WO2009065774A1 - Greffage de monomères à insaturation éthylénique sur des polymères dans du dioxyde de carbone supercritique - Google Patents

Greffage de monomères à insaturation éthylénique sur des polymères dans du dioxyde de carbone supercritique Download PDF

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WO2009065774A1
WO2009065774A1 PCT/EP2008/065549 EP2008065549W WO2009065774A1 WO 2009065774 A1 WO2009065774 A1 WO 2009065774A1 EP 2008065549 W EP2008065549 W EP 2008065549W WO 2009065774 A1 WO2009065774 A1 WO 2009065774A1
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alkyl
polymer
styrene
butyl
tert
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PCT/EP2008/065549
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Enrique SALDÍVAR-GUERRA
Gabriel LUNA-BÁRCENAS
Jorge C. RAMÍREZ-CONTRERAS
José BONILLA-CRUZ
Rudolf Pfaendner
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Basf Se
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    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • 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
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • 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
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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
    • C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • a method is atom transfer radical polymerization (ATRP), which is a radical polymerization with reversible termination by halogen transfer to a metal complex.
  • a second main method is labeled reversible addition fragmentation transfer (RAFT), which is a radical polymerization with reversible chain transfer.
  • a third method involves reversible termination by coupling with a stable free radical, of which nitroxide mediated polymerization (NMP) is the best example.
  • NMP nitroxide mediated polymerization
  • One aspect of the invention is a process for the preparation of a grafted thermoplastic or elastomeric polymer, which process comprises in a first step A
  • step C2) heating and letting the mixture react until the desired functionalization with nitroxyl groups is achieved and isolating the polymer and in a second step D D1 ) adding to the functionalized polymer, obtained in step C2), an ethylenically unsaturated monomer and CO 2 ; and applying pressure and heat until CO 2 is in its supercritical state; letting the mixture react and isolating the resulting polymer.
  • A1 mixing a radical initiator, a stable free nitroxyl radical, a thermoplastic or elastomeric polymer and CO 2 and applying pressure and heat until CO 2 is in its supercritical state; A2) letting the mixture react until the desired functionalization with nitroxyl groups is achieved and isolating the polymer; and in a second step B
  • step B1 adding to the functionalized polymer, obtained in step A2), an ethylenically unsaturated monomer and CO 2 ; and applying pressure and heat until CO 2 is in its supercritical state; letting the mixture react and isolating the resulting polymer; or
  • step B2) adding to the functionalized polymer obtained in step A2) an ethylenically unsaturated monomer and an organic solvent, heating, reacting the mixture and isolating the resulting polymer.
  • thermoplastic or elastomeric polymers examples include acrylic, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrenethacrylate, polystyrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene
  • Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, po- lybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight poly- ethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
  • HDPE high density polyethylene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high density and ultrahigh molecular weight poly- ethylene
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
  • a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table.
  • These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either p- or s-coordinated.
  • These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide.
  • These catalysts may be soluble or insoluble in the polymerisation medium.
  • the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, Na and/or Ilia of the Periodic Table.
  • the activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard
  • Mixtures of the polymers mentioned under 1 for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
  • Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethy- lene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl ace- tate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and
  • Hydrocarbon resins for example C 5 -C 9
  • hydrogenated modifications thereof e.g. tackifiers
  • mixtures of polyalkylenes and starch
  • Graft copolymers of styrene or a-methylstyrene for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl meth- acrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylo- nitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styren
  • Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
  • Polymers derived from ⁇ , ⁇ -unsatu rated acids and derivatives thereof such as polyacry- lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni- triles, impact-modified with butyl acrylate.
  • Copolymers of the monomers mentioned under 9) with each other or with other unsatu- rated monomers for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
  • Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace- tals thereof for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1 ) above.
  • Polyureas Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
  • Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, polylacticacid as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS. 19. Polycarbonates and polyester carbonates.
  • Blends of the aforementioned polymers for example PP/EPDM, PoIy- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/PUR, PC/PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or
  • the polymer to be grafted on contains preferably unsaturated moieties selected from the group consisting of polydienes, co-, block-, random- and tapered polymers of styrene, terpolymers with diolefins and copolymers with diolefins.
  • thermoplastic or elastomeric polymers are polyethylene, polypropylene, polystyrene, styrene block-copolymers, polybutadiene or polyisoprene, EPDM (ethylene- propylene diene monomer) or EPR (ethylene-propylene rubber).
  • the free radical source is an azo compound, a peroxide or a hydroperoxide.
  • agents are used, such as for example
  • WO 98/44008 discloses specific nitroxyls based on morpholinones, piperazinones and piperazindiones.
  • the preparation of open chain nitroxyl radicals is for example also described in WO 99/03894 or in WO 00/07981.
  • Nitroxyl radicals based on tetraalkyl piperidine are, for example, described in GB 2 335 1290 or in GB 2 361 235. Further heterocyclic nitroxyl radicals are described in GB 2 342 649.
  • tetramethylpiperidine precursors are partially commercially available or can be prepared according to known methods.
  • US 5 096 950 and the documents cited therein describe the preparation of the precursors.
  • the oxidation process can be done as described above.
  • the stable free nitroxyl radical contains a structural element of formula (XXX)
  • G 5 , G 6 independently are H, CrCi 8 alkyl, phenyl, naphthyl or a group COOCi-Ci 8 alkyl.
  • Gi, G 2 , G 3 , G 4 are independently d-C 6 alkyl or Gi and G 2 or G 3 and G 4 , or Gi and G 2 and G 3 and G 4 together form a C 5 -Ci 2 cycloalkyl group;
  • G 5 , G 6 independently are H, CrCi 8 alkyl, phenyl, naphthyl or a group COOCi-Ci 8 alkyl m is 1 ,
  • R 2 is Ci-Ci 8 alkyl, C 5 -C 7 cycloalkyl, C 3 -Ci 2 alkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula -CH 2 CH(OH)-Z or of the formula -CO-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl.
  • Alkyl with up to 18 carbon atoms is, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
  • the alkyl groups may be linear or branched.
  • C 3 -Ci 8 alkyl which is interrupted by one or more oxygen atoms is preferably derived from ethylene oxide or propylene oxide.
  • C 3 -Ci 8 alkyl interrupted by at least one O atom is for example -CH 2 -CH 2 -O-CH 2 -CH 3 , -CH 2 -
  • C 3 -Ci 2 alkenyl is linear or branched and for example propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, dodecenyl including their isomers.
  • C 5 -Ci 2 cycloalkyl is typically, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl.
  • Cycloalkyl which is interrupted by at least one O or N atom is for example 2-tetrahydropyran- yl, tetrahydrofurane-yl, 1 ,4 dioxan-yl, pyrrolidin-yl, tetrahydrothiophen-yl, pyrazolidin-yl, imidazolidin-yl, butyrolactone-yl, caprolactame-yl
  • C 2 -Ci 8 alkylcarbonyl is for example acetyl, propionyl, butyryl, pentylcarbonyl, hexylcarbonyl or dodecylcarbonyl.
  • Examples of a monovalent radical of a carboxylic acid are an acetyl, caproyl, stearoyl, acryloyl, methacryloyl, cyclohexylcarboxylic acid, benzoyl or ⁇ -(3,5-di-tert-butyl-4- hydroxyphenyl)propionyl radical.
  • Further examples are derived from propionic acid, laurinic acid or methyl ethyl acetic acid or the other isomers of valeric acid.
  • a cycloaliphatic carboxylic acid is for example cyclohexane carboxylic acid or cyclopentane carboxylic acid.
  • Typical unsaturated carboxylic acids are acrylic acid, methacrylic acid or crotonic acid.
  • the ethylenically unsaturated monomer is selected from the group consisting of styrene, substituted styrene, conjugated dienes, maleic acid anhydride, acrolein, vinyl acetate, (alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters or (alkyl)acrylamides.
  • R 3 is hydrogen or methyl
  • R b is NH 2 , gycidyl, unsubstituted or with hydroxy substituted Ci-C 4 alkoxy, unsubstituted Ci-C 4 alkylamino, di(Ci-C 4 alkyl)amino, hydroxy- substituted Ci-C 4 alkylamino or hydroxy-substituted di(C-i-C 4 alkyl)amino
  • Z is oxygen.
  • the present invention postulates using, instead of organic solvents supercritical carbon dioxide.
  • supercritical carbon dioxide will be understood as meaning CO 2 whose pressure and temperature are above the critical pressure and the critical temperature.
  • CO 2 is added in an amount sufficient to provide a pressure of 68900 hPa ( ⁇ 1000 psi) to 413 700 hPa (-6000 psi) at 23° C.
  • heating in step A) is from 1 hour to 60 hours at a temperature from 60° C to 170° C, preferably from 80° to 150° C.
  • the heating in step B) is typically carried out for 1 minute to 10 hours at a temperature from 100° C to 170° C.
  • step C heating is carried out typically for 1 minute to 10 hours at a temperature from 100° C to 250° C and in step D) from 1 hour to 60 hours at a temperature from 60° C to 170° C.
  • the stable nitroxyl radical is present in an amount from 0.1 % to 30%, more preferably in an amount from 0.1 % to 20% and most preferably in an amount from 0.5% to 10% based on the weight of the polymer.
  • radical initiator is present in an amount of from 0.1% to 30% based on the weight of the polymer.
  • the weight ratio of stable free nitroxyl radical to radical initiator is from 1 :5 to 5:1.
  • the weight ratio of the reaction product of step A2) to the ethylenically unsaturated monomer or oligomer added in step B) is from 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • the monomer to polymer conversion in step B is at least 50%.
  • Step B) may be carried out in supercritical CO 2 or in a classical way in solution.
  • Step B1 ) carried out in supercritical CO 2 is, however, preferred.
  • the grafted polymers are useful in many applications such as compatibilizers in polymer blends or alloys, adhesion promoters between two different substrates, surface modification agents, nucleating agents, coupling agents between filler and polymer matrix or dispersing agents.
  • the process is particularly useful for the preparation of grafted block copolymers.
  • Block copolymers which may be grafted are, for example, block copolymers of polystyrene and polyacrylate (e.g., poly(styrene-b-acrylate) or poly(styrene-b-acrylate-b-styrene). They are useful as adhesives or as compatibilizers for polymer blends or as polymer toughening agents. Poly(methylmethacrylate-b- acrylate) diblock copolymers or poly(methylacrylate-b- acrylate-b-methacrylate) triblock copolymers are useful as dispersing agents for coating systems, as coating additives (e.g.
  • graft block copolymers of this invention wherein the grafted blocks have polar monomers on a non polar polymer are useful in many applications as amphiphilic surfactants or dispersants for preparing highly uniform polymer blends.
  • the present invention also encompasses in the synthesis novel graft block, multi-block, star, gradient, random, hyperbranched and dendritic copolymers.
  • the polymers prepared by the present invention are particularly useful for following applications: adhesives, detergents, dispersants, emulsifiers, surfactants, defoamers, adhesion promoters, corrosion inhibitors, viscosity improvers, lubricants, rheology modifiers, thickeners, crosslinkers, paper treatment, water treatment, electronic materials, paints, coatings, photography, ink materials, imaging materials, superabsorbants, cosmetics, hair products, preser- vatives, biocide materials or modifiers for asphalt, leather, textiles, ceramics and wood.
  • the present graft polymerizaton is a "living" polymerization, it can be started and stopped practically at will. Furthermore, the polymer product retains the functional alkoxyamine group allowing a continuation of the polymerization in a living matter.
  • a second monomer can then be added to form a second block on the growing graft polymer chain in a second polymerization step. Therefore it is possible to carry out additional graft polymerizations with the same or different monomer(s) to prepare multi- block graft copolymers.
  • graft blocks can be prepared in essentially any order.
  • step A or/and in step B a processing stabilizer or/and a phenolic antioxidant is additionally added.
  • processing stabilizers or/and a phenolic antioxidants are mentioned below.
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methylunde
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl- thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4- nonylphenol.
  • Hydroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu- tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy- droxyphenyl) adipate.
  • 2,6-di-tert-butyl-4-methoxy- phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amyl
  • Hydroxylated thiodiphenyl ethers for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)- disulfide.
  • 2,2'-thiobis(6-tert-butyl-4-methylphenol 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6
  • Alkylidenebisphenols for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4- methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl- phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-( ⁇ -methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -dimethyl
  • Hydroxybenzylated malonates for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di- dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 ,1 ,3,3-te- tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate di-octadecyl-2-(3-tert-butyl-4-
  • Aromatic hydroxybenzyl compounds for example 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy- anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5-tri- azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxyben- zyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl
  • Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl-S-tert-butyM-hydroxy-S-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
  • Acylaminophenols for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol- propane, 4-hydroxy
  • esters of ⁇ -(3,5-dicvclohexyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-triox
  • esters of 3,5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[
  • Aminic antioxidants for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-bu- tyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3- methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicy- clohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p- phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl
  • a further aspect of the invention is a grafted thermoplastic or elastomeric polymer obtainable according to the process as described above.
  • the reactor is cooled overnight then the polymer is recovered and purified in order to remove residual nitroxide and initiator by several cycles of dissolution in chloroform and re-precipitation into methanol, and dried under vacuum at ambient temperature for 48 h.
  • the recovered polymer is characterized by 1 H NMR (100 scans in an FT-NMR Joel Eclipse 300 MHz spectrometer at room temperature using CDCI 3 ) and GPC (Hewlett-Packard Instrument series 1 100 with refractive index detector and three Hewlett-Packard PLGeI columns: 103, 105 and 107 A).
  • the NMR spectra show signals at chemical shifts of 3.9-4.1 assigned to the allylic hydrogens adjacent to either cis-trans butadiene units or vinyl units and linked to the carbon atom bonded to the nitroxide. Another signal at around 2.7 ppm is assigned to the proton on the carbon neighbor to a double bond and also neighbor to the carbon attached to the nitroxide. Based on the NMR signals associated with the nitroxide, a functionalization efficiency (nitroxide linked to the rubber / nitroxide charged) of 20.8 % is obtained. The GPC chromatogram shows slight displacement of the molecular weight towards higher molecular weights with respect to the virgin rubber, which is characteristic for the rubber after functionalization. 1.3 % of crosslinked material is also recovered.
  • the GPC traces show clearly a shift of the molecular weight towards higher molecular weights after the grafting reaction took place; being more pronounced the shifting in the 9 h reaction than in the 7 h reaction; the M p average molecular weight is 10,619 for the functionalized rubber, 11 ,540 for the 7 h grafted material and 38,764 for the 9 h grafted rubber, based on polystyrene standards.
  • a gel content of around 50 % is obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention porte sur un procédé de greffage à deux étapes pour greffer des monomères insaturés sur des polymères, suivant lequel au moins une étape est effectuée en présence d'un radical nitroxyle libre stable dans du dioxyde de carbone supercritique.
PCT/EP2008/065549 2007-11-23 2008-11-14 Greffage de monomères à insaturation éthylénique sur des polymères dans du dioxyde de carbone supercritique WO2009065774A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013007095A1 (fr) * 2011-07-08 2013-01-17 中国石油天然气股份有限公司 Procédé de modification par greffage en phase solide assisté par du dioxyde de carbone supercritique pour du polypropylène
US8557926B2 (en) 2010-05-07 2013-10-15 The Yokohama Rubber Co., Ltd. Method for producing modified polymer
CN110655614A (zh) * 2019-11-04 2020-01-07 绵阳鸿琪新材料科技有限公司 一种聚丙烯增容剂及其制备方法、聚丙烯改性塑料及其制备方法和应用
CN113136147A (zh) * 2021-05-07 2021-07-20 浙江祥邦科技股份有限公司 一种柔性组件用截止型热塑性poe封装胶膜及其制备方法
WO2022112190A1 (fr) * 2020-11-30 2022-06-02 Basf Se Procédé de production de dispersions polymères
CN115175957A (zh) * 2020-02-26 2022-10-11 原子能和替代能源委员会 用于聚合物组分的化学改性方法
WO2024032237A1 (fr) * 2022-08-10 2024-02-15 华为技术有限公司 Matériau préexpansé, et son procédé de préparation et son utilisation

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EP0735051A1 (fr) * 1995-03-30 1996-10-02 Xerox Corporation Polymérisation par radicaux libres stables sous des conditions supercritiques et polymères ainsi produits
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CN1486998A (zh) * 2003-07-24 2004-04-07 华东理工大学 采用超临界co2介质制备不饱和有机酸接枝聚丙烯的方法
CN1605596A (zh) * 2004-09-07 2005-04-13 华东理工大学 超临界co2环境中聚丙烯固相接枝马来酸酐的方法

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EP0135280A2 (fr) * 1983-07-11 1985-03-27 Commonwealth Scientific And Industrial Research Organisation Procédé de polymérisation et polymères ainsi produits
EP0735051A1 (fr) * 1995-03-30 1996-10-02 Xerox Corporation Polymérisation par radicaux libres stables sous des conditions supercritiques et polymères ainsi produits
US5663237A (en) * 1995-06-15 1997-09-02 The University Of Akron Graft copolymerization in supercritical media
DE19905947A1 (de) * 1999-02-12 2000-08-17 Fraunhofer Ges Forschung Verfahren zur Herstellung von Superabsorbern und mittels eines solchen Verfahrens hergestellte Superabsorber
CN1486998A (zh) * 2003-07-24 2004-04-07 华东理工大学 采用超临界co2介质制备不饱和有机酸接枝聚丙烯的方法
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8557926B2 (en) 2010-05-07 2013-10-15 The Yokohama Rubber Co., Ltd. Method for producing modified polymer
DE112011101593B4 (de) * 2010-05-07 2014-01-30 The Yokohama Rubber Co., Ltd. Verfahren zur Herstellung von modifiziertem Dienkautschuk
WO2013007095A1 (fr) * 2011-07-08 2013-01-17 中国石油天然气股份有限公司 Procédé de modification par greffage en phase solide assisté par du dioxyde de carbone supercritique pour du polypropylène
CN110655614A (zh) * 2019-11-04 2020-01-07 绵阳鸿琪新材料科技有限公司 一种聚丙烯增容剂及其制备方法、聚丙烯改性塑料及其制备方法和应用
CN110655614B (zh) * 2019-11-04 2022-05-03 绵阳鸿琪新材料科技有限公司 一种聚丙烯增容剂及其制备方法、聚丙烯改性塑料及其制备方法和应用
CN115175957A (zh) * 2020-02-26 2022-10-11 原子能和替代能源委员会 用于聚合物组分的化学改性方法
WO2022112190A1 (fr) * 2020-11-30 2022-06-02 Basf Se Procédé de production de dispersions polymères
CN113136147A (zh) * 2021-05-07 2021-07-20 浙江祥邦科技股份有限公司 一种柔性组件用截止型热塑性poe封装胶膜及其制备方法
WO2024032237A1 (fr) * 2022-08-10 2024-02-15 华为技术有限公司 Matériau préexpansé, et son procédé de préparation et son utilisation

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