WO2024067013A1

WO2024067013A1 - Multi-component copolymer, preparation method therefor, and use thereof, and halogenated branched butyl rubber, preparation method therefor, and use thereof

Info

Publication number: WO2024067013A1
Application number: PCT/CN2023/117573
Authority: WO
Inventors: 徐典宏; 魏绪玲; 燕鹏华; 赵志超; 梁滔; 牛承祥; 杨珊珊; 孟令坤; 朱晶
Original assignee: 中国石油天然气股份有限公司
Priority date: 2022-09-26
Filing date: 2023-09-07
Publication date: 2024-04-04
Also published as: CN117801191A

Abstract

The present invention relates to the technical field of rubber preparation, and disclosed are a multi-component copolymer, a preparation method therefor, and use thereof, and a halogenated branched butyl rubber, a preparation method therefor, and use thereof. 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 phase structure represented by formula (1), the structural unit B has a phase structure represented by formula (2), and the structural unit C has a phase structure represented by formula (3); wherein R1, R2, R3, R4, R5, R6, R7 and R8 are each independently hydrogen or a C1-C10 phase linear chain or branched alkyl; X is halogen, and n is any integer of 1 to 10; the phase tail end of the multi-component copolymer contains a phase structural unit from a conjugated diene. According to the present invention, the halogenated branched butyl rubber is prepared by taking the multi-component copolymer as a grafting agent, so that an effective damping temperature range and the phase stability of the damping performance of the halogenated branched butyl rubber are improved.

Description

Multi-component copolymer and preparation method and application thereof, halogenated branched butyl rubber and preparation method and application thereof

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of Chinese patent application 202211173637.1 filed on September 26, 2022, the contents of which are incorporated herein by reference.

Technical Field

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.

Background technique

With the rapid development of modern science and technology, mechanical equipment in many fields such as high-speed rail, aerospace, naval ships, mechanical engineering, automobiles, and electronic appliances tends to be high-frequency and high-speed, which brings convenience to daily production and life, but also creates a series of problems, such as high-frequency vibration and noise. These problems not only accelerate the fatigue damage of mechanical structural materials and shorten their service life, but also pose an increasingly prominent threat to the safety of people's lives and property. Therefore, shock absorption and noise reduction have become one of the problems that need to be solved urgently in today's society. Therefore, it is crucial to develop high-efficiency damping materials with excellent performance and improve their application effect of damping and shock absorption to improve the operating environment of machinery and ensure human health and safety.

Diene rubber is an unsaturated rubber containing two C=C double bonds. Its main industrial products include butadiene rubber, isoprene rubber, butyl rubber, etc. Diene rubber is widely used in various fields of daily production and life. However, the butyl rubber molecular chain has a high degree of unsaturation and the methyl substituents are arranged symmetrically. This molecular structure determines that it inevitably has problems such as poor ozone aging resistance, long vulcanization scorch time, low vulcanization speed, and low damping performance. As a result, butyl rubber cannot meet the increasingly diverse processing needs and application scenarios, which has become a bottleneck for the expansion of butyl rubber materials.

Bromobutyl rubber (BIIR) 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. Compared with IIR, 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. Secondly, due to the introduction of 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.

At present, in practical applications, it is often necessary to have a damping function within the range of -50℃ to +50℃. However, the effective damping function area of bromobutyl rubber (damping factor tanδ>0.3) is mainly concentrated in the low temperature part. The damping value is low above 15℃, which cannot meet the use requirements of wide temperature range damping materials. Therefore, how to broaden the effective damping function area of butyl rubber above room temperature is one of the research hotspots of rubber damping materials today.

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.

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 polymer network I and poly(styrene-methyl methacrylate) [P(St-MMA)] as polymer network II, 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.

Although the existing technologies can expand the effective damping temperature range of rubber and improve the damping performance of rubber to a certain extent through blending, copolymerization and interpenetrating network polymer methods, these methods still have certain limitations, which will lead to problems such as decreased mechanical properties of rubber materials, complex processes, difficulties in actual operations, large addition amounts, high costs, and difficulty in removing organic solvents, causing environmental pollution.

Therefore, there is an urgent need to develop a rubber material with a wide effective damping temperature range, high damping performance and excellent mechanical properties, and an easy-to-operate and pollution-free preparation method.

Summary of the invention

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.

In order to achieve the above object, 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).

wherein 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;

Adding a conjugated diene monomer to the polymer solution to perform a capping reaction to obtain the multi-component copolymer;

Wherein, 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.

Through the above technical solution, the beneficial technical effects achieved by the present invention are as follows:

(1) 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. When the multi-polymer is 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 δ ≥ 0.3) exceeding the range of -50°C to 62°C and a tan δ _max of 1.9 or more.

(2) In the multi-polymer of the present invention, 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". When 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.

(3) 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.

(4) In the preparation process of the halogenated branched butyl rubber, there is no volatile organic compound (VOC) The preparation method is green and environmentally friendly, with a short process flow, low production cost, and is suitable for industrial production.

BRIEF DESCRIPTION OF THE DRAWINGS

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).

Detailed ways

The endpoints and 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. For numerical ranges, 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).

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.

In the present invention, 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.

In the present invention, the value of n in the structure represented by formula (1) can be selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.

In some embodiments of the present invention, 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.

In some preferred embodiments of the present invention, R ₆ is methyl.

In some preferred embodiments of the present invention, X is selected from Cl and/or Br.

In some preferred embodiments of the present invention, n is any integer from 1 to 5, preferably any integer from 1 to 3.

In some preferred embodiments of the present invention, the conjugated diene is butadiene and/or isoprene.

In some preferred embodiments of the present invention, 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, and 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.

In the present invention, the multi-polymer is a block copolymer or a random copolymer.

In some embodiments of the present invention, 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. When the mass ratio of each structural unit in the multi-polymer meets the above range, a high-damping brominated branched butyl rubber with a wide temperature range and an effective damping temperature range (tan δ ≥ 0.3) exceeding -50°C to 62°C, a maximum damping factor tan δ _max ≥ 1.9 and a tensile strength of 22MPa-24MPa can be provided.

The above ratio can be measured by infrared spectroscopy and nuclear magnetic resonance methods, or determined based on the preparation and feeding relationship.

In some preferred embodiments of the present invention, 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%. When 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. In the present invention, the halogen content is determined by using a Q600 TG/DTG thermogravimetric analyzer.

In some embodiments of the present invention, 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.

In some preferred embodiments of the present invention, 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.

In the present invention, the number average molecular weight and the molecular weight distribution index are both tested by gel chromatography.

In some embodiments of the present invention, the multi-polymer has an apparent viscosity of 8-40 cps at 25°C.

In the present invention, the apparent viscosity of the multi-polymer at 25° C. is tested using an Ubbelohde viscometer according to GB/T10247-2008.

In the present invention, the preparation method has the characteristics of complete reaction, no by-product generation, stable structure of the prepared multi-polymer and regular arrangement of molecular chains.

In some preferred embodiments of the present invention, R ₆ is methyl.

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.

In some embodiments, 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, and the monomer represented by formula (III) is methyl methacrylate (MMA), ethyl methacrylate, butyl methacrylate or tert-butyl methacrylate.

In some embodiments of the present invention, the conjugated diene is butadiene and/or isoprene.

In some preferred embodiments of the present invention, 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. In the present invention, 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 (tanδ≥0.3) exceeding the range of -50°C to 62°C and a maximum damping factor tanδ _max ≥1.9 can be obtained.

In some preferred embodiments of the present invention, the polymerization reaction is carried out under a protective atmosphere, and the protective atmosphere is preferably an inert atmosphere.

In some preferred embodiments of the present invention, 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.

In some preferred embodiments of the present invention, 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. In the invention, 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".

In some preferred embodiments of the present invention, 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.

In some preferred embodiments of the present invention, 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.

In some preferred embodiments of the present invention, 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.

In some preferred embodiments of the present invention, 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.

In some embodiments, 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 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.

In some preferred embodiments of the present invention, 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.

In some embodiments of the invention, the method comprises the following steps:

(1) mixing the monomer represented by formula (I), a structure regulator, a solvent and an initiator to undergo a first polymerization reaction to obtain a first polymer product;

(2) adding the monomer represented by formula (II) and the structure regulator to the first polymer product to mix and cause a second polymerization reaction to obtain a second polymer product;

(3) adding the monomer represented by formula (III) and the structure regulator to the second polymer product and mixing them to cause a third polymerization reaction to obtain a third polymer product;

(4) Adding a conjugated diene to the third polymerization product to undergo a capping reaction to obtain the multi-polymer.

In the above-mentioned preparation method of the present invention, 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.

In some preferred embodiments of the present invention, 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. By controlling the mass ratio of the monomer represented by formula (I) to the structure regulator within the above range, a block polymer with high isotacticity can be produced.

In some preferred embodiments of the present invention, 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. By controlling the mass ratio of the monomer represented by formula (II) to the structure regulator within the above range, a block polymer with high isotacticity can be produced.

In some preferred embodiments of the present invention, 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. By controlling the mass ratio of the monomer represented by formula (III) to the structure regulator within the above range, a block polymer with high isotacticity can be produced.

In some embodiments of the present invention, 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.

In some preferred embodiments of the present invention, 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.

In some preferred embodiments of the present invention, 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.

According to a particularly preferred embodiment of the present invention, under an inert atmosphere, the polymerization kettle 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;

Wherein, 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.

In some embodiments of the present invention, 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;

Wherein, the halogenated grafting agent is the aforementioned multi-polymer.

In some embodiments of the present invention, based on the total weight of the halogenated branched butyl rubber, 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. In the present invention, 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 (tanδ≥0.3) exceeding -50°C to 62°C can be obtained; the maximum damping factor tanδ _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. When the multi-polymer is used as a halogenated grafting agent for preparing halogenated branched butyl rubber, 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 δ≥0.3) exceeding the range of -50°C to 62°C and a tan δ _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:

In the presence of a diluent, an organic solvent and a co-initiator, isobutylene, isoprene and the aforementioned multi-polymer are contacted for cationic polymerization to obtain the halogenated branched 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 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 (tanδ _max ≥0.3) of the halogenated branched butyl rubber prepared by the present invention exceeds the range of -50°C to 62°C.

In addition, there is no emission of volatile organic compounds (VOC) and by-product HBr during the preparation process, the preparation method is green and environmentally friendly, has a short process flow, low production cost, and is suitable for industrial production.

In some embodiments of the present invention, 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. In the present invention, 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.

In some preferred embodiments of the present invention, 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.

In some preferred embodiments of the present invention, the diluent is selected from at least one of methyl chloride, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane.

In some preferred embodiments of the present invention, 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. In the present invention, the mass ratio of isobutylene to the diluent is controlled within a specific range to prepare a butyl rubber with a high molecular weight.

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.

In some preferred embodiments of the present invention, the co-initiator comprises an alkylaluminum halide and a protonic acid.

In some preferred embodiments of the present invention, 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.

In some preferred embodiments of the present invention, 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.

In some preferred embodiments of the present invention, 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 .

In some preferred embodiments of the present invention, 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.

In some preferred embodiments of the present invention, 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.

In the present invention, 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.

According to a particularly preferred embodiment of the present invention, a mixed solvent (V _(diluent) : V _(solvent) is 70-30/30-70) and 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 rubber;

Wherein, 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 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.

The present invention will be described in detail below through examples.

In the following examples and comparative examples, if no specific conditions are specified, the experiments are carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used, if no manufacturer is specified, are conventional products that can be obtained through commercial channels. The mass ratio of each structural unit contained in the obtained multi-polymer product and the halogenated branched butyl rubber is determined according to the raw material feed amount.

(1) Source of raw materials:

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.

Other reagents are commercially available products.

(2) Analytical testing methods:

Determination of number average molecular weight and Mn distribution index (Mw/Mn): Determination was performed using a 2414 gel permeation chromatograph (GPC) produced by Waters, USA. The polystyrene standard was used as the calibration curve, the mobile phase was tetrahydrofuran, the column temperature was 40°C, the sample concentration was 1 mg/mL, the injection volume was 50 μL, the elution time was 40 min, and the flow rate was 1 mL·min ^-1 .

Determination of bromine content: Weigh 10 mg of sample and use Q600 TG/DTG thermogravimetric analyzer, with a heating rate of 10℃/min, in a nitrogen atmosphere with a flow rate of 50mL/min to thermally degrade the sample. The first stage of thermal degradation is the debromination of the bromine-containing units of the sample to form HBr, and then the bromine content (X) in the sample is inferred from the percentage of HBr removed. The calculation formula is as follows:

Where: Y-the percentage of the sample at 220°C; 79.904-the relative atomic mass of bromine; 1.008-the relative atomic mass of hydrogen.

Determination of apparent viscosity: using Ubbelohde viscometer according to GB/T 10247-2008.

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., and the test sample is a circular sea piece with a diameter of 8 cm and a thickness of 1 mm.

Dynamic mechanical analysis (DMA): The tensile mode was used in a 242C dynamic mechanical The sample size is 10 mm long, 6 mm wide, and 2 mm thick, the temperature range is -90°C to 90°C, the heating rate is 3°C/min, and the data at a frequency of 10 Hz are selected for analysis.

Tensile strength: Execute the method in standard GB/T528-2009.

Example 1

This example is used to illustrate the preparation of a multi-polymer.

First, in a 15L stainless steel reactor with a jacket, argon gas was replaced three times, and 3000g hexane, 1000g p-bromomethylstyrene, and 5.0g THF were added to the polymerization kettle in sequence, the temperature was raised to 50°C, and 18.5mmol n-butyl lithium was added to start the reaction for 100min; then 300g p-methylstyrene and 3.0g THF were added to the polymerization kettle, the temperature was raised to 70°C, and the reaction was carried out for 60min; then 150g MMA and 2.0g THF were added to the polymerization kettle, and the reaction was carried out for 40min; finally, 20g isoprene was added to the polymerization kettle, and the end-capping reaction was carried out for 20min until there was no free monomer. The glue was wet-coagulated and dried to obtain the multi-polymer S-1. Among them, 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.

Example 2

This example is used to illustrate the preparation of a multi-polymer.

First, in a 15L stainless steel reactor with a jacket, argon gas was replaced three times, and 3100g hexane, 1000g p-bromomethylstyrene, 5.4g THF were added to the polymerization kettle in sequence, the temperature was raised to 52°C, and 19.3mmol n-butyl lithium was added to start the reaction for 105min; then 310g p-methylstyrene and 3.5g THF were added to the polymerization kettle, the temperature was raised to 72°C, and the reaction was carried out for 62min; then 160g MMA and 2.2g THF were added to the polymerization kettle, and the reaction was carried out for 42min; finally, 22g isoprene was added to the polymerization kettle, and the end-capping reaction was carried out for 21min until there was no free monomer. The glue was wet-coagulated and dried to obtain the multi-polymer S-2. Among them, 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.

Example 3

This example is used to illustrate the preparation of a multi-polymer.

First, in a 15L stainless steel reactor with a jacket, argon gas was replaced 4 times, and 3300g hexane, 1000g p-bromomethylstyrene, 5.7g THF were added to the polymerization kettle in sequence, the temperature was raised to 55°C, and 21.5mmol n-butyl lithium was added to start the reaction for 110min; then 330g p-methylstyrene and 4.0g THF were added to the polymerization kettle, the temperature was raised to 74°C, and the reaction was carried out for 64min; then 170g MMA and 2.4g THF were added to the polymerization kettle, and the reaction was carried out for 44min; finally, 24g isoprene was added to the polymerization kettle, and the end-capping reaction was carried out for 23min until there was no free monomer. The glue was wet-coagulated and dried to obtain the multi-polymer S-3. Among them, 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.

Example 4

This example is used to illustrate the preparation of a multi-polymer.

First, in a 15L stainless steel reactor with a jacket, argon was replaced 4 times, 3500g of hexane, 1000g of p-bromomethylstyrene, and 6.0g of THF were added to the polymerization reactor in sequence, the temperature was raised to 57°C, and 22.6 mmol n-butyl lithium was used to start the reaction for 113 minutes; then 360 g p-methylstyrene and 4.4 g THF were added to the polymerization kettle, the temperature was raised to 76°C, and the reaction was carried out for 66 minutes; then 180 g MMA and 2.6 g THF were added to the polymerization kettle, and the reaction was carried out for 46 minutes; finally 25 g isoprene was added to the polymerization kettle, and the end-capping reaction was carried out for 25 minutes until no free monomers were present. The glue was wet-coagulated and dried to obtain the multi-polymer S-4. Among them, 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.

Example 5

This example is used to illustrate the preparation of a multi-polymer.

First, in a 15L stainless steel reactor with a jacket, argon gas was replaced 5 times, and 3700g hexane, 1000g p-bromomethylstyrene, and 6.5g THF were added to the polymerization kettle in sequence, the temperature was raised to 59°C, and 23.4mmol n-butyl lithium was added to start the reaction for 115min; then 380g p-methylstyrene and 4.8g THF were added to the polymerization kettle, the temperature was raised to 78°C, and the reaction was carried out for 68min; then 190g MMA and 2.8g THF were added to the polymerization kettle, and the reaction was carried out for 48min; finally, 27g isoprene was added to the polymerization kettle, and the end-capping reaction was carried out for 27min until there was no free monomer. The glue was wet-coagulated and dried to obtain the multi-polymer S-5. Among them, the mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA and isoprene was 100:38:19:2.7.

After testing, 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.

Example 6

This example is used to illustrate the preparation of a multi-polymer.

First, in a 15L stainless steel reactor with a jacket, argon gas was replaced 5 times, and 4000g hexane, 1000g p-bromomethylstyrene, 7.0g THF were added to the polymerization kettle in sequence, the temperature was raised to 60°C, and 24.8mmol n-butyl lithium was added to start the reaction for 120min; then 400g p-n-butylstyrene and 5.0g THF were added to the polymerization kettle, the temperature was raised to 80°C, and the reaction was carried out for 70min; then 200g MMA and 3.0g THF were added to the polymerization kettle, and the reaction was carried out for 50min; finally, 30g isoprene was added to the polymerization kettle, and the end-capping reaction was carried out for 30min until there was no free monomer. The glue was wet-coagulated and dried to obtain the multi-polymer S-6. Among them, 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.

Example 7

This example is used to illustrate the preparation of a multi-polymer.

First, in a 15L stainless steel reactor with a jacket, nitrogen was replaced 5 times, and 4000g hexane, 1000g p-bromomethylstyrene, 7.0g THF were added to the polymerization kettle in sequence, the temperature was raised to 40°C, and 16mmol n-butyl lithium was added to start the reaction for 80min; then 200g p-n-butylstyrene and 5.0g THF were added to the polymerization kettle, the temperature was raised to 60°C, and the reaction was carried out for 50min; then 100g MMA and 3.0g THF were added to the polymerization kettle, and the reaction was carried out for 30min; finally, 10g isoprene was added to the polymerization kettle, and the end-capping reaction was carried out for 10min until there was no free monomer. The glue was wet-coagulated and dried to obtain the multi-polymer S-7. Among them, the mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA and isoprene was 100:20:20:1.

After testing, 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.

Example 8

This example is used to illustrate the preparation of a multi-polymer.

First, in a 15L stainless steel reactor with a jacket, argon gas was replaced 5 times, and 4000g hexane, 1000g p-bromomethylstyrene, and 7.0g THF were added to the polymerization kettle in sequence, the temperature was raised to 80°C, and 30mmol n-butyl lithium was added to start the reaction for 150min; then 500g p-n-butylstyrene and 5.0g THF were added to the polymerization kettle, the temperature was raised to 90°C, and the reaction was carried out for 80min; then 250g MMA and 3.0g THF were added to the polymerization kettle, and the reaction was carried out for 60min; finally, 50g isoprene was added to the polymerization kettle, and the end-capping reaction was carried out for 45min until there was no free monomer. The glue was wet-coagulated and dried to obtain the multi-polymer S-8. Among them, 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.

Example 9

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.

Example 10

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.

After testing, 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.

Embodiment 11

This example is used to illustrate the preparation of halogenated branched butyl rubber.

First, in a 4L stainless steel reactor with a jacket, nitrogen was replaced three times, and 350g of dichloromethane, 150g of hexane, and 35g of multipolymer S-1 were added to the polymerization reactor, and stirred and dissolved for 60min until completely dissolved; then when the temperature dropped to -75°C, 500g of chloromethane, 500g of isobutylene, and 20g of isoprene were added in sequence, and stirred and mixed until the temperature of the polymerization system dropped to -85°C, and then 50g of chloromethane, 1.05g of sesquiethylaluminum chloride and 0.012g of HCl were mixed and aged for 50min at -90°C, and then added together to the polymerization system and stirred for reaction for 3.0h, and finally 15g of methanol was added, and the material was condensed, washed, and dried to obtain a brominated branched butyl rubber product. Among them, the mass ratio of isobutylene, isoprene and multipolymer S-1 in the preparation raw material is 100:4:7.

Sampling and analysis: Standard specimens were made and the test performance is shown in Table 1.

Example 12

First, in a 4L stainless steel reactor with a jacket, nitrogen was replaced three times, 300g of dichloromethane, 200g of hexane, and 37g of multi-polymer S-2 were added to the polymerization reactor, and stirred for 62 minutes until they were completely dissolved. Then, when the temperature is lowered to -77°C, 600g of methyl chloride, 500g of isobutylene, and 22g of isoprene are added in sequence, and the mixture is stirred until the temperature of the polymerization system drops to -86°C, and then 60g of methyl chloride, 1.13g of sesquiethylaluminum chloride, and 0.015g of HCl are mixed and aged for 52min at -92°C, and then added together into the polymerization system and stirred for reaction for 3.2h, and finally 17g of methanol is added, and the material is condensed, washed, and dried to obtain a brominated branched butyl rubber product. The mass ratio of isobutylene, isoprene, and multi-polymer S-2 in the preparation raw material is 100:4.4:7.4.

Example 13

First, in a 4L stainless steel reactor with a jacket, nitrogen was replaced 4 times, and 200g of dichloromethane, 300g of hexane, and 40g of multipolymer S-3 were added to the polymerization reactor, and stirred and dissolved for 64 minutes until completely dissolved; then when the temperature dropped to -80°C, 700g of chloromethane, 500g of isobutylene, and 24g of isoprene were added in sequence, and stirred and mixed until the temperature of the polymerization system dropped to -87°C, and then 70g of chloromethane, 1.24g of sesquiethylaluminum chloride and 0.021g of HCl were mixed and aged for 54 minutes at -94°C, and then added together to the polymerization system and stirred for reaction for 3.4 hours, and finally 19g of methanol was added, and the material was condensed, washed, and dried to obtain a brominated branched butyl rubber product. Among them, the mass ratio of isobutylene, isoprene and multipolymer S-3 in the preparation raw material is 100:4.8:8.

Embodiment 14

First, in a 4L stainless steel reactor with a jacket, nitrogen was replaced 4 times, and 700g of dichloromethane, 300g of hexane, and 43g of multipolymer S-4 were added to the polymerization reactor, and stirred and dissolved for 65min until completely dissolved; then when the temperature dropped to -81°C, 800g of chloromethane, 500g of isobutylene, and 26g of isoprene were added in sequence, and stirred and mixed until the temperature of the polymerization system dropped to -88°C, and then 80g of chloromethane, 1.36g of sesquiethylaluminum chloride and 0.035g of HCl were mixed and aged for 56min at -96°C, and then added together to the polymerization system and stirred for reaction for 3.6h, and finally 20g of methanol was added, and the material was condensed, washed, and dried to obtain a brominated branched butyl rubber product. Among them, the mass ratio of isobutylene, isoprene and multipolymer S-4 in the preparation raw material is 100:5.5:8.6.

Embodiment 15

First, in a 4L stainless steel reactor with a jacket, nitrogen was replaced 5 times, and 500g of dichloromethane, 500g of hexane, and 48g of multipolymer S-5 were added to the polymerization reactor, and stirred and dissolved for 67 minutes until completely dissolved; then when the temperature was cooled to -83°C, 900g of chloromethane, 500g of isobutylene, and 28g of isoprene were added in sequence, and stirred and mixed until the temperature of the polymerization system dropped to -89°C, and then 90g of chloromethane, 1.41g of sesquiethylaluminum chloride and 0.042g of HCl were mixed and aged for 58 minutes at -98°C, and then added together to the polymerization system and stirred for reaction for 3.9 hours, and finally 23g of methanol was added, and the material was condensed, washed, and dried to obtain a brominated branched butyl rubber product. Among them, the mass ratio of isobutylene, isoprene and multipolymer S-5 in the preparation raw material is 100:5.6:9.6.

Example 16

First, in a 4L stainless steel reactor with a jacket, nitrogen was replaced 5 times, 300g of dichloromethane, 700g of hexane, and 50g of multipolymer S-6 were added to the polymerization reactor, and stirred and dissolved for 70min until completely dissolved; then when the temperature was lowered to -85°C, 1000g of chloromethane, 500g of isobutylene, and 30g of isoprene were added in sequence, and stirred and mixed until the temperature of the polymerization system dropped to -90°C, and then 100g of chloromethane, 1.50g of sesquiethylaluminum chloride and 0.065g of HCl were mixed and aged for 60min at -100°C, and then added together to the polymerization system and stirred for reaction for 4.0h, and finally 25g of methanol was added, and the material was condensed, washed, and dried to obtain a brominated branched butyl rubber product. Among them, the mass ratio of isobutylene, isoprene and multipolymer S-6 in the preparation raw material is 100:6:10.

Embodiment 17

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.

Embodiment 18

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.

Embodiment 19

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-9 to obtain the brominated branched butyl rubber product.

Embodiment 20

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.

Comparative Example 1

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.

Comparative Example 2

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.

Comparative Example 3

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.

Table 1

From the results in Table 1, it can be seen that the monomers used to prepare the multi-copolymers in Comparative Examples 1-3 are different from those in the present invention, and therefore the effective damping temperature range, damping performance, air tightness and mechanical properties are not good. The brominated branched butyl rubber products prepared in Examples 11-20 of the present invention have a wider effective damping temperature range, better damping performance, better air tightness, and better mechanical properties than Comparative Examples 1-3.

As can be seen from FIG. 1 , 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.

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.

In the preparation process of the halogenated branched butyl rubber, no volatile organic compounds (VOC) and by-product HBr are emitted, and the preparation method is green and environmentally friendly, has a short process flow, low production cost, is suitable for industrial production, and the like.

The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

A multi-component copolymer, characterized in that 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).

wherein 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 according to claim 1, wherein 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 6 linear or branched alkyl group;

and/or, X is selected from Cl and/or Br;

and/or, n is any integer from 1 to 5;

and/or, the conjugated diene is butadiene and/or isoprene;

and/or, the mass ratio of the structural unit A, the structural unit B, the structural unit C and the structural unit derived from the conjugated diene is 100:20-50:10-25:1-5;

And/or, the mass percentage of halogen in the multi-component copolymer is 2.5-5.5%.
The multi-component copolymer according to claim 2, wherein 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 4 linear or branched alkyl group;

and/or, n is any integer from 1 to 3;

and/or, the mass ratio of the structural unit A, the structural unit B, the structural unit C and the structural unit derived from the conjugated diene is 100:30-40:15-20:2-3;

And/or, the mass percentage of halogen in the multi-component copolymer is 4-5%.
The multi-component copolymer according to claim 3, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, methyl or ethyl.
The multi-component copolymer according to claim 1, wherein R 6 is a methyl group.
The multi-polymer according to claim 1 or 2, wherein the number average molecular weight of the multi-polymer is 25,000-60,000 g/mol;

And/or, the molecular weight distribution index of the multi-polymer is 1.2-2;

And/or, the multi-polymer has an apparent viscosity of 8-40 cps at 25°C.
The multi-polymer according to claim 6, wherein the number average molecular weight of the multi-polymer is 40,000-50,000 g/mol;

And/or, the molecular weight distribution index of the multi-polymer is 1.45-1.95.
A method for preparing a multi-component copolymer, characterized in that the 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;

Adding a conjugated diene monomer to the polymer solution to perform a capping reaction to obtain the multi-component copolymer;

Wherein, 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 preparation method according to claim 8, wherein 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 6 straight or branched alkyl group;

and/or, X is selected from Cl and/or Br;

And/or, n is any integer from 1 to 5.
The preparation method according to claim 9, wherein 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 4 straight or branched alkyl group;

And/or, n is any integer from 1 to 3.
The preparation method according to claim 10, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, methyl or ethyl.
The preparation method according to claim 8, wherein R6 is methyl.
The preparation method according to claim 8, wherein the conjugated diene is butadiene and/or isoprene;

and/or, 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;

And/or, the polymerization reaction is carried out under a protective atmosphere;

and/or, the initiator is a hydrocarbon monolithium compound;

and/or, relative to 1000g of the monomer represented by formula (I), the amount of the initiator used is 16-30mmol;

and/or, the structure regulator is a polar organic compound;

And/or, the organic solvent is a hydrocarbon solvent.
The preparation method according to claim 13, wherein 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 100:30-40:15-20:2-3;

And/or, the protective atmosphere is an inert atmosphere;

And/or, the initiator is 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;

and/or, relative to 1000g of the monomer represented by formula (I), the amount of the initiator used is 18-25mmol;

and/or, the structure regulator is at least one selected from diethylene glycol dimethyl ether, tetrahydrofuran, ethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether and triethylamine;

And/or, the organic solvent is at least one of linear alkanes, aromatic hydrocarbons and cycloalkanes.
The preparation method according to claim 14, wherein 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;

And/or, the organic solvent is at least one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene.
The preparation method according to claim 8, wherein the polymerization reaction conditions include: the polymerization reaction temperature is 50-80°C, and the polymerization reaction time is 220-270min;

And/or, the end-capping reaction temperature is 60-90° C., and the end-capping reaction time is 10-45 min.
The preparation method according to claim 16, wherein the end-capping reaction temperature is 70-80°C and the end-capping reaction time is 20-30 min.
The preparation method according to claim 8, wherein the method comprises the following steps:

(1) mixing the monomer represented by formula (I), a structure regulator, an organic solvent and an initiator to undergo a first polymerization reaction to obtain a first polymerization product;

(2) adding the monomer represented by formula (II) and the structure regulator to the first polymer product to mix and cause a second polymerization reaction to obtain a second polymer product;

(3) adding the monomer represented by formula (III) and the structure regulator to the second polymer product and mixing them to cause a third polymerization reaction to obtain a third polymer product;

(4) Adding a conjugated diene to the third polymerization product to carry out a capping reaction to obtain the multi-polymer.
The preparation method according to claim 18, wherein the mass ratio of the monomer represented by formula (I) to the structure regulator in step (1) is 100:0.5-0.7;

and/or, in step (2), the mass ratio of the monomer represented by formula (II) to the structure regulator is 30-40:0.3-0.5;

and/or, in step (3), the mass ratio of the monomer represented by formula (III) to the structure regulator is 15-20:0.2-0.3;

and/or, the first polymerization reaction temperature is 40-80° C., and the first polymerization reaction time is 80-150 min;

and/or, the second polymerization reaction temperature is 60-90° C., and the second polymerization reaction time is 50-80 min;

And/or, the third polymerization reaction temperature is 60-90° C., and the third polymerization reaction time is 30-60 min.
The preparation method according to claim 19, wherein the first polymerization reaction temperature is 50-60° C., and the first polymerization reaction time is 100-120 min;

and/or, the second polymerization reaction temperature is 70-80° C., and the second polymerization reaction time is 60-70 min;

And/or, the third polymerization reaction temperature is 70-80° C., and the third polymerization reaction time is 40-50 min.
A multi-polymer obtained by the preparation method according to any one of claims 8 to 20.
Use of the multi-polymer described in any one of claims 1 to 7 and 21 as a grafting agent in the preparation of diene rubber.
The use according to claim 22, wherein the diene rubber is butyl rubber.
A halogenated branched butyl rubber, characterized in that 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 a multipolymer as described in any one of claims 1-7 or 21.
The halogenated branched butyl rubber according to claim 24, wherein the mass ratio of the structural unit I, the structural unit II and the structural unit III is 100:4-6:7-10 based on the total weight of the halogenated branched butyl rubber.
A method for preparing a halogenated branched butyl rubber according to claim 24 or 25, characterized in that the method comprises:

In the presence of a diluent, an organic solvent and a co-initiator, isobutylene, isoprene and the multi-polymer according to any one of claims 1 to 7 and 21 are contacted for cationic polymerization to obtain the halogenated branched butyl rubber.
The preparation method according to claim 26, wherein the mass ratio of isobutylene, isoprene and the multi-polymer is 100:4-6:7-10;

and/or, the diluent is a halogenated alkane;

and/or, the diluent is selected from at least one of methyl chloride, methylene chloride, carbon tetrachloride, ethylene dichloride, tetrachloropropane, heptachloropropane, methyl fluoride, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane;

and/or, the mass ratio of the isobutylene to the diluent is 100:180-320;

and/or, the organic solvent is a hydrocarbon solvent;

and/or, the co-initiator comprises an alkyl aluminum halide and a protic acid;

and/or, the molar ratio of the alkyl aluminum halide to the protonic acid in the co-initiator is 10-100:1;

And/or, the alkyl aluminum halide is at least one selected from diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloride, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, n-propylaluminum dichloride, isopropylaluminum dichloride, dimethylaluminum chloride and ethylaluminum chloride;

and/or, 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 ;

and/or, the mass ratio of the isobutylene to the co-initiator is 100:0.1-0.3;

And/or, the conditions of the cationic polymerization include: the cationic polymerization temperature is -100°C to -75°C; the cationic polymerization time is 3-4h.
The preparation method according to claim 27, wherein the halogen atom in the halogenated alkane is F, Cl or Br;

and/or, the halogenated alkane is a halogenated alkane having 1 to 4 carbon atoms;

And/or, the organic solvent is at least one of linear alkanes, aromatic hydrocarbons and cycloalkanes.
The preparation method according to claim 28, wherein the organic solvent is at least one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene.
A halogenated branched butyl rubber obtained according to the preparation method according to any one of claims 26 to 29.
Use of the halogenated branched butyl rubber as described in any one of claims 24, 25 and 30 in instrument shock absorbers and electrical shock absorbers.