatic group. When A is an aliphatic group, A preferably contains 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms, especially 1 to 3 carbon atoms. When A is an aromatic group, A preferably contains 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. As divalent group A is particularly suitable an alkylene group containing 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms. As the divalent group A containing 1 to 3 carbon atoms, the methylene group is suitable.
    [0007] As divalent group A may also be suitable arylene group containing preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Particularly suitable 1,3-dipolar compounds are compounds selected from the group consisting of nitrile oxides, nitrile imines and nitrones, in which case Q contains a -C1 10, -CNN- or -C = I moiety. 1 (0) -. According to the particular embodiment of the invention in which Q comprises a -C.1 -> 0 motif, Q preferably comprises the unit corresponding to formula (II) in which four of the five identical or different symbols R1 to R5, are each an atom or a group of atoms and the fifth symbol denotes a direct or indirect attachment to A, wherein R1 and R5 are both different from H. The four of the five symbols R1 to R5 may be aliphatic groups or aromatics. The aliphatic groups may contain 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms. The aromatic groups can contain 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms.
    [0008] R5 R4, R3 and R5 are each preferably an alkyl group of 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, more preferably a methyl or ethyl group. According to a variant of this particular embodiment of the invention, R1, R3 and R5 are identical. According to this variant in which they are identical, R 1, R 3 and R 5 are each preferably an alkyl group of 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, even more preferentially a methyl or ethyl group. In the case where the fifth symbol denotes an indirect attachment to A, the fifth symbol preferably represents a heteroatom, preferably oxygen. More preferably, the 1,3-dipolar compound is the 3- (2-ethoxy-2-oxoethoxy) -2,4,6-trimethylbenzonitrile oxide compound having the formula (IIa). Particular embodiment of the invention wherein Q comprises a unit -C = N (O) -, Q preferably comprises the unit corresponding to formula (111) or (IV) Y1-HCNI '. O Y2 Y 02-HC ,, ,. N (IV) Y1 in which: Y1 is an aliphatic group, preferably an alkyl group preferably containing 1 to 12 carbon atoms, or an aromatic group containing 6 to 20 carbon atoms, preferentially an alkylaryl group, more preferably a phenyl group or tolyl, and Y 2 is an aliphatic group, preferably an alkyl group preferably containing 1 to 12 carbon atoms, or an aromatic group preferably containing 6 to 20 carbon atoms and having on its benzene ring a direct attachment to A. The process according to the invention comprises the reaction of the 1,3-dipolar compound described above on at least one unsaturation of an unsaturated polymer. According to any embodiment of the invention, the 1,3-dipolar compound preferably reacts on several unsaturations of the unsaturated polymer, in which case the process according to the invention allows the synthesis of an unsaturated polymer comprising several functions. carboxylic acid ester along the polymer chain. We mean by several unsaturations at least 2 unsaturations. The reaction of the 1,3-dipolar compound on the polymer is an addition reaction, in this case [3 + 2] cycloaddition.
    [0009] According to a preferred embodiment of the invention, the unsaturations of the polymer are carbon-carbon bonds, preferably carbon-carbon double bonds. The reaction of the 1,3-dipolar compound on the polymer can be carried out in bulk, for example in an internal mixer or an external mixer such as a roll mill. The mixture comprising the 1,3-dipolar compound and the polymer is, for example, brought to a temperature of the external mixer or of the internal mixer below 60 ° C., then placed in a press or in an oven at temperatures ranging from 80 ° C. to 200 ° C. ° C. Alternatively the mixture is brought to a temperature of the external mixer or the internal mixer above 60 ° C without subsequent heat treatment. The addition reaction of the 1,3-dipolar compound on the polymer can also be carried out in solution. The temperature at which the reaction is conducted is easily adjusted by one skilled in the art from his general knowledge taking into account the concentration of the reaction medium, the reflux temperature of the solvent, the thermal stability of the polymer and the compound. 1,3-dipolar. For example, a temperature around 60 ° C may be suitable. The polymer thus modified can be separated from its solution by any type of means known to those skilled in the art and in particular by an operation of evaporation of the solvent under reduced pressure or by a stripping operation with water vapor . In the addition reaction of the 1,3-dipolar compound on the polymer, the 1,3-dipolar compound is reacted with a preferred stoichiometry of between 0 and 5 molar equivalents, more preferably between 0 and 2 molar equivalents, and even more preferably between 0 and 1 mole equivalent, of carboxylic acid ester function per 100 moles of monomer units constituting the polymer. For each of these preferred ranges, the lower limit is advantageously at least 0.1 molar equivalent of 1,3-dipolar compound. The amount of 1,3-dipolar compound used is expressed in molar equivalents of carboxylic acid ester function. For example, if the 1,3-dipolar compound contains a single carboxylic acid ester function, one mole of 1,3-dipolar compound corresponds to one mole of carboxylic acid ester function. If the 1,3-dipolar compound contains two carboxylic acid ester functions to one mole of 1,3-dipolar compound corresponds to two moles of carboxylic acid ester functions. In the latter case, the use of the 1,3-dipolar compound according to a molar equivalent of carboxylic acid ester function corresponds to a half-mole of 1,3-dipolar compound. Preferably, the reaction of the 1,3-dipolar compound on the polymer is carried out in solution or in bulk, the polymer is previously antioxidized to prevent possible degradation of the macrostructure of the polymer during the reaction. The unsaturated polymer before undergoing the addition reaction of the 1,3-dipolar compound has at least one and preferably several unsaturations which are capable of reacting with the 1,3-dipolar compound according to the invention. .
    [0010] The unsaturated polymer is preferably a diene polymer, more preferably a diene elastomer. The term "diene polymer" is intended to include a polymer comprising diene monomeric units, in particular 1,3-diene monomer units. By "diene" elastomer (or indistinctly rubber) is to be understood in known manner an elastomer consisting at least in part (ie, a homopolymer or a copolymer) of monomeric diene units (monomers carrying two carbon-carbon double bonds, conjugated or not). These diene elastomers can be classified into two categories: "essentially unsaturated" or "essentially saturated". The term "essentially unsaturated" is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%); Thus, diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may in particular be described as "essentially saturated" diene elastomers ( low or very low diene origin, always less than 15%). In the category of "essentially unsaturated" diene elastomers, the term "highly unsaturated" diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
    [0011] These definitions being given, the term "diene elastomer" may be understood more particularly to be used in the compositions according to the invention: (a) - any homopolymer of a conjugated diene monomer, especially any homopolymer obtained by polymerization of a diene monomer conjugate having from 4 to 12 carbon atoms; (b) - any copolymer obtained by copolymerization of one or more conjugated dienes with each other or with one or more vinyl aromatic compounds having from 8 to 20 carbon atoms; (c) - a ternary copolymer obtained by copolymerization of ethylene, an α-olefin having 3 to 6 carbon atoms with a non-conjugated diene monomer having 6 to 12 carbon atoms, as per examples elastomers obtained from ethylene, propylene with a non-conjugated diene monomer of the aforementioned type such as in particular 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene; (d) - a copolymer of isobutene and isoprene (butyl rubber), as well as the halogenated versions, in particular chlorinated or brominated, of this type of copolymer. Although it applies to any type of diene elastomer, one skilled in the art of the tire will understand that the present invention is preferably carried out with essentially unsaturated diene elastomers, in particular of the type (a) or (b). ) above. In the case of copolymers of type (b), these contain from 20 to 99% by weight of diene units and from 1 to 80% by weight of vinylaromatic units. As conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5 alkyl) -1,3-butadienes, such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3 butadiene, an aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene. Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, "vinyl-toluene" commercial mixture, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene. Preferably, the diene elastomer is a substantially unsaturated elastomer selected from the group consisting of polybutadienes (BR), polyisoprenes, butadiene copolymers, isoprene copolymers, and mixtures of these elastomers. As diene elastomer is particularly suitable polybutadiene (BR), a copolymer of butadiene and styrene (SBR), a natural rubber (NR) or a synthetic polyisoprene (IR) preferably having a molar ratio of cis-bond 1.4 greater than 90%. The invention also relates to the polymer which can be obtained by the process described in any one of its embodiments. The polymer according to the invention may be used in a polymer composition which may contain, in addition to the polymer according to the invention, a filler, preferably a reinforcing filler. As a reinforcing filler, mention may be made of carbon black, a reinforcing inorganic filler such as silica with which a coupling agent is associated in known manner, or a mixture of these two types. as a reinforcing silica or a carbon black. The coupling agent, in particular a silane, (or bonding agent) is at least bifunctional intended to ensure a sufficient connection, of a chemical and / or physical nature, between the inorganic filler (surface of its particles) and the polymer. In particular, organosilanes or at least bifunctional polyorganosiloxanes are used. In particular, polysulfide silanes, called "symmetrical" or "asymmetrical" silanes according to their particular structure, are used, as described, for example, in claims WO 03/002648 (or US 2005/016651) and WO 00/002649 (or US 2005/016650). In particular, polysulphide silanes having the general formula (V) Z - A - Sx - A - Z (V) in which: - x is an integer of 2 to 8 ( preferably from 2 to 5); the symbols A, which are identical or different, represent a divalent hydrocarbon radical (preferably a C 1 -C 18 alkylene group or a C 6 -C 12 arylene group, more particularly a C 1 -C 4, especially C 1 -C 4, alkylene, especially propylene); the symbols Z, which are identical or different, correspond to one of the following three formulas: ## STR2 ## in which: the radicals R 1, substituted or unsubstituted, identical or different from each other, represent a C1-C18 alkyl, C5-C18 cycloalkyl or C6-C18 aryl group (preferably C1-C6 alkyl, cyclohexyl or phenyl groups, especially alkyl groups; C1-C4, more particularly methyl and / or ethyl). the radicals R2, substituted or unsubstituted, which are identical to or different from one another, represent a C1-C18 alkoxyl or a C5-C18 cycloalkoxyl group (preferably a group chosen from C1-C8 alkoxyls and C5-C8 cycloalkoxyls, plus still more preferably a group chosen from C1-C4 alkoxyls, in particular methoxyl and ethoxyl). The composition may also comprise all or part of the usual additives usually used in polymer compositions, for example plasticizers or extension oils, pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants, anti-fatigue agents, a crosslinking system. The aforementioned features of the present invention, as well as others, will be better understood on reading the following description of several embodiments of the invention, given by way of illustration and not limitation. II. EXAMPLES OF EMBODIMENT OF THE INVENTION II.1-Measurements and Tests Used: NMR Analysis: The structural analysis as well as the determination of the molar purities of the synthesis molecules are carried out by NMR analysis. The spectra are acquired on a BRUKER Avance 3 400 MHz spectrometer equipped with a 5 mm BBFO-zgrad "broadband" probe. The quantitative 1H NMR experiment uses a 30 ° single pulse sequence and a 3 second repetition time between each of the 64 acquisitions. The samples are solubilized in deuterated dimethylsulfoxide (DMSO). This solvent is also used for the lock signal. Calibration is performed on the deuterated DMSO proton signal at 2.44 ppm and on the deuterated DMSO carbons at 39.5ppm against a TMS reference at Oppm. The 1H NMR spectrum coupled to the 2D experiments HSQC 1H / 13C and HMBC 1H / 13C allow the structural determination of the molecules (see tables of attributions). The molar quantifications are made from the quantitative 1H 1H NMR spectrum.
    [0012] II.2-Synthesis of the 1,3-dipolar compound 3- (2-ethoxy-2-oxoethoxy) -2,4,6-trimethylbenzonitrile oxide: This compound can be prepared according to the following reaction scheme: TiCl 4, CH 2 Cl 2 HO 0 EtO ## STR2 ## The preparation of the compound 3-hydroxy-2,4,6-trimethylbenzaldehyde is described in the article Yabukov, AP; Tsyganov, D.V .; Belen'kii, L.I. ; Krayushkin, M.M .; Bulletin of the Academy of Sciences of the USSR, Division od Chemical Science (English Translation); flight. 40; 7.2; (1991); p. 1427-1432; lzvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; nb. 7 (1991); p 1609-1615. 11.2-1-Synthesis of ethyl-2- (3-formyl-2,4,6-trimethylphenoxy) acetate: EtOAc K2CO3, DMF A mixture of 3-hydroxy-2,4,6-trimethylbenzaldehyde (30, 00 g, 0.183 mol) and K2CO3 (18.94 g, 0.137 mol) in DMF (110 mL) is stirred at room temperature for 10-15 minutes. To this mixture is added ethyl chloroacetate (22.4 g, 0.183 mol) in DMF (15 ml). The temperature of the mixture is raised to 74 ° C for 4 hours. After cooling to room temperature, the mixture is diluted with water (800 ml) and CH2Cl2 (150 ml). The aqueous phase is extracted with CH 2 Cl 2 (3 times in 50 ml). The organic phases are combined and washed with a solution of NaOH (5.0 g, 0.125 mol) in water (100 ml), washed with water (4 times per 100 ml) and concentrated under reduced pressure until the reaction is complete. at 21 mbar (36 ° C). A white solid (42.96 g, 94% yield) with a melting point of 55 ° C. is obtained. The molar purity is greater than 98% (1 H NMR). NMR analysis: ## STR2 ## ## STR13 ## 12 3 0H3 11 14 1 Solvent: DMSO N ° 6 iH (ppm) 6 13C (ppm) 1 1.18 14.4 2 4.13 60.9 3 / 168.8 4 4.37 49.5 5 / 153.9 6/10/13 / Between 130 and 140 7 2.39 12.4 8 / 131.7 P10-3329 No. 6 iH (ppm) 6 13C (ppm) 9 10.36 194.1 11 2.39 19.7 12 6.94 132.1 14 2.20 16.7 11.2-2-Synthesis of ethyl-2- (3 - ((hydroxyimino) methyl) -2,4,6-trimethylphenoxy) acetate: NH 2 OH, OH CH 2 Cl 2 to a solution of ethyl-2- (3-formyl-2,4,6-trimethylphenoxy) acetate (42.5 g, 0.170 mol) in EtOH ( 250 ml) at 40 ° C is added an aqueous solution of hydroxylamine (13.5 g, 0.204 mol, 50% in water, Aldrich) in EtOH (25 ml). The reaction medium is then stirred at a temperature between 45 ° C and 50 ° C. After 4 hours at this temperature, water (50 ml) is added to the reaction medium. The reaction medium is evaporated under reduced pressure (Tbain 37 2C, 80 mbar) until a suspension is obtained. The precipitate obtained is filtered and washed on the filter with EtOH / water (15 ml / 45 ml), then with EtOH / petroleum ether (15 ml / 45 ml) and finally with petroleum ether (2 x 30 ml). The product obtained is dried under atmospheric pressure at room temperature. A white solid (31.83 g, 73% yield) with a melting point of 89 ° C. is obtained. The molar purity is greater than 99% (NMR NMR analysis: H 3 C 1 H 2 O 3 H 3 C77 9 9 N-O-CH 1 3-4 6-8 / 1 O O 5 11 11 3 13- 12 H3C 14 Solvent: DMSO No. 6 iH (ppm) 6 13C (ppm) 1 1.17 13.8 2 4.13 60.2 3 / 168.5 4 4.34 68.8 5 / 152.9 P10-3329 - 12 - No. 6 iH (ppm) 6 13C (ppm ) 6/8/10/13 / Between 129.2 and 132.2 7 2.17 13.2 9 8.19 147.3 11 2.18 20.1 12 6.86 130.3 14 2.14 15.6 11.2-3-Synthesis of 3- (2-ethoxy-2-oxoethoxy) -2,4 6-trimethylbenzonitrile oxide: NaOCI CH 2 Cl 2 A solution of ethyl 2- (3 - ((hydroxyimino) methyl) -2,4,6-trimethylphenoxy) acetate (20.0 g, 0.075 mol) in CH 2 Cl 2 (450 ml) is cooled to -4 ° C. Once at this temperature, bleach (4% active chlorine, Aldrich) (92 ml) is added dropwise for 5 minutes. the addition is maintained between -4 ° C. and-1 ° C. The reaction medium is then stirred for 35 minutes between 0 and 5 ° C. and then stirred until it returns to ambient temperature (3 ° C.). 0 - 3.5 hours) The aqueous phase is separated and washed with CH 2 Cl 2 (3 times in 20 ml). The combined organic phases are washed with water (3 times with 75 ml) and concentrated under reduced pressure (Tbain 2C) until 50 ml (97 g). The solution obtained is diluted with petroleum ether (120 ml, fractions 40/60 ° C) and concentrated under reduced pressure (Tbain 2C) until a precipitate forms. After 4-5 hours at -18 ° C., the precipitate is filtered and washed on the filter with CH 2 Cl 2 / petroleum ether (5 ml / 20 ml) and then with petroleum ether (2 times each). ml, 40/60 ° C fractions) and finally dried for 12 hours at atmospheric pressure at room temperature. A white solid (13.67 g, 0.052 mol, 69% yield) with a melting point of 102 ° C. is obtained. The molar purity is greater than 99% (1 H NMR). NMR analysis: H 3 C 0-1 + 2 -0 H 3 C, 9 = N = 7- / 3-4 68 // -1 0-5 // 1 O-I-1 3 13-12 / H 3 C 14 Solvent: DMSO P10-3329 - 13 - No.6 1.H (ppm) 6 13C (ppm) 1 1.17 13.7 2 4.13 60.3 3 / 168.3 4 4.41 68.8 / 152.8 6/10 / 133.8 / 137.1 7 2.27 14.3 8 / 111.8 9 / / 11 2.27 19.5 12 7.01 130.0 13 / 134.3 14 2.18 16.0 II.3-Addition of the 1,3-dipolar compound 3- (2-ethoxy-2-oxoethoxy) -2,4,6-trimethylbenzonitrile oxide to a Polymer: The 1,3-dipolar compound obtained was used according to the procedure described above. The polymer is an SBR which contains 26% styrene and 24% 1.2 units of the butadiene moiety. Ethyl-2- (3- (nitrileoxide) methyl) -2,4,6-trimethylphenoxy) acetate (0.79 g, 3.01 mmol), with a purity of 99% molar NMR, is incorporated at 20 g of SBR on roll tool (external mixer at 30 ° C). The mixture is homogenized in 15 wall passes. This mixing phase is followed by a heat treatment at 120 ° C. for 10 minutes in a press at 10 bar pressure. 1 H NMR analysis made it possible to determine a molar addition rate of the 1,3-dipolar compound of 0.91 mol% and a molar addition yield of 91%.
    [0013] P10-3329
    权利要求:
    Claims (19)
    [0001]
    REVENDICATIONS1. A process for synthesizing an unsaturated polymer having at least one carboxylic acid ester function along the polymer chain which comprises reacting a 1,3-dipolar compound on at least one unsaturation of the unsaturated polymer, which compound comprises dipolar comprises a group Q and a group B linked together by a group A in which: Q comprises a dipole containing at least and preferably a nitrogen atom, B represents a carboxylic acid ester function, A, preferably divalent , is an atom or a group of atoms connecting Q to B.
    [0002]
    2. The process as claimed in claim 1, in which B corresponds to the formula (I) -C (OR) = O (I) in which R is a carbon group that may contain at least one heteroatom.
    [0003]
    3. Method according to claim 2 wherein the carbon group contains 1 to 20, preferably 1 to 12, more preferably 1 to 6, more preferably 1 to 3 carbon atoms.
    [0004]
    4. Process according to any one of claims 1 to 3 wherein A is a group containing up to 20 carbon atoms and may contain at least one heteroatom.
    [0005]
    5. Process according to claim 4, in which A is an aliphatic group preferably containing 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferentially 1 to 6 carbon atoms, or an aromatic group preferably containing 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
    [0006]
    The process of claim 5 wherein A is an alkylene group preferably containing 1 to 3 carbon atoms.
    [0007]
    7. Process according to any one of claims 1 to 6 wherein the 1,3-dipolar compound is selected from the group consisting of nitrile oxides, nitrile imines and nitrones. P10-3329- 15 -
    [0008]
    8. Process according to any one of claims 1 to 7 wherein Q comprises the unit of formula (11): R5 R4 wherein: four of the five symbols R1 to R5 identical or different, are each an atom or a group of atoms, preferably an aliphatic group or an aromatic group and the fifth symbol designates a direct or indirect attachment to A, knowing that R1 and R5 are both different from H.
    [0009]
    9. The method of claim 8 wherein R1, R3 and R5 are the same.
    [0010]
    10. Process according to any one of claims 8 to 9 wherein R1, R3 and R5 are each an alkyl group of 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
    [0011]
    11. The process of claim 10 wherein R1, R3 and R5 are each methyl or ethyl.
    [0012]
    12. Method according to any one of claims 8 to 11 wherein the fifth symbol denotes an indirect attachment to A.
    [0013]
    13. The method of claim 12 wherein the fifth symbol is a heteroatom, preferably oxygen.
    [0014]
    14. The method of claim 13 wherein the 1,3-dipolar compound is of formula (IIa)
    [0015]
    15. Process according to any one of Claims 1 to 7, in which Q comprises the unit corresponding to formula (III) or (IV): ## STR2 ##
    [0016]
    Wherein Y1 is an aliphatic group, preferably an alkyl group preferably containing 1 to 12 carbon atoms, or an aromatic group containing 6 to 20 carbon atoms, preferentially an alkylaryl group, more preferably a phenyl or tolyl group, and Y2 is an aliphatic group, preferably an alkyl group preferably containing 1 to 12 carbon atoms, or an aromatic group preferably containing 6 to 20 carbon atoms and comprising on its benzene ring a direct attachment to A. 16. Process according to any one of claims 1 to 15 wherein the 1,3-dipolar compound is reacted with a stoichiometry of between 0 and 5 molar equivalents, preferably between 0 and 2 equivalents. molar, more preferably between 0 and 1 molar equivalent ester function per 100 mol of monomer units constituting the polymer.
    [0017]
    17. Process according to any one of claims 1 to 16 wherein the unsaturated polymer is a diene polymer, preferably a diene elastomer, more preferably a substantially unsaturated diene elastomer, still more preferably a substantially unsaturated elastomer selected from the group consisting of polybutadienes, polyisoprenes, butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
    [0018]
    18. Polymer obtainable by the method defined according to any one of claims 1 to 17.
    [0019]
    19. Composition which comprises a filler and a polymer defined according to claim 18. P10-3329
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2943065A1|2009-03-16|2010-09-17|Michelin Soc Tech|RUBBER COMPOSITION|
    FR2981354A1|2011-10-18|2013-04-19|Michelin Soc Tech|DIENE COPOLYMER HAVING AT LEAST TWO BLOCKS, METHOD OF SYNTHESIS AND RUBBER COMPOSITION CONTAINING THE SAME|
    AT465208T|2001-06-28|2010-05-15|Michelin Soc Tech|TIRE RUNNING REINFORCED BY SILICA WITH LOW SPECIFIC SURFACE|
    WO2003002649A1|2001-06-28|2003-01-09|Societe De Technologie Michelin|Tyre tread reinforced with silica having a very low specific surface area|
    BR0214390B1|2001-11-26|2012-12-25|cross-linked or cross-linked rubber composition usable for constituting a tire tread, process for preparing a rubber composition and tire tread and cover.|
    US7186845B2|2004-10-20|2007-03-06|Bridgestone Corporation|Polymer-filler coupling additives|
    JP5761427B1|2014-05-16|2015-08-12|横浜ゴム株式会社|Rubber composition for bead filler and pneumatic tire|FR3044316B1|2015-11-27|2017-12-08|Michelin & Cie|RUBBER COMPOSITION|
    FR3060571A1|2016-12-19|2018-06-22|Compagnie Generale Des Etablissements Michelin|PROCESS FOR PREPARING A DIODE MODIFIED ELASTOMER WITH 1,3-DIPOLAR COMPOUND|
    FR3060570A1|2016-12-19|2018-06-22|Compagnie Generale Des Etablissements Michelin|PROCESS FOR THE PREPARATION OF A DIODE MODEL ELASTOMER MODIFIED BY A 1,3-DIPOLAR COMPOUND BY REACTIVE EXTRUSION|
    FR3105237A1|2019-12-24|2021-06-25|Compagnie Generale Des Etablissements Michelin|MASTER MIXTURE BASED ON A MODIFIED POLYMER AND AN ORGANOPHOSPHORUS ADDITIVE AND ITS MANUFACTURING PROCESS|
    法律状态:
    2015-05-21| PLFP| Fee payment|Year of fee payment: 2 |
    2015-11-27| PLSC| Publication of the preliminary search report|Effective date: 20151127 |
    2016-05-20| PLFP| Fee payment|Year of fee payment: 3 |
    2017-05-23| PLFP| Fee payment|Year of fee payment: 4 |
    2018-05-22| PLFP| Fee payment|Year of fee payment: 5 |
    2020-02-14| ST| Notification of lapse|Effective date: 20200108 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1454660A|FR3021320B1|2014-05-23|2014-05-23|METHOD FOR GRATING ESTER FUNCTION OF CARBOXYLIC ACID ON AN UNSATURATED POLYMER.|FR1454660A| FR3021320B1|2014-05-23|2014-05-23|METHOD FOR GRATING ESTER FUNCTION OF CARBOXYLIC ACID ON AN UNSATURATED POLYMER.|
    US15/310,418| US10392448B2|2014-05-23|2015-05-19|Method for grafting a carboxylic acid ester function onto an unsaturated polymer|
    PCT/EP2015/060927| WO2015177105A1|2014-05-23|2015-05-19|Method for grafting a carboxylic acid ester function onto an unsaturated polymer|
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