WO2024067013A1 - Copolymère multicomposants, son procédé de préparation et son utilisation, et caoutchouc butyle ramifié halogéné, son procédé de préparation et son utilisation - Google Patents

Copolymère multicomposants, son procédé de préparation et son utilisation, et caoutchouc butyle ramifié halogéné, son procédé de préparation et son utilisation Download PDF

Info

Publication number
WO2024067013A1
WO2024067013A1 PCT/CN2023/117573 CN2023117573W WO2024067013A1 WO 2024067013 A1 WO2024067013 A1 WO 2024067013A1 CN 2023117573 W CN2023117573 W CN 2023117573W WO 2024067013 A1 WO2024067013 A1 WO 2024067013A1
Authority
WO
WIPO (PCT)
Prior art keywords
structural unit
preparation
polymer
formula
butyl rubber
Prior art date
Application number
PCT/CN2023/117573
Other languages
English (en)
Chinese (zh)
Inventor
徐典宏
魏绪玲
燕鹏华
赵志超
梁滔
牛承祥
杨珊珊
孟令坤
朱晶
Original Assignee
中国石油天然气股份有限公司
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 中国石油天然气股份有限公司 filed Critical 中国石油天然气股份有限公司
Publication of WO2024067013A1 publication Critical patent/WO2024067013A1/fr

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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • C08F210/10—Isobutene
    • C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • 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
    • C08F236/08—Isoprene
    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the invention relates to the technical field of rubber preparation, and in particular to a multi-component copolymer and a preparation method and application thereof, and a halogenated branched butyl rubber and a preparation method and application thereof.
  • Bromobutyl rubber is obtained by introducing bromine atoms into the molecular chain of butyl rubber (IIR) through an electrophilic substitution reaction under the action of molecular bromine.
  • IIR butyl rubber
  • BIIR has good adhesion, fast vulcanization speed, good thermal stability and corrosion resistance in addition to its excellent air tightness, and can be used in extreme environments such as strong corrosion or high temperature.
  • bromine atoms not only the polarity of the molecular chain is increased, but also the relaxation resistance of the chain segment is increased, and the internal friction is large. It has excellent damping performance, so it is one of the most widely used basic damping rubbers.
  • CN112574333A discloses a bromination process of star-branched butyl rubber.
  • the process comprises: a) dissolving the star-branched butyl rubber in aliphatic hydrocarbon to obtain a rubber solution; b) mixing the above-mentioned rubber solution with branching agent scavenger ethanol to obtain a mixed solution; c) adding an oxidizing agent hydrogen peroxide and a brominating agent Br2 to the above-mentioned mixed solution, and the molar ratio of bromine element to unsaturated double bonds in the star-branched butyl rubber is (0.75-2):1 to carry out bromination reaction, and finally neutralize and recover the product to obtain brominated star-branched butyl rubber.
  • CN106749816A discloses a method for preparing brominated butyl rubber, wherein n-alkane is first used to dissolve butyl rubber, and then a specific organic bromide such as phenyltrimethylammonium tribromide, benzyltrimethylammonium tribromide, or dibromoisocyanuric acid is used as a brominating agent, and Br2 or HBr is used as a bromination accelerator to carry out a bromination reaction in a solvent to obtain brominated butyl rubber.
  • a specific organic bromide such as phenyltrimethylammonium tribromide, benzyltrimethylammonium tribromide, or dibromoisocyanuric acid
  • Br2 or HBr is used as a bromination accelerator to carry out a bromination reaction in a solvent to obtain brominated butyl rubber.
  • Liao Mingyi et al. (Journal of Dalian Maritime University, 2008, 34(2):83-86) disclosed a step-by-step method for improving the damping performance of butyl rubber (IIR).
  • IIR isomer network
  • P(St-MMA) poly(styrene-methyl methacrylate)
  • a butyl rubber/poly(styrene-methyl methacrylate) interpenetrating polymer network [IIR/P(St-MMA)] was prepared by graft polymerization to prepare a wide temperature range, high damping butyl rubber material.
  • the purpose of the present invention is to overcome the problems in the prior art that the rubber materials cannot have a wide effective damping temperature range, high damping performance and good mechanical properties, and the preparation is complex and causes pollution, and to provide a multi-polymer and a preparation method and application thereof, a halogenated branched butyl rubber and a preparation method and application thereof.
  • the present invention provides a multi-component copolymer in a first aspect, wherein the multi-component copolymer comprises: a structural unit A, a structural unit B and a structural unit C; wherein the structural unit A has a structure shown in formula (1), the structural unit B has a structure shown in formula (2), and the structural unit C has a structure shown in formula (3).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen or a C 1 -C 10 straight or branched chain alkyl group;
  • X is a halogen, and n is any integer from 1 to 10;
  • the terminal of the multi-component copolymer contains a structural unit derived from a conjugated diene.
  • the second aspect of the present invention provides a method for preparing a multi-component copolymer, wherein the preparation method comprises: under polymerization conditions, in the presence of an initiator, an optional structure regulator and an organic solvent, polymerizing a monomer represented by formula (I), a monomer represented by formula (II) and a monomer represented by formula (III) to obtain a polymer solution;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen or a C 1 -C 10 straight or branched chain alkyl group;
  • X is a halogen, and n is any integer from 1 to 10.
  • the third aspect of the present invention provides a multi-polymer obtained by the aforementioned preparation method.
  • a fourth aspect of the present invention provides a use of the aforementioned multi-polymer as a grafting agent in the preparation of diene rubber.
  • the fifth aspect of the present invention provides a halogenated branched butyl rubber, wherein the halogenated branched butyl rubber comprises: a structural unit I derived from isobutylene, a structural unit II derived from isoprene and a structural unit III derived from a halogenated grafting agent; wherein the halogenated grafting agent is the aforementioned multipolymer.
  • the sixth aspect of the present invention provides a method for preparing the aforementioned halogenated branched butyl rubber, wherein the method comprises: in the presence of a diluent, an organic solvent and a co-initiator, contacting isobutylene, isoprene and the aforementioned multi-polymer to carry out cationic polymerization to obtain the halogenated branched butyl rubber.
  • the seventh aspect of the present invention provides a halogenated branched butyl rubber obtained by the aforementioned preparation method.
  • the eighth aspect of the present invention provides the use of the aforementioned halogenated branched butyl rubber in instrument shock absorbers and electrical appliance shock absorbers.
  • the multi-polymer provided by the present invention combines p-alkylphenyl, p-halogenated alkylbenzene and ester group on a macromolecular chain to form an interpenetrating polymer network (IPN), so that p-alkylphenyl, halogen atom and ester group have the characteristics of high rigidity, high steric hindrance and strong adsorption.
  • IPN interpenetrating polymer network
  • the multi-polymer When used as a halogenated grafting agent for preparing halogenated branched butyl rubber, it can produce a significant "synergistic effect" in broadening the effective damping temperature range of the halogenated branched butyl rubber, greatly broadening the effective damping temperature range of the halogenated branched butyl rubber, and can prepare a wide temperature range high damping halogenated branched butyl rubber with an effective damping temperature range (tan ⁇ ⁇ 0.3) exceeding the range of -50°C to 62°C and a tan ⁇ max of 1.9 or more.
  • the p-alkylphenyl group, the p-halogenated alkylbenzene group and the ester group are arranged on the molecular chain, thereby producing a superposition of a "group effect" and a "structural effect".
  • the multi-polymer is used as a halogenated grafting agent for preparing a halogenated branched butyl rubber, not only is the damping property of the halogenated branched butyl rubber not reduced due to the widening of the effective damping temperature range, but also the molecular weight distribution is not widened due to branching, thereby causing the mechanical properties and air tightness of the butyl rubber to decrease. The tensile strength and air tightness of the butyl rubber are improved.
  • the halogenated branched butyl rubber prepared by the present invention is produced by addition polymerization using a multi-polymer as a grafting agent rather than by ion substitution, thereby blocking the conditions for halogen structural isomerization, improving the effective damping temperature range of the halogenated branched butyl rubber and the stability of the damping performance, and broadening the application scope of the halogenated branched butyl rubber.
  • VOC volatile organic compound
  • FIG. 1 is a dynamic mechanical spectrum of the brominated branched butyl rubber product prepared in Example 11 of the present invention (curve #1) and the existing brominated butyl rubber (BIIR) 2302 (curve #2).
  • any values of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values.
  • the endpoint values of each range, the endpoint values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this article.
  • the first aspect of the present invention provides a multi-component copolymer, wherein the multi-component copolymer comprises: a structural unit A, a structural unit B and a structural unit C; wherein the structural unit A has a structure shown in formula (1), the structural unit B has a structure shown in formula (2), and the structural unit C has a structure shown in formula (3).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen or a C 1 -C 10 straight or branched chain alkyl group;
  • X is a halogen, and n is any integer from 1 to 10;
  • the terminal of the multi-component copolymer contains a structural unit derived from a conjugated diene.
  • the multi-component copolymer of the present invention contains p-alkylphenyl, p-halogenated alkylbenzene and ester group at the same time to form an interpenetrating polymer network (IPN), so that the p-alkylphenyl, halogen atom and ester group have the characteristics of high rigidity, high steric hindrance and strong adsorption, and the end of the copolymer contains a conjugated diene structural unit, so that the multi-component copolymer has high polymerization activity and can be used as a grafting agent for preparing branched diene rubber, in particular, for preparing halogenated branched diene rubber.
  • IPN interpenetrating polymer network
  • examples of the C1 - C10 straight or branched alkyl group may be any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, 2-methylhexyl, 2-ethylhexyl, 1-methylheptyl, 2-methylheptyl, n-octyl, isooctyl, n-nonyl, isononyl and 3,5,5-trimethylhexyl.
  • n in the structure represented by formula (1) can be selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen or C 1 -C 6 linear or branched alkyl, preferably hydrogen or C 1 -C 4 linear or branched alkyl, more preferably hydrogen, methyl or ethyl.
  • R 6 is methyl
  • X is selected from Cl and/or Br.
  • n is any integer from 1 to 5, preferably any integer from 1 to 3.
  • the conjugated diene is butadiene and/or isoprene.
  • the structural unit represented by formula (1) may be a structural unit derived from p-bromomethylstyrene
  • the structural unit represented by formula (2) may be a structural unit derived from p-alkylstyrene, such as p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-n-butylstyrene, p-isobutylstyrene or p-isopentylstyrene
  • the structural unit represented by formula (3) may be a structural unit derived from an unsaturated acrylic acid ester, such as methyl methacrylate (MMA), ethyl methacrylate, butyl methacrylate or tert-butyl methacrylate.
  • the multi-polymer is a block copolymer or a random copolymer.
  • the mass ratio of structural unit A, structural unit B, structural unit C and structural unit derived from conjugated diene is 100:20-50:10-25:1-5, for example, 100:20:25:1, 100:50:10:5, 100:30:15:2, 100:40:20:4, 100:25:12:3, and any value within the range of any two of the above values, preferably 100:30-40:15-20:2-3.
  • the above ratio can be measured by infrared spectroscopy and nuclear magnetic resonance methods, or determined based on the preparation and feeding relationship.
  • the mass percentage of halogen in the multi-polymer is 2.5-5.5%, such as 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, and any value within the range of any two of the above values, preferably 4-5%.
  • the mass percentage of halogen in the multi-polymer meets the above range, the damping property and vulcanization processability of butyl rubber can be improved.
  • the halogen content is determined by using a Q600 TG/DTG thermogravimetric analyzer.
  • the number average molecular weight (Mn) of the multi-polymer is 25,000-60,000 g/mol, for example, 25,000 g/mol, 30,000 g/mol, 35,000 g/mol, 40,000 g/mol, 45,000 g/mol, 50,000 g/mol, 55,000 g/mol, 60,000 g/mol, and any value within the range of any two of the above values, preferably 40,000-50,000 g/mol.
  • the molecular weight distribution index (Mw/Mn) of the multipolymer is 1.2-2, for example, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, and any value within the range of any two of the above values, preferably 1.45-1.95.
  • the number average molecular weight and the molecular weight distribution index are both tested by gel chromatography.
  • the multi-polymer has an apparent viscosity of 8-40 cps at 25°C.
  • the apparent viscosity of the multi-polymer at 25° C. is tested using an Ubbelohde viscometer according to GB/T10247-2008.
  • the second aspect of the present invention provides a method for preparing a multi-component copolymer, wherein the preparation method comprises: under polymerization conditions, in the presence of an initiator, an optional structure regulator and an organic solvent, polymerizing a monomer represented by formula (I), a monomer represented by formula (II) and a monomer represented by formula (III) to obtain a polymer solution;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen or a C 1 -C 10 straight or branched chain alkyl group;
  • X is a halogen, and n is any integer from 1 to 10.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen or C 1 -C 6 linear or branched alkyl, preferably hydrogen or C 1 -C 4 linear or branched alkyl, more preferably hydrogen, methyl or ethyl.
  • R 6 is methyl
  • X is selected from Cl and/or Br.
  • n is any integer from 1 to 5, preferably any integer from 1 to 3.
  • Examples of the C 1 -C 10 straight-chain or branched-chain alkyl group described in the second aspect of the present invention are the same as those described in the first aspect of the present invention, and will not be described in detail herein.
  • the monomer represented by formula (I) is p-bromomethylstyrene
  • the monomer represented by formula (II) is p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-n-butylstyrene, p-isobutylstyrene or p-isopentylstyrene
  • the monomer represented by formula (III) is methyl methacrylate (MMA), ethyl methacrylate, butyl methacrylate or tert-butyl methacrylate.
  • the conjugated diene is butadiene and/or isoprene.
  • the mass ratio of the monomer represented by formula (I), the monomer represented by formula (II), the monomer represented by formula (III) and the conjugated diene is 100:20-50:10-25:1-5, for example, 100:20:25:1, 100:50:10:5, 100:30:15:2, 100:40:20:4, 100:25:12:3, and any value within the range of any two of the above values, preferably 100:30-40:15-20:2-3.
  • the mass ratio of the monomer represented by formula (I), the monomer represented by formula (II), the monomer represented by formula (III) and the conjugated diene is controlled within a specific range, and a butyl rubber having an effective damping temperature range (tan ⁇ 0.3) exceeding the range of -50°C to 62°C and a maximum damping factor tan ⁇ max ⁇ 1.9 can be obtained.
  • the polymerization reaction is carried out under a protective atmosphere, and the protective atmosphere is preferably an inert atmosphere.
  • the initiator is a hydrocarbon monolithium compound, preferably RLi, wherein R is at least one selected from a C 1 -C 20 saturated aliphatic hydrocarbon group, a C 3 -C 20 alicyclic hydrocarbon group and a C 6 -C 20 aromatic hydrocarbon group.
  • the initiator is selected from at least one of n-butyl lithium, sec-butyl lithium, methylbutyl lithium, phenylbutyl lithium, naphthalene lithium, cyclohexyl lithium and dodecyl lithium.
  • the above-mentioned initiator can be selected to make each monomer undergo anionic polymerization to form a block copolymer, thereby achieving the superposition effect of "structural effect" and "group effect”.
  • the amount of the initiator is 16-30 mmol, preferably 18-25 mmol, relative to 1000 g of the monomer represented by formula (I). Too little initiator will result in a smaller molecular weight of the prepared multi-polymer, which will affect the wide temperature range and damping performance of butyl rubber during application and fail to achieve the modification effect; too much initiator will result in a wider molecular weight distribution of the prepared multi-polymer, resulting in a decrease in the air tightness and mechanical strength of butyl rubber.
  • the structure regulator is a polar organic compound.
  • the structure regulator of the present invention is a polar organic compound, which can produce a solvation effect in the polymerization system, and can adjust the reactivity ratio of alkyl styrene and isoprene, so that the two can undergo block copolymerization.
  • the structure regulator is selected from at least one of diethylene glycol dimethyl ether, tetrahydrofuran, ethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether and triethylamine.
  • the organic solvent is a hydrocarbon solvent, preferably at least one of straight-chain alkanes, aromatic hydrocarbons and cycloalkanes, and further preferably at least one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene.
  • the polymerization reaction conditions include: the polymerization reaction temperature is 50-80°C, such as 50°C, 60°C, 70°C, 80°C, and any value within the range of any two of the above values. If the polymerization reaction temperature is too low, the reaction activity will be reduced, the reaction rate will be slow, and the reaction will be incomplete, and the wide temperature range and high damping modification effect of butyl rubber cannot be achieved when it is used; if the polymerization reaction temperature is too high, the reaction activity will be increased, the reaction rate will be increased, and the molecular structure will be irregularly arranged, which will cause the strength and air tightness of butyl rubber to decrease when it is used.
  • the polymerization reaction temperature is 50-80°C, such as 50°C, 60°C, 70°C, 80°C, and any value within the range of any two of the above values. If the polymerization reaction temperature is too low, the reaction activity will be reduced, the reaction rate will be slow, and the reaction will be incomplete, and the wide temperature range and
  • the polymerization reaction time is 220-270 minutes, such as 220 minutes, 230 minutes, 240 minutes, 250 minutes, 260 minutes, 270 minutes, and any value within the range of any two of the above values. If the polymerization reaction time is too short, the wide temperature range and high damping modification effect of butyl rubber cannot be achieved when applied; if the polymerization reaction time is too long, the energy consumption is too high, and no obvious effect will be seen in the wide temperature range and high damping modification degree of butyl rubber when applied.
  • the end-capping reaction temperature is 60-90°C, for example, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, and any value within the range of any two of the above values, preferably 70-80°C. If the end-capping reaction temperature is too low, the end-capping will be incomplete, the reactive sites will be reduced, and the grafting rate will be reduced, which will result in poor modification of the wide temperature range and damping performance of butyl rubber when used; if the end-capping reaction temperature is too high, the conjugated diene will easily self-polymerize and fail to play the end-capping role.
  • the end-capping reaction time is 10-45min, for example, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, preferably 20-30min. If the end-capping reaction time is too short, the end-capping will be incomplete and the reaction active points will be reduced, and the wide temperature range and high damping modification effects of butyl rubber cannot be achieved during application. If the end-capping reaction time is too long, the flexibility of the prepared multi-polymer chain segments will increase, which will destroy the damping performance and mechanical strength of butyl rubber during application.
  • the method comprises the following steps:
  • an anionic polymerization method is adopted to obtain a multi-polymer with three blocks, which has the characteristics of controllable structure, stable bromine structure, high isotacticity, complete reaction, and no by-products. It can bring about the effects of wide applicable temperature range, high damping, excellent mechanical strength and vulcanization processability of halogenated branched diene rubber.
  • the mass ratio of the monomer represented by formula (I) to the structure regulator in step (1) is 100:0.5-0.7, such as 100:0.5, 100:0.6, 100:0.7, and any value within the range of any two of the above values.
  • the mass ratio of the monomer represented by formula (II) to the structure regulator in step (2) is 30-40:0.3-0.5, such as 30:0.3, 35:0.35, 40:0.5, and any value within the range of any two of the above values.
  • the mass ratio of the monomer represented by formula (III) to the structure regulator in step (3) is 15-20:0.2-0.3, such as 15:0.2, 18:0.25:20:0.3, and any value within the range of any two of the above values.
  • the first polymerization reaction temperature is 40-80°C, for example, 40°C, 45°C, 55°C, 65°C, 70°C, 75°C, 80°C, and any value within the range of any two of the above values, preferably 50-60°C. If the first polymerization reaction temperature is too low, the bromine content will be too low; if the first polymerization reaction temperature is too high, the bromine structure will be destroyed.
  • the first polymerization reaction time is 80-150min, for example, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, and any value within the range of any two of the above values, preferably 100-120min. If the first polymerization reaction time is too short, the molecular weight will become smaller and the bromine content will become lower; if the first polymerization reaction time is too long, the molecular weight change is not obvious, and the modification effect is not obvious.
  • the second polymerization reaction temperature is 60-90°C, for example, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, and any value within the range of any two of the above values, preferably 70-80°C. If the second polymerization reaction temperature is too low, the benzene ring structure content will be too low, resulting in a decrease in strength and air tightness; if the second polymerization reaction temperature is too high, the damping modification effect will not be obvious.
  • the second polymerization reaction time is 50-80min, for example, 50min, 55min, 60min, 65min, 70min, 75min, 80min, and any value within the range of any two of the above values, preferably 60-70min. If the second polymerization reaction time is too short, the molecular weight will be reduced, the benzene ring structure will be reduced, and the damping increase will be small; if the second polymerization reaction time is too long, the energy consumption will be high, the benzene ring structure will not change significantly, and the damping increase will not change significantly.
  • the third polymerization reaction temperature is 60-90°C, for example, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, and any value within the range of any two of the above values, preferably 70-80°C. If the third polymerization reaction temperature is too low, the polar group ester group content will be too low, causing the damping temperature range of butyl rubber to narrow when used; if the third polymerization reaction temperature is too high, the applicable temperature range of butyl rubber will not be significantly widened when used.
  • the third polymerization reaction time is 30-60min, for example, 30min, 35min, 40min, 45min, 50min, 55min, 60min, and any value within the range of any two of the above values, preferably 40-50min. If the third polymerization reaction time is too short, the polar group ester group content will be too low, and the wide temperature range modification effect of butyl rubber will not be achieved when used; if the third polymerization reaction time is too long, the applicable temperature range of butyl rubber will not be significantly widened when used.
  • the polymerization kettle under an inert atmosphere, is sequentially added with Add an organic solvent, p-bromomethylstyrene and a structure regulator, raise the temperature to 50-60°C, add an initiator and react for 100-120 minutes; then add p-alkylstyrene and a structure regulator to the polymerization kettle, raise the temperature to 70-80°C, and react for 60-70 minutes; then add unsaturated acrylate and a structure regulator to the polymerization kettle, and react for 40-50 minutes; finally, add isoprene to the polymerization kettle for end-capping, and react for 20-30 minutes until no free monomer exists, and the glue solution is wet-coagulated and dried to obtain the above-mentioned multi-polymer;
  • the mass ratio of p-bromomethylstyrene, p-alkylstyrene, unsaturated acrylate and isoprene is 100:30-40:15-20:2-3;
  • the mass ratio of p-bromomethylstyrene to the structure regulator is 100:0.5-0.7;
  • the mass ratio of p-alkylstyrene to structure regulator is 30-40:0.3-0.5;
  • the mass ratio of unsaturated acrylate to structure regulator is 15-20:0.2-0.3.
  • the third aspect of the present invention provides a multi-polymer obtained by the aforementioned preparation method.
  • a fourth aspect of the present invention provides a use of the aforementioned multi-polymer as a grafting agent in the preparation of diene rubber.
  • the diene rubber is butyl rubber.
  • the fifth aspect of the present invention provides a halogenated branched butyl rubber, wherein the halogenated branched butyl rubber comprises: a structural unit I derived from isobutylene, a structural unit II derived from isoprene and a structural unit III derived from a halogenated grafting agent;
  • the halogenated grafting agent is the aforementioned multi-polymer.
  • the mass ratio of the structural unit I, the structural unit II and the structural unit III is 100:4-6:7-10, for example, 100:4:7, 100:5:6, 100:6:10, and any value within the range of any two of the above values.
  • the mass ratio of the structural unit I, the structural unit II and the structural unit III is controlled within a specific range, and an effective damping temperature range (tan ⁇ 0.3) exceeding -50°C to 62°C can be obtained; the maximum damping factor tan ⁇ max ⁇ 1.9; and a butyl rubber having a tensile strength of 22MPa-24MPa.
  • the multi-polymer provided by the present invention combines p-alkylphenyl, p-halogenated alkylbenzene and ester group on a macromolecular chain to form an interpenetrating polymer network (IPN), so that the p-alkylphenyl, halogen atom and ester group have the characteristics of high rigidity, high steric hindrance and strong adsorption, and the like.
  • IPN interpenetrating polymer network
  • a significant "synergistic effect" can be produced in broadening the effective damping temperature range of the halogenated branched butyl rubber, and the effective damping temperature range of the halogenated branched butyl rubber is greatly broadened, and a wide-temperature-range high-damping halogenated branched butyl rubber with an effective damping temperature range (tan ⁇ 0.3) exceeding the range of -50°C to 62°C and a tan ⁇ max of 1.9 or more can be prepared.
  • a sixth aspect of the present invention provides a method for preparing the aforementioned halogenated branched butyl rubber, wherein the method comprises:
  • the halogenated branched butyl rubber prepared by the present invention is generated by addition polymerization using a multi-polymer as a grafting agent, rather than by ion substitution, thereby blocking the conditions for halogen structural isomerization, improving the effective damping temperature range and the stability of the damping performance of the halogenated branched butyl rubber, and broadening the application range of the halogenated branched butyl rubber.
  • the effective damping temperature range (tan ⁇ max ⁇ 0.3) of the halogenated branched butyl rubber prepared by the present invention exceeds the range of -50°C to 62°C.
  • the preparation method is green and environmentally friendly, has a short process flow, low production cost, and is suitable for industrial production.
  • the mass ratio of isobutylene, isoprene and the aforementioned multi-polymer is 100:4-6:7-10, for example 100:4:7, 100:5:6, 100:6:10, and any two of the above values.
  • the mass ratio of isobutylene, isoprene and the aforementioned multi-polymer is controlled within a specific range, which can effectively ensure the complete reaction of the multi-polymer in the preparation reaction of butyl rubber.
  • the diluent is a halogenated alkane, wherein the halogen atom in the halogenated alkane is preferably F, Cl or Br, and the number of carbon atoms in the halogenated alkane is preferably 1-4, such as 1, 2, 3, 4.
  • the diluent is selected from at least one of methyl chloride, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane.
  • the mass ratio of the isobutylene to the diluent is 100:180-320, such as 100:180, 100:220, 100:250, 100:300, 100:320, and any value within the range of any two of the above values.
  • the mass ratio of isobutylene to the diluent is controlled within a specific range to prepare a butyl rubber with a high molecular weight.
  • the organic solvent is a hydrocarbon solvent, preferably at least one of straight-chain alkanes, aromatic hydrocarbons and cycloalkanes, and further preferably at least one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene.
  • the amount of the organic solvent used there is no particular limitation on the amount of the organic solvent used, and it can be added according to the conventional amount in the art.
  • the co-initiator comprises an alkylaluminum halide and a protonic acid.
  • the molar ratio of the alkyl aluminum halide to the protonic acid in the co-initiator is 10-100:1, for example, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, and any value within the range consisting of any two of the above values.
  • the alkyl aluminum halide is selected from at least one of diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloride, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, n-propylaluminum dichloride, isopropylaluminum dichloride, dimethylaluminum chloride and ethylaluminum chloride.
  • the protonic acid is selected from at least one of HCl, HF, HBr, H 2 SO 4 , H 2 CO 3 , H 3 PO 4 and HNO 3 .
  • the mass ratio of the isobutylene to the co-initiator is 100:0.1-0.3, for example, 100:0.1, 100:0.15, 100:0.2, 100:0.25, 100:0.3, and any value within the range of any two of the above values.
  • the conditions for cationic polymerization include: the cationic polymerization temperature is -100°C to -75°C, for example, -100°C, -95°C, -90°C, -85°C, -80°C, -75°C, and any value within the range composed of any two of the above values. If the cationic polymerization temperature is too low, the reaction time will be too long and the structure control will be difficult; if the cationic polymerization temperature is too high, a chain transfer reaction will occur, resulting in a decrease in molecular weight.
  • the cationic polymerization time is 3-4h, for example, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, and any value within the range composed of any two of the above values. If the cationic polymerization time is too short, the molecular weight will be reduced; if the cationic polymerization time is too long, the structure will be unstable.
  • a terminator may be added to obtain the halogenated branched butyl rubber.
  • the terminator of the present invention may be selected from at least one of methanol, ethanol and butanol.
  • a mixed solvent V (diluent) : V (solvent) is 70-30/30-70
  • V (solvent) is 70-30/30-70
  • the aforementioned multi-polymer are added to a polymerization kettle under an inert atmosphere, and stirred and dissolved for 60-70 minutes until the multi-polymer is completely dissolved; then the temperature is lowered to -85°C to -75°C, and the diluent, isobutylene and isoprene are added in sequence, and stirred and mixed until the temperature of the polymerization system drops to -90 to -85°C, and then the diluent and the co-initiator are mixed and aged for 50-60 minutes at -100°C to -90°C, and then added together to the polymerization system, stirred and reacted for 3-4 hours, and finally a terminator is added, and the material is condensed, washed, and dried to obtain a halogenated branched Butyl
  • the mass ratio of isobutylene, isoprene and multi-polymer is 100:4-6:7-10;
  • the mass ratio of isobutylene to diluent is 100:180-320;
  • the mass ratio of isobutylene to the co-initiator is 100:0.1-0.3.
  • the seventh aspect of the present invention provides a halogenated branched butyl rubber obtained by the aforementioned preparation method.
  • the eighth aspect of the present invention provides the use of the aforementioned halogenated branched butyl rubber in instrument shock absorbers and electrical appliance shock absorbers.
  • the halogenated branched butyl rubber described in the present invention not only solves the problem that the effective damping temperature range of the halogenated branched butyl rubber becomes wider, thereby causing the damping performance to decrease, but also improves the tensile strength and air tightness of the halogenated branched butyl rubber, and can be fully applied to electromechanical devices, such as instrument shock absorbers, electrical shock absorbers, etc., which require damping performance in a wide temperature range.
  • Isobutylene, isoprene polymer grade, from Zhejiang Xinhui New Materials Co., Ltd.
  • p-Methylstyrene polymer grade, from Jiande Langfeng Chemical Co., Ltd.
  • n-Butylstyrene polymer grade, from Luoyang Boyu Energy Technology Co., Ltd.
  • p-Bromomethylstyrene polymer grade, from Hubei Shuangyan Chemical Co., Ltd.
  • Methyl methacrylate (MMA) from Tianjin Chemical Reagent Factory No. 2
  • n-Butyl lithium 98% pure, from Nanjing Tonglian Chemical Co., Ltd.
  • Sesquiethylaluminum chloride 98% pure, from J&K Technology Co., Ltd.
  • Mw/Mn number average molecular weight and Mn distribution index
  • Air tightness test The air permeability is measured using an automated air tightness tester in accordance with ISO 2782:1995.
  • the test gas is N 2
  • the test temperature is 23° C.
  • the test sample is a circular sea piece with a diameter of 8 cm and a thickness of 1 mm.
  • DMA Dynamic mechanical analysis
  • Tensile strength Execute the method in standard GB/T528-2009.
  • This example is used to illustrate the preparation of a multi-polymer.
  • the glue was wet-coagulated and dried to obtain the multi-polymer S-1.
  • the mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA and isoprene was 100:30:15:2.
  • the multipolymer S-1 was tested to have an Mn of 40100, an Mw/Mn of 1.45, a bromine content of 4.05%, and an apparent viscosity of 8 cps at 25°C.
  • This example is used to illustrate the preparation of a multi-polymer.
  • the glue was wet-coagulated and dried to obtain the multi-polymer S-2.
  • the mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA and isoprene was 100:31:16:2.2.
  • the multipolymer S-2 was tested to have an Mn of 42,300, an Mw/Mn of 1.51, a bromine content of 4.21%, and an apparent viscosity of 11.2 cps at 25°C.
  • This example is used to illustrate the preparation of a multi-polymer.
  • the glue was wet-coagulated and dried to obtain the multi-polymer S-3.
  • the mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA and isoprene was 100:33:17:2.4.
  • the multipolymer S-3 was tested to have an Mn of 45100, an Mw/Mn of 1.63, a bromine content of 4.48%, and an apparent viscosity of 14.5 cps at 25°C.
  • This example is used to illustrate the preparation of a multi-polymer.
  • the glue was wet-coagulated and dried to obtain the multi-polymer S-4.
  • the mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA and isoprene was 100:36:18:2.5.
  • the multipolymer S-4 was tested to have an Mn of 46,500, an Mw/Mn of 1.76, a bromine content of 4.62%, and an apparent viscosity of 20.5 cps at 25°C.
  • This example is used to illustrate the preparation of a multi-polymer.
  • the glue was wet-coagulated and dried to obtain the multi-polymer S-5.
  • the mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA and isoprene was 100:38:19:2.7.
  • the multipolymer S-5 had an Mn of 48,900, an Mw/Mn of 1.87, a bromine content of 4.85%, and an apparent viscosity of 24.1 cps at 25°C.
  • This example is used to illustrate the preparation of a multi-polymer.
  • the glue was wet-coagulated and dried to obtain the multi-polymer S-6.
  • the mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA and isoprene was 100:40:20:30.
  • the multipolymer S-6 was tested to have an Mn of 49,700, an Mw/Mn of 1.95, a bromine content of 4.98%, and an apparent viscosity of 29.1 cps at 25°C.
  • This example is used to illustrate the preparation of a multi-polymer.
  • the glue was wet-coagulated and dried to obtain the multi-polymer S-7.
  • the mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA and isoprene was 100:20:20:1.
  • the multipolymer S-7 had an Mn of 25,000, an Mw/Mn of 1.2, a bromine content of 2.5%, and an apparent viscosity of 35.4 cps at 25°C.
  • This example is used to illustrate the preparation of a multi-polymer.
  • the glue was wet-coagulated and dried to obtain the multi-polymer S-8.
  • the mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA and isoprene was 100:50:25:5.
  • the multipolymer S-8 was tested to have an Mn of 60,000, an Mw/Mn of 2, a bromine content of 5.5%, and an apparent viscosity of 40.0 cps at 25°C.
  • This example is used to illustrate the preparation of a multi-polymer.
  • the multi-polymer S-9 was prepared according to the method of Example 1, except that 5 g of isoprene was added during the preparation process, wherein the mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA and isoprene was 100:30:15:0.5.
  • the multipolymer S-9 was tested to have an Mn of 39,900, an Mw/Mn of 1.43, a bromine content of 4.09%, and an apparent viscosity of 8.5 cps at 25°C.
  • This example is used to illustrate the preparation of a multi-polymer.
  • the multi-polymer S-10 was prepared according to the method of Example 1, except that 60 g of isoprene was added during the preparation process, wherein the mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA and isoprene was 100:30:15:6.
  • the multipolymer S-10 had an Mn of 41,000, an Mw/Mn of 1.51, a bromine content of 4.01%, and an apparent viscosity of 8.9 cps at 25°C.
  • This example is used to illustrate the preparation of halogenated branched butyl rubber.
  • This example is used to illustrate the preparation of halogenated branched butyl rubber.
  • This example is used to illustrate the preparation of halogenated branched butyl rubber.
  • This example is used to illustrate the preparation of halogenated branched butyl rubber.
  • This example is used to illustrate the preparation of halogenated branched butyl rubber.
  • This example is used to illustrate the preparation of halogenated branched butyl rubber.
  • the halogenated branched butyl rubber was prepared according to the method of Example 11, except that the multipolymer S-1 was replaced by the multipolymer S-7 to obtain the brominated branched butyl rubber product.
  • the halogenated branched butyl rubber was prepared according to the method of Example 11, except that the multipolymer S-1 was replaced by the multipolymer S-8 to obtain the brominated branched butyl rubber product.
  • the halogenated branched butyl rubber was prepared according to the method of Example 11, except that the multipolymer S-1 was replaced with the multipolymer S-10 to obtain the brominated branched butyl rubber product.
  • a multipolymer was prepared according to the method of Example 1, except that p-bromomethylstyrene was replaced with methylallyl bromide to obtain a multipolymer D-1.
  • the halogenated branched butyl rubber was prepared according to the method of Example 11, except that the multipolymer S-1 was replaced by the multipolymer D-1 to obtain a brominated branched butyl rubber product.
  • the multipolymer D-2 was obtained by preparing the multipolymer according to the method of Example 3, except that p-bromomethylstyrene was not added during the preparation process.
  • the halogenated branched butyl rubber was prepared according to the method of Example 13, except that the multipolymer S-3 was replaced by the multipolymer D-2 to obtain a brominated branched butyl rubber product.
  • the multi-polymer was prepared according to the method of Example 4, except that MMA was not added during the preparation process.
  • the multi-polymer D-3 was obtained.
  • the halogenated branched butyl rubber was prepared according to the method of Example 14, except that the multipolymer S-4 was replaced by the multipolymer D-3 to obtain a brominated branched butyl rubber product.
  • FIG. 1 is a dynamic mechanical spectrum of the brominated branched butyl rubber product prepared in Example 11 of the present invention (curve #1) and the existing brominated butyl rubber (BIIR) 2302 (curve #2).
  • the brominated branched butyl rubber product prepared in Example 11 of the present invention has a larger damping factor than the existing brominated butyl rubber (BIIR) 2302 in a wide effective damping temperature range.
  • BIIR brominated butyl rubber
  • the halogenated branched butyl rubber prepared by the present invention is generated by addition polymerization using a multi-polymer as a grafting agent rather than by ion substitution, thereby blocking the conditions for halogen structural isomerization, improving the effective damping temperature range of the halogenated branched butyl rubber and the stability of the damping performance, and broadening the application scope of the halogenated branched butyl rubber.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne le domaine technique de la préparation de caoutchouc, et concerne un copolymère multicomposants, son procédé de préparation et son utilisation, et un caoutchouc butyle ramifié halogéné, son procédé de préparation et son utilisation. Le copolymère à multicomposants comprend : un motif structural A, un motif structural B et un motif structural C, le motif structural A présentant une structure de phase représentée par la formule (1), le motif structural B présentant une structure de phase représentée par la formule (2), et le motif structural C présentant une structure de phase représentée par la formule (3) ; R1, R2, R3, R4, R5, R6, R7 et R8 sont chacun indépendamment l'hydrogène ou un groupe alkyle ramifié ou à chaîne linéaire de phase en C1-C10 ; X est un halogène, et n est un nombre entier quelconque de 1 à 10 ; l'extrémité de queue de phase du copolymère multicomposants contient un motif structural de phase à partir d'un diène conjugué. Selon la présente invention, le caoutchouc butyle ramifié halogéné est préparé en prenant le copolymère multicomposants en tant qu'agent de greffage, de façon à améliorer une plage de températures d'amortissement efficaces et la stabilité de phase des performances d'amortissement du caoutchouc butyle ramifié halogéné.
PCT/CN2023/117573 2022-09-26 2023-09-07 Copolymère multicomposants, son procédé de préparation et son utilisation, et caoutchouc butyle ramifié halogéné, son procédé de préparation et son utilisation WO2024067013A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202211173637.1A CN117801191A (zh) 2022-09-26 2022-09-26 多元共聚物及其制备方法和应用、卤化支化丁基橡胶及其制备方法和应用
CN202211173637.1 2022-09-26

Publications (1)

Publication Number Publication Date
WO2024067013A1 true WO2024067013A1 (fr) 2024-04-04

Family

ID=90424016

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/117573 WO2024067013A1 (fr) 2022-09-26 2023-09-07 Copolymère multicomposants, son procédé de préparation et son utilisation, et caoutchouc butyle ramifié halogéné, son procédé de préparation et son utilisation

Country Status (2)

Country Link
CN (1) CN117801191A (fr)
WO (1) WO2024067013A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0422837A1 (fr) * 1989-10-09 1991-04-17 The Dow Chemical Company Composition de polymère renforcée par du caoutchouc incorporant un agent de greffage
CN101353403A (zh) * 2007-07-27 2009-01-28 中国石油化工股份有限公司 星形支化聚异丁烯或丁基橡胶的制备方法
CN101353386A (zh) * 2007-07-27 2009-01-28 北京石油化工学院 用于星形支化聚异丁烯或丁基橡胶正离子聚合的引发体系
CN113493548A (zh) * 2020-04-08 2021-10-12 中国石油天然气股份有限公司 支化丁基橡胶的制备方法
CN113831476A (zh) * 2020-06-24 2021-12-24 中国石油天然气股份有限公司 一种低饱和度丁基橡胶的制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0422837A1 (fr) * 1989-10-09 1991-04-17 The Dow Chemical Company Composition de polymère renforcée par du caoutchouc incorporant un agent de greffage
CN101353403A (zh) * 2007-07-27 2009-01-28 中国石油化工股份有限公司 星形支化聚异丁烯或丁基橡胶的制备方法
CN101353386A (zh) * 2007-07-27 2009-01-28 北京石油化工学院 用于星形支化聚异丁烯或丁基橡胶正离子聚合的引发体系
CN113493548A (zh) * 2020-04-08 2021-10-12 中国石油天然气股份有限公司 支化丁基橡胶的制备方法
CN113831476A (zh) * 2020-06-24 2021-12-24 中国石油天然气股份有限公司 一种低饱和度丁基橡胶的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MARCUS SCHÄFER: "Synthesis of new graft copolymers containing polyisobutylene by a combination of the 1,1‐diphenylethylene technique and cationic polymerization", JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY, JOHN WILEY & SONS, INC., US, vol. 40, no. 21, 1 November 2002 (2002-11-01), US , pages 3725 - 3733, XP093156954, ISSN: 0887-624X, DOI: 10.1002/pola.10472 *

Also Published As

Publication number Publication date
CN117801191A (zh) 2024-04-02

Similar Documents

Publication Publication Date Title
Zhiquan et al. The characteristics of lanthanide coordination catalysts and the cis‐polydienes prepared therewith
US4002815A (en) Cyclopentene-dicyclopentadiene copolymers and method of making same
CN103626926B (zh) 一种聚丁二烯接枝异戊橡胶及其制备方法和硫化胶及混炼胶
WO1998007783A1 (fr) Caoutchouc de butadiene et compositions a base de resine vinylique aromatique resistantes aux chocs
WO2024067013A1 (fr) Copolymère multicomposants, son procédé de préparation et son utilisation, et caoutchouc butyle ramifié halogéné, son procédé de préparation et son utilisation
CN113493548A (zh) 支化丁基橡胶的制备方法
WO2024066787A1 (fr) Agent de greffage halogéné et caoutchouc butyle ramifié halogéné, leur procédé de préparation et leur utilisation
CN116410413A (zh) 一种仲位溴化支化丁基橡胶的制备方法
CN113831470B (zh) 一种中门尼粘度、低饱和度丁基橡胶的制备方法
CN116355153A (zh) 一种溴化接枝剂及其制备方法和应用
CN117801190A (zh) 高分子阻尼溴化接枝剂及高阻尼溴化支化丁基橡胶的制备
CN117801187A (zh) 功能化阻尼溴化接枝剂及阻尼溴化支化丁基橡胶的制备
CN117757008A (zh) 高分子复合阻尼溴化接枝剂及溴化支化丁基橡胶的制备
CN117986502A (zh) 高分子阻尼溴化剂、高阻尼溴化丁基橡胶组合物及其制备
CN117801182A (zh) 高分子复合功能溴化接枝剂及溴化支化丁基橡胶的制备
CA1042132A (fr) Production de composes polymeres ayant des groupes terminaux fonctionnels
CN101585891B (zh) 制备异烯烃均聚物或共聚物的引发剂体系以及使用该体系制备异烯烃均聚物或共聚物的方法
CN117801149A (zh) 高分子阻尼剂及高阻尼溴化丁基橡胶的制备
JPH0245508A (ja) ポリブタジエンおよびそれを用いた耐衝撃性ポリスチレン系樹脂組成物
CN105330763B (zh) 稀土催化剂用组合物和稀土催化剂及其制备方法和应用和烯烃聚合方法
US3773854A (en) Production of alternating copolymers of conjugated dienes and conjugated polar vinyl monomers
CN113493551B (zh) 一种支化丁基橡胶的制备方法
CN114874374B (zh) 三元乙丙橡胶及其制备方法与应用
CN109880008B (zh) 间戊二烯-异戊二烯共聚橡胶及其制备方法
CN116410418A (zh) 一种三臂溴化支化丁基橡胶的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23870252

Country of ref document: EP

Kind code of ref document: A1