WO2024067013A1 - 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 - Google Patents

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 Download PDF

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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
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structural unit
preparation
polymer
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butyl rubber
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French (fr)
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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
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Petrochina Co Ltd
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Petrochina Co Ltd
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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
    • 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
    • C08F297/048—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 polymerising vinyl aromatic monomers, conjugated dienes and polar monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • 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
    • C08L51/006—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 grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

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.

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Abstract

本发明涉及橡胶制备技术领域，公开了一种多元共聚物及其制备方法和应用、一种卤化支化丁基橡胶及其制备方法和应用。所述多元共聚物包括：结构单元A、结构单元B和结构单元C；其中，结构单元A具有式(1)所示相结构，结构单元B具有式(2)所示相结构，结构单元C具有式(3)所示相结构，其中，R1、R2、R3、R4、R5、R6、R7和R8各自独立地为氢或C1-C10相直链或支链烷基；X为卤素，n为1-10相任意整数；所述多元共聚物相末端含有来自共轭二烯烃相结构单元。本发明利用多元共聚物作为接枝剂制备卤化支化丁基橡胶，提高了卤化支化丁基橡胶有效阻尼温域和阻尼性能相稳定性，

Description

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
相关申请的交叉引用
本申请要求2022年09月26日提交的中国专利申请202211173637.1的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及橡胶制备技术领域，具体涉及一种多元共聚物及其制备方法和应用、一种卤化支化丁基橡胶及其制备方法和应用。
背景技术
随着现代科学技术的迅速发展，在高铁、航空航天、海军舰船、机械工程、汽车和电子电器等诸多领域中机械设备趋于高频高速，给日常生产生活带来便利的同时也产生了一系列问题，如高频振动以及噪音。这些问题不仅加速了机械结构材料的疲劳损坏，缩短其使用寿命，对人民生命财产安全的威胁也越来越突出。因此，减震降噪已经成为当今社会亟待解决的难题之一。因此，研制性能优异的高效阻尼材料，提高其阻尼减震的应用效果，对于改善机械的运行环境和保证人类的健康安全是至关重要的。
二烯烃橡胶是含有两个C＝C双键的不饱和橡胶，主要工业化产品有顺丁橡胶、异戊橡胶、丁基橡胶等。二烯烃橡胶被广泛用于日常生产生活中的各个领域。然而，丁基橡胶分子链具有较高的不饱和度且取代基甲基呈对称排列，这种分子结构决定了其不可避免的存在耐臭氧老化差、硫化焦烧时间长，硫化速度低、阻尼性能低等问题，导致丁基橡胶无法满足日渐多样化的加工需求和应用场景，成为丁基橡胶材料拓展应用的瓶颈。
溴化丁基橡胶(BIIR)是在分子溴作用下按亲电取代反应，在丁基橡胶(IIR)的分子链中引入溴原子得到的。BIIR相比于IIR，除了具有同样优良的气密性之外，还具有粘着性好、硫化速度快以及良好的热稳定性和耐腐蚀性，能够在强腐蚀或者高温等极端环境下使用。其次，由于溴原子的引入，不仅使分子链极性增大，链段的弛豫阻力增大，内耗较大，其具有优良的阻尼性能，因而它是应用最广的基础阻尼橡胶之一。
目前在实际应用中，往往需要在-50℃至+50℃范围内具有阻尼功能，然而溴化丁基橡胶目前还存在着有效阻尼功能区(阻尼因子tanδ>0.3)主要集中在低温部分，在15℃以上阻尼值偏低，不能较好地满足对宽温域阻尼材料的使用要求，因此如何拓宽丁基类橡胶室温以上的有效阻尼功能区是当今橡胶阻尼材料的研究热点之一。
CN112574333A公开了一种星形支化丁基橡胶的溴化工艺。所述工艺包括：a)将星形支化丁基橡胶溶于脂肪烃中，得到胶液；b)将上述胶液与支化剂捕捉剂乙醇混合，得到混合液；c)对上述混合液中加入氧化剂过氧化氢和溴化剂Br2且溴元素与星形支化丁基橡胶中不饱和双键的摩尔比为(0.75-2):l进行溴化反应、最后中和及产品回收得到溴化星形支化丁基橡胶。
CN106749816A公开了一种溴化丁基橡胶的制备方法。所述方法首先采用正烷烃对丁基橡胶进行溶解，然后以特定的有机溴化物如苯基三甲基三溴化胺、苄基三甲基三溴化胺、二溴异氰尿酸作为溴化剂，以Br2或HBr作为溴化促进剂在溶剂中进行溴化反应，得到溴化丁基橡胶。
廖明义等(大连海事大学学报，2008，34(2):83-86)公开了一种提高丁基橡胶(IIR)的阻尼性能采用分步方法，以IIR为聚合物网络I，聚(苯乙烯-甲基丙烯酸甲酯)[P(St-MMA)]为聚合物网络II，通过接枝聚合制备了丁基橡胶/聚(苯乙烯-甲基丙烯酸甲酯)互穿聚合物网络[IIR/P(St-MMA)]，制备出宽温域、高阻尼丁基橡胶材料。
虽然现有技术通过共混法、共聚法和互穿网络聚合物法等可以在一定程度上扩宽橡胶的有效阻尼温域，提高橡胶的阻尼性能，但是这些方法仍存在一定的局限性，会导致橡胶材料的力学性能下降、工艺复杂、实际操作困难、添加量大、成本高、有机溶剂难以排除而造成环境污染等问题。
因此，亟需研发一种具有宽有效阻尼温域、高阻尼性能和优异力学性能且制备方法易操作无污染的橡胶材料。
发明内容
本发明的目的是为了克服现有技术存在的橡胶材料无法兼具宽有效阻尼温域、高阻尼性能和良好力学性能以及制备复杂造成污染的问题，提供一种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。
为了实现上述目的，本发明第一方面提供一种多元共聚物，其中，所述多元共聚物包括：结构单元A、结构单元B和结构单元C；其中，结构单元A具有式(1)所示的结构，结构单元B具有式(2)所示的结构，结构单元C具有式(3)所示的结构，
其中，R1、R2、R3、R4、R5、R6、R7和R8各自独立地为氢或C1-C10的直链或支链烷基；X为卤素，n为1-10的任意整数；
所述多元共聚物的末端含有来自共轭二烯烃的结构单元。
本发明第二方面提供一种多元共聚物的制备方法，其中，所述制备方法包括：在聚合反应条件下，在引发剂、可选的结构调节剂和有机溶剂存在下，使式(I)所示单体、式(II)所示单体、式(III)所示单体进行聚合反应得到聚合物溶液；
向所述聚合物溶液中加入共轭二烯烃单体进行封端反应得到所述多元共聚物；
其中，R1、R2、R3、R4、R5、R6、R7和R8各自独立地为氢或C1-C10的直链或支链烷基；X为卤素，n为1-10的任意整数。
本发明第三方面提供一种前述的制备方法得到的多元共聚物。
本发明第四方面提供一种前述的多元共聚物在制备二烯烃橡胶中作为接枝剂的应用。
本发明第五方面提供一种卤化支化丁基橡胶，其中，所述卤化支化丁基橡胶包括：来自异丁烯的结构单元I，来自异戊二烯的结构单元II和来自卤化接枝剂的结构单元III；其中，所述卤化接枝剂为前述的多元共聚物。
本发明第六方面提供一种前述的卤化支化丁基橡胶的制备方法，其中，所述方法包括：在稀释剂、有机溶剂和共引发剂的存在下，将异丁烯、异戊二烯和前述的多元共聚物接触进行阳离子聚合，得到所述卤化支化丁基橡胶。
本发明第七方面提供一种前述的制备方法得到的卤化支化丁基橡胶。
本发明第八方面提供前述的卤化支化丁基橡胶橡胶在仪表减震器和电器减震器中的应用。
通过上述技术方案，本发明所取得的有益技术效果如下：
(1)本发明提供的多元共聚物将对烷基苯基、对卤烷基苯和酯基组合在一个大分子链上，形成互穿聚合物网络(IPN)，使得对烷基苯基、卤素原子和酯基具有刚性大、空间位阻大和吸附力强等特点，将该多元共聚物作为卤化接枝剂用于制备卤化支化丁基橡胶时，能够在拓宽卤化支化丁基橡胶的有效阻尼温域方面产生显著的“协同效应”，极大地拓宽卤化支化丁基橡胶的有效阻尼温域，可制备出有效阻尼温域(tanδ≥0.3)超过-50℃至62℃范围、tanδmax为1.9以上的宽温域高阻尼卤化支化丁基橡胶。
(2)本发明的多元共聚物中对烷基苯基、对卤烷基苯和酯基在分子链上排列，从而产生“基团效应”和“结构效应”的叠加，将该多元共聚物作为卤化接枝剂用于制备卤化支化丁基橡胶时，不但避免了卤化支化丁基橡胶因有效阻尼温域范围的拓宽使得阻尼性下降，而且还避免了因支化出现分子量分布变宽，从而导致丁基橡胶力学性能和气密性下降的问题，提高了丁基橡胶的拉伸强度和气密性。
(3)本发明制备的卤化支化丁基橡胶是利用多元共聚物作为接枝剂通过加成聚合生成，而非离子取代生成，阻断了卤素结构异构化的条件，提高了卤化支化丁基橡胶有效阻尼温域和阻尼性能的稳定性，拓宽了卤化支化丁基橡胶的适用范围。
(4)本发明在卤化支化丁基橡胶的制备过程中，无挥发性有机化合物(VOC) 和副产物HBr的排放，其制备方法绿色环保，工艺流程短，生产成本低，适合工业化生产等特点。
附图说明
图1是本发明实施例11所制备的溴化支化丁基橡胶产品(曲线#1)与现有溴化丁基橡胶(BIIR)2302(曲线#2)的动态力学谱图。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明第一方面提供一种多元共聚物，其中，所述多元共聚物包括：结构单元A、结构单元B和结构单元C；其中，结构单元A具有式(1)所示的结构，结构单元B具有式(2)所示的结构，结构单元C具有式(3)所示的结构，
其中，R1、R2、R3、R4、R5、R6、R7和R8各自独立地为氢或C1-C10的直链或支链烷基；X为卤素，n为1-10的任意整数；
所述多元共聚物的末端含有来自共轭二烯烃的结构单元。
本发明的多元共聚物中同时包含对烷基苯基、对卤烷基苯和酯基，形成互穿聚合物网络(IPN)，使得对烷基苯基、卤素原子和酯基具有刚性大、空间位阻大和吸附力强等特点，并且共聚物的末端含有共轭二烯结构单元，使得该多元共聚物具有高的聚合活性，能够作为接枝剂用于制备支化二烯烃橡胶，特别地，用于制备卤化支化二烯烃橡胶。
在本发明中，所述C1-C10的直链或支链烷基的实例，例如可以为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、异戊基、叔戊基、新戊基、正己基、异己基、正庚基、异庚基、2-甲基己基、2-乙基己基、1-甲基庚基、2-甲基庚基、正辛基、异辛基、正壬基、异壬基和3,5,5-三甲基己基中的任意一种。
在本发明中，式(1)所示的结构中n的值可选择1、2、3、4、5、6、7、8、9、10。
在本发明的一些实施方式中，其中，R1、R2、R3、R4、R5、R6、R7和R8各自独立地为氢或C1-C6的直链或支链烷基，优选为氢或C1-C4的直链或支链烷基，更优选为氢、甲基或乙基。
在本发明的一些优选实施方式中，R6为甲基。
在本发明的一些优选实施方式中，X选自Cl和/或Br。
在本发明的一些优选实施方式中，n为1-5的任意整数，优选为1-3的任意整数。
在本发明的一些优选实施方式中，所述共轭二烯烃为丁二烯和/或异戊二烯。
在本发明的一些优选实施方式中，式(1)所示结构单元可以为来自对溴甲基苯乙烯的结构单元，式(2)所示结构单元可以为来自对烷基苯乙烯，例如对甲基苯乙烯、对乙基苯乙烯、对丙基苯乙烯、对正丁基苯乙烯、对异丁基苯乙烯或对异戊基苯乙烯的结构单元，式(3)所示结构单元可以为来自不饱和丙烯酸酯，例如甲基丙烯酸甲酯(MMA)、甲基丙烯酸乙酯、甲基丙烯酸丁酯或甲基丙烯酸叔丁酯的结构单元。
在本发明中，所述多元共聚物为嵌段共聚物或无规共聚物。
在本发明的一些实施方式中，其中，结构单元A、结构单元B、结构单元C和来自共轭二烯烃的结构单元的质量比为100:20-50:10-25:1-5，例如100:20:25:1、100:50:10:5、100:30:15:2、100:40:20:4、100:25:12:3，以及上述任意两个数值组成的范围内的任意值，优选为100:30-40:15-20:2-3。当多元共聚物中各结构单元的质量比满足上述范围时，能够提供一种有效阻尼温域(tanδ≥0.3)超过-50℃至62℃范围、最大阻尼因子tanδmax≥1.9和拉伸强度为22MPa-24MPa的宽温域高阻尼溴化支化丁基橡胶。
上述比例可以通过红外光谱和核磁共振的方法测定，或根据制备投料关系确定。
在本发明的一些优选实施方式中，所述多元共聚物中卤素的质量百分含量为2.5-5.5％，例如2.5％、3％、3.5％、4％、4.5％、5％、5.5％，以及上述任意两个数值组成的范围内的任意值，优选为4-5％。当多元共聚物中卤素的质量百分含量满足上述范围时，能够提高丁基橡胶的阻尼性和硫化加工性。本发明中，采用Q600型TG/DTG热重分析仪测定卤素含量。
在本发明的一些实施方式中，所述多元共聚物的数均分子量(Mn)为2.5万-6万g/mol，例如2.5万g/mol、3万g/mol、3.5万g/mol、4万g/mol、4.5万g/mol、5万g/mol、5.5万g/mol、6万g/mol，以及上述任意两个数值组成的范围内的任意值，优选为4万-5万g/mol。
在本发明的一些优选实施方式中，所述多元共聚物的分子量分布指数(Mw/Mn)为1.2-2，例如1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2，以及上述任意两个数值组成的范围内的任意值，优选为1.45-1.95。
在本发明中，数均分子量和分子量分布指数均采用凝胶色谱法进行测试。
在本发明的一些实施方式中，所述多元共聚物在25℃下的表观粘度为8-40cps。
在本发明中，多元共聚物在25℃下的表观粘度采用乌氏粘度计根据GB/T10247-2008进行测试。
本发明第二方面提供一种多元共聚物的制备方法，其中，所述制备方法包括：在聚合反应条件下，在引发剂、可选的结构调节剂和有机溶剂的存在下，使式(I)所示单体、式(II)所示单体和式(III)所示单体进行聚合反应得到聚合物溶液；
向所述聚合物溶液中加入共轭二烯烃单体进行封端反应得到所述多元共聚物；
其中，R1、R2、R3、R4、R5、R6、R7和R8各自独立地为氢或C1-C10的直链或支链烷基；X为卤素，n为1-10的任意整数。
本发明中，采用上述制备方法具有反应完全、无副产物生成、制备出的多元共聚物结构稳定、分子链排列规整的特点。
在本发明的一些实施方式中，其中，R1、R2、R3、R4、R5、R6、R7和R8各自独立地为氢或C1-C6的直链或支链烷基，优选为氢或C1-C4的直链或支链烷基，更优选为氢、甲基或乙基。
在本发明的一些优选实施方式中，R6为甲基。
在本发明的一些优选实施方式中，X选自Cl和/或Br。
在本发明的一些优选实施方式中，n为1-5的任意整数，优选为1-3的任意整数。
本发明第二方面所述的C1-C10的直链或支链烷基的实例如上述本发明第一方面所述，此处不再赘述。
在一些实施方式中，式(I)所示单体为对溴甲基苯乙烯，式(II)所示单体为对甲基苯乙烯、对乙基苯乙烯、对丙基苯乙烯、对正丁基苯乙烯、对异丁基苯乙烯或对异戊基苯乙烯，式(III)所示单体为甲基丙烯酸甲酯(MMA)、甲基丙烯酸乙酯、甲基丙烯酸丁酯或甲基丙烯酸叔丁酯。
在本发明的一些实施方式中，其中，所述共轭二烯烃为丁二烯和/或异戊二烯。
在本发明的一些优选实施方式中，式(I)所示单体、式(II)所示单体、式(III)所示单体和共轭二烯烃的质量比为100:20-50:10-25:1-5，例如100:20:25:1、100:50:10:5、100:30:15:2、100:40:20:4、100:25:12:3，以及上述任意两个数值组成的范围内的任意值，优选为100:30-40:15-20:2-3。在本发明中，将式(I)所示单体、式(II)所示单体、式(III)所示单体和共轭二烯烃的质量比控制在特定范围内，可以得到有效阻尼温域(tanδ≥0.3)超过-50℃至62℃范围；最大阻尼因子tanδmax≥1.9的丁基橡胶。
在本发明的一些优选实施方式中，所述聚合反应在保护性气氛下进行，所述保护性气氛优选为惰性气氛。
在本发明的一些优选实施方式中，所述引发剂为烃基单锂化合物，优选为RLi，其中R选自C1-C20的饱和脂肪族烃基、C3-C20的脂环族烃基和C6-C20的芳烃基中的至少一种。
在本发明的一些优选实施方式中，所述引发剂选自正丁基锂、仲丁基锂、甲基丁基锂、苯基丁基锂、萘锂、环己基锂和十二烷基锂中的至少一种。在本发 明中，选择上述引发剂，可以使各单体发生阴离子聚合，形成嵌段共聚物，从而达到“结构效应”和“基团效应”的叠加作用。
在本发明的一些优选实施方式中，相对于1000g式(I)所示单体，所述引发剂的用量为16-30mmo1，优选为18-25mmo1。引发剂过少，导致所制备的多元共聚物分子量变小，应用时会影响丁基橡胶的宽温域和阻尼性能，达不到改性效果；引发剂过多，导致所制备的多元共聚物分子量分布变宽造成丁基橡胶的气密性和机械强度下降。
在本发明的一些优选实施方式中，所述结构调节剂为极性有机化合物。
本发明所述的结构调节剂是一种极性有机化合物，能够在聚合体系中产生溶剂化效应，能够调节对烷基苯乙烯与异戊二烯的竞聚率，使两者发生嵌段共聚。
在本发明的一些优选实施方式中，所述结构调节剂选自二乙二醇二甲醚、四氢呋喃、乙醚、乙基甲醚、苯甲醚、二苯醚、乙二醇二甲醚和三乙胺中的至少一种。
在本发明的一些优选实施方式中，所述有机溶剂为烃类溶剂，优选为直链烷烃、芳烃和环烷烃中的至少一种，进一步优选为戊烷、己烷、辛烷、庚烷、环己烷、苯、甲苯、二甲苯和乙苯中的至少一种。
在一些实施方式中，所述聚合反应的条件包括：聚合反应温度为50-80℃，例如50℃、60℃、70℃、80℃，以及上述任意两个数值组成的范围内的任意值。聚合反应温度过低，导致反应活性变小、反应速率变慢、反应不完全，应用时达不到丁基橡胶的宽温域和高阻尼的改性效果；聚合反应温度过高，导致反应活性变大、反应速率变大、分子结构排列不规整，应用时造成丁基橡胶的强度和气密性下降。
聚合反应时间为220-270min，例如220min、230min、240min、250min、260min、270min，以及上述任意两个数值组成的范围内的任意值。聚合反应时间过短，应用时达不到丁基橡胶的宽温域和高阻尼的改性效果；聚合反应时间过长，造成能耗过高，应用时在丁基橡胶的宽温域和高阻尼的改性程度方面不会出现明显的效果。
在本发明的一些优选实施方式中，封端反应温度为60-90℃，例如60℃、65℃、70℃、75℃、80℃、85℃、90℃，以及上述任意两个数值组成的范围内的任意值，优选为70-80℃。封端反应温度过低，导致封端不完全，反应活性点变少，接枝率降低，应用时使其丁基橡胶的宽温域和阻尼性能改性效果不佳；封端反应温度过高，易使共轭二烯烃发生自聚，无法起到封端作用。封端反应时间为10-45min，例如10min、15min、20min、25min、30min、35min、40min、45min，优选为20-30min。封端反应时间过短，导致封端不完全，反应活性点变少，应用时达不到丁基橡胶的宽温域和高阻尼的改性效果；封端反应时间过长，导致所制备的多元共聚物链段柔顺性增大，应用时会破坏丁基橡胶的阻尼性能和机械强度。
在本发明的一些实施方式中，所述方法包括以下步骤：
(1)将式(I)所示单体、结构调节剂、溶剂和引发剂进行混合发生第一聚合反应，得到第一聚合产物；
(2)向第一聚合产物中加入式(II)所示单体和结构调节剂进行混合发生第二聚合反应，得到第二聚合产物；
(3)向第二聚合产物中加入式(III)所示单体和结构调节剂进行混合发生第三聚合反应，得到第三聚合产物；
(4)向第三聚合产物中加入共轭二烯烃发生封端反应，得到所述多元共聚物。
本发明上述制备方法中，采用阴离子聚合方法，能够制得具有三嵌段的多元共聚物，具有结构可控、溴结构稳定、等规度高、反应完全、无副产物等特点，能够带来卤化支化二烯烃橡胶适用温域宽、阻尼性高、机械强度和硫化加工性优异的效果。
在本发明的一些优选实施方式中，步骤(1)中式(I)所示单体与结构调节剂的质量比为100:0.5-0.7，例如100:0.5、100:0.6、100:0.7，以及上述任意两个数值组成的范围内的任意值。将式(I)所示单体与结构调节剂的质量比控制在上述范围内，可以生产等规度高的嵌段聚合物。
在本发明的一些优选实施方式中，步骤(2)中式(II)所示单体与结构调节剂的质量比为30-40:0.3-0.5，例如30:0.3、35:0.35、40:0.5，以及上述任意两个数值组成的范围内的任意值。将式(II)所示单体与结构调节剂的质量比控制在上述范围内，可以生产等规度高的嵌段聚合物。
在本发明的一些优选实施方式中，步骤(3)中式(III)所示单体与结构调节剂的质量比为15-20:0.2-0.3，例如15:0.2、18:0.25:20:0.3，以及上述任意两个数值组成的范围内的任意值。将式(III)所示单体与结构调节剂的质量比控制在上述范围内，可以生产等规度高的嵌段聚合物。
在本发明的一些实施方式中，第一聚合反应温度为40-80℃，例如40℃、45℃、55℃、65℃、70℃、75℃、80℃，以及上述任意两个数值组成的范围内的任意值，优选为50-60℃。第一聚合反应温度过低，会导致溴含量过低；第一聚合反应温度过高，会破坏溴结构。第一聚合反应时间为80-150min，例如80min、90min、100min、110min、120min、130min、140min、150min，以及上述任意两个数值组成的范围内的任意值，优选为100-120min。第一聚合反应时间过短，会导致分子量变小，溴含量变低；第一聚合反应时间过长，分子量变化不明显，改性效果不明显。
在本发明的一些优选实施方式中，第二聚合反应温度为60-90℃，例如60℃、65℃、70℃、75℃、80℃、85℃、90℃，以及上述任意两个数值组成的范围内的任意值，优选为70-80℃。第二聚合反应温度过低，会导致苯环结构含量过低，造成强度和气密性下降；第二聚合反应温度过高，阻尼改性效果不明显。第二聚合反应时间为50-80min，例如50min、55min、60min、65min、70min、75min、80min，以及上述任意两个数值组成的范围内的任意值，优选为60-70min。第二聚合反应时间过短，会导致分子量变小，苯环结构变少，阻尼增加幅度小；第二聚合反应时间过长，能耗高，苯环结构无明显变化，阻尼增加幅度无明显变化。
在本发明的一些优选实施方式中，第三聚合反应温度为60-90℃，例如60℃、65℃、70℃、75℃、80℃、85℃、90℃，以及上述任意两个数值组成的范围内的任意值，优选为70-80℃。第三聚合反应温度过低，会导致极性基团酯基含量过低，应用时造成丁基橡胶的阻尼温域变窄；第三聚合反应温度过高，应用时丁基橡胶适用温域变宽不明显。第三聚合反应时间为30-60min，例如30min、35min、40min、45min、50min、55min、60min，以及上述任意两个数值组成的范围内的任意值，优选为40-50min。第三聚合反应时间过短，会导致极性基团酯基含量过低，应用时达不到丁基橡胶的宽温域改性效果；第三聚合反应时间过长，应用时丁基橡胶适用温域变宽幅度不明显。
根据本发明一种特别优选的实施方式，在惰性气氛下，向聚合釜中依次加 入有机溶剂、对溴甲基苯乙烯和结构调节剂，升温至50-60℃后，加入引发剂反应100-120min；随后再向聚合釜中加入对烷基苯乙烯和结构调节剂，升温至70-80℃，反应60-70min；然后再向聚合釜中加入不饱和丙烯酸酯和结构调节剂，反应40-50min；最后再向聚合釜中加入异戊二烯进行封端，反应20-30min直至无游离单体存在时为止，胶液经湿法凝聚、烘干，制得上述多元共聚物；
其中，对溴甲基苯乙烯、对烷基苯乙烯、不饱和丙烯酸酯和异戊二烯的质量比为100:30-40:15-20:2-3；
对溴甲基苯乙烯和结构调节剂的质量比为100:0.5-0.7；
对烷基苯乙烯和结构调节剂的质量比为30-40:0.3-0.5；
不饱和丙烯酸酯和结构调节剂的质量比为15-20:0.2-0.3。
本发明第三方面提供一种前述的制备方法得到的多元共聚物。
本发明第四方面提供一种前述的多元共聚物在制备二烯烃橡胶中作为接枝剂的应用。
在本发明的一些实施方式中，所述二烯烃橡胶为丁基橡胶。
本发明第五方面提供一种卤化支化丁基橡胶，其中，所述卤化支化丁基橡胶包括：来自异丁烯的结构单元I，来自异戊二烯的结构单元II和来自卤化接枝剂的结构单元III；
其中，所述卤化接枝剂为前述的多元共聚物。
在本发明的一些实施方式中，基于卤化支化丁基橡胶的总重量，结构单元I、结构单元II和结构单元III的质量比为100:4-6:7-10，例如100:4:7、100:5:6、100:6:10，以及上述任意两个数值组成的范围内的任意值。在本发明中，将结构单元I、结构单元II和结构单元III的质量比控制在特定范围内，可以得到有效阻尼温域(tanδ≥0.3)超过-50℃至62℃范围；最大阻尼因子tanδmax≥1.9；拉伸强度为22MPa-24MPa的丁基橡胶。
本发明提供的多元共聚物将对烷基苯基、对卤烷基苯和酯基组合在一个大分子链上，形成互穿聚合物网络(IPN)，使得对烷基苯基、卤素原子和酯基具有刚性大、空间位阻大和吸附力强等特点，将该多元共聚物作为卤化接枝剂用于制备卤化支化丁基橡胶时，能够在拓宽卤化支化丁基橡胶的有效阻尼温域方面产生显著的“协同效应”，极大地拓宽卤化支化丁基橡胶的有效阻尼温域，可制备出有效阻尼温域(tanδ≥0.3)超过-50℃至62℃范围、tanδmax为1.9以上的宽温域高阻尼卤化支化丁基橡胶。
本发明第六方面提供一种前述的卤化支化丁基橡胶的制备方法，其中，所述方法包括：
在稀释剂、有机溶剂和共引发剂的存在下，将异丁烯、异戊二烯和前述的多元共聚物接触进行阳离子聚合，得到所述卤化支化丁基橡胶。
本发明制备的卤化支化丁基橡胶是利用多元共聚物作为接枝剂通过加成聚合生成，而非离子取代生成，阻断了卤素结构异构化的条件，提高了卤化支化丁基橡胶有效阻尼温域和阻尼性能的稳定性，拓宽了卤化支化丁基橡胶的适用范围。本发明所制备的卤化支化丁基橡胶的有效阻尼温域(tanδmax≥0.3)超过-50℃至62℃范围。
另外，在制备过程中没有挥发性有机化合物(VOC)和副产物HBr的排放，制备方法绿色环保，工艺流程短，生产成本低，适合工业化生产等特点。
在本发明的一些实施方式中，异丁烯、异戊二烯和前述的多元共聚物的质量比为100:4-6:7-10，例如100:4:7、100:5:6、100:6:10，以及上述任意两个数值 组成的范围内的任意值。在本发明中，将异丁烯、异戊二烯和前述的多元共聚物的质量比控制在特定范围内，可以有效保证丁基橡胶的制备反应中多元共聚物的完全反应。
在本发明的一些优选实施方式中，所述稀释剂为卤代烷烃，其中所述卤代烷烃中的卤素原子优选为F、Cl或Br，所述卤代烷烃中的碳原子数优选为1-4，例如1、2、3、4。
在本发明的一些优选实施方式中，所述稀释剂选自一氯甲烷、二氯甲烷、四氯化碳、二氯乙烷、四氯丙烷、七氯丙烷、一氟甲烷、二氟甲烷、四氟乙烷、六氟化碳和氟丁烷中的至少一种。
在本发明的一些优选实施方式中，所述异丁烯与所述稀释剂的质量比为100:180-320，例如100:180、100:220、100:250、100:300、100:320，以及上述任意两个数值组成的范围内的任意值。在本发明中，将异丁烯与稀释剂的质量比控制在特定范围内，可以制备出分子量高的丁基橡胶。
在本发明的一些优选实施方式中，所述有机溶剂为烃类溶剂，优选为直链烷烃、芳烃和环烷烃中的至少一种，进一步优选为戊烷、己烷、辛烷、庚烷、环己烷、苯、甲苯、二甲苯和乙苯中的至少一种。
对于有机溶剂的用量没有特别限定，可以按照本领域的常规用量添加。
在本发明的一些优选实施方式中，所述共引发剂包括烷基卤化铝和质子酸。
在本发明的一些优选实施方式中，所述共引发剂中所述烷基卤化铝与所述质子酸的摩尔比为10-100:1，例如10:1、20:1、30:1、40:1、50:1、60:1、70:1、80:1、90:1、100:1，以及上述任意两个数值组成的范围内的任意值。
在本发明的一些优选实施方式中，所述烷基卤化铝选自一氯二乙基铝、一氯二异丁基铝、二氯甲基铝、倍半乙基氯化铝、倍半异丁基氯化铝、二氯正丙基铝、二氯异丙基铝、二甲基氯化铝和乙基氯化铝中的至少一种。
在本发明的一些优选实施方式中，所述质子酸选自HCI、HF、HBr、H2SO4、H2CO3、H3PO4和HNO3中的至少一种。
在本发明的一些优选实施方式中，所述异丁烯与所述共引发剂的质量比为100:0.1-0.3，例如100:0.1、100:0.15、100:0.2、100:0.25、100:0.3，以及上述任意两个数值组成的范围内的任意值。
在本发明的一些优选实施方式中，所述阳离子聚合的条件包括：阳离子聚合温度为-100℃至-75℃，例如-100℃、-95℃、-90℃、-85℃、-80℃、-75℃，以及上述任意两个数值组成的范围内的任意值。阳离子聚合温度过低，造成反应时间过长，结构控制困难；阳离子聚合温度过高，会发生链转移反应，导致分子量变小。阳离子聚合时间为3-4h，例如3h、3.2h、3.4h、3.6h、3.8h、4h，以及上述任意两个数值组成的范围内的任意值。阳离子聚合时间过短，导致分子量变小；阳离子聚合时间过长，会出现结构不稳定。
在本发明中，可以加入终止剂以出料获得所述卤化支化丁基橡胶。本发明所述的终止剂可以选自甲醇、乙醇和丁醇中的至少一种。
根据本发明一种特别优选的实施方式，在惰性气氛下，向聚合釜中加入混合溶剂(V(稀释剂):V(溶剂)为70-30/30-70)和前述多元共聚物，搅拌溶解60-70min，直到多元共聚物完全溶解；然后降温至-85℃至-75℃时，再依次加入稀释剂，异丁烯和异戊二烯，搅拌混合至聚合体系温度降到-90至-85℃时，然后将稀释剂和共引发剂在-100℃至-90℃条件下，混合陈化50-60min后，一起加入到聚合体系里搅拌反应3-4h后，最后加入终止剂后，出料凝聚，洗涤，干燥得到卤化支化 丁基橡胶；
其中，异丁烯、异戊二烯和多元共聚物的质量比为100:4-6:7-10；
异丁烯与稀释剂的质量比为100:180-320；
异丁烯与共引发剂的质量比为100:0.1-0.3。
本发明第七方面提供一种前述的制备方法得到的卤化支化丁基橡胶。
本发明第八方面提供前述的卤化支化丁基橡胶橡胶在仪表减震器和电器减震器中的应用。
本发明所述的卤化支化丁基橡胶不仅解决了卤化支化丁基橡胶有效阻尼温域的范围变宽从而导致阻尼性能下降的问题，而且还提高了卤化支化丁基橡胶的拉伸强度和气密性，完全能够应用在机电装置中，如仪表减震器、电器减震器等对宽温域阻尼性能的要求。
以下将通过实施例对本发明进行详细描述。
以下实施例和对比例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购途径获得的常规产品。制得多元共聚物产品和卤化支化丁基橡胶中包含的各结构单元的质量比关系按照原料投料量确定。
(1)原料来源：
异丁烯、异戊二烯：聚合级，来自浙江信汇新材料股份有限公司
对甲基苯乙烯：聚合级，来自建德市浪峰化学有限公司
对正丁基苯乙烯：聚合级，来自洛阳博昱能源科技有限公司
对溴甲基苯乙烯：聚合级，来自湖北双炎化工有限公司
甲基丙烯酸甲酯(MMA)：来自天津市化学试剂二厂
正丁基锂：纯度为98％，来自南京通联化工有限公司
倍半乙基氯化铝：纯度为98％，来自百灵威科技有限公司
其它试剂均为市售工业品。
(2)分析测试方法：
数均分子量及Mn分布指数(Mw/Mn)的测定：采用美国Waters公司生产的2414凝胶渗透色谱仪(GPC)测定。以聚苯乙烯标样为校正曲线，流动相为四氢呋喃，柱温为40℃，样品浓度为1mg/mL，进样量为50μL，洗脱时间为40min，流速为1mL·min-1。
溴含量测定：称取10mg样品，采用Q600型TG/DTG热重分析仪，升温速率10℃/min，在流量为50mL/min氮气气氛中，对样品进行热降解。第一阶段热降解是由样品含溴单元脱溴形成HBr，再由脱去的HBr百分含量来反推样品中的溴含量(X)，计算公式如下：
式中：Y-样品在220℃时的百分含量；79.904-溴元素相对原子质量；1.008-氢元素相对原子质量。
表观粘度的测定：采用乌氏粘度计，根据GB/T 10247-2008进行测定。
气密性的测定：采用自动化气密性测试仪，依据ISO 2782:1995测定透气数。测试气体为N2，测试温度为23℃，测试样片为8cm直径圆形海片，厚度为1mm。
动态力学分析(DMA)：采用拉伸模式在德国Netzsch公司242C型动态力学 分析仪上测定。样品尺寸为长10mm，宽6mm，厚2mm，温度范围-90℃至90℃，升温速度3℃/min，选取频率10Hz下的数据进行分析。
拉伸强度：执行标准GB/T528-2009中方法。
实施例1
本实施例用于说明多元共聚物的制备。
首先在带有夹套的15L不锈钢反应釜中，通氩气置换3次，向聚合釜中依次加入3000g己烷，1000g对溴甲基苯乙烯，5.0g THF，升温至50℃，加入18.5mmo1正丁基锂开始反应100min；随后再向聚合釜中加入300g对甲基苯乙烯，3.0g THF，升温至70℃，反应60min；然后再向聚合釜中加入150g MMA，2.0g THF，反应40min；最后再向聚合釜中加入20g异戊二烯，进行封端反应20min，直至无游离单体存在时为止，胶液经湿法凝聚、烘干，制得多元共聚物S-1。其中，对溴甲基苯乙烯、对甲基苯乙烯、MMA和异戊二烯的质量比为100:30:15:2。
经测试，多元共聚物S-1的Mn为40100，Mw/Mn为1.45，溴含量为4.05％，在25℃下的表观粘度为8cps。
实施例2
本实施例用于说明多元共聚物的制备。
首先在带有夹套的15L不锈钢反应釜中，通氩气置换3次，向聚合釜中依次加入3100g己烷，1000g对溴甲基苯乙烯，5.4g THF，升温至52℃，加入19.3mmo1正丁基锂开始反应105min；随后再向聚合釜中加入310g对甲基苯乙烯，3.5g THF，升温至72℃，反应62min；然后再向聚合釜中加入160g MMA，2.2g THF，反应42min；最后再向聚合釜中加入22g异戊二烯，进行封端反应21min，直至无游离单体存在时为止，胶液经湿法凝聚、烘干，制得多元共聚物S-2。其中，对溴甲基苯乙烯、对甲基苯乙烯、MMA和异戊二烯的质量比为100:31:16:2.2。
经测试，多元共聚物S-2的Mn为42300，Mw/Mn为1.51，溴含量为4.21％，在25℃下的表观粘度为11.2cps。
实施例3
本实施例用于说明多元共聚物的制备。
首先在带有夹套的15L不锈钢反应釜中，通氩气置换4次，向聚合釜中依次加入3300g己烷，1000g对溴甲基苯乙烯，5.7g THF，升温至55℃，加入21.5mmo1正丁基锂开始反应110min；随后再向聚合釜中加入330g对甲基苯乙烯，4.0g THF，升温至74℃，反应64min；然后再向聚合釜中加入170g MMA，2.4g THF，反应44min；最后再向聚合釜中加入24g异戊二烯，进行封端反应23min，直至无游离单体存在时为止，胶液经湿法凝聚、烘干，制得多元共聚物S-3。其中，对溴甲基苯乙烯、对甲基苯乙烯、MMA和异戊二烯的质量比为100:33:17:2.4。
经测试，多元共聚物S-3的Mn为45100，Mw/Mn为1.63，溴含量为4.48％，在25℃下的表观粘度为14.5cps。
实施例4
本实施例用于说明多元共聚物的制备。
首先在带有夹套的15L不锈钢反应釜中，通氩气置换4次，向聚合釜中依次加入3500g己烷，1000g对溴甲基苯乙烯，6.0g THF，升温至57℃，加入 22.6mmo1正丁基锂开始反应113min；随后再向聚合釜中加入360g对甲基苯乙烯，4.4g THF，升温至76℃，反应66min；然后再向聚合釜中加入180g MMA，2.6g THF，反应46min；最后再向聚合釜中加入25g异戊二烯，进行封端反应25min，直至无游离单体存在时为止，胶液经湿法凝聚、烘干，制得多元共聚物S-4。其中，对溴甲基苯乙烯、对甲基苯乙烯、MMA和异戊二烯的质量比为100:36:18:2.5。
经测试，多元共聚物S-4的Mn为46500，Mw/Mn为1.76，溴含量为4.62％，在25℃下的表观粘度为20.5cps。
实施例5
本实施例用于说明多元共聚物的制备。
首先在带有夹套的15L不锈钢反应釜中，通氩气置换5次，向聚合釜中依次加入3700g己烷，1000g对溴甲基苯乙烯，6.5g THF，升温至59℃，加入23.4mmo1正丁基锂开始反应115min；随后再向聚合釜中加入380g对甲基苯乙烯，4.8g THF，升温至78℃，反应68min；然后再向聚合釜中加入190g MMA，2.8g THF，反应48min；最后再向聚合釜中加入27g异戊二烯，进行封端反应27min，直至无游离单体存在时为止，胶液经湿法凝聚、烘干，制得多元共聚物S-5。其中，对溴甲基苯乙烯、对甲基苯乙烯、MMA和异戊二烯的质量比为100:38:19:2.7。
经测试，多元共聚物S-5的Mn为48900，Mw/Mn为1.87，溴含量为4.85％，在25℃下的表观粘度为24.1cps。
实施例6
本实施例用于说明多元共聚物的制备。
首先在带有夹套的15L不锈钢反应釜中，通氩气置换5次，向聚合釜中依次加入4000g己烷，1000g对溴甲基苯乙烯，7.0g THF，升温至60℃，加入24.8mmo1正丁基锂开始反应120min；随后再向聚合釜中加入400g对正丁基苯乙烯，5.0g THF，升温至80℃，反应70min；然后再向聚合釜中加入200g MMA，3.0g THF，反应50min；最后再向聚合釜中加入30g异戊二烯，进行封端反应30min，直至无游离单体存在时为止，胶液经湿法凝聚、烘干，制得多元共聚物S-6。其中，对溴甲基苯乙烯、对甲基苯乙烯、MMA和异戊二烯的质量比为100:40:20:30。
经测试，多元共聚物S-6的Mn为49700，Mw/Mn为1.95，溴含量为4.98％，在25℃下的表观粘度为29.1cps。
实施例7
本实施例用于说明多元共聚物的制备。
首先在带有夹套的15L不锈钢反应釜中，通氮气置换5次，向聚合釜中依次加入4000g己烷，1000g对溴甲基苯乙烯，7.0g THF，升温至40℃，加入16mmo1正丁基锂开始反应80min；随后再向聚合釜中加入200g对正丁基苯乙烯，5.0g THF，升温至60℃，反应50min；然后再向聚合釜中加入100g MMA，3.0g THF，反应30min；最后再向聚合釜中加入10g异戊二烯，进行封端反应10min，直至无游离单体存在时为止，胶液经湿法凝聚、烘干，制得多元共聚物S-7。其中，对溴甲基苯乙烯、对甲基苯乙烯、MMA和异戊二烯的质量比为100:20:20:1。
经测试，多元共聚物S-7的Mn为25000，Mw/Mn为1.2，溴含量为2.5％，在25℃下的表观粘度为35.4cps。
实施例8
本实施例用于说明多元共聚物的制备。
首先在带有夹套的15L不锈钢反应釜中，通氩气置换5次，向聚合釜中依次加入4000g己烷，1000g对溴甲基苯乙烯，7.0g THF，升温至80℃，加入30mmo1正丁基锂开始反应150min；随后再向聚合釜中加入500g对正丁基苯乙烯，5.0g THF，升温至90℃，反应80min；然后再向聚合釜中加入250g MMA，3.0g THF，反应60min；最后再向聚合釜中加入50g异戊二烯，进行封端反应45min，直至无游离单体存在时为止，胶液经湿法凝聚、烘干，制得多元共聚物S-8。其中，对溴甲基苯乙烯、对甲基苯乙烯、MMA和异戊二烯的质量比为100:50:25:5。
经测试，多元共聚物S-8的Mn为60000，Mw/Mn为2，溴含量为5.5％，在25℃下的表观粘度为40.0cps。
实施例9
本实施例用于说明多元共聚物的制备。
按照实施例1的方法制备多元共聚物，不同的是，制备过程中异戊二烯的加入量为5g得到多元共聚物S-9。其中，对溴甲基苯乙烯、对甲基苯乙烯、MMA和异戊二烯的质量比为100:30:15:0.5。
经测试，多元共聚物S-9的Mn为39900，Mw/Mn为1.43，溴含量为4.09％，在25℃下的表观粘度为8.5cps。
实施例10
本实施例用于说明多元共聚物的制备。
按照实施例1的方法制备多元共聚物，不同的是，制备过程中异戊二烯的加入量为60g得到多元共聚物S-10。其中，对溴甲基苯乙烯、对甲基苯乙烯、MMA和异戊二烯的质量比为100:30:15:6。
经测试，多元共聚物S-10的Mn为41000，Mw/Mn为1.51，溴含量为4.01％，在25℃下的表观粘度为8.9cps。
实施例11
本实施例用于说明卤化支化丁基橡胶的制备。
首先在带有夹套的4L不锈钢反应釜中，通氮气置换3次，向聚合釜中加入二氯甲烷350g，己烷150g，多元共聚物S-1 35g，搅拌溶解60min，直到完全溶解；然后降温至-75℃时，再依次加入一氯甲烷500g，异丁烯500g，异戊二烯20g，搅拌混合至聚合体系温度降到-85℃时，然后将一氯甲烷50g，倍半乙基氯化铝1.05g和HCl 0.012g在-90℃条件下，混合陈化50min后，一起加入到聚合体系里搅拌反应3.0h后，最后加入15g甲醇后，出料凝聚，洗涤，干燥得到溴化支化丁基橡胶产品。其中，制备原料中异丁烯、异戊二烯和多元共聚物S-1的质量比为100:4:7。
取样分析：制成标准试样，测试性能见表1。
实施例12
本实施例用于说明卤化支化丁基橡胶的制备。
首先在带有夹套的4L不锈钢反应釜中，通氮气置换3次，向聚合釜中加入二氯甲烷300g，己烷200g，多元共聚物S-2 37g，搅拌溶解62min，直到完全溶 解；然后降温至-77℃时，再依次加入一氯甲烷600g，异丁烯500g，异戊二烯22g，搅拌混合至聚合体系温度降到-86℃时，然后将一氯甲烷60g，倍半乙基氯化铝1.13g和HCl 0.015g在-92℃条件下，混合陈化52min后，一起加入到聚合体系里搅拌反应3.2h后，最后加入17g甲醇后，出料凝聚，洗涤，干燥得到溴化支化丁基橡胶产品。其中，制备原料中异丁烯、异戊二烯和多元共聚物S-2的质量比为100:4.4:7.4。
取样分析：制成标准试样，测试性能见表1。
实施例13
本实施例用于说明卤化支化丁基橡胶的制备。
首先在带有夹套的4L不锈钢反应釜中，通氮气置换4次，向聚合釜中加入二氯甲烷200g，己烷300g，多元共聚物S-3 40g，搅拌溶解64min，直到完全溶解；然后降温至-80℃时，再依次加入一氯甲烷700g，异丁烯500g，异戊二烯24g，搅拌混合至聚合体系温度降到-87℃时，然后将一氯甲烷70g，倍半乙基氯化铝1.24g和HCl 0.021g在-94℃条件下，混合陈化54min后，一起加入到聚合体系里搅拌反应3.4h后，最后加入19g甲醇后，出料凝聚，洗涤，干燥得到溴化支化丁基橡胶产品。其中，制备原料中异丁烯、异戊二烯和多元共聚物S-3的质量比为100:4.8:8。
取样分析：制成标准试样，测试性能见表1。
实施例14
本实施例用于说明卤化支化丁基橡胶的制备。
首先在带有夹套的4L不锈钢反应釜中，通氮气置换4次，向聚合釜中加入二氯甲烷700g，己烷300g，多元共聚物S-4 43g，搅拌溶解65min，直到完全溶解；然后降温至-81℃时，再依次加入一氯甲烷800g，异丁烯500g，异戊二烯26g，搅拌混合至聚合体系温度降到-88℃时，然后将一氯甲烷80g，倍半乙基氯化铝1.36g和HCl 0.035g在-96℃条件下，混合陈化56min后，一起加入到聚合体系里搅拌反应3.6h后，最后加入20g甲醇后，出料凝聚，洗涤，干燥得到溴化支化丁基橡胶产品。其中，制备原料中异丁烯、异戊二烯和多元共聚物S-4的质量比为100:5.5:8.6。
取样分析：制成标准试样，测试性能见表1。
实施例15
本实施例用于说明卤化支化丁基橡胶的制备。
首先在带有夹套的4L不锈钢反应釜中，通氮气置换5次，向聚合釜中加入二氯甲烷500g，己烷500g，多元共聚物S-5 48g，搅拌溶解67min，直到完全溶解；然后降温至-83℃时，再依次加入一氯甲烷900g，异丁烯500g，异戊二烯28g，搅拌混合至聚合体系温度降到-89℃时，然后将一氯甲烷90g，倍半乙基氯化铝1.41g和HCl 0.042g在-98℃条件下，混合陈化58min后，一起加入到聚合体系里搅拌反应3.9h后，最后加入23g甲醇后，出料凝聚，洗涤，干燥得到溴化支化丁基橡胶产品。其中，制备原料中异丁烯、异戊二烯和多元共聚物S-5的质量比为100:5.6:9.6。
取样分析：制成标准试样，测试性能见表1。
实施例16
本实施例用于说明卤化支化丁基橡胶的制备。
首先在带有夹套的4L不锈钢反应釜中，通氮气置换5次，向聚合釜中加入二氯甲烷300g，己烷700g，多元共聚物S-6 50g，搅拌溶解70min，直到完全溶解；然后降温至-85℃时，再依次加入一氯甲烷1000g，异丁烯500g，异戊二烯30g，搅拌混合至聚合体系温度降到-90℃时，然后将一氯甲烷100g，倍半乙基氯化铝1.50g和HCl 0.065g在-100℃条件下，混合陈化60min后，一起加入到聚合体系里搅拌反应4.0h后，最后加入25g甲醇后，出料凝聚，洗涤，干燥得到溴化支化丁基橡胶产品。其中，制备原料中异丁烯、异戊二烯和多元共聚物S-6的质量比为100:6:10。
取样分析：制成标准试样，测试性能见表1。
实施例17
按照实施例11的方法制备卤化支化丁基橡胶，不同的是，将多元共聚物S-1替换为多元共聚物S-7得到溴化支化丁基橡胶产品。
实施例18
按照实施例11的方法制备卤化支化丁基橡胶，不同的是，将多元共聚物S-1替换为多元共聚物S-8得到溴化支化丁基橡胶产品。
实施例19
按照实施例11的方法制备卤化支化丁基橡胶，不同的是，将多元共聚物S-1替换为多元共聚物S-9得到溴化支化丁基橡胶产品。
实施例20
按照实施例11的方法制备卤化支化丁基橡胶，不同的是，将多元共聚物S-1替换为多元共聚物S-10得到溴化支化丁基橡胶产品。
对比例1
按照实施例1的方法制备多元共聚物，不同的是，将对溴甲基苯乙烯替换为甲基烯丙基溴得到多元共聚物D-1。
按照实施例11的方法制备卤化支化丁基橡胶，不同的是，将多元共聚物S-1替换为多元共聚物D-1得到溴化支化丁基橡胶产品。
取样分析：制成标准试样，测试性能见表1。
对比例2
按照实施例3的方法制备多元共聚物，不同的是，制备过程中不加入对溴甲基苯乙烯得到多元共聚物D-2。
按照实施例13的方法制备卤化支化丁基橡胶，不同的是，将多元共聚物S-3替换为多元共聚物D-2得到溴化支化丁基橡胶产品。
取样分析：制成标准试样，测试性能见表1。
对比例3
按照实施例4的方法制备多元共聚物，不同的是，制备过程中不加入MMA 得到多元共聚物D-3。
按照实施例14的方法制备卤化支化丁基橡胶，不同的是，将多元共聚物S-4替换为多元共聚物D-3得到溴化支化丁基橡胶产品。
取样分析：制成标准试样，测试性能见表1。
表1
通过表1的结果可以看出，对比例1-3中制备多元共聚物的单体与本发明不同，因此在有效阻尼温域、阻尼性能、气密性及力学性能方面表现不佳。本发明实施例11-20所制备的溴化支化丁基橡胶产品相比对比例1-3具有更宽的有效阻尼温域、阻尼性能更好、气密性更好，并且具有更好的力学性能。
图1为本发明实施例11所制备的溴化支化丁基橡胶产品(曲线#1)与现有溴化丁基橡胶(BIIR)2302(曲线#2)的动态力学谱图。
由图1可以看出，本发明实施例11所制备的溴化支化丁基橡胶产品相比现有溴化丁基橡胶(BIIR)2302在宽的有效阻尼温域内具有更大的阻尼因子。
本发明制备的卤化支化丁基橡胶是利用多元共聚物作为接枝剂通过加成聚合生成，而非离子取代生成，阻断了卤素结构异构化的条件，提高了卤化支化丁基橡胶有效阻尼温域和阻尼性能的稳定性，拓宽了卤化支化丁基橡胶的适用范围。
本发明在卤化支化丁基橡胶的制备过程中，无挥发性有机化合物(VOC)和副产物HBr的排放，其制备方法绿色环保，工艺流程短，生产成本低，适合工业化生产等特点。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (31)

  1. 一种多元共聚物，其特征在于，所述多元共聚物包括：结构单元A、结构单元B和结构单元C；其中，结构单元A具有式(1)所示的结构，结构单元B具有式(2)所示的结构，结构单元C具有式(3)所示的结构，
    其中，R1、R2、R3、R4、R5、R6、R7和R8各自独立地为氢或C1-C10的直链或支链烷基；X为卤素，n为1-10的任意整数；
    所述多元共聚物的末端含有来自共轭二烯烃的结构单元。
  2. 根据权利要求1所述的多元共聚物，其中，R1、R2、R3、R4、R5、R6、R7和R8各自独立地为氢或C1-C6的直链或支链烷基；
    和/或，X选自Cl和/或Br；
    和/或，n为1-5的任意整数；
    和/或，所述共轭二烯烃为丁二烯和/或异戊二烯；
    和/或，结构单元A、结构单元B、结构单元C和来自共轭二烯烃的结构单元的质量比为100∶20-50∶10-25∶1-5；
    和/或，所述多元共聚物中卤素的质量百分含量为2.5-5.5％。
  3. 根据权利要求2所述的多元共聚物，其中，R1、R2、R3、R4、R5、R6、R7和R8各自独立地为氢或C1-C4的直链或支链烷基；
    和/或，n为1-3的任意整数；
    和/或，结构单元A、结构单元B、结构单元C和来自共轭二烯烃的结构单元的质量比为100∶30-40∶15-20∶2-3；
    和/或，所述多元共聚物中卤素的质量百分含量为4-5％。
  4. 根据权利要求3所述的多元共聚物，其中，R1、R2、R3、R4、R5、R6、R7和R8各自独立地为氢、甲基或乙基。
  5. 根据权利要求1所述的多元共聚物，其中，R6为甲基。
  6. 根据权利要求1或2所述的多元共聚物，其中，所述多元共聚物的数均分子量为2.5万-6万g/mol；
    和/或，所述多元共聚物的分子量分布指数为1.2-2；
    和/或，所述多元共聚物在25℃下的表观粘度为8-40cps。
  7. 根据权利要求6所述的多元共聚物，其中，所述多元共聚物的数均分子量为4万-5万g/mol；
    和/或，所述多元共聚物的分子量分布指数为1.45-1.95。
  8. 一种多元共聚物的制备方法，其特征在于，所述制备方法包括：在聚合反应条件下，在引发剂、可选的结构调节剂和有机溶剂的存在下，使式(I)所示单体、式(II)所示单体和式(III)所示单体进行聚合反应得到聚合物溶液；
    向所述聚合物溶液中加入共轭二烯烃单体进行封端反应得到所述多元共聚物；
    其中，R1、R2、R3、R4、R5、R6、R7和R8各自独立地为氢或C1-C10的直链或支链烷基；X为卤素，n为1-10的任意整数。
  9. 根据权利要求8所述的制备方法，其中，R1、R2、R3、R4、R5、R6、R7和R8各自独立地为氢或C1-C6的直链或支链烷基；
    和/或，X选自Cl和/或Br；
    和/或，n为1-5的任意整数。
  10. 根据权利要求9所述的制备方法，其中，R1、R2、R3、R4、R5、R6、R7和R8各自独立地为氢或C1-C4的直链或支链烷基；
    和/或，n为1-3的任意整数。
  11. 根据权利要求10所述的制备方法，其中，R1、R2、R3、R4、R5、R6、R7和R8各自独立地为氢、甲基或乙基。
  12. 根据权利要求8所述的制备方法，其中，R6为甲基。
  13. 根据权利要求8所述的制备方法，其中，所述共轭二烯烃为丁二烯和/或异戊二烯；
    和/或，式(I)所示单体、式(II)所示单体、式(III)所示单体和共轭二烯烃的质量比为100∶20-50∶10-25∶1-5；
    和/或，所述聚合反应在保护性气氛下进行；
    和/或，所述引发剂为烃基单锂化合物；
    和/或，相对于1000g式(I)所示单体，所述引发剂的用量为16-30mmol；
    和/或，所述结构调节剂为极性有机化合物；
    和/或，所述有机溶剂为烃类溶剂。
  14. 根据权利要求13所述的制备方法，其中，式(I)所示单体、式(II)所示单体、式(III)所示单体和共轭二烯烃的质量比为100∶30-40∶15-20∶2-3；
    和/或，所述保护性气氛为惰性气氛；
    和/或，所述引发剂为RLi，其中R选自C1-C20的饱和脂肪族烃基、C3-C20的脂环族烃基和C6-C20的芳烃基中的至少一种；
    和/或，相对于1000g式(I)所示单体，所述引发剂的用量为18-25mmol；
    和/或，所述结构调节剂选自二乙二醇二甲醚、四氢呋喃、乙醚、乙基甲醚、苯甲醚、二苯醚、乙二醇二甲醚和三乙胺中的至少一种；
    和/或，所述有机溶剂为直链烷烃、芳烃和环烷烃中的至少一种。
  15. 根据权利要求14所述的制备方法，其中，所述引发剂选自正丁基锂、仲丁基锂、甲基丁基锂、苯基丁基锂、萘锂、环己基锂和十二烷基锂中的至少一种；
    和/或，所述有机溶剂为戊烷、己烷、辛烷、庚烷、环己烷、苯、甲苯、二甲苯和乙苯中的至少一种。
  16. 根据权利要求8所述的制备方法，其中，所述聚合反应的条件包括：聚合反应温度为50-80℃，聚合反应时间为220-270min；
    和/或，封端反应温度为60-90℃，封端反应时间为10-45min。
  17. 根据权利要求16所述的制备方法，其中，封端反应温度为70-80℃，封端反应时间为20-30min。
  18. 根据权利要求8所述的制备方法，其中，所述方法包括以下步骤：
    (1)将式(I)所示单体、结构调节剂、有机溶剂和引发剂进行混合发生第一聚合反应，得到第一聚合产物；
    (2)向第一聚合产物中加入式(II)所示单体和结构调节剂进行混合发生第二聚合反应，得到第二聚合产物；
    (3)向第二聚合产物中加入式(III)所示单体和结构调节剂进行混合发生第三聚合反应，得到第三聚合产物；
    (4)向第三聚合产物中加入共轭二烯烃进行封端反应，得到所述多元共聚物。
  19. 根据权利要求18所述的制备方法，其中，步骤(1)中式(I)所示单体与结构调节剂的质量比为100∶0.5-0.7；
    和/或，步骤(2)中式(II)所示单体与结构调节剂的质量比为30-40∶0.3-0.5；
    和/或，步骤(3)中式(III)所示单体与结构调节剂的质量比为15-20∶0.2-0.3；
    和/或，第一聚合反应温度为40-80℃，第一聚合反应时间为80-150min；
    和/或，第二聚合反应温度为60-90℃，第二聚合反应时间为50-80min；
    和/或，第三聚合反应温度为60-90℃，第三聚合反应时间为30-60min。
  20. 根据权利要求19所述的制备方法，其中，第一聚合反应温度为50-60℃，第一聚合反应时间为100-120min；
    和/或，第二聚合反应温度为70-80℃，第二聚合反应时间为60-70min；
    和/或，第三聚合反应温度为70-80℃，第三聚合反应时间为40-50min。
  21. 一种权利要求8-20中任意一项所述的制备方法得到的多元共聚物。
  22. 权利要求1-7和21中任意一项所述的多元共聚物在制备二烯烃橡胶中作为接枝剂的应用。
  23. 根据权利要求22所述的应用，其中，所述二烯烃橡胶为丁基橡胶。
  24. 一种卤化支化丁基橡胶，其特征在于，所述卤化支化丁基橡胶包括：来自异丁烯的结构单元I，来自异戊二烯的结构单元II和来自卤化接枝剂的结构单元III；
    其中，所述卤化接枝剂为权利要求1-7或21中任意一项所述的多元共聚物。
  25. 根据权利要求24所述的卤化支化丁基橡胶，其中，基于卤化支化丁基橡胶的总重量，结构单元I、结构单元II和结构单元III的质量比为100∶4-6∶7-10。
  26. 一种根据权利要求24或25所述的卤化支化丁基橡胶的制备方法，其特征在于，所述方法包括：
    在稀释剂、有机溶剂和共引发剂的存在下，将异丁烯、异戊二烯和权利要求1-7和21中任意一项所述的多元共聚物接触进行阳离子聚合，得到所述卤化支化丁基橡胶。
  27. 根据权利要求26所述的制备方法，其中，异丁烯、异戊二烯和多元共聚物的质量比为100∶4-6∶7-10；
    和/或，所述稀释剂为卤代烷烃；
    和/或，所述稀释剂选自一氯甲烷、二氯甲烷、四氯化碳、二氯乙烷、四氯丙烷、七氯丙烷、一氟甲烷、二氟甲烷、四氟乙烷、六氟化碳和氟丁烷中的至少一种；
    和/或，所述异丁烯与所述稀释剂的质量比为100∶180-320；
    和/或，所述有机溶剂为烃类溶剂；
    和/或，所述共引发剂包括烷基卤化铝和质子酸；
    和/或，所述共引发剂中所述烷基卤化铝与所述质子酸的摩尔比为10-100∶1；
    和/或，所述烷基卤化铝选自一氯二乙基铝、一氯二异丁基铝、二氯甲基铝、倍半乙基氯化铝、倍半异丁基氯化铝、二氯正丙基铝、二氯异丙基铝、二甲基氯化铝和乙基氯化铝中的至少一种；
    和/或，所述质子酸选自HCI、HF、HBr、H2SO4、H2CO3、H3PO4和HNO3中的至少一种；
    和/或，所述异丁烯与所述共引发剂的质量比为100∶0.1-0.3；
    和/或，所述阳离子聚合的条件包括：阳离子聚合温度为-100℃至-75℃；阳离子聚合时间为3-4h。
  28. 根据权利要求27所述的制备方法，其中，所述卤代烷烃中的卤素原子 为F、Cl或Br；
    和/或，所述卤代烷烃为碳原子数1-4的卤代烷烃；
    和/或，所述有机溶剂为直链烷烃、芳烃和环烷烃中的至少一种。
  29. 根据权利要求28所述的制备方法，其中，所述有机溶剂为戊烷、己烷、辛烷、庚烷、环己烷、苯、甲苯、二甲苯和乙苯中的至少一种。
  30. 一种根据权利要求26-29中任意一项所述的制备方法得到的卤化支化丁基橡胶。
  31. 权利要求24、25和30中任意一项所述的卤化支化丁基橡胶橡胶在仪表减震器和电器减震器中的应用。
PCT/CN2023/117573 2022-09-26 2023-09-07 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 Ceased WO2024067013A1 (zh)

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