WO2024066787A1 - Agent de greffage halogéné et caoutchouc butyle ramifié halogéné, leur procédé de préparation et leur utilisation - Google Patents

Agent de greffage halogéné et caoutchouc butyle ramifié halogéné, leur procédé de préparation et leur utilisation Download PDF

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WO2024066787A1
WO2024066787A1 PCT/CN2023/113586 CN2023113586W WO2024066787A1 WO 2024066787 A1 WO2024066787 A1 WO 2024066787A1 CN 2023113586 W CN2023113586 W CN 2023113586W WO 2024066787 A1 WO2024066787 A1 WO 2024066787A1
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halogenated
structural unit
grafting agent
butyl rubber
preparation
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PCT/CN2023/113586
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English (en)
Chinese (zh)
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徐典宏
燕鹏华
赵志超
梁滔
魏绪玲
牛承祥
杨珊珊
孟令坤
朱晶
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中国石油天然气股份有限公司
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Publication of WO2024066787A1 publication Critical patent/WO2024066787A1/fr

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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
    • 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
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • 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 field of rubber damping materials, and in particular to a halogenated grafting agent and a halogenated branched butyl rubber, and a preparation method and application thereof.
  • rubber damping materials Due to the unique viscoelasticity of polymers, rubber damping materials have obvious damping effects in reducing vibration and noise, and improving the working environment of humans and machines. They have been widely used in many fields such as high-speed rail, aerospace, naval ships, mechanical engineering, automobiles, and electronic appliances. In particular, the vibration and noise of the cabinet caused by the rotation of the fan in the data storage system of various IT equipment such as servers, computers, workstations, switches, etc. seriously affect the service life of the hard disk. The demand for high-efficiency damping and vibration reduction products is very urgent. In addition, as the application environment of electronic equipment faces a complex use environment with lower temperatures and higher temperatures, extremely high requirements are placed on rubber damping materials.
  • Diolefin rubber is widely used in various fields of daily production and life. Its main industrial products include butadiene rubber, isoprene rubber, butyl rubber, halogenated butyl rubber, etc.
  • Bromobutyl rubber is an important type of halogenated butyl rubber. Bromobutyl rubber (BIIR) has excellent damping performance and is one of the most widely used basic damping rubbers.
  • BIIR Bromobutyl rubber
  • brominated butyl rubber currently still has defects such as insufficient damping value, unstable damping performance, insufficient effective damping temperature range, and poor mechanical properties. It cannot meet the requirements of large-scale equipment and precision instruments for material damping performance, thus becoming a bottleneck for the expansion of brominated butyl rubber materials.
  • CN103113682A discloses a high-performance damping rubber and a preparation method thereof.
  • the high-performance damping rubber is obtained by blending and polymerizing a first precursor and a second precursor, wherein the first precursor has a molecular chain with a cationic group, and the second precursor has a molecular chain with an anionic group, and the molar ratio of the cationic group to the anionic group in the rubber is 1:1.
  • the obtained high-performance damping rubber has a breaking strength of 5-20MPa, an elongation at break of 200%-300%, a repair efficiency of up to 90%, a repair temperature of 20-100°C, a wide damping temperature range and high repair efficiency.
  • CN103113682A discloses a wide temperature range high damping material for electronic products and a preparation method thereof.
  • a supramolecular network structure is formed through the interaction between non-polar butyl rubber, brominated tert-octylphenol formaldehyde resin and polar small molecule hindered phenol A060, and the temperature range can reach -60 to 100°C.
  • 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), using IIR as the polymer network I, poly(styrene-methyl The butyl rubber/poly(styrene-methyl methacrylate) [P(St-MMA)] was used as the polymer network II, and the butyl rubber/poly(styrene-methyl methacrylate) interpenetrating polymer network [IIR/P(St-MMA)] was prepared by graft polymerization to prepare a butyl rubber material with a wide temperature range and high damping.
  • IIR butyl rubber
  • the purpose of the present invention is to overcome the problem of low damping performance and mechanical properties of rubber materials in the prior art, and to provide a halogenated grafting agent and a halogenated branched butyl rubber and a preparation method and application thereof.
  • the halogenated grafting agent can be used to prepare the halogenated branched butyl rubber to obtain the halogenated branched butyl rubber with a higher maximum damping factor.
  • the method of the present invention solves the problems of low damping and halogenated structural isomer rearrangement in butyl rubber, not only avoiding the damage of the damping brominated grafting agent to the mechanical properties and air permeability of butyl rubber, but also improving the damping performance and tensile strength of butyl rubber.
  • the first aspect of the present invention provides a halogenated grafting agent, which comprises a structural unit A, an optional structural unit B, a structural unit C and a structural unit D; wherein the structural unit A has a structure shown in formula (1); the structural unit C has a structure shown in formula (2); the structural unit B is connected to the structural unit A and the structural unit C respectively; the structural unit D is a terminal capping structural unit; the structural unit B and the structural unit D are each independently derived from a conjugated diene;
  • R1 and R2 are each independently hydrogen or a C1 - C5 straight chain or branched alkyl group;
  • R3 is a C1 - C8 straight chain or branched alkyl group;
  • R4 and R5 are each independently hydrogen or a C1 - C4 straight chain or branched alkyl group;
  • X is a halogen.
  • the second aspect of the present invention provides a method for preparing a halogenated grafting agent, the preparation method comprising:
  • step S2 subjecting the polymer product obtained in step S1 or the third product obtained in step (2) to a second end-capping reaction with the first conjugated diene to obtain the halogenated grafting agent;
  • R1 and R2 are each independently hydrogen or a C1 -C5 straight chain or branched alkyl group;
  • R3 is a C1 - C8 straight chain or branched alkyl group;
  • R4 and R5 are each independently hydrogen or a C1 - C4 straight chain or branched alkyl group;
  • X is a halogen.
  • the third aspect of the present invention provides a halogenated grafting agent obtained by the aforementioned preparation method.
  • the fourth aspect of the present invention provides the use of the aforementioned halogenated grafting agent as a grafting agent in the preparation of diene rubber.
  • the fifth aspect of the present invention provides a halogenated branched butyl rubber, which comprises: a structural unit E derived from isobutylene, a structural unit F derived from isoprene and a structural unit G derived from a halogenated grafting agent; wherein the halogenated grafting agent is the aforementioned halogenated grafting agent.
  • a sixth aspect of the present invention provides a method for preparing a halogenated branched butyl rubber, the method comprising the following steps:
  • 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 automobiles and electronic appliances.
  • the halogenated grafting agent provided by the present invention combines a p-alkylphenyl structural unit and a halogenated alkyl structural unit on a macromolecular chain, and the molecular chain has the characteristics of high rigidity, large steric hindrance, strong adsorption force and multiple active points, so that the p-alkylphenyl and the halogen atoms produce a significant "synergistic effect" in improving the damping property of the material.
  • the damping property of the halogenated branched butyl rubber can be greatly improved, and a high-damping halogenated branched butyl rubber with a high maximum damping factor can be prepared.
  • the halogenated grafting agent prepared by free radical polymerization and anionic polymerization of the present invention contains non-polar
  • the alkylbenzene ring structure has the characteristics of high rigidity and large steric hindrance, which not only avoids the problem of widening of molecular weight distribution of butyl rubber due to branching, thereby leading to a decrease in the mechanical properties and air tightness of butyl rubber, but also improves the tensile strength of butyl rubber.
  • the halogenated branched butyl rubber prepared by the present invention is produced by addition polymerization using a high molecular weight damping halogenated grafting agent rather than by ion substitution.
  • the para-alkylphenyl and secondary bromine halogen structures in the grafting agent are embedded in the main chain segment of the butyl rubber, blocking the conditions for molecular structure isomerization, improving the stability of the damping performance of the halogenated branched butyl rubber, and broadening the application range of the high damping halogenated branched butyl rubber.
  • FIG. 1 is an infrared spectrum of the halogenated grafting agent obtained in Preparation Example 1.
  • 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 halogenated grafting agent, which comprises a structural unit A, an optional structural unit B, a structural unit C and a structural unit D; wherein the structural unit A has a structure shown in formula (1); the structural unit C has a structure shown in formula (2); the structural unit B is connected to the structural unit A and the structural unit C respectively; the structural unit D is a terminal capping structural unit; the structural unit B and the structural unit D are independently derived from a conjugated diene;
  • R1 and R2 are each independently hydrogen or a C1 - C5 straight chain or branched alkyl group;
  • R3 is a C1 - C8 straight chain or branched alkyl group;
  • R4 and R5 are each independently hydrogen or a C1 - C4 straight chain or branched alkyl group;
  • X is a halogen white.
  • the halogenated grafting agent of the present invention combines a para-alkylphenyl structural unit and a halogenated alkyl structural unit on a macromolecular chain, and the molecular chain has the characteristics of high rigidity, high steric hindrance, strong adsorption force and multiple active points, 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.
  • the grafting agent of the present invention contains a large number of benzene ring structures in a regular arrangement, so that the characteristics of high rigidity and large steric hindrance can be fully utilized, and the modulus and barrier properties of the halogenated grafting agent can be greatly improved, so that the halogenated branched diene rubber prepared therefrom has high damping performance while maintaining its excellent mechanical strength and air tightness.
  • the stability of the bromine structure in the grafting agent of the present invention not only improves the high damping performance of the halogenated branched diene rubber, but also helps to solve the problem of butyl rubber having few double bonds and being difficult to vulcanize due to its high saturation, helps to increase its vulcanization speed, and can improve the vulcanization processability of the halogenated branched diene rubber.
  • the grafting agent of the present invention contains a large number of benzene ring structures, stable halogen structures and high isotacticity.
  • the halogenated branched diene rubber prepared by the grafting agent has high damping performance while also having excellent air tightness, mechanical strength and vulcanization processability to meet various application requirements.
  • examples of the C1 - C8 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 and isooctyl.
  • R 1 and R 2 are each independently hydrogen or a C 1 -C 3 straight or branched alkyl group, preferably hydrogen, methyl, ethyl or propyl.
  • R 3 is a C 1 -C 5 straight or branched alkyl group; preferably a methyl group, an ethyl group, a n-propyl group or an isopropyl group.
  • R 4 and R 5 are each independently hydrogen or C 1 -C 2 alkyl; preferably hydrogen, methyl or ethyl.
  • X is selected from at least one of Cl and Br, preferably Br.
  • the conjugated diene is butadiene and/or isoprene.
  • the structural unit represented by formula (1) 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.
  • p-alkylstyrene such as p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-n-butylstyrene, p-isobutylstyrene or p-isopentylstyrene.
  • the structural unit represented by formula (2) can be a structural unit derived from a halogenated olefin, such as vinyl bromide, vinyl chloride, 1-bromo-1-propylene, 2-bromo-1-propylene, 1-bromo-1-butene or 2-bromo-1-butene, preferably a structural unit derived from vinyl bromide or 2-bromo-1-butene.
  • a halogenated olefin such as vinyl bromide, vinyl chloride, 1-bromo-1-propylene, 2-bromo-1-propylene, 1-bromo-1-butene or 2-bromo-1-butene, preferably a structural unit derived from vinyl bromide or 2-bromo-1-butene.
  • the mass ratio of the structural unit A, the structural unit B, the structural unit C and the structural unit D is 100:0-2:15-70:3-7, for example, 100:0.3:30:4, 100:0.5:40:5, 100:0.6:50:6, 100:0.8:60:7, 100:0.9:70:5, 100:1:65:4, 100:1.2:50:5, 100:1.3:55:6, 100:1.4:45:3, 100:1.5:80:5, 100:1.8:78:5, and any value within the range composed of any two of the above values, preferably 100:0.3-1.5:30-68:4-6.
  • the mass ratio of each structural unit can be expressed by the feed mass ratio of the monomers corresponding to each structural unit.
  • the structural unit B is derived from butadiene; and the structural unit D is derived from isoprene.
  • the structure of the halogenated grafting agent of the present invention is shown in the general formula I1-A1-B1-C-B2-A2-I2, wherein I1 and I2 are structural units derived from isoprene; A1 and A2 are structural units shown in formula (1); B1 and B2 are structural units derived from butadiene; and C is a structural unit shown in formula (2).
  • the mass percentage of halogen in the halogenated grafting agent is 3-7 wt %, preferably 4-6 wt %.
  • the halogen content is determined by using a Q600 TG/DTG thermogravimetric analyzer.
  • the number average molecular weight of the halogenated grafting agent is 25,000-50,000 g/mol, preferably 30,000-40,000 g/mol.
  • the molecular weight distribution index (Mw/Mn) of the halogenated grafting agent is 1.5-4, such as 1.6, 1.9, 2, 2.5, 2.8, 3, 3.5, 3.7, and any value within the range of any two of the above values, preferably 2-3.5.
  • the halogenated grafting agent is a block copolymer or a random copolymer.
  • the apparent viscosity of the halogenated grafting agent at 25° C. is 5-35 mPa ⁇ s.
  • the apparent viscosity of the halogenated grafting agent is tested using an Ubbelohde viscometer according to the viscosity measurement method of GB/T 10247-2008.
  • the second aspect of the present invention provides a method for preparing a halogenated grafting agent, the preparation method comprising:
  • step S2 subjecting the polymer product obtained in step S1 or the third product obtained in step (2) to a second end-capping reaction with the first conjugated diene to obtain the halogenated grafting agent;
  • R1 and R2 are each independently hydrogen or a C1 - C5 straight chain or branched alkyl group;
  • R3 is a C1 - C8 straight chain or branched alkyl group;
  • R4 and R5 are each independently hydrogen or a C1 - C4 straight chain or branched alkyl group;
  • X is a halogen.
  • R 1 and R 2 are each independently hydrogen or a C 1 -C 3 straight or branched alkyl group, preferably hydrogen, methyl, ethyl or propyl.
  • R 3 is a C 1 -C 5 straight or branched alkyl group; preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl or isopentyl.
  • R 4 and R 5 are each independently hydrogen or C 1 -C 2 alkyl; preferably hydrogen, methyl or ethyl.
  • X is selected from at least one of Cl and Br, preferably Br.
  • the invention first synthesizes a macromolecular halogenating agent with anionic reaction activity; secondly, alkyl lithium is used as an initiator to synthesize a high molecular damping halogenated grafting agent from p-alkyl styrene and the macromolecular halogenating agent; and the high molecular damping halogenated grafting agent, isobutylene and isoprene are subjected to cationic polymerization in a catalytic system of alkyl aluminum halide and protonic acid to prepare a high damping halogenated branched butyl rubber.
  • the benzene rings and halogen atoms are arranged in a regularity, thereby increasing the steric hindrance effect of the molecular chain, enhancing the polarity, resulting in an increase in the movement resistance of the chain segment, an increase in the internal friction, and an increase in the relaxation tension of the chain segment.
  • the grafting preparation process of butyl rubber not only the damage of the damping halogenated grafting agent to the mechanical properties and air permeability of the butyl rubber is avoided, but also the damping performance and tensile strength of the butyl rubber are improved.
  • the method of the invention can prepare high-damping halogenated branched butyl rubber with a high maximum damping factor, even tan ⁇ max ⁇ 1.5.
  • the mass ratio of the monoconjugated diene is 100:0-2:15-70:3-7, for example, 100:0.3:30:4, 100:0.5:40:5, 100:0.6:50:6, 100:0.8:60:7, 100:0.9:70:5, 100:1:65:4, 100:1.2:50:5, 100:1.3:55:6, 100:1.4:45:3, 100:1.5:80:5, 100:1.8:78:5, and any value within the range of any two of the above values, preferably 100:0.3-1.5:30-68:4-6.
  • the mass ratio of the monomer represented by formula (I), the second conjugated diene, the monomer represented by formula (II) and the first conjugated diene is controlled within a specific range, which can effectively ensure the normal reaction of the polymer grafting agent and the grafted butyl rubber preparation.
  • the second conjugated diene and the first conjugated diene are used as end-capping agents, and their dosage has an important influence on the polymerization reaction. Too much dosage will increase the flexibility of the grafting agent chain segment and destroy the damping performance and mechanical strength of the butyl rubber. Too little dosage will lead to incomplete end-capping, fewer reactive sites, and lower grafting rate, which will deteriorate the damping performance and mechanical strength modification effect of the butyl rubber.
  • the monomer represented by formula (II) is a halogenated olefin, preferably at least one selected from vinyl bromide, vinyl chloride, 1-bromo-1-propylene, 2-bromo-1-propylene, 1-bromo-1-butene and 2-bromo-1-butene; preferably vinyl bromide or 2-bromo-1-butene.
  • the monomer represented by formula (I) is p-alkylstyrene, preferably at least one selected from p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-n-butylstyrene, p-isobutylstyrene and p-isopentylstyrene; preferably p-methylstyrene.
  • the second conjugated diene is butadiene and/or isoprene, preferably isoprene.
  • the first conjugated diene butadiene and/or isoprene is preferably 1,3-butadiene.
  • the first initiator is an organic peroxide, preferably at least one selected from dicumyl peroxide (DCP), cumyl hydroperoxide and benzoyl peroxide (BPO), more preferably benzoyl peroxide (BPO).
  • DCP dicumyl peroxide
  • BPO benzoyl peroxide
  • the second initiator is a hydrocarbon monolithium compound R-Li, wherein R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or a composite group of the above groups containing 1 to 20 carbon atoms, preferably selected from at least one of n-butyl lithium, sec-butyl lithium, methyl butyl lithium, phenyl butyl lithium, naphthalene lithium, cyclohexyl lithium and dodecyl lithium, and more preferably n-butyl lithium.
  • R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or a composite group of the above groups containing 1 to 20 carbon atoms, preferably selected from at least one of n-butyl lithium, sec-butyl lithium, methyl butyl lithium, phenyl butyl lithium, naphthalene lithium, cyclohexyl lithium and dodecyl lithium, and more preferably n
  • the molecular weight regulator is selected from at least one of tert-decyl mercaptan, tert-dodecyl mercaptan, tert-tetradecyl mercaptan and tert-hexadecyl mercaptan, preferably tert-dodecyl mercaptan.
  • the structure regulator is a polar organic compound, preferably at least one selected from diethylene glycol dimethyl ether (DGE), tetrahydrofuran (THF), ethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME) and triethylamine, more preferably tetrahydrofuran (THF).
  • DGE diethylene glycol dimethyl ether
  • THF tetrahydrofuran
  • ethyl ether ethyl ether
  • anisole anisole
  • diphenyl ether ethylene glycol dimethyl ether
  • DME ethylene glycol dimethyl ether
  • triethylamine more preferably tetrahydrofuran
  • the structure regulator in the present invention is a polar organic compound that generates a solvent in the polymerization system. Chemical effect, structure regulator is used to adjust the ionic reaction activity, can adjust the reactivity ratio of alkyl styrene and isoprene, so that the two can be randomly copolymerized.
  • the first solvent and the second solvent are each independently a hydrocarbon solvent, preferably at least one selected from linear alkanes, aromatic hydrocarbons and cycloalkanes, and more preferably at least one selected from pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene.
  • a hydrocarbon solvent preferably at least one selected from linear alkanes, aromatic hydrocarbons and cycloalkanes, and more preferably at least one selected from pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene.
  • the amount of the molecular weight regulator, structure regulator, solvent, etc. there is no particular limitation on the amount of the molecular weight regulator, structure regulator, solvent, etc., and they can be added according to conventional amounts in the art.
  • the conditions of the first polymerization reaction include: a reaction temperature of 50-60° C. and a reaction time of 4-6 h.
  • the conditions of the first end-capping reaction include: a reaction temperature of 50-60° C. and a reaction time of 20-40 min.
  • the conditions of the second polymerization reaction include: a reaction temperature of 60-70° C. and a reaction time of 70-90 min.
  • the conditions of the third polymerization reaction include: reaction temperature of 80-90° C., and reaction time of 80-100 min.
  • the conditions of the second capping reaction include: a reaction temperature of 80-90° C. and a reaction time of 30-40 min.
  • the method of the present invention further comprises adding a terminator to terminate the reaction after the polymerization is completed.
  • the terminator can be selected from one or more of methanol, ethanol and butanol.
  • the polymerization reaction is carried out in an oxygen-free and water-free environment, preferably in an inert gas environment.
  • the polymerization and dissolution processes are completed in hydrocarbon solvents.
  • vinyl bromide and p-methylstyrene can be directly polymerized without adding a capping agent in the middle. Since vinyl bromide cannot undergo anionic polymerization, the polymerization can only be carried out by free radical polymerization, using an organic peroxide such as BPO to initiate the reaction.
  • the third aspect of the present invention provides a halogenated grafting agent obtained by the aforementioned preparation method.
  • the fourth aspect of the present invention provides the use of the aforementioned halogenated grafting agent as a grafting agent in the preparation of diene rubber.
  • the fifth aspect of the present invention provides a halogenated branched butyl rubber, which comprises: a structural unit E derived from isobutylene, a structural unit F derived from isoprene and a structural unit G derived from a halogenated grafting agent; wherein the halogenated grafting agent is the aforementioned halogenated grafting agent.
  • the mass ratio of the structural unit E, the structural unit F and the structural unit G is 100:2-6:3-8, preferably 100:3-5:4-7.
  • a sixth aspect of the present invention provides a method for preparing a halogenated branched butyl rubber, the method comprising the following steps:
  • the mass ratio of isobutylene, isoprene and the halogenated grafting agent is 100:2-6:3-8, preferably 100:3-5:4-7.
  • the diluent is a halogenated alkane, wherein the halogen atom in the halogenated alkane is F, Cl or Br, and the number of carbon atoms in the halogenated alkane is 1-4; preferably, the diluent is selected from at least one of monochloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane and carbon tetrafluoride.
  • the solvent is a hydrocarbon solvent, preferably at least one of linear alkanes, aromatic hydrocarbons and cycloalkanes, and more preferably at least one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene.
  • the co-initiator comprises a protonic acid and an alkylaluminum halide; preferably, the molar ratio of the protonic acid to the alkylaluminum halide in the co-initiator is 1:10-100; preferably, the protonic acid is selected from at least one of HCl, HF, HBr, H2SO4 , H2CO3 , H3PO4 and HNO3 ; the alkylaluminum 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 mass ratio of the isobutylene to the co-initiator is 100:0.01-0.5.
  • the conditions for the cationic polymerization include: a polymerization temperature of -100°C to -80°C; and a cationic polymerization time of 3-4h.
  • the seventh aspect of the present invention provides a halogenated branched butyl rubber obtained by the above-mentioned preparation method.
  • the halogenated branched butyl rubber of the present invention is preferably a brominated branched butyl rubber.
  • the eighth aspect of the present invention provides the application of the aforementioned halogenated branched butyl rubber in various fields such as automobiles and electronic appliances.
  • the halogenated grafting agent is a linear block copolymer polymerized from isoprene, 1,3-butadiene, p-alkylstyrene and vinyl bromide.
  • the preparation method of the halogenated grafting agent specifically comprises the following steps:
  • a second initiator is added and the reaction is carried out for 70-90 minutes; then, 20%-40% of the macromolecular brominating agent and 0.1%-0.2% of the structure regulator are added to the polymerization kettle, the temperature is raised to 80-90°C, and the reaction is carried out for 80-100 minutes; finally, 3-5 parts of isoprene are added to the polymerization kettle for end-capping, and the reaction is carried out for 30-40 minutes until no free monomers are present.
  • the glue solution is subjected to wet coagulation and drying to obtain a halogenated grafting agent.
  • the method for preparing halogenated branched butyl rubber from the above-mentioned halogenated grafting agent specifically comprises the following steps:
  • 1,3-Butadiene polymerization grade, purchased from PetroChina Lanzhou Petrochemical Company;
  • Isobutylene and isoprene polymer grade, purchased from Zhejiang Xinhui New Materials Co., Ltd.;
  • p-Methylstyrene polymer grade, purchased from Jiande Langfeng Chemical Co., Ltd.;
  • p-Butylstyrene polymerization grade, purchased from Luoyang Boyu Energy Technology Co., Ltd.;
  • Vinyl bromide polymer grade, purchased from Wuhan Fuxinyuan Technology Co., Ltd.;
  • Benzoyl peroxide (BPO) purchased from Lanzhou Additive Factory;
  • n-Butyl lithium purity 98%, purchased from Nanjing Tonglian Chemical Co., Ltd.;
  • Sesquiethylaluminum chloride purity 98%, purchased from Bailingwei Technology Co., Ltd.;
  • Mn number average molecular weight
  • Mw/Mn distribution index
  • DMA Dynamic mechanical analysis
  • Air tightness determination The air permeability number was determined using an automated air tightness tester in accordance with ISO 2782:1995.
  • the test gas was N 2
  • the test temperature was 23° C.
  • the test sample was a circular sea piece with a diameter of 8 cm and a thickness of 1 mm.
  • Tensile strength Execute the method in standard GB/T528-2009.
  • the mass ratio of the monomer feed is equal to the mass ratio of the corresponding structural units in the prepared halogenated grafting agent.
  • halogenated grafting agent S1 in which the mass ratio of the structural units from vinyl bromide, 1,3-butadiene, p-methylstyrene and isoprene was 100:0.67:67:5.
  • the halogenated grafting agent S1 had an Mn of 30350, an Mw/Mn of 2, a bromine content of 5.97%, and an apparent viscosity of 8 mPa ⁇ s at 25°C.
  • the asymmetric secondary vibration double absorption peak of the benzene ring appears at wave numbers 3005-3100 cm- 1 ; the secondary vibration absorption peak of the methyl group ( CH3 ) appears at wave numbers 2950-2800 cm -1 ; the secondary vibration absorption peak of the "carbon-carbon double bond" appears at wave numbers 1680-1500 cm -1 ; the secondary vibration single absorption peak of the para-substituted benzene ring appears at wave numbers 900-850 cm -1 ; the secondary vibration single absorption peak of the bromine atom appears at wave numbers 700-650 cm -1 , indicating that the halogenated grafting agent prepared from vinyl bromide, 1,3-butadiene, p-methylstyrene and isoprene contains p-methylbenzene structure and bromine substitution structure.
  • the Mn of the halogenated grafting agent S2 was 31500, the Mw/Mn was 2.3, the bromine content was 5.63%, and the apparent viscosity at 25°C was 12 mPa ⁇ s.
  • n-butyl lithium 15.5mmol of n-butyl lithium was added to start the reaction for 78min; then 300g of macromolecular brominating agent and 1.4g of THF were added to the polymerization reactor, and the temperature was raised to 85°C and the reaction was carried out for 90min; finally, 40g of isoprene was added to the polymerization reactor and the end-capping reaction was carried out for 34min until no free monomer was present.
  • the gel was The halogenated grafting agent S3 was prepared by wet condensation and drying, wherein the mass ratio of the structural units derived from vinyl bromide, 1,3-butadiene, p-methylstyrene and isoprene was 100:0.86:43:5.7.
  • the halogenated grafting agent S3 was tested to have a Mn of 33600, a Mw/Mn of 2.7, a bromine content of 5.03%, and an apparent viscosity of 17 mPa ⁇ s at 25°C.
  • the halogenated grafting agent S4 had an Mn of 36100, an Mw/Mn of 3, a bromine content of 4.68%, and an apparent viscosity of 23 mPa ⁇ s at 25°C.
  • halogenated grafting agent S5 in which the mass ratio of the structural units from vinyl bromide, 1,3-butadiene, p-methylstyrene and isoprene was 100:1.1:38:5.9.
  • the halogenated grafting agent S5 had an Mn of 38200, an Mw/Mn of 3.3, a bromine content of 4.45%, and an apparent viscosity of 26 mPa ⁇ s at 25°C.
  • halogenated grafting agent S6 in which the mass ratio of the structural units from vinyl bromide, 1,3-butadiene, p-methylstyrene and isoprene was 100:1:25:6.25.
  • the halogenated grafting agent S6 had a Mn of 39600, a Mw/Mn of 3.5, a bromine content of 4.12%, and an apparent viscosity of 30 mPa ⁇ s at 25°C.
  • the halogenated grafting agent was prepared according to the method of Preparation Example 1, except that the amount of 1,3-butadiene added during the preparation process was 20 g, and other conditions remained unchanged, to obtain the halogenated grafting agent S7, wherein the mass ratio of the structural units from vinyl bromide, 1,3-butadiene, p-methylstyrene and isoprene was 100:1.34:67:5.
  • a halogenated grafting agent was prepared according to the method of Preparation Example 1, except that 30 g of 1,3-butadiene was added during the preparation process to obtain a halogenated grafting agent S8, wherein the mass ratio of the structural units from vinyl bromide, 1,3-butadiene, p-methylstyrene and isoprene was 100:1.94:67:5.
  • the halogenated grafting agent S8 had a Mn of 31000, a Mw/Mn of 2.2, a bromine content of 5.91%, and an apparent viscosity of 11.2 mPa ⁇ s at 25°C.
  • the halogenated grafting agent was prepared according to the method of Preparation Example 1, except that the amount of p-methylstyrene added during the preparation process was 700 g, and other conditions remained unchanged, to obtain the halogenated grafting agent S9, wherein the mass ratio of the structural units from vinyl bromide, 1,3-butadiene, p-methylstyrene and isoprene was 100:0.57:57:4.
  • the halogenated grafting agent S9 had a Mn of 33,000, a Mw/Mn of 2.5, a bromine content of 5.23%, and an apparent viscosity of 16 mPa ⁇ s at 25°C.
  • the halogenated grafting agent was prepared according to the method of Preparation Example 1, except that the amount of p-methylstyrene added during the preparation process was 800 g, and other conditions remained unchanged, to obtain the halogenated grafting agent S10, wherein the mass ratio of the structural units from vinyl bromide, 1,3-butadiene, p-methylstyrene and isoprene was 100:0.49:50:4.
  • the halogenated grafting agent was prepared according to the method of Preparation Example 1, except that vinyl chloride was used instead of vinyl bromide in Preparation Example 1 during the preparation process, and other conditions remained unchanged to obtain halogenated grafting agent S11, wherein the mass ratio of the structural units from vinyl chloride, 1,3-butadiene, p-methylstyrene and isoprene was 100:0.67:67:5.
  • argon gas was replaced twice, and 1000g of cyclohexane, 1000g of vinyl bromide, 600g of p-methylstyrene and 2g of tert-dodecyl mercaptan were added to the reactor in turn, stirred and heated, and when the temperature of the reactor reached 50°C, 0.1g of BPO was added and reacted for 4h. Finally, 30g of isoprene was added to the polymerization kettle and the end-capping reaction was carried out for 30min until no free monomers were present. The gel was wet-coagulated and dried to obtain the halogenated grafting agent S12, in which the mass ratio of the structural units from vinyl bromide, p-methylstyrene and isoprene was 100:17:5.
  • the halogenated grafting agent S12 had a Mn of 50,000, a Mw/Mn of 4, a bromine content of 12.1%, and an apparent viscosity of 35 mPa ⁇ s at 25°C.
  • the halogenated grafting agent was prepared according to the method of Preparation Example 1, except that in the preparation process of the halogenated grafting agent in step (2), the amount of the macromolecular brominating agent added was 200 g, and other conditions remained unchanged, to obtain the halogenated grafting agent S13, wherein the mass ratio of the structural units from vinyl bromide, 1,3-butadiene, p-methylstyrene and isoprene was 100:0.34:33:5.
  • the halogenated grafting agent S13 was tested to have a Mn of 25,000, a Mw/Mn of 1.5, a bromine content of 4.91%, and an apparent viscosity of 5 mPa ⁇ s at 25°C.
  • the halogenated grafting agent was prepared according to the method of Preparation Example 1, except that in the preparation process of the halogenated grafting agent in step (2), the amount of the macromolecular brominating agent added was 300 g, and other conditions remained unchanged, to obtain the halogenated grafting agent S14, wherein the mass ratio of the structural units from vinyl bromide, 1,3-butadiene, p-methylstyrene and isoprene was 100:0.5:50:5.
  • the halogenated grafting agent S14 was tested to have a Mn of 28,000, a Mw/Mn of 1.7, a bromine content of 5.38%, and an apparent viscosity of 7 mPa ⁇ s at 25°C.
  • a halogenated grafting agent was prepared according to the method of Preparation Example 1, except that in the preparation process of the halogenated grafting agent in step (2), styrene was used instead of p-methylstyrene. Other conditions remained unchanged to obtain a halogenated grafting agent D1, in which the mass ratio of the structural units derived from vinyl bromide, 1,3-butadiene, styrene and isoprene was 100:0.67:67:5.
  • a halogenated grafting agent was prepared according to the method of Preparation Example 1, except that ethylene was used instead of vinyl bromide in the preparation of the macromolecular brominating agent in step (1), and other conditions remained unchanged to obtain a halogenated grafting agent D2, in which the mass ratio of the structural units derived from ethylene, 1,3-butadiene, p-methylstyrene and isoprene was 100:0.67:67:5.
  • the halogenated grafting agent D2 had an Mn of 21000, an Mw/Mn of 2.4, a bromine content of 0%, and an apparent viscosity of 3.1 mPa ⁇ s at 25°C.
  • the brominated branched butyl rubber product was prepared according to the method of Example 1, except that the halogenated grafting agent S1 was replaced by any one of the halogenated grafting agents S2-S14, and other conditions remained unchanged to obtain the halogenated branched butyl rubber product.
  • Sampling and analysis Standard samples were prepared, and the test properties are shown in Table 1.
  • the brominated branched butyl rubber product was prepared according to the method of Example 1, except that the amount of halogenated grafting agent S1 added during the preparation process was 25 g, and other conditions remained unchanged to obtain a brominated branched butyl rubber product.
  • the mass ratio of the structural units from isobutylene, isoprene and halogenated grafting agent S1 was 100:3:5.
  • the brominated branched butyl rubber product was prepared according to the method of Example 1, except that the halogen
  • the amount of halogenated grafting agent S1 added was 30 g, and other conditions remained unchanged to obtain a brominated branched butyl rubber product.
  • the mass ratio of the structural units from isobutylene, isoprene and halogenated grafting agent S1 was 100:3:6.
  • Sampling analysis Standard samples were prepared, and the test properties are shown in Table 1.
  • the brominated branched butyl rubber product was prepared according to the method of Example 1, except that the amount of halogenated grafting agent S1 added during the preparation process was 35 g, and other conditions remained unchanged to obtain a brominated branched butyl rubber product.
  • the mass ratio of the structural units from isobutylene, isoprene and halogenated grafting agent S1 was 100:3:7.
  • Sampling analysis Standard samples were prepared, and the test properties are shown in Table 1.
  • the brominated branched butyl rubber product was prepared according to the method of Example 1, except that the amount of isoprene added during the preparation process was 20 g, and other conditions remained unchanged to obtain a brominated branched butyl rubber product.
  • the mass ratio of the structural units from isobutylene, isoprene and halogenated grafting agent S1 was 100:4:4.
  • the brominated branched butyl rubber product was prepared according to the method of Example 1, except that the amount of isoprene added during the preparation process was 25 g, and other conditions remained unchanged to obtain a brominated branched butyl rubber product.
  • the mass ratio of the structural units from isobutylene, isoprene and halogenated grafting agent S1 was 100:5:4.
  • the brominated branched butyl rubber product was prepared according to the method of Example 1, except that 1.05 g of sesquiethylaluminum chloride and 0.011 g of HCl were replaced with g of aluminum chloride, and the other conditions remained unchanged to obtain the brominated branched butyl rubber product.
  • Sampling and analysis Standard samples were prepared, and the test performance is shown in Table 1.
  • the brominated branched butyl rubber product was prepared according to the method of Example 1, except that the halogenated grafting agent S1 was replaced by the halogenated grafting agent D1, and other conditions remained unchanged to obtain the brominated branched butyl rubber product.
  • Sampling and analysis Standard samples were prepared, and the test properties are shown in Table 1.
  • the brominated branched butyl rubber product was prepared according to the method of Example 1, except that the halogenated grafting agent S1 was replaced by the halogenated grafting agent D2, and other conditions remained unchanged to obtain the brominated branched butyl rubber product.
  • Sampling and analysis Standard samples were prepared, and the test properties are shown in Table 1.

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Abstract

La présente invention concerne le domaine des matériaux d'amortissement en caoutchouc, et concerne un agent de greffage halogéné et un caoutchouc butyle ramifié halogéné, leur procédé de préparation et leur utilisation. L'agent de greffage halogéné comprend un motif structural A, un motif structural facultatif B, un motif structural C et un motif structural D, le motif structural A présentant une structure représentée par la formule (1) ; le motif structural C présentant une structure représentée par la formule (2) ; le motif structural B étant relié au motif structural A et au motif structural C, respectivement ; le motif structural D étant un motif structural à extrémité coiffée terminale ; le motif structural B et le motif structural D étant chacun indépendamment dérivés d'un diène conjugué. Le procédé de la présente invention résout les problèmes de faible performance d'amortissement et de réarrangement hétérogène d'une structure halogénée dans le caoutchouc butyle, il empêche la propriété mécanique et la perméabilité à l'air du caoutchouc butyle d'être détériorées par l'agent de greffage bromé amortisseur, et la performance d'amortissement et la résistance à la traction du caoutchouc butyle sont également améliorées.
PCT/CN2023/113586 2022-09-27 2023-08-17 Agent de greffage halogéné et caoutchouc butyle ramifié halogéné, leur procédé de préparation et leur utilisation WO2024066787A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0344021A2 (fr) * 1988-05-27 1989-11-29 Exxon Chemical Patents Inc. Copolymères de para-alkylstyrène et d'isooléfines
US5162445A (en) * 1988-05-27 1992-11-10 Exxon Chemical Patents Inc. Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof
IN174816B (fr) * 1989-05-09 1995-03-18 Exxon Chemical Patents Inc
US5548023A (en) * 1987-11-12 1996-08-20 Exxon Chemical Patents, Inc. Graft copolymers of para-alkylstyrene/isoolefin copolymers as blend compatibilizers
CN104892813A (zh) * 2014-03-06 2015-09-09 中国石油化工股份有限公司 一种支化聚合物的卤化物及其制备方法
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
CN116410413A (zh) * 2021-12-29 2023-07-11 中国石油天然气股份有限公司 一种仲位溴化支化丁基橡胶的制备方法
CN116410419A (zh) * 2021-12-29 2023-07-11 中国石油天然气股份有限公司 一种阴离子溴化支化丁基橡胶的制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5548023A (en) * 1987-11-12 1996-08-20 Exxon Chemical Patents, Inc. Graft copolymers of para-alkylstyrene/isoolefin copolymers as blend compatibilizers
EP0344021A2 (fr) * 1988-05-27 1989-11-29 Exxon Chemical Patents Inc. Copolymères de para-alkylstyrène et d'isooléfines
US5162445A (en) * 1988-05-27 1992-11-10 Exxon Chemical Patents Inc. Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof
IN174816B (fr) * 1989-05-09 1995-03-18 Exxon Chemical Patents Inc
CN104892813A (zh) * 2014-03-06 2015-09-09 中国石油化工股份有限公司 一种支化聚合物的卤化物及其制备方法
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
CN116410413A (zh) * 2021-12-29 2023-07-11 中国石油天然气股份有限公司 一种仲位溴化支化丁基橡胶的制备方法
CN116410419A (zh) * 2021-12-29 2023-07-11 中国石油天然气股份有限公司 一种阴离子溴化支化丁基橡胶的制备方法

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