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
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• • 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
  • C08C19/25—Incorporating silicon atoms into the molecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/06—Copolymers with styrene

Definitions

• the present invention relates to a process for synthesizing a modified polymer comprising epoxy groups along the polymer chain. More particularly, the present invention relates to obtaining these epoxidized polymers by functionalization of an unsaturated diene polymer. The invention also relates to the functional polymer obtained and the crosslinkable composition containing it. Polymers carrying epoxide functions are widely used for the reactivity of the epoxide function in various applications. They are mainly used in industry fields using elastomers that need to be cross-linked in some other way than via sulfur.
• the epoxide function can be carried directly by the carbon skeleton of the diene polymer, and is then mainly obtained by epoxidation of carbon-carbon double bonds initially present after copolymerization.
• This epoxidation of unsaturated polymers is well known to those skilled in the art, and can be carried out, for example, by chlorohydrin or bromohydrin-based processes, direct oxidation processes or hydrogen peroxide-based processes. alkyl hydroperoxides or peracids (such as peracetic acid or performic acid).
• the epoxide function may also be pendant and is then either already present in a monomer involved in the copolymerization with the other monomer (s) constituting the polymer (this monomer may be, for example, glycidyl methacrylate, allyl glycidyl ether or glycidyl ether) ,.
• this monomer may be, for example, glycidyl methacrylate, allyl glycidyl ether or glycidyl ether
• the technical problem that arises with respect to the state of the art is to provide a method for synthesizing a polymer carrying epoxy functions along the chain in a simple and controlled manner with productivity in line with a production. industrial.
• the inventors have now developed a new process for synthesizing a polymer bearing pendant epoxide functional groups along the chain by grafting a hydrogenosilane carrying an epoxide function on the unsaturations of the polymer by reaction. hydrosilylation.
• the grafting yield is high since it can reach 100% on unsaturations.
• the process according to the invention is simple, reproducible and capable of being used on an industrial scale.
• Patent applications WO2003085024A1, JP4586966B2, JP2006002035A, JP07133347A and JP05339504A report the use of hydrogenosilanes to introduce an epoxy end-chain function of vinyl or allyl terminated polymers.
• functions are terminated at the end of the polymer chain by hydrosilylation using functional epoxy hydrogenosilanes.
• WO2003085024A1 the authors are interested in the functionalization of polyisobutylene terminated allyl.
• JP4586966B2 and JP2006002035A the authors are interested in the functionalization of fluorinated polyethers and vinyl-terminated polyimides.
• JP07133347A the authors are interested in the functionalization of vinyl-terminated polysiloxanes.
• JP05339504A the authors are interested in the functionalization of aromatic polyether terminated allyl.
• a first object of the invention relates to a process for synthesizing a diene polymer comprising epoxide functions along the chain, characterized in that it comprises the step of modifying an unsaturated polymer comprising unsaturations. along the chain by hydrosilylation, by reacting the unsaturated polymer with an epoxidized hydrogenosilane of formula 1 in the presence of a catalyst
• R and R 2 identical or different, each being an alkyl group C 1 -C 5, C 6 -C 4, aromatic C 7 -Cn alkyl;
• R 3 , R 4 and R 5 which may be identical or different, each being a hydrogen atom or a C 1 -C 5 alkyl, C 6 -C 4 aryl or C 7 aromatic alkyl group;
• Y is a bridging group with a valence equal to i + 1; and i is an integer of from 1 to 3.
• Another subject of the invention is the diene polymer comprising epoxide functional groups along the chain that can be obtained by the method which is also the subject of the invention.
• the subject of the invention is also a rubber composition comprising such 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).
• a majority compound when reference is made to a "majority" compound, it is understood in the sense of the present invention that this compound is predominant among the compounds of the same type in the composition, that is to say that is the one which represents the largest quantity by mass among the compounds of the same type.
• a majority elastomer is the elastomer representing the largest mass relative to the total mass of the elastomers in the composition.
• a so-called majority charge is that representing the largest mass among the charges of the composition.
• a "minor" compound is a compound that does not represent the largest mass fraction among compounds of the same type.
• the polymer includes pendant groups of this type or unsaturations at several points in the chain. This includes the end or ends of the chain but is not limited to these locations.
• the polymer also comprises at least one other pendant group of this type or another unsaturation at another position in the chain.
• graft means the lateral group attached to the main chain of the polymer from the hydrosilylation grafting of the epoxidized hydrogenosilane.
• epoxidized means the lateral group attached to the main chain of the polymer from the hydrosilylation grafting of the epoxidized hydrogenosilane.
• epoxidized means the lateral group attached to the main chain of the polymer from the hydrosilylation grafting of the epoxidized hydrogenosilane.
• epoxidized epoxy functional
• epoxy functional epoxy functional
• a first object of the invention is a process for synthesizing a diene polymer comprising pendant epoxide functions along the chain of modifying a polymer comprising unsaturations along the chain by a hydrosilylation reaction in the presence an epoxidized hydrogenosilane of formula I and a catalyst.
• the invention comprises the distinct but combinable variants which follow concerning the nature of the hydrogenosilane of formula I.
• Rx denotes an alkyl radical, it has 1 to 5 carbon atoms, preferably 1 to 4, more preferably 1 to 3 carbon atoms.
• Rx denotes an alkyl radical, it has 1 to 5 carbon atoms, preferably 1 to 4, more preferably 1 to 3 carbon atoms.
• R 1 when R 1 represents an aryl radical, it has 6 to 14 carbon atoms.
• R 1 when R 1 represents an aryl radical, it has 6 to 14 carbon atoms.
• aryl radical By way of example, mention may be made of phenyl, naphthyl and anthracenyl radicals.
• Rx is an alkyl aromatic radical, it has 7 to 11 carbon atoms.
• Rx is an alkyl aromatic radical, it has 7 to 11 carbon atoms.
• R 3 , R 4 and R 5 are preferably identical and represent a hydrogen atom.
• R 1 and R 2 which may be identical or different, preferably denote a C 1 -C 5 alkyl group.
• Y preferably represents a hydrocarbon chain, linear, branched, cyclic, which may contain one or more aromatic radicals, and / or one or more heteroatoms, such as, for example, N, O or Si.
• the bridging group Y is a linear or branched C1-C24, preferably C1-C10, alkyl chain, optionally interrupted by one or more silicon and / or oxygen atoms.
• Y is a linear C 1 -C 6 alkyl chain interrupted by one or more silicon and / or oxygen atoms.
• the hydrocarbon chain Y comprises at least one silicon atom, it may be substituted preferably by at least one C 1 -C 4 alkyl radical, preferably methyl or ethyl.
• the hydrocarbon chain Y comprises at least one oxygen atom, it is preferably separated from the epoxy group by a methylene group.
• i is preferably 1.
• the epoxidized hydrogenosilane that can be used in the context of the process of the invention has at least one of the following four characteristics, preferably the four: R 1 and R 2 , which are identical or different, denote an alkyl radical C1-C5, preferably methyl and ethyl,
• R 3 , R 4 and R 5 are identical and represent a hydrogen atom
• Y is a linear C 1 -C 6 alkyl chain interrupted by at least one oxygen atom separated from the epoxy group by a methylene group and by at least one silicon atom substituted with two identical or different alkyl radicals, in d-C 5 preferably methyl and ethyl,
• i 1.
• Silanes such as, for example, (3-glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane (Formula A), may be used as molecules for grafting within the context of the invention.
• the hydrogenosilane described above reacts by hydrosilylation with the unsaturations of an unsaturated diene polymer.
• diene polymer should be understood according to the invention any polymer derived at least in part (i.e., a homopolymer or a copolymer) of monomers dienes (monomers bearing two carbon-carbon double bonds, conjugated or not).
• the diene polymer according to the invention comprises unsaturations of the carbon-carbon double bond type.
• the polymer according to the invention preferably has between unsaturations, unsaturations hanging along the chain. According to certain variants, these pendant unsaturation are so-called unsaturations of vinyl origin. Unsaturations of vinyl origin are termed pendant unsaturation of the polymer chain from a vinyl type insertion of the diene monomer into the polymer.
• unsaturations of vinyl origin mention may be made of those resulting from a type 1 insertion, 2 for example butadiene, isoprene or any other diene having a C1 unsaturation, or else type 3,4- inserts of isoprene for example ...
• the unsaturated polymer according to the invention may belong to any category of diene polymers derived at least in part from diene monomers, conjugated or otherwise. It is any type of polymer in the sense known to those skilled in the art, whether of a thermoplastic or elastomeric nature, provided that this polymer is unsaturated.
• the unsaturated diene polymer is chosen from diene elastomers.
• the unsaturated diene polymer according to the invention comprises unsaturations along the chain. The mass ratio of the monomeric units carrying these unsaturations varies in a wide range which makes it possible to encompass the different categories of polymers.
• the diene polymers suitable for being used in the process of the invention may be weakly unsaturated with a mass content of unsaturated monomeric units of at least 1% relative to the total weight of the polymer. According to variants this rate can then be at least 5% by weight, or even at least 10% by weight.
• the diene polymers suitable for use in the process of the invention may also be highly unsaturated, with a mass ratio of unsaturated monomeric units greater than 20% and up to 100% based on the total weight of the polymer. According to some variants, this rate can then be at least 40% and even at least 50%. When the mass ratio of unsaturated monomeric units is less than 1%, the intended technical effect of the epoxidized polymer may be insufficient.
• any diene polymer comprising at least unsaturated units, part of which is derived from an insertion of the conjugated or non-conjugated diene monomer, leading to a pendant unsaturation, in particular according to some of these variants, is suitable according to the invention.
• iene polymer that may be used in the invention is more particularly understood to mean a diene polymer corresponding to one of the following categories:
• conjugated diene monomer for the synthesis of polymers (a), (b) and (h), 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-butadiene and 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, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.
• 1,3-butadiene 2-methyl-1,3-butadiene, 2,3-butadiene and di (C 1 -C 5) -alkyl-1,3-butadienes
• vinylaromatic compounds having 8 to 20 carbon atoms for example styrene, ortho-, meta-, para-methylstyrene, the commercial mixture vinylmesitylene, divinylbenzene, vinylnaphthalene; vinyl nitrile monomers having 3 to 12 carbon atoms, for example acrylonitrile or methacrylonitrile; acrylic ester monomers derived from acrylic acid or methacrylic acid with alcohols having 1 to 12 carbon atoms, for example methyl acrylate, ethyl acrylate or propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate;
• the copolymers (b) or (d) may contain between 99% and 1% by weight of diene units and between 1% and 99% by weight of vinylaromatic units, vinyl nitriles and / or acrylic esters.
• a mono-olefin monomer suitable for the synthesis of the polymers (h) mention may be made of ethylene, an oolefin having 3 to 6 carbon atoms, for example propylene.
• the mono-olefin monomer is ethylene.
• the olefinic copolymer (h) that can be used in the process of the invention is a copolymer whose chain comprises olefinic monomeric units, that is to say units resulting from the insertion of less a mono-olefin, and diene units derived from at least one conjugated diene.
• the units are not integrally units derived from diene monomers and monoolefinic monomers.
• other units resulting for example from an ethylenically unsaturated monomer as described above, are present in the carbon chain.
• the olefinic monomeric units in the polymer (h) are in the majority, more preferably, the molar level of these units is greater than 50% relative to the polymer.
• the molar rate can be at least 65% and at most 95%, or even at most 85%.
• diene polymers derived from at least one conjugated diene monomer used in the context of the modification process according to the invention
• non-exclusive examples include polybutadiene, polyisoprene, polychloroprene and their hydrogenated versions, polyisobutylene.
• block copolymers of butadiene and isoprene with styrene and their hydrogenated versions such as poly styrene-b-butadiene (SB), poly styrene-b-butadiene-b-styrene (SBS), poly styrene-b-isoprene-b-styrene (SIS), poly styrene-b- (isoprene-st-butadiene) -b-styrene or poly styrene-b-isoprene-b-butadiene-b-styrene (SIBS), SBS hydrogen (SEBS), poly styrene-b- butadiene-b-methyl methacrylate (SBM), as well as its hydrogenated version (SEBM), the random copolymers of butadiene with styrene (SBR) and acrylonitrile (NBR) and their hydrogenated versions,
• the diene polymer (s) used in the invention are very particularly chosen from the group of diene polymers consisting of polybutadienes (abbreviated as "BR"), synthetic polyisoprenes (IR) and natural rubber (NR). ), butadiene copolymers, isoprene copolymers, ethylene-diene copolymers and mixtures of these polymers.
• BR polybutadienes
• IR synthetic polyisoprenes
• NR natural rubber
• Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR), isoprene-copolymers of butadiene-styrene (SBIR) and ethylene-butadiene copolymers (EBR).
• SBR butadiene-styrene copolymers
• BIR isoprene-butadiene copolymers
• SIR isoprene-styrene copolymers
• EBR ethylene-butadiene copolymers
• the polymers that can be used according to the invention can be obtained according to conventional polymerization techniques well known to those skilled in the art.
• the polymers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and their quantity.
• the polymers may be, for example, block, random, sequenced or microsequential, and may be prepared in dispersion, in emulsion or in solution; they can be coupled and / or starred or further functionalized with a suitable functionalization agent.
• the process comprises dissolving in an apolar solvent at least one unsaturated diene polymer, an epoxy functional hydrogenosilane and a hydrosilylation catalyst. This solubilization can be done according to any implementation at the disposal of the skilled person.
• the unsaturated polymer, the epoxy functional hydrogenosilane and the catalyst are dissolved in the apolar solvent with stirring.
• any inert hydrocarbon solvent which may be, for example, an aliphatic or alicyclic hydrocarbon such as pentane, hexane, heptane, isooctane, hexane, hexane, isooctane or octane, may be used according to the process according to the invention.
• cyclohexane, methylcyclohexane or an aromatic hydrocarbon such as benzene, toluene, xylene, and mixtures thereof.
• methylcyclohexane or toluene is used.
• catalyst it is possible to use according to the invention any known catalyst for the catalysis of hydrosilylation based on transition metals generally of group VIII such as platinum, palladium, rhodium, ruthenium, iron, Among these different catalysts used for the hydrosilylation reaction, platinum-based catalysts such as hexachloroplatinic acid hexahydrate (Speier catalyst) and platinum-1,1,3,3-catalyst will preferably be selected. 1-tetramethyl-1,3-divinylsiloxane (Karstedt catalyst) and more preferably the Karstedt catalyst.
• the catalyst may be added to the reaction mixture in any customary form, however, preferably in the form of a solution in a solvent.
• the amount of total solvent, or solvent of the reaction medium is such that the mass concentration of polymer is between 1 and 40% by weight, preferably between 2 and 20% and even more preferably between 2 and 10%. in said solvent.
• total solvent, or solvent of the reaction medium is meant all the solvents used to solubilize the unsaturated polymer, the epoxy functional hydrogenosilane and the hydrosilylation catalyst.
• the process according to the invention may advantageously comprise a step of heating the homogeneous reaction mixture obtained in the preceding step to the temperature of the grafting reaction.
• the grafting reaction temperature is at least 20 ° C and at most 120 ° C, preferably it is at least 50 ° C, or even at least 60 ° C and at most 100 ° C, or at most 90 ° C .
• the degree of grafting can be adjusted in a manner known to those skilled in the art, by varying different operating conditions, such as in particular the amount of molecules to be grafted, the temperature or the reaction time. It is possible to achieve quantitative grafting yields.
• the degree of grafting is preferably at least 0.1 mol% of grafts relative to the modified polymer.
• the degree of grafting is preferably at most 50 mol% of grafts relative to the modified polymer, and according to some variants the degree of grafting is less than 20 mol% of grafts relative to the modified polymer.
• the variants and the preferred aspects described above are combinable with each other.
• the grafting method thus defined makes it possible to achieve significantly high grafting yields, ranging from 30% to 100%, or, depending on particular implementations, yields ranging from 70% to 100%, or even even from 80% to 100%, and this in relatively short times especially with respect to an epoxidation reaction. Indeed, according to some variants, the reaction times can be divided by at least 10.
• the process of the invention makes it possible to synthesize a diene polymer comprising epoxide functions along the chain.
• This polymer is also the subject of the invention.
• This diene polymer comprises units (i.e. at least two of which at least one is located in the chain as opposed to the end position of the chain) carrying a pendant epoxide function along the chain and bonded to those by means of a silicon atom.
• these epoxidized units carry a pendant epoxide function along the chain corresponding to formula 2
• R 1, R 2, R 4 and R 5 are as defined above, including the advantageous or preferred variants.
• these epoxidized units carry a pendant epoxide function along the chain according to one of the following formulas AB 'and C:
• the epoxidized diene polymer comprises units carrying a pendant epoxide function along the chain and bonded thereto via a silicon atom in a molar ratio of at least 0 , 1% and not more than 50%.
• this level is preferably at most 20%, more preferably at most 10% molar.
• the epoxidized diene polymer according to the invention therefore comprises non-epoxidized units at a molar ratio of at most 99.9%.
• this level of non-epoxidized units is preferably at least 80 mol%.
• the molar levels are measured relative to the totality of the polymer.
• these non-epoxidized units comprise units derived from at least one diene monomer, conjugated or otherwise, as described above.
• conjugated diene monomer mention may be made of butadiene and isoprene
• these non-epoxidized units comprise units that may be derived from at least one monoolefin as described above.
• the non-epoxidized units comprise units derived from at least one ethylenically unsaturated monomer.
• vinylaromatic monomers having from 8 to 20 carbon atoms, vinyl nitrile monomers having 3 to 12 carbon atoms and acrylic ester monomers derived from acrylic acid or methacrylic acid with an alcohol having 1 to 12 carbon atoms as described above.
• acrylic ester monomers derived from acrylic acid or methacrylic acid with an alcohol having 1 to 12 carbon atoms as described above.
• Another object of the invention is a crosslinkable rubber composition comprising this epoxy functional polymer as described above or prepared by hydrolysis according to the method described above.
• diene polymers grafted according to the process of the invention can be used as such or in mixtures with one or more other compounds.
• the presence of epoxide groups grafted along the chain makes it possible to envisage the use in similar applications of diene polymers functionalized with these same epoxide groups.
• the graft polymer according to the invention makes it possible to envisage its use in the manufacture of various products based on reinforced rubber depending on the nature of the grafted epoxidized hydrogenosilane derivative.
• the epoxide groups have a very particular reactivity with certain compounds. It is thus possible to envisage a use of the graft polymer according to the invention in applications where such reactivity is necessary.
• a tire of which one of these components comprises a rubber composition based on an epoxidized diene polymer described above by its structure or its method of synthesis, is also an object of the invention.
• the elastomers are characterized, before cooking, as indicated below. Ch romatograph of steric excl u sity
• SEC Size Exclusion Chromatography
• the SEC allows to apprehend the distribution of the molar masses of a polymer.
• Preparation of the polymer There is no particular treatment of the polymer sample before analysis. This is simply solubilized in (tetrahydrofuran + 1% vol of distilled water) at a concentration of about 1 g / l. Then the solution is filtered on 0.45 ⁇ porosity filter before injection.
• SEC analysis The equipment used is a "WATERS alliance" chromatograph. The elution solvent is tetrahydrofuran. The flow rate is 0.7 ml / min, the system temperature 35 ° C and the analysis time 90 min. A set of four WATERS columns in series, trade names "STYRAGEL HMW7", “STYRAGEL HMW6E” and two “STYRAGEL HT6E” are used. The injected volume of the solution of the polymer sample is 100 ⁇ l. The detector is a differential refractometer "WATERS 2410" and the chromatographic data exploitation software is the "WATERS EMPOWER" system.
• the average molar masses calculated relate to a calibration curve made from commercial standard polystyrene "PSS READY CAL-KIT". Tem of tra ns ition vitreu
• the glass transition temperatures Tg of the polymers are measured by means of a differential scanning calorimeter. The analysis is performed according to the requirements of ASTM D3418-08.
• SBR2 copolymer of butadiene and styrene prepared in solution having the following microstructure characteristics by 1 H NMR:
• Copolymer EBR1 of butadiene and ethylene prepared in solution according to patent EP 1 954 705 B1, exhibiting the following microstructure characteristics by 1 H NMR:
• the starting polymer is subjected to an antioxidant treatment by the addition of 0.4 parts per hundred parts of elastomers (phr) of 4,4'-methylene-bis-2,6-tert-butylphenol and 0.4 parts by weight. one hundred parts elastomers (phr) of N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine.
• Epoxy functional silicone used is
• Example 1 2 g of SBR1 are dissolved in 100 ml of toluene in a 250 ml reactor equipped with mechanical stirring. 4.05 mmol (1 g) of (3-glycidoxypropyl) - 1, 1, 3,3-tetramethyldisiloxane and 200, uL of platinum-1, 1, 3,3-tetramethyl-1, 3- divinylsiloxane in solution in xylene (Karstedt catalyst) (CAS No. 68478-92-2) are added to the polymer solution and the reaction medium is heated to 60 ° C.
• Karstedt catalyst CAS No. 68478-92-2
• reaction medium After 2 hours at 60 ° C with stirring, the reaction medium is allowed to return to room temperature. Once it has returned to ambient temperature, the reaction medium is then coagulated in 250 ml of methanol and then rinsed with 250 ml of methanol.
• the solution polymer then undergoes an antioxidant treatment of 0.4 parts per hundred parts elastomers (phr) of 4,4'-methylene-bis-2,6-tert-butylphenol and 0.4 parts for one hundred parts elastomers (phr) of N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine.
• the functionalized SBR is dried by vacuum baking (200 torr) at 60 ° C for 1 day.
• the degree of graft function determined by 1 H NMR spectroscopy is 1.19 mol% over the entire copolymer.
• the graft yield is 95%.
• reaction medium After 2 hours at 60 ° C with stirring, the reaction medium is allowed to return to room temperature. Once it has returned to ambient temperature, the reaction medium is then coagulated in 250 ml of methanol and then rinsed with 250 ml of methanol.
• the solution polymer then undergoes an antioxidant treatment of 0.4 parts per hundred parts elastomers (phr) of 4,4'-methylene-bis-2,6-tert-butylphenol and 0.4 parts for one hundred parts elastomers (phr) of N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine.
• the functionalized SBR is dried by vacuum baking (200 torr) at 60 ° C for 1 day.
• the degree of graft function determined by 1 H NMR spectroscopy is 14.4 mol% over the entire copolymer.
• the grafting yield is 96%.
• reaction medium After 2 hours at 60 ° C with stirring, the reaction medium is allowed to return to room temperature. Once it has returned to ambient temperature, the reaction medium is then coagulated in 250 ml of methanol and then rinsed with 250 ml of methanol.
• the polymer then undergoes an antioxidant treatment of 0.4 parts per hundred parts elastomers (phr) of 4,4'-methylene-bis-2,6-tert-butylphenol and 0.4 parts per hundred parts d elastomers (phr) of N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine.
• the functionalized SBR is dried by vacuum baking (200 torr) at 60 ° C for 1 day.
• the degree of graft function determined by 1 H NMR spectroscopy is 9.4 mol% over the entire copolymer.
• the grafting yield is 96%. Distribution of each of the patterns over the entire copolymer

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