EP3105260A1 - An den kettenenden thiol-funktionalisiertes polyphosphorpolymer und herstellungsverfahren dafür - Google Patents

An den kettenenden thiol-funktionalisiertes polyphosphorpolymer und herstellungsverfahren dafür

Info

Publication number
EP3105260A1
EP3105260A1 EP15703585.8A EP15703585A EP3105260A1 EP 3105260 A1 EP3105260 A1 EP 3105260A1 EP 15703585 A EP15703585 A EP 15703585A EP 3105260 A1 EP3105260 A1 EP 3105260A1
Authority
EP
European Patent Office
Prior art keywords
polymer
chain
thiol
function
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15703585.8A
Other languages
English (en)
French (fr)
Inventor
Charlotte Dire
Rachid Matmour
Issam BLIDI
Olivier COUTELIER
Mathias Destarac
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Compagnie Generale des Etablissements Michelin SCA
Universite Toulouse III Paul Sabatier
Original Assignee
Michelin Recherche et Technique SA Switzerland
Centre National de la Recherche Scientifique CNRS
Compagnie Generale des Etablissements Michelin SCA
Michelin Recherche et Technique SA France
Universite Toulouse III Paul Sabatier
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Michelin Recherche et Technique SA Switzerland, Centre National de la Recherche Scientifique CNRS, Compagnie Generale des Etablissements Michelin SCA, Michelin Recherche et Technique SA France, Universite Toulouse III Paul Sabatier filed Critical Michelin Recherche et Technique SA Switzerland
Publication of EP3105260A1 publication Critical patent/EP3105260A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/24—Incorporating phosphorus atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains

Definitions

  • the present invention relates to a process for synthesizing a polymer carrying phosphonate and / or phosphonic functions pendant along the chain, functionalized thiol end chain.
  • the present invention also relates to such a poly (phosphorus) polymer terminated thiol.
  • 1,3-dipolar cycloaddition reactions in the presence of nitrile oxide or nitrone are also known for the functionalization (WO 2012007441 A1, WO 2006045088 A2) or the diene polymer crosslinking (FR 1583406, WO 2006081415 A2).
  • the radical grafting of functional or non-functional thiols via photochemical or chemical catalysts is part of these functionalization reactions of diene polymers (natural and synthetic rubber) in the same way as the cycloaddition or hydrosilylation reactions mentioned. upper.
  • the thiol-ene coupling (reaction of a thiol on a double bond) on polydienes offers some versatility for molecular design. Indeed, the good tolerance of the Thiol-ene chemistry with respect to many functional groups and the good availability of polydienes containing various microstructures made it possible to produce series of original materials by varying the nature of the grafted functionality.
  • the Applicants are particularly interested within the scope of the invention in obtaining diene polymer carrying phosphorus functional groups along the chain.
  • phosphorus polymers have recently gained increasing interest because of their utility in a wide range of applications such as for example fuel cells (J. Fuel Cells, 2005, 5, (3), 355), membranes electrolytes (cation exchange membranes) (J.App.Poly Sci, 1999, 74, 83), flame retardants (Macromolecules, 1998, 31, 1010, Rhodia Chimie WO 2003076531), dental cement additives (J. Dent Res, 1974, 53, (4), 867), biomaterials (orthopedic applications) (J. Mater Sci Lett, 1990, 9, 1058, Macromol Rapid Commun 2006,20, 1719-24), solubilization of drugs (hydrogels for drug release) (J.
  • This macrostructure evolution observed in the context of radical grafting is generally due to secondary reactions (radical-radical bimolecular coupling, transfer reaction, etc.); the proportion of these secondary reactions increasing with the target graft rate.
  • This evolution of macrostructure is often responsible for a degradation of the elastomeric properties of the polymer, and therefore a drop in its performance in the intended application, such as in tires.
  • the technical problem that arises with respect to the state of the art is to have a simple and reproducible method for synthesizing a polymer having a high molar ratio of phosphorus functions along the chain while overcoming the drawbacks related to the use of high proportions of thiol molecules carrying a phosphorus function.
  • the inventors have now developed a novel phosphorous molecule which allows the preparation of diene polymers having a high molar ratio of phosphonate and / or phosphonic functions along the chain, while retaining the benefit of thiol-ene coupling while at the same time limiting significant evolution of polymer macrostructure related to grafting of high proportions of functions.
  • the inventors have synthesized a poly (phosphorus) polymer carrying a thiol function at the end of the chain which can be grafted by thiol-ene coupling on a diene polymer.
  • the subject of the invention is a poly (phosphorus) polymer carrying a thiol function at the chain end.
  • the invention also relates to a process for synthesizing such a polymer.
  • the term "phosphorus”, whether it is the function or the polymer, means that a group or a polymeric unit, as the case may be, comprises at least one phosphonate function. , a phosphonic hemiacide function or a phosphonic diacid function.
  • a phosphonic function is used to refer to a phosphonic hemiacide function or a phosphonic diacid function.
  • the term "unit" of a polymer any unit derived from a monomer of the backbone of the polymer in question.
  • terminal thiol refers to the poly (phosphorus) polymer, the fact of carrying a thiol function at one end of the chain.
  • the number of moles of these units in the polymer relative to the total number of moles of the units present in said polymer is defined as the molar percentage or percentage of a unit in a polymer.
  • any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the term “from a to b” means the range from a to b (i.e., including the strict limits a and b).
  • the polyphosphorus polymer carrying an end thiol function is a thiol derivative whose polymer chain comprises units carrying at least one phosphonate function and / or at least one phosphonic function pendant along the chain.
  • the polymer chain may be any homopolymer obtained by polymerization of a monomer carrying at least one phosphorus functional group, or of any copolymer of one or more monomers bearing at least one phosphorus functional group with one another or with one or more comonomers.
  • the polyphosphorus polymer carrying a thiol function at the end of the chain may be represented by the formula RP-SH, R representing an alkyl, acyl, aryl, alkenyl or alkynyl group, a saturated or unsaturated carbon cycle, optionally aromatic, a heterocycle, saturated or unsaturated, optionally aromatic; or a polymer chain, and P representing the polyphosphorus chain.
  • the poly (phosphorus) terminated thiol polymer corresponds to the following general formula (I):
  • these groups and rings (i), (ii) and (iii) may be substituted by substituted phenyl groups, substituted aromatic groups or groups: alkoxycarbonyl or aryloxycarbonyl (-COOR '), carboxy (-COOH), acyloxy (- 0 2 CR '), carbamoyl (-CONR' 2 ), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidimo, hydroxy (-OH), amino (-NR ' 2 ), halogen, allyl, epoxy, alkoxy (-OR '), S-alkyl, S-aryl, groups having a hydrophilic or ionic character such as the alkaline salts of carboxylic acids, the alkaline salts of sulfonic acid, the polyalkylene oxide chains (POE,
  • X, X ' which may be identical or different, represent H, a halogen or a group R 1,
  • R 1 is chosen from alkyl, aryl, aralkyl, alkylaryl, alkene or organosilyl groups, optionally perfluorinated and optionally substituted by one or more carboxyl groups, epoxy , hydroxyl, alkoxy, amino, halogen or sulfonic acid.
  • Y, or Y', or both contain at least one phosphorus functional group -P (O) (OR 2 ) (OR 3 ), R 2 and R 3 , identical or different, representing a hydrogen atom or an alkyl radical, optionally haloalkyl.
  • the poly (phosphorus) terminated thiol polymer may consist of a type of monomer unit comprising Y and Y '.
  • the poly (phosphorus) terminated thiol polymer is then a thiol derivative of a homopolymer of a monomer carrying at least one phosphorus functional group.
  • the poly (phosphorus) terminated thiol polymer may consist of several types of monomeric units comprising Y and Y ', Y and Y' then being different from one type of unit to another .
  • the poly (phosphorus) terminated thiol polymer is then a thiol derivative of a copolymer of several monomers carrying at least one phosphorus function.
  • the sequence of the different monomer units comprising Y and Y ' may be random or blocky.
  • the poly (phosphorus) terminated thiol polymer may consist of one or more types of monomeric units comprising Y and Y ', and one or more types of monomeric units containing X and X ', Y and Y' on the one hand, and X and X 'on the other hand, then being different from one type of unit to another.
  • the poly (phosphorus) terminated thiol polymer is then a thiol derivative of a copolymer of one or more monomers carrying at least one phosphorus functional group and one or more comonomers comprising X, X '.
  • the sequence of the different monomeric units, comprising X, X 'on the one hand, and on the other hand Y and Y', can be statistical or block.
  • alkyl denotes a linear or branched hydrocarbon radical of 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl or octyl. , nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or icosyl.
  • alkenyl is meant a linear or branched hydrocarbon chain of 2 to 20 carbon atoms comprising one or more double bonds.
  • alkynyl is meant a linear or branched hydrocarbon chain of 2 to 20 carbon atoms comprising one or more triple bonds.
  • particularly preferred alkynyl groups are alkynyl groups having one triple bond such as-CH 2 -CH 2 -C ⁇ CH.
  • cycloalkyl saturated hydrocarbon groups which may be mono-or polycyclic and comprise from 3 to 12 carbon atoms, preferably from 3 to 8. Particularly preferred monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl.
  • cycloalkenyl is meant according to the invention a group derived from a cycloalkyl group as defined above, having one or more double bonds, preferably a double bond.
  • cycloalkynyl is meant according to the invention a group derived from a cycloalkyl group as defined above, having one or more triple bonds, preferably a triple bond.
  • aryl is meant an aromatic mono- or bicyclic hydrocarbon group comprising 6 to 10 carbon atoms, such as phenyl or naphthyl.
  • alkaryl is meant an alkyl group as defined above, substituted with an aryl group.
  • aralkyl is meant an alkyl group as defined above, substituted with an aryl group.
  • alkoxy is meant an O-alkyl group generally having 1 to 20 carbon atoms, especially methoxy, ethoxy, propoxy and butoxy.
  • the heterocyclic group (iii) denotes saturated or preferably unsaturated monocyclic or bicyclic carbon rings having 5 to 12 members and having 1, 2 or 3 endocyclic heteroatoms selected from O, N and S. These are generally derivatives of heteroaryl groups.
  • heteroaryl means 5- to 7-membered monocyclic aromatic groups or 6- to 12-membered bicycles comprising one, two or three endocyclic heteroatoms chosen from O, N and S.
  • Examples are furyl groups, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrazinyl and triazinyl.
  • the heterocycle when unsaturated comprises a single double bond.
  • unsaturated heterocycles are dihydrofuryl, dihydrothienyl, dihydropyrrolyl, pyrrolinyl, oxazolinyl, thiazolinyl, imidazolinyl, pyrazolinyl, isoxazolinyl, isothiazolinyl, oxadiazolinyl, pyranyl and mono-unsaturated derivatives of piperidine, dioxane, piperazine, trithiane.
  • R is as defined in WO 98/58974, WO 00/75207 and WO 01/42312 (definition of Ri), WO 98/01478 and WO 99/31 144 (definition of R ), or WO 02/26836 (definition of Ri).
  • R is more particularly a cyanomethyl group CNCH 2 -, 1 -phenylethyl CH 3 (C 6 H 5 ) CH- or methylpropionyl CH 3 (CO 2 CH 3 ) CH-.
  • the mole fraction of monomer units with X and X ' may be zero, and is generally from 0 to 0.5, preferably from 0 to 0.25, more preferably from 0 to 0.1.
  • the monomers from which the units carrying phosphorus functional groups in Y and Y 'that are useful in the present invention are vinyl phosphonic acid, vinyl phosphonic acid dimethyl ester, bis (2-chloroethyl) ester, and the like; vinyl phosphonic acid, vinylidene diphosphonic acid, vinylidene diphosphonic acid tetraisopropyl ester, alpha-styrene phosphonic acid, dimethyl-p-vinylbenzylphosphonate, diethyl-p-vinylbenzylphosphonate, dimethyl (methacryloyloxy) ) methyl phosphonate, diethyl (methacryloyloxy) methyl phosphonate, diethyl-2- (acrylamido) ethylphosphonate, more generally any styrene unsaturated monomer, acrylate or methacrylate, acrylamido or methacrylamido, vinyl or allyl carrier of at least one dialky
  • hydrophilic (h) or hydrophobic (H) monomers chosen from the following monomers.
  • hydrophilic monomers (h) mention may be made of:
  • neutral acrylamido monomers such as acrylamide, ⁇ , ⁇ -dimethylacrylamide and N-isopropylacrylamide.
  • cyclic amides of vinylamine such as N-vinylpyrrolidone and vinylcaprolactam.
  • ethylenically unsaturated mono- and di-carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or fumaric acid.
  • the ethylenic monomers comprising a sulphonic acid group or an alkali or ammonium salt thereof, for example vinylsulphonic acid, vinylbenzene sulfonic acid, alpha-acrylamido-methylpropanesulfonic acid, or 2-sulfoethylene-methacrylate, or
  • the hydrophilic monomeric units (h) are chosen from acrylic acid (AA), dimethylaminopropyl acrylamide, and N-vinylpyrrolidone.
  • hydrophobic monomers H
  • hydrophobic monomers H
  • styrenic derived monomers such as styrene, alphamethylstyrene, paramethylstyrene or paratertiobutylstyrene, or
  • vinyl nitriles containing from 3 to 12 carbon atoms and in particular acrylonitrile or methacrylonitrile,
  • vinyl esters of carboxylic acids such as vinyl acetate (VAc), vinyl versatate, or vinyl propionate,
  • vinyl or vinylidene halides for example vinyl chloride, vinylidene chloride and vinylidene fluoride, and
  • diene monomers for example butadiene or isoprene.
  • the hydrophobic monomer units (H) of the copolymers of the invention are butadiene, isoprene, butyl acrylate and styrene.
  • the poly (phosphorus) functional thiol polymer as defined above has an average number of units of at least 2 and at most equal to 1000.
  • the poly (phosphorus) functional thiol polymer at the end of the chain may be obtained by any method allowing the functionalization at the chain end by a thiol function of any poly (phosphorus) polymer obtained by homopolymerization of a monomer carrying at least one functional group. phosphorus, or by copolymerization of one or more monomers carrying at least one phosphorus functional group with one another or with one or more comonomers. Depending on the processes, the functionalization may be concomitant with the polymerization or may be posterior thereto.
  • the poly (phosphorus) functional thiol polymer at the end of the chain is obtained by controlled RAFT or MADIX controlled radical (co) polymerization of at least one monomer carrying at least one phosphorus functional group in the presence of a source of free radicals and a thiocarbonylthio chain transfer agent of general formula II
  • these groups and rings (i), (ii) and (iii) may be substituted by substituted phenyl groups, substituted aromatic groups or groups: alkoxycarbonyl or aryloxycarbonyl (-COOR '), carboxy (-COOH), acyloxy (- 0 2 CR '), carbamoyl (-CONR' 2 ), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidimo, hydroxy (-OH), amino (-NR ' 2 ), halogen, allyl, epoxy, alkoxy (-OR '), S-alkyl, S-aryl, groups having a hydrophilic or ionic nature such as the alkali metal salts of carboxylic acids, the alkali metal salts of sulfonic acid, the polyalkyleneoxide chains (
  • Z is an oxygen atom, a carbon atom, a sulfur atom, a nitrogen atom or a phosphorus atom, these atoms being substituted with one, two or three hydrocarbon radicals R ", so as to have a suitable valency, which may comprise at least one heteroatom, such that R "represents a group as defined above for R.
  • R and R" are as defined in the documents WO 98/58974. , WO 00/75207 and WO 01/42312 (definition of respectively R 2 ), WO 98/01478 and WO 99/31144 (definition of R respectively of Z and Ei), or WO 02/26836 (definition of R 1 respectively nitrogen group).
  • R is more particularly a cyanomethyl group CNCH 2 -, 1 -phenylethyl CH 3 (C 6 H 5 ) CH- or methylpropionyl CH 3 ( C0 2 CH 3 ) CH-.
  • Z denotes a group OR 'with R' denoting a C 1 -C 5 alkyl radical, preferentially
  • the poly (phosphorus) polymers of formula I can be obtained by controlled radical polymerization RAFT or MADIX monomers comprising Y and Y 'and, where appropriate, the monomers comprising X and X', listed above.
  • the initiator of polymerization RAFT OR MADIX may be chosen from the initiators conventionally used in radical polymerization.
  • One of the advantages of the RAFT or MADIX polymerization process is the ability to control the length of the poly (phosphorus) polymer by adjusting the molar ratio of the monomer and the transfer agent.
  • the molar ratio of the monomer to the transfer agent is generally at least 2. According to variants of the invention related to the choice of the phosphorus monomer, this ratio is at most 1000.
  • the thiol derivative RP-SH is obtained by chemical modification of this finished thiocarbonylthio product in a conventional manner and known to those skilled in the art.
  • the aminolysis reaction generally carried out with primary or secondary amine compounds.
  • the poly (phosphorus) terminated thiol polymer RP-SH is formed directly by thermolysis of particular thiocarbonylthio groups, for example xanthates derived from secondary alcohol.
  • the polyphosphor thiol-terminated polymer of the invention is particularly suitable for participating in a thiol-ene coupling reaction.
  • the carbon-carbon double bonds are advantageously unsaturations of a diene polymer, allowing thus grafting the polyphosphorus polymers of the invention on diene polymers. It is thus possible to prepare polymers with a high phosphonate or phosphonic function content by significantly reducing the macrostructure evolutions of the polymers and the secondary reactions occurring during grafting of monophosphorus thiol molecules in order to achieve the same level of functions in the polymer. polymer.
  • the elastomers are characterized, before cooking, as indicated below.
  • Excludable sterilization chemistry The number-average molar masses M n of the polymers and their dispersions were obtained by steric exclusion chromatography (SEC) with tetrahydrofuran (THF) as eluent at 1 ml. / min.
  • SEC steric exclusion chromatography
  • THF tetrahydrofuran
  • PS polystyrene
  • the CES chain is equipped with a Waters 2414 RI detector and a set of 2 columns (Shodex KF-802.5 and KF-804) thermostatically controlled at 35 ° C.
  • the glass transition temperature determination analyzes were carried out with a Netzsch DSC (Phoenix) apparatus. An aluminum crucible comprising 5 to 10 mg of sample is deposited on a platinum boat. The rate of temperature rise used for all the samples is 10 ° C.min-1. The analyzes were conducted under nitrogen.
  • the DMVP-C4 monoadduct 250 mg, 7.37 ⁇ 10 -4 mol
  • the 1,2-dichlorobenzene solvent (3 ml)
  • the reaction mixture is degassed with argon for 15 minutes and then kept at reflux of the solvent (200 ° C) in the absence of light and for 5 minutes.
  • the yield of the thermolysis is 70%.
  • the PDMVP-C4 250 mg, 3.47 ⁇ 10 -4 mol
  • the 1,2-dichlorobenzene solvent (3 ml)
  • the reaction mixture is degassed with argon for 15 minutes and then kept at reflux of the solvent (200 ° C.) in the dark and for 15 minutes
  • the yield of the thermolysis is 72% (determined by 31 P NMR).
  • Example 7 Thermolysis of the DMVP-C4 monoadduct followed by grafting on SBR
  • the DMVP-C4 monoadduct 250 mg, 7.37 ⁇ 10 -4 mol
  • the 1,2-dichlorobenzene solvent (3 ml)
  • the mixture is degassed with argon for 15 minutes and then kept at reflux of the solvent (200 ° C) in the absence of light and for 5 minutes.
  • the polymer is solubilized in dichloromethane and then antioxidized with 1 ml of a solution of A02246 at 10 g / l.
  • the polymer is then dried under vacuum at 60 ° C.
  • the grafting yield is 37.5% (determined by 1 H NMR). Table 1 below summarizes the characteristics of polymers synthesized by grafting DMVP.
  • Example 8 Thermolysis of PDMVP-C4 followed by grafting on SBR
  • the PDMVP-C4 oligomer 250 mg, 3.47 ⁇ 10 -4 mol
  • the 1,2-dichlorobenzene solvent (3 ml)
  • Table 1 summarizes the characteristics of polymers synthesized by grafting DMVP.
  • Example 8 Compared with the use of a thiol-terminated monophosphonate (Example 7), the grafting of thiol-terminated poly (phosphonates) (Example 8) makes it possible to obtain phosphonate-modified diene polymer having high phosphonate function levels without having to aim for high grafting rates.
  • the use of a poly (phosphorus) polymer in this case poly (phosphonate) bearing a thiol function at the end of the chain makes it possible to overcome the drawbacks associated with the use of thiol-functionalized small phosphonate molecules.
  • the use of poly (phosphonate) polymers makes it possible to obtain a modified diene polymer having a high molar content of phosphonate functions along the chain, aiming for low grafting levels and without modifying the final polymer macrostructure.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP15703585.8A 2014-02-11 2015-02-10 An den kettenenden thiol-funktionalisiertes polyphosphorpolymer und herstellungsverfahren dafür Withdrawn EP3105260A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1451036A FR3017387B1 (fr) 2014-02-11 2014-02-11 Polymere polyphosphore fonctionnalise thiol en extremite de chaine et son procede d'obtention.
PCT/EP2015/052701 WO2015121223A1 (fr) 2014-02-11 2015-02-10 Polymère polyphosphoré fonctionnalisé thiol en extrémité de chaîne et son procédé d'obtention

Publications (1)

Publication Number Publication Date
EP3105260A1 true EP3105260A1 (de) 2016-12-21

Family

ID=50829106

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15703585.8A Withdrawn EP3105260A1 (de) 2014-02-11 2015-02-10 An den kettenenden thiol-funktionalisiertes polyphosphorpolymer und herstellungsverfahren dafür

Country Status (5)

Country Link
US (1) US20170218099A1 (de)
EP (1) EP3105260A1 (de)
CN (1) CN105960420A (de)
FR (1) FR3017387B1 (de)
WO (1) WO2015121223A1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3045610B1 (fr) * 2015-12-21 2018-01-05 Michelin & Cie Procede de synthese d'un polymere porteur d'au moins un groupe phosphonate, polymere issu de ce procede et composition le contenant
CN111356596B (zh) * 2017-11-21 2022-06-21 米其林集团总公司 橡胶组合物
CA3117601C (en) 2018-10-26 2022-06-14 University Of South Alabama Functionalized materials and compounds
CN114481172B (zh) * 2022-02-28 2023-07-18 华南理工大学 一种(z)-2-乙烯基硫代-噁二唑类化合物的电化学制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8283436B2 (en) * 2006-02-23 2012-10-09 Commonwealth Scientific And Industrial Research Organisation Process for synthesizing thiol terminated polymers
WO2008154279A1 (en) * 2007-06-06 2008-12-18 3M Innovative Properties Company Fluorinated compositions and surface treatments made therefrom
CN103554384B (zh) * 2013-10-26 2016-08-17 贵阳绿洲苑建材有限公司 一种含膦基的聚羧酸减水剂及其制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2015121223A1 *

Also Published As

Publication number Publication date
FR3017387A1 (fr) 2015-08-14
US20170218099A1 (en) 2017-08-03
WO2015121223A1 (fr) 2015-08-20
CN105960420A (zh) 2016-09-21
FR3017387B1 (fr) 2016-02-12

Similar Documents

Publication Publication Date Title
EP3105269A1 (de) Verfahren zur herstellung von dienpolymeren mit funktionellen phosphorgruppen, aus diesem verfahren resultierende produkte und zusammensetzung damit
EP1044231B1 (de) Verfahren zur herstellung von blockcopolymeren durch eine kontrollierte radikalpolymerisation mit dithioester
EP1392737B1 (de) Verfahren zur radikalen reduzierung von dithiocarbonyl- und dithiophosphorylfunktionen von polymeren
EP1913044A2 (de) Verfahren für die herstellung eines polymermaterials mit einem aus kontrollierter freiradikalpolymerisaton gewonnenen multiblockcopolymer
CA2375849A1 (fr) Procede de synthese de polymeres par polymerisation radicalaire controlee a l'aide de xanthates halogenes
EP1319027B1 (de) Verfahren zur herstellung von blockcopolymeren durch eine kontrollierte radikalpolymerisation in gegenwart von einer disulfidverbindung
FR2987838A1 (fr) Polyolefine telechelique, et son procede d'obtention
WO2002010223A2 (fr) Procede de synthese de polymeres a blocs par polymerisation radicalaire controlee
EP3105260A1 (de) An den kettenenden thiol-funktionalisiertes polyphosphorpolymer und herstellungsverfahren dafür
FR2861394A1 (fr) Procede de preparation de polyalcoaxymines utilisables comme amorceurs pour la polymerisation radicalaire de (co)polymeres vivants polyfonctionnels
FR2893621A1 (fr) Procede de preparation d'un polymere vivant comprenant des unites methacryliques et/ou methacrylates
FR2924714A1 (fr) Procede de preparation d'une dispersion aqueuse de particules de polymeres par un procede de polymerisation radicalaire en dispersion, dispersions obtenues et revetements prepares avec celles-ci.
EP1309638A1 (de) Herstellungsverfahren von siliciumorganischen hybridcopolymeren durch kontrollierte radikalische polymerisation
WO2015121225A1 (fr) Polymère porteur de fonctions phosphorées et d'au moins une fonction azoture, son procédé de synthèse et son utilisation
WO2015121228A1 (fr) Copolymère à blocs diénique et phosphoré, son procédé de synthèse et composition de caoutchouc le contenant
FR3029921A1 (fr) Procede de controle de la synthese d'un copolymere a blocs contenant au moins un bloc apolaire et au moins un bloc polaire et utilisation d'un tel copolymere a blocs dans des applications de nano-lithographie par auto-assemblage direct.
EP1527105B1 (de) Synthese von statistischen mikrogelen durch kontrollierte radikalpolymerisation
Coutelier et al. Xanthate-derived mercaptophosphonates for thiol-ene modification of styrene-butadiene rubber
WO2001027176A1 (fr) Procede de preparation de polymeres greffes
WO2004078793A1 (fr) Procede de synthese de copolymeres ramifies par polymerisation radicalaire controlee
MXNL04000104A (es) Metodo para la preparacion de copolimeros segmentados compuestos de segmentos polidienicos.
US20040030041A1 (en) Synthesis of block polymers obtained by controlled free radical polymerization
FR2829138A1 (fr) Procede de reduction radicalaire de fonctions dithiocarbonylees ou dithiophosphorylees portees par un polymere

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20160912

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIN1 Information on inventor provided before grant (corrected)

Inventor name: COUTELIER, OLIVIER

Inventor name: MATMOUR, RACHID

Inventor name: BLIDI, ISSAM

Inventor name: DIRE, CHARLOTTE

Inventor name: DESTARAC, MATHIAS

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNIVERSITE PAUL SABATIER

Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (C.N.

Owner name: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20180320

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNIVERSITE PAUL SABATIER

Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (C.N.

Owner name: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20180731