Multicomponent copolymers, methods of making and using the same, and halogenated branched butyl rubber, methods of making and using the same

Abstract

The application relates to the technical field of rubber preparation, and discloses a multi-component copolymer and a preparation method and application thereof, and a halogenated branched butyl rubber and a preparation method and application thereof. The multi-component copolymer comprises structural unit A, structural unit B and structural unit C; wherein the structural unit A has the structure shown in formula (1), the structural unit B has the structure shown in formula (2), and the structural unit C has the structure shown in formula (3), wherein R1, R2, R3, R4, R5, R6, R7 and R8 are each independently hydrogen or a C1-C10 linear or branched alkyl; X is halogen, and n is any integer from 1 to 10; and the end of the multi-component copolymer contains a structural unit from a conjugated diene. 10 The application utilizes the multi-component copolymer as a grafting agent to prepare the halogenated branched butyl rubber, improves the effective damping temperature range and the stability of the damping performance of the halogenated branched butyl rubber, and improves the damping performance of the halogenated branched butyl rubber.

Description

Technical Field

[0001] This invention relates to the field of rubber preparation technology, specifically to a multi-component copolymer and its preparation method and application, and a halogenated branched butyl rubber and its preparation method and application. Background Technology

[0002] With the rapid development of modern science and technology, mechanical equipment in many fields such as high-speed rail, aerospace, naval vessels, mechanical engineering, automobiles, and electronics is trending towards high frequency and high speed. While bringing convenience to daily production and life, this has also generated a series of problems, such as high-frequency vibration and noise. These problems accelerate the fatigue damage of mechanical structural materials and shorten their service life. Therefore, vibration reduction and noise reduction have become one of the most pressing problems to be solved in today's society. Thus, developing high-performance, high-efficiency damping materials and improving their damping and vibration reduction effects is crucial for improving the operating environment of machinery and ensuring human health and safety.

[0003] Diene rubber is an unsaturated rubber containing two C=C double bonds. Major industrial products include butadiene rubber, isoprene rubber, and butyl rubber. Diene rubber is widely used in various fields of daily production and life. However, butyl rubber has a high degree of unsaturation in its molecular chain and its substituent methyl groups are symmetrically arranged. This molecular structure inevitably leads to problems such as poor ozone aging resistance, long vulcanization scorch time, low vulcanization rate, and low damping performance. As a result, butyl rubber cannot meet the increasingly diverse processing requirements and application scenarios, becoming a bottleneck for the expansion of butyl rubber materials' applications.

[0004] Brominated butyl rubber (BIIR) is obtained by introducing bromine atoms into the molecular chain of butyl rubber (IIR) through an electrophilic substitution reaction under the influence of molecular bromine. Compared to IIR, BIIR, in addition to possessing the same excellent airtightness, also exhibits better adhesion, faster vulcanization speed, and good thermal stability and corrosion resistance, enabling its use in extreme environments such as highly corrosive or high-temperature conditions. Furthermore, the introduction of bromine atoms increases the polarity of the molecular chain, leading to increased relaxation resistance and greater internal friction, resulting in excellent damping properties. Therefore, it is one of the most widely used basic damping rubbers.

[0005] In practical applications, damping functionality is often required within the temperature range of -50℃ to +50℃. However, the effective damping functional range (damping factor tanδ>0.3) of brominated butyl rubber is mainly concentrated in the low-temperature range, with low damping values ​​above 15℃. This does not adequately meet the requirements for wide-temperature-range damping materials. Therefore, expanding the effective damping functional range of butyl rubber above room temperature is one of the current research hotspots in rubber damping materials.

[0006] CN112574333A discloses a bromination process for star-branched butyl rubber. The process includes: a) dissolving star-branched butyl rubber in an aliphatic hydrocarbon to obtain a rubber solution; b) mixing the above rubber solution with a branching agent and a scavenging agent ethanol to obtain a mixture; c) adding an oxidant hydrogen peroxide and a brominating agent Br2 to the above mixture, with the molar ratio of bromine to the unsaturated double bonds in the star-branched butyl rubber being (0.75-2):1, performing a bromination reaction, and finally neutralizing and recovering the product to obtain brominated star-branched butyl rubber.

[0007] CN106749816A discloses a method for preparing brominated butyl rubber. The method first dissolves butyl rubber in n-alkane, then uses specific organic bromides such as phenyltrimethyltribromoamine, benzyltrimethyltribromoamine, or dibromoisocyanuric acid as brominating agents, and Br2 or HBr as bromination accelerators to carry out the bromination reaction in a solvent, thereby obtaining brominated butyl rubber.

[0008] Liao Mingyi et al. (Journal of Dalian Maritime University, 2008, 34(2):83-86) disclosed a stepwise method to improve 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, thus preparing a wide-temperature-range, high-damping butyl rubber material.

[0009] Although existing technologies such as blending, copolymerization, and interpenetrating polymer networks can broaden the effective damping temperature range of rubber and improve its damping performance to some extent, these methods still have certain limitations. They can lead to problems such as decreased mechanical properties of rubber materials, complex processes, difficult practical operation, large addition amounts, high costs, and difficulty in removing organic solvents, resulting in environmental pollution.

[0010] 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 whose preparation method is easy to operate and pollution-free. Summary of the Invention

[0011] The purpose of this invention is to overcome the problems of existing rubber materials that cannot simultaneously possess a wide effective damping temperature range, high damping performance, and good mechanical properties, as well as the pollution caused by complex preparation. This invention provides a multi-component copolymer and its preparation method and application, as well as halogenated branched butyl rubber and its preparation method and application.

[0012] To achieve the above objectives, a first aspect of the present invention provides a multi-component copolymer, wherein the multi-component copolymer comprises: structural unit A, structural unit B, and structural unit C; wherein structural unit A has the structure shown in formula (1), structural unit B has the structure shown in formula (2), and structural unit C has the structure shown in formula (3).

[0013]

[0014] Among them, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently hydrogen or C1-C. 10 Straight-chain or branched alkyl groups; X is a halogen, and n is any integer from 1 to 10;

[0015] The ends of the multi-component copolymer contain structural units derived from conjugated dienes.

[0016] A second aspect of the present invention provides a method for preparing a multi-component copolymer, wherein the method comprises: under polymerization reaction conditions, in the presence of an initiator, an optional structure modifier and an organic solvent, performing a polymerization reaction on a monomer shown in formula (I), a monomer shown in formula (II) and a monomer shown in formula (III) to obtain a polymer solution;

[0017]

[0018] The multi-component copolymer is obtained by adding a conjugated diene monomer to the polymer solution and carrying out an end-capping reaction.

[0019] Among them, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently hydrogen or C1-C. 10 Straight-chain or branched alkyl groups; X is a halogen, and n is any integer from 1 to 10.

[0020] A third aspect of the present invention provides a multi-component copolymer obtained by the aforementioned preparation method.

[0021] A fourth aspect of the present invention provides the application of the aforementioned multi-component copolymer as a grafting agent in the preparation of diene rubber.

[0022] A fifth aspect of the present invention provides a halogenated branched butyl rubber, wherein the halogenated branched butyl rubber comprises: structural unit I from isobutylene, structural unit II from isoprene, and structural unit III from a halogenated grafting agent; wherein the halogenated grafting agent is the aforementioned multi-component copolymer.

[0023] The sixth aspect of the present invention provides a method for preparing the aforementioned halogenated branched butyl rubber, wherein the method comprises: cationicly polymerizing isobutylene, isoprene and the aforementioned multi-component copolymer in the presence of a diluent, an organic solvent and a co-initiator to obtain the halogenated branched butyl rubber.

[0024] The seventh aspect of the present invention provides a halogenated branched butyl rubber obtained by the aforementioned preparation method.

[0025] The eighth aspect of the present invention provides the application of the aforementioned halogenated branched butyl rubber in instrument dampers and electrical dampers.

[0026] The beneficial technical effects achieved by the present invention through the above technical solution are as follows:

[0027] (1) The multi-component copolymer provided by this invention combines p-alkylphenyl, p-haloalkylphenyl, and ester groups on a single macromolecular chain to form an interpenetrating polymer network (IPN). This results in p-alkylphenyl, halogen atoms, and ester groups exhibiting high rigidity, large steric hindrance, and strong adsorption. When this multi-component copolymer is used as a halogenation grafting agent to prepare halogenated branched butyl rubber, it can produce a significant "synergistic effect" in broadening the effective damping temperature range of halogenated branched butyl rubber. This greatly expands the effective damping temperature range of halogenated branched butyl rubber, enabling the preparation of rubbers with an effective damping temperature range (tanδ≥0.3) exceeding -50℃ to 62℃ and tanδ... max It is a wide-temperature-range, high-damping halogenated branched butyl rubber with a resistance of 1.9 or higher.

[0028] (2) In the multi-component copolymer of the present invention, the p-alkylphenyl, p-haloalkylphenyl and ester groups are arranged on the molecular chain, thereby generating the superposition of "group effect" and "structural effect". When the multi-component copolymer is used as a halogenation grafting agent to prepare halogenated branched butyl rubber, it not only avoids the decrease in damping performance of halogenated branched butyl rubber due to the widening of the effective damping temperature range, but also avoids the problem of decreased mechanical properties and air tightness of butyl rubber due to the widening of molecular weight distribution caused by branching, thus improving the tensile strength and air tightness of butyl rubber.

[0029] (3) The halogenated branched butyl rubber prepared by the present invention is generated by addition polymerization using a multi-component copolymer as a grafting agent, rather than by ionic substitution, which blocks the conditions for halogen structural isomerization, improves the effective damping temperature range and damping performance stability of the halogenated branched butyl rubber, and broadens the application range of the halogenated branched butyl rubber.

[0030] (4) In the preparation process of halogenated branched butyl rubber, there is no emission of volatile organic compounds (VOC) and by-product HBr. The preparation method is green and environmentally friendly, with a short process flow, low production cost, and is suitable for industrial production. Attached Figure Description

[0031] Figure 1 These are the dynamic mechanical spectra of the brominated branched butyl rubber product (curve #1) prepared in Example 11 of the present invention and the existing brominated butyl rubber (BIIR) 2302 (curve #2). Detailed Implementation

[0032] The endpoints and any values ​​of the ranges disclosed herein 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 the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0033] The first aspect of the present invention provides a multi-component copolymer, wherein the multi-component copolymer comprises: structural unit A, structural unit B, and structural unit C; wherein structural unit A has the structure shown in formula (1), structural unit B has the structure shown in formula (2), and structural unit C has the structure shown in formula (3).

[0034]

[0035] Among them, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently hydrogen or C1-C. 10 Straight-chain or branched alkyl groups; X is a halogen, and n is any integer from 1 to 10;

[0036] The ends of the multi-component copolymer contain structural units derived from conjugated dienes.

[0037] The multi-component copolymer of the present invention simultaneously contains p-alkylphenyl, p-haloalkylphenyl and ester groups to form an interpenetrating polymer network (IPN), which makes the p-alkylphenyl, halogen atoms and ester groups have the characteristics of high rigidity, large steric hindrance and strong adsorption. Furthermore, the ends of the copolymer contain conjugated diene structural units, which makes the multi-component copolymer have high polymerization activity and can be used as a grafting agent to prepare branched diene rubber, particularly for the preparation of halogenated branched diene rubber.

[0038] In this invention, the C1-C 10 Examples of straight-chain or branched alkyl groups include, for example, 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.

[0039] In this invention, the value of n in the structure shown in formula (1) can be selected as 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0040] In some embodiments of the present invention, R1, R2, R3, R4, R5, R6, R7 and R8 are each independently hydrogen or a straight-chain or branched alkyl group of C1-C6, preferably hydrogen or a straight-chain or branched alkyl group of C1-C4, more preferably hydrogen, methyl or ethyl.

[0041] In some preferred embodiments of the present invention, R6 is methyl.

[0042] In some preferred embodiments of the present invention, X is selected from Cl and / or Br.

[0043] In some preferred embodiments of the present invention, n is any integer from 1 to 5, preferably any integer from 1 to 3.

[0044] In some preferred embodiments of the present invention, the conjugated diene is butadiene and / or isoprene.

[0045] In some preferred embodiments of the present invention, the structural unit shown in formula (1) may be a structural unit derived from p-bromomethylstyrene, the structural unit shown in 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 shown in formula (3) may be a structural unit derived from unsaturated acrylates, such as methyl methacrylate (MMA), ethyl methacrylate, butyl methacrylate or tert-butyl methacrylate.

[0046] In this invention, the multi-component copolymer is a block copolymer or a random copolymer.

[0047] In some embodiments of the present invention, the mass ratio of structural unit A, structural unit B, structural unit C, and structural unit 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-component copolymer meets the above range, it is possible to provide an effective damping temperature range (tanδ≥0.3) exceeding -50°C to 62°C and a maximum damping factor tanδ. max Wide-temperature-range high-damping brominated branched butyl rubber with a tensile strength of ≥1.9 and 22MPa-24MPa.

[0048] The above ratios can be determined by infrared spectroscopy and nuclear magnetic resonance, or based on the feeding relationship during preparation.

[0049] In some preferred embodiments of the present invention, the halogen content in the multi-component copolymer is 2.5-5.5% by mass, for example 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, and any value within any range of any two of the above values, preferably 4-5%. When the halogen content in the multi-component copolymer meets the above range, the damping properties and vulcanization processability of butyl rubber can be improved. In this invention, the halogen content is determined using a Q600 TG / DTG thermogravimetric analyzer.

[0050] In some embodiments of the present invention, the number-average molecular weight (Mn) of the multi-component copolymer 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.

[0051] In some preferred embodiments of the present invention, the molecular weight distribution index (Mw / Mn) of the multi-component copolymer 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.

[0052] In this invention, both the number-average molecular weight and the molecular weight distribution index are tested using gel chromatography.

[0053] In some embodiments of the present invention, the apparent viscosity of the multi-component copolymer at 25°C is 8-40 cps.

[0054] In this invention, the apparent viscosity of the multi-component copolymer at 25°C was tested using an Ubbelohde viscometer according to GB / T 10247-2008.

[0055] A second aspect of the present invention provides a method for preparing a multi-component copolymer, wherein the method comprises: under polymerization reaction conditions, in the presence of an initiator, an optional structure modifier and an organic solvent, performing a polymerization reaction on a monomer shown in formula (I), a monomer shown in formula (II) and a monomer shown in formula (III) to obtain a polymer solution;

[0056]

[0057] The multi-component copolymer is obtained by adding a conjugated diene monomer to the polymer solution and carrying out an end-capping reaction.

[0058] Among them, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently hydrogen or C1-C. 10 Straight-chain or branched alkyl groups; X is a halogen, and n is any integer from 1 to 10.

[0059] In this invention, the above-mentioned preparation method has the characteristics of complete reaction, no by-product generation, stable structure of the prepared multi-component copolymer, and regular molecular chain arrangement.

[0060] In some embodiments of the present invention, R1, R2, R3, R4, R5, R6, R7 and R8 are each independently hydrogen or a straight-chain or branched alkyl group of C1-C6, preferably hydrogen or a straight-chain or branched alkyl group of C1-C4, more preferably hydrogen, methyl or ethyl.

[0061] In some preferred embodiments of the present invention, R6 is methyl.

[0062] In some preferred embodiments of the present invention, X is selected from Cl and / or Br.

[0063] In some preferred embodiments of the present invention, n is any integer from 1 to 5, preferably any integer from 1 to 3.

[0064] C1-C as described in the second aspect of the present invention 10 Examples of straight-chain or branched alkyl groups are described in the first aspect of the present invention above, and will not be repeated here.

[0065] 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.

[0066] In some embodiments of the present invention, the conjugated diene is butadiene and / or isoprene.

[0067] In some preferred embodiments of the present invention, the mass ratio of the monomer shown in formula (I), the monomer shown in formula (II), the monomer shown in 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, by controlling the mass ratio of the monomer shown in formula (I), the monomer shown in formula (II), the monomer shown in formula (III), and the conjugated diene within a specific range, an effective damping temperature range (tanδ≥0.3) exceeding -50℃ to 62℃ can be obtained; the maximum damping factor tanδ max Butyl rubber with a viscosity of ≥1.9.

[0068] In some preferred embodiments of the present invention, the polymerization reaction is carried out under a protective atmosphere, preferably an inert atmosphere.

[0069] In some preferred embodiments of the present invention, the initiator is a hydrocarbon-based monolithium compound, preferably RLi, wherein R is selected from C1-C1. 20 Saturated aliphatic hydrocarbon groups, C3-C 20 Alicyclic hydrocarbon groups and C6-C 20 At least one of the aromatic groups.

[0070] In some preferred embodiments of the present invention, the initiator is selected from at least one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthium lithium, cyclohexyllithium, and dodecyllithium. In the present invention, selecting the above-mentioned initiator allows the monomers to undergo anionic polymerization to form block copolymers, thereby achieving a synergistic effect of "structural effect" and "group effect".

[0071] In some preferred embodiments of the present invention, the amount of initiator relative to 1000g of the monomer shown in formula (I) is 16-30 mmol, preferably 18-25 mmol. Insufficient initiator results in a smaller molecular weight of the prepared multi-component copolymer, which affects the wide temperature range and damping properties of butyl rubber during application, failing to achieve the desired modification effect; excessive initiator leads to a wider molecular weight distribution of the prepared multi-component copolymer, causing a decrease in the airtightness and mechanical strength of the butyl rubber.

[0072] In some preferred embodiments of the present invention, the structure modifier is a polar organic compound.

[0073] The structure modifier described in this invention is a polar organic compound that can produce a solvation effect in the polymerization system, thereby adjusting the reactivity ratio of alkylstyrene and isoprene and enabling them to undergo block copolymerization.

[0074] In some preferred embodiments of the present invention, the structure modifier is selected from at least one of diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, and triethylamine.

[0075] In some preferred embodiments of the present invention, the organic solvent is a hydrocarbon solvent, preferably at least one of straight-chain alkanes, aromatics and cycloalkanes, and more preferably at least one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene.

[0076] In some embodiments, the polymerization reaction conditions include a polymerization temperature of 50-80°C, such as 50°C, 60°C, 70°C, 80°C, or any value within the range of any two of the above values. If the polymerization temperature is too low, the reactivity decreases, the reaction rate slows down, and the reaction becomes incomplete, failing to achieve the wide temperature range and high damping modification effect of butyl rubber in application. If the polymerization temperature is too high, the reactivity increases, the reaction rate increases, and the molecular structure becomes irregular, resulting in a decrease in the strength and airtightness of butyl rubber in application.

[0077] The polymerization reaction time is 220-270 min, for example, 220 min, 230 min, 240 min, 250 min, 260 min, 270 min, or 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 will not be achieved in application; if the polymerization reaction time is too long, the energy consumption will be too high, and no significant effect will be achieved in terms of the wide temperature range and high damping modification of butyl rubber in application.

[0078] 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, or 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, resulting in fewer reactive sites and a lower grafting rate, thus hindering the modification of the butyl rubber's wide temperature range and damping properties. If the end-capping reaction temperature is too high, the conjugated diene is prone to self-polymerization, failing to achieve the end-capping effect. The end-capping reaction time is 10-45 min, for example, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, preferably 20-30 min. If the end-capping reaction time is too short, the end-capping will be incomplete, resulting in fewer reactive sites. As a result, the wide temperature range and high damping modification effect of butyl rubber cannot be achieved in application. If the end-capping reaction time is too long, the flexibility of the prepared multi-component copolymer segments will increase, which will damage the damping properties and mechanical strength of butyl rubber in application.

[0079] In some embodiments of the present invention, the method includes the following steps:

[0080] (1) The monomer, structure modifier, solvent and initiator shown in formula (I) are mixed to carry out the first polymerization reaction to obtain the first polymerization product;

[0081] (2) Add the monomer and structure modifier shown in formula (II) to the first polymerization product and mix to carry out a second polymerization reaction to obtain the second polymerization product;

[0082] (3) Add the monomer and structure modifier shown in formula (III) to the second polymerization product and mix to carry out the third polymerization reaction to obtain the third polymerization product;

[0083] (4) Add a conjugated diene to the third polymerization product to conduct an end-capping reaction, thereby obtaining the multi-component copolymer.

[0084] In the above preparation method of the present invention, anionic polymerization is used to obtain triblock multi-component copolymers with controllable structure, stable bromine structure, high isotacticity, complete reaction, and no by-products. This can bring about the effect of wide applicable temperature range, high damping, excellent mechanical strength and vulcanization processability of halogenated branched diene rubber.

[0085] In some preferred embodiments of the present invention, the mass ratio of the monomer to the structure modifier shown in formula (I) in step (1) is 100:0.5-0.7, for example 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 to the structure modifier shown in formula (I) within the above range, block polymers with high isotacticity can be produced.

[0086] In some preferred embodiments of the present invention, the mass ratio of the monomer to the structure modifier shown in formula (II) in step (2) is 30-40:0.3-0.5, for example 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 to the structure modifier shown in formula (II) within the above range, block polymers with high isotacticity can be produced.

[0087] In some preferred embodiments of the present invention, the mass ratio of the monomer to the structure modifier shown in formula (III) in step (3) is 15-20:0.2-0.3, for example 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 to the structure modifier shown in formula (III) within the above range, block polymers with high isotacticity can be produced.

[0088] 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, or 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 80-150 min, for example, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min, 150 min, or any value within the range of any two of the above values, preferably 100-120 min. If the first polymerization reaction time is too short, the molecular weight will decrease, and the bromine content will be low; if the first polymerization reaction time is too long, the change in molecular weight will be insignificant, and the modification effect will be insignificant.

[0089] 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, or 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 airtightness; if the second polymerization reaction temperature is too high, the damping modification effect will be insignificant. The second polymerization reaction time is 50-80 min, for example, 50 min, 55 min, 60 min, 65 min, 70 min, 75 min, 80 min, or any value within the range of any two of the above values, preferably 60-70 min. If the second polymerization reaction time is too short, the molecular weight will decrease, the benzene ring structure will decrease, and the increase in damping will be small; if the second polymerization reaction time is too long, energy consumption will be high, the benzene ring structure will not change significantly, and the increase in damping will not change significantly.

[0090] 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, or 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 content of polar ester groups will be too low, resulting in a narrowing of the damping temperature range of butyl rubber during application; if the third polymerization reaction temperature is too high, the widening of the applicable temperature range of butyl rubber during application will not be significant. The third polymerization reaction time is 30-60 min, for example, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, or any value within the range of any two of the above values, preferably 40-50 min. If the third polymerization reaction time is too short, the content of polar ester groups will be too low, and the wide-temperature-range modification effect of butyl rubber will not be achieved during application; if the third polymerization reaction time is too long, the widening of the applicable temperature range of butyl rubber during application will not be significant.

[0091] According to a particularly preferred embodiment of the present invention, under an inert atmosphere, an organic solvent, p-bromomethylstyrene, and a structure modifier are sequentially added to a polymerization reactor. After heating to 50-60°C, an initiator is added and the reaction proceeds for 100-120 min. Subsequently, p-alkylstyrene and the structure modifier are added to the polymerization reactor, and the temperature is raised to 70-80°C, and the reaction proceeds for 60-70 min. Then, unsaturated acrylate and the structure modifier are added to the polymerization reactor, and the reaction proceeds for 40-50 min. Finally, isoprene is added to the polymerization reactor for end-capping, and the reaction proceeds for 20-30 min until no free monomers are present. The resulting solution is then wet-coagulated and dried to obtain the aforementioned multi-component copolymer.

[0092] The mass ratio of p-bromomethylstyrene, p-alkylstyrene, unsaturated acrylate and isoprene is 100:30-40:15-20:2-3.

[0093] The mass ratio of p-bromomethylstyrene to the structure modifier is 100:0.5-0.7;

[0094] The mass ratio of alkylstyrene to structure modifier is 30-40:0.3-0.5;

[0095] The mass ratio of unsaturated acrylate to structure modifier is 15-20:0.2-0.3.

[0096] A third aspect of the present invention provides a multi-component copolymer obtained by the aforementioned preparation method.

[0097] A fourth aspect of the present invention provides the application of the aforementioned multi-component copolymer as a grafting agent in the preparation of diene rubber.

[0098] In some embodiments of the present invention, the diene rubber is butyl rubber.

[0099] 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;

[0100] The halogenated grafting agent is the aforementioned multi-component copolymer.

[0101] In some embodiments of the present invention, based on the total weight of the halogenated branched butyl rubber, the mass ratio of structural unit I, structural unit II, and 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, by controlling the mass ratio of structural unit I, structural unit II, and structural unit III within a specific range, an effective damping temperature range (tanδ≥0.3) exceeding -50℃ to 62℃ can be obtained; the maximum damping factor tanδ max Butyl rubber with a tensile strength of ≥1.9 and 22MPa-24MPa.

[0102] The multi-component copolymer provided by this invention combines p-alkylphenyl, p-haloalkylphenyl, and ester groups on a single macromolecular chain to form an interpenetrating polymer network (IPN). This results in the p-alkylphenyl, halogen atoms, and ester groups exhibiting high rigidity, large steric hindrance, and strong adsorption. When this multi-component copolymer is used as a halogenation grafting agent to prepare halogenated branched butyl rubber, it produces a significant "synergistic effect" in broadening the effective damping temperature range of halogenated branched butyl rubber. This greatly expands the effective damping temperature range of halogenated branched butyl rubber, enabling the preparation of rubbers with an effective damping temperature range (tanδ≥0.3) exceeding -50℃ to 62℃. max It is a wide-temperature-range, high-damping halogenated branched butyl rubber with a resistance of 1.9 or higher.

[0103] A sixth aspect of the present invention provides a method for preparing the aforementioned halogenated branched butyl rubber, wherein the method comprises:

[0104] In the presence of a diluent, an organic solvent, and a co-initiator, isobutylene, isoprene, and the aforementioned multi-component copolymer are subjected to cationic polymerization to obtain the halogenated branched butyl rubber.

[0105] The halogenated branched butyl rubber prepared by this invention is generated through addition polymerization using a multi-component copolymer as a grafting agent, rather than through ionic substitution. This process blocks the conditions for halogen structural isomerization, improves the effective damping temperature range and the stability of damping performance of the halogenated branched butyl rubber, and broadens its application range. The effective damping temperature range (tanδ) of the halogenated branched butyl rubber prepared by this invention is... max ≥0.3) Exceeding the range of -50℃ to 62℃.

[0106] In addition, there is no emission of volatile organic compounds (VOCs) or byproduct HBr during the preparation process. The preparation method is green and environmentally friendly, with a short process flow, low production cost, and is suitable for industrial production.

[0107] In some embodiments of the present invention, the mass ratio of isobutylene, isoprene, and the aforementioned multi-component copolymer 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, controlling the mass ratio of isobutylene, isoprene, and the aforementioned multi-component copolymer within a specific range can effectively ensure the complete reaction of the multi-component copolymer in the preparation reaction of butyl rubber.

[0108] In some preferred embodiments of the present invention, the diluent is a haloalkane, wherein the halogen atom in the haloalkane is preferably F, Cl or Br, and the number of carbon atoms in the haloalkane is preferably 1-4, for example 1, 2, 3 or 4.

[0109] In some preferred embodiments of the present invention, the diluent is selected from at least one of chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, fluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.

[0110] In some preferred embodiments of the present invention, the mass ratio of isobutylene to the diluent is 100:180-320, for example 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, by controlling the mass ratio of isobutylene to the diluent within a specific range, high molecular weight butyl rubber can be prepared.

[0111] In some preferred embodiments of the present invention, the organic solvent is a hydrocarbon solvent, preferably at least one of straight-chain alkanes, aromatics and cycloalkanes, and more preferably at least one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene.

[0112] There are no particular limitations on the amount of organic solvent used; it can be added according to the conventional amounts used in this field.

[0113] In some preferred embodiments of the present invention, the co-initiator includes alkyl aluminum halide and protic acid.

[0114] In some preferred embodiments of the present invention, the molar ratio of the alkyl aluminum halide to the protic 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 of any two of the above values.

[0115] In some preferred embodiments of the present invention, the alkyl aluminum halide is selected from at least one of diethylaluminum chloride, diisobutylaluminum chloride, dichloromethylaluminum, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, dichloro-n-propylaluminum, dichloroisopropylaluminum, dimethylaluminum chloride, and ethylaluminum chloride.

[0116] In some preferred embodiments of the present invention, the protic acid is selected from at least one of HCl, HF, HBr, H2SO4, H2CO3, H3PO4 and HNO3.

[0117] In some preferred embodiments of the present invention, the mass ratio of 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.

[0118] In some preferred embodiments of the present invention, the conditions for cationic polymerization include: a cationic polymerization temperature of -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 of any two of the above values. If the cationic polymerization temperature is too low, the reaction time will be too long, making structural control difficult; if the cationic polymerization temperature is too high, chain transfer reactions will occur, leading to a decrease in molecular weight. The cationic polymerization time is 3-4 hours, for example 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, and any value within the range of any two of the above values. If the cationic polymerization time is too short, the molecular weight will be too small; if the cationic polymerization time is too long, structural instability will occur.

[0119] In this invention, a terminator can be added to obtain the halogenated branched butyl rubber by discharge. The terminator described in this invention can be selected from at least one of methanol, ethanol, and butanol.

[0120] According to a particularly preferred embodiment of the present invention, a mixed solvent (V) is added to the polymerization reactor under an inert atmosphere. (稀释剂) :V (溶剂) The 70-30 / 30-70) and the aforementioned multi-component copolymer were stirred and dissolved for 60-70 minutes until the multi-component copolymer was completely dissolved. Then, the temperature was lowered to -85℃ to -75℃, and the diluent, isobutylene and isoprene were added in sequence. The mixture was stirred and mixed until the temperature of the polymerization system dropped to -90℃ to -85℃. Then, the diluent and co-initiator were mixed and aged at -100℃ to -90℃ for 50-60 minutes, and then added to the polymerization system and stirred for 3-4 hours. Finally, the terminator was added, and the mixture was discharged, coagulated, washed, and dried to obtain halogenated branched butyl rubber.

[0121] The mass ratio of isobutylene, isoprene, and the multi-component copolymer is 100:4-6:7-10.

[0122] The mass ratio of isobutylene to diluent is 100:180-320;

[0123] The mass ratio of isobutylene to co-initiator is 100:0.1-0.3.

[0124] The seventh aspect of the present invention provides a halogenated branched butyl rubber obtained by the aforementioned preparation method.

[0125] The eighth aspect of the present invention provides the application of the aforementioned halogenated branched butyl rubber in instrument dampers and electrical dampers.

[0126] The halogenated branched butyl rubber of this invention not only solves the problem of the widening of the effective damping temperature range of halogenated branched butyl rubber, which leads to a decrease in damping performance, but also improves the tensile strength and air tightness of halogenated branched butyl rubber. It can be fully applied in electromechanical devices, such as instrument dampers and electrical dampers, which require wide temperature range damping performance.

[0127] The present invention will be described in detail below through embodiments.

[0128] Unless otherwise specified in the following examples and comparative examples, conditions were performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments used, unless otherwise specified, were all commercially available products. The mass ratio of each structural unit in the resulting multi-component copolymer product and the halogenated branched butyl rubber was determined based on the amount of raw materials fed.

[0129] (1) Source of raw materials:

[0130] Isobutylene and isoprene: Polymer grade, from Zhejiang Xinhui New Material Co., Ltd.

[0131] p-Methylstyrene: Polymer grade, from Jiande Langfeng Chemical Co., Ltd.

[0132] p-Butylstyrene: Polymer grade, from Luoyang Boyu Energy Technology Co., Ltd.

[0133] p-Bromomethylstyrene: Polymer grade, from Hubei Shuangyan Chemical Co., Ltd.

[0134] Methyl methacrylate (MMA): from Tianjin Chemical Reagent Factory No. 2

[0135] n-Butyllithium: 98% purity, sourced from Nanjing Tonglian Chemical Co., Ltd.

[0136] Sesquiethylaluminum chloride: 98% purity, from Bailingwei Technology Co., Ltd.

[0137] All other reagents are commercially available industrial products.

[0138] (2) Analysis and testing methods:

[0139] Number-average molecular weight and Mn distribution index (Mw / Mn) were determined using a Waters 2414 gel permeation chromatography (GPC) system. A polystyrene standard was used as the calibration curve. The mobile phase was tetrahydrofuran, the column temperature was 40℃, 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 .

[0140] Bromine content determination: Weigh 10 mg of sample and use a Q600 TG / DTG thermogravimetric analyzer at a heating rate of 10℃ / min in a nitrogen atmosphere with a flow rate of 50 mL / min to perform thermal degradation of the sample. The first stage of thermal degradation involves the debromination of bromine-containing units in the sample to form HBr. The bromine content (X) in the sample is then inferred from the percentage of HBr removed, using the following formula:

[0141]

[0142] In the formula: Y - percentage content of the sample at 220℃; 79.904 - relative atomic mass of bromine; 1.008 - relative atomic mass of hydrogen.

[0143] Apparent viscosity was determined using an Ubbelohde viscometer according to GB / T 10247-2008.

[0144] Air tightness determination: An automated air tightness tester was used to determine the air permeability number according to ISO 2782:1995. The test gas was N2, the test temperature was 23℃, and the test sample was an 8cm diameter circular seaweed sheet with a thickness of 1mm.

[0145] Dynamic mechanical analysis (DMA): Measurements were performed in tensile mode on a Netzsch 242C dynamic mechanical analyzer (Germany). Sample dimensions were 10 mm long, 6 mm wide, and 2 mm thick. The temperature range was -90 °C to 90 °C, with a heating rate of 3 °C / min. Data were analyzed at a frequency of 10 Hz.

[0146] Tensile strength: The method specified in standard GB / T528-2009 shall be applied.

[0147] Example 1

[0148] This example illustrates the preparation of multi-component copolymers.

[0149] First, in a jacketed 15L stainless steel reactor, argon gas was purged three times. Then, 3000g hexane, 1000g p-bromomethylstyrene, and 5.0g THF were added sequentially to the polymerization reactor. The temperature was raised to 50℃, and 18.5 mmol of n-butyllithium was added to initiate the reaction for 100 min. Next, 300g p-methylstyrene and 3.0g THF were added, and the temperature was raised to 70℃, reacting for 60 min. Then, 150g MMA and 2.0g THF were added, reacting for 40 min. Finally, 20g isoprene was added to the polymerization reactor for end-capping reaction for 20 min, until no free monomers remained. The resulting solution was wet-coagulated and dried to obtain the multi-component copolymer S-1. The mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA, and isoprene was 100:30:15:2.

[0150] Tests showed that the Mn content of the multi-component copolymer S-1 was 40100, the Mw / Mn ratio was 1.45, the bromine content was 4.05%, and the apparent viscosity at 25°C was 8 cps.

[0151] Example 2

[0152] This example illustrates the preparation of multi-component copolymers.

[0153] First, in a jacketed 15L stainless steel reactor, argon gas was purged three times. Then, 3100g hexane, 1000g p-bromomethylstyrene, and 5.4g THF were added sequentially to the polymerization reactor. The temperature was raised to 52℃, and 19.3 mmol of n-butyllithium was added to initiate the reaction for 105 min. Next, 310g p-methylstyrene and 3.5g THF were added, and the temperature was raised to 72℃, reacting for 62 min. Then, 160g MMA and 2.2g THF were added, reacting for 42 min. Finally, 22g isoprene was added, and a capping reaction was initiated for 21 min until no free monomers remained. The resulting solution was wet-coagulated and dried to obtain the multi-component copolymer S-2. The mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA, and isoprene was 100:31:16:2.2.

[0154] Tests showed that the Mn content of the multi-component copolymer S-2 was 42300, the Mw / Mn ratio was 1.51, the bromine content was 4.21%, and the apparent viscosity at 25°C was 11.2 cps.

[0155] Example 3

[0156] This example illustrates the preparation of multi-component copolymers.

[0157] First, in a jacketed 15L stainless steel reactor, argon gas was purged four times. Then, 3300g hexane, 1000g p-bromomethylstyrene, and 5.7g THF were added sequentially to the polymerization reactor. The temperature was raised to 55℃, and 21.5 mmol of n-butyllithium was added to initiate the reaction for 110 min. Next, 330g p-methylstyrene and 4.0g THF were added, and the temperature was raised to 74℃, reacting for 64 min. Then, 170g MMA and 2.4g THF were added, reacting for 44 min. Finally, 24g isoprene was added, and a capping reaction was initiated for 23 min until no free monomers remained. The resulting solution was wet-coagulated and dried to obtain the multi-component copolymer S-3. The mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA, and isoprene was 100:33:17:2.4.

[0158] Tests showed that the Mn content of the multi-component copolymer S-3 was 45100, the Mw / Mn ratio was 1.63, the bromine content was 4.48%, and the apparent viscosity at 25°C was 14.5 cps.

[0159] Example 4

[0160] This example illustrates the preparation of multi-component copolymers.

[0161] First, in a jacketed 15L stainless steel reactor, argon gas was purged four times. Then, 3500g hexane, 1000g p-bromomethylstyrene, and 6.0g THF were added sequentially to the polymerization reactor. The temperature was raised to 57℃, and 22.6 mmol of n-butyllithium was added to initiate the reaction for 113 min. Next, 360g p-methylstyrene and 4.4g THF were added, and the temperature was raised to 76℃, reacting for 66 min. Then, 180g MMA and 2.6g THF were added, reacting for 46 min. Finally, 25g isoprene was added, and a capping reaction was initiated for 25 min until no free monomers remained. The resulting solution was wet-coagulated and dried to obtain the multi-component copolymer S-4. The mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA, and isoprene was 100:36:18:2.5.

[0162] Tests showed that the Mn content of the multi-component copolymer S-4 was 46,500, the Mw / Mn ratio was 1.76, the bromine content was 4.62%, and the apparent viscosity at 25°C was 20.5 cps.

[0163] Example 5

[0164] This example illustrates the preparation of multi-component copolymers.

[0165] First, in a jacketed 15L stainless steel reactor, argon gas was purged five times. Then, 3700g of hexane, 1000g of p-bromomethylstyrene, and 6.5g of THF were added sequentially. The temperature was raised to 59℃, and 23.4 mmol of n-butyllithium was added to initiate the reaction for 115 min. Next, 380g of p-methylstyrene and 4.8g of THF were added, and the temperature was raised to 78℃, reacting for 68 min. Then, 190g of MMA and 2.8g of THF were added, reacting for 48 min. Finally, 27g of isoprene was added, and a capping reaction was initiated for 27 min until no free monomers remained. The resulting solution was wet-coagulated and dried to obtain the multi-component copolymer S-5. The mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA, and isoprene was 100:38:19:2.7.

[0166] Tests showed that the Mn content of the multi-component copolymer S-5 was 48900, the Mw / Mn ratio was 1.87, the bromine content was 4.85%, and the apparent viscosity at 25°C was 24.1 cps.

[0167] Example 6

[0168] This example illustrates the preparation of multi-component copolymers.

[0169] First, in a jacketed 15L stainless steel reactor, argon gas was purged five times. Then, 4000g hexane, 1000g p-bromomethylstyrene, and 7.0g THF were added sequentially to the polymerization reactor. The temperature was raised to 60℃, and 24.8 mmol of n-butyllithium was added to initiate the reaction for 120 min. Next, 400g p-n-butylstyrene and 5.0g THF were added, and the temperature was raised to 80℃, reacting for 70 min. Then, 200g MMA and 3.0g THF were added, reacting for 50 min. Finally, 30g isoprene was added, and a sealing reaction was initiated for 30 min until no free monomers remained. The resulting solution was wet-coagulated and dried to obtain the multi-component copolymer S-6. The mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA, and isoprene was 100:40:20:30.

[0170] Tests showed that the Mn content of the multi-component copolymer S-6 was 49,700, the Mw / Mn ratio was 1.95, the bromine content was 4.98%, and the apparent viscosity at 25°C was 29.1 cps.

[0171] Example 7

[0172] This example illustrates the preparation of multi-component copolymers.

[0173] First, in a jacketed 15L stainless steel reactor, nitrogen was purged five times. Then, 4000g hexane, 1000g p-bromomethylstyrene, and 7.0g THF were added sequentially to the polymerization reactor. The temperature was raised to 40℃, and 16 mmol of n-butyllithium was added to initiate the reaction for 80 min. Next, 200g p-n-butylstyrene and 5.0g THF were added, and the temperature was raised to 60℃, reacting for 50 min. Then, 100g MMA and 3.0g THF were added, reacting for 30 min. Finally, 10g isoprene was added, and a sealing reaction was initiated for 10 min until no free monomers remained. The resulting solution was wet-coagulated and dried to obtain the multi-component copolymer S-7. The mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA, and isoprene was 100:20:20:1.

[0174] Tests showed that the Mn content of the multi-component copolymer S-7 was 25,000, the Mw / Mn ratio was 1.2, the bromine content was 2.5%, and the apparent viscosity at 25°C was 35.4 cps.

[0175] Example 8

[0176] This example illustrates the preparation of multi-component copolymers.

[0177] First, in a jacketed 15L stainless steel reactor, argon gas was purged five times. Then, 4000g hexane, 1000g p-bromomethylstyrene, and 7.0g THF were added sequentially to the polymerization reactor. The temperature was raised to 80℃, and 30mmol of n-butyllithium was added to initiate the reaction for 150min. Next, 500g p-n-butylstyrene and 5.0g THF were added, and the temperature was raised to 90℃, reacting for 80min. Then, 250g MMA and 3.0g THF were added, reacting for 60min. Finally, 50g isoprene was added, and the reaction was capped for 45min until no free monomers remained. The resulting solution was wet-coagulated and dried to obtain the multi-component copolymer S-8. The mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA, and isoprene was 100:50:25:5.

[0178] Tests showed that the multi-component copolymer S-8 has a Mn content of 60,000, a Mw / Mn ratio of 2, a bromine content of 5.5%, and an apparent viscosity of 40.0 cps at 25°C.

[0179] Example 9

[0180] This example illustrates the preparation of multi-component copolymers.

[0181] The multi-component copolymer was prepared according to the method of Example 1, except that 5g of isoprene was added during the preparation process to obtain multi-component copolymer S-9. The mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA, and isoprene was 100:30:15:0.5.

[0182] Tests showed that the Mn content of the multi-component copolymer S-9 was 39900, the Mw / Mn ratio was 1.43, the bromine content was 4.09%, and the apparent viscosity at 25°C was 8.5 cps.

[0183] Example 10

[0184] This example illustrates the preparation of multi-component copolymers.

[0185] The multi-component copolymer was prepared according to the method of Example 1, except that 60g of isoprene was added during the preparation process to obtain multi-component copolymer S-10. The mass ratio of p-bromomethylstyrene, p-methylstyrene, MMA, and isoprene was 100:30:15:6.

[0186] Tests showed that the Mn content of the multi-component copolymer S-10 was 41000, the Mw / Mn ratio was 1.51, the bromine content was 4.01%, and the apparent viscosity at 25°C was 8.9 cps.

[0187] Example 11

[0188] This embodiment illustrates the preparation of halogenated branched butyl rubber.

[0189] First, in a jacketed 4L stainless steel reactor, nitrogen was purged three times. Then, 350g of dichloromethane, 150g of hexane, and 35g of the multi-component copolymer S-1 were added to the polymerization reactor and stirred for 60 minutes until completely dissolved. Next, the temperature was lowered to -75℃, and then 500g of monochloromethane, 500g of isobutylene, and 20g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -85℃. Then, 50g of monochloromethane, 1.05g of sesquiethylaluminum chloride, and 0.012g of HCl were mixed and aged at -90℃ for 50 minutes, and then added to the polymerization system. The mixture was stirred and reacted for 3.0 hours. Finally, 15g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain the brominated branched butyl rubber product. The mass ratio of isobutylene, isoprene, and multi-component copolymer S-1 in the raw materials was 100:4:7.

[0190] Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0191] Example 12

[0192] This embodiment illustrates the preparation of halogenated branched butyl rubber.

[0193] First, in a jacketed 4L stainless steel reactor, nitrogen was purged three times. Then, 300g of dichloromethane, 200g of hexane, and 37g of the multi-component copolymer S-2 were added to the polymerization reactor and stirred for 62 minutes until completely dissolved. Next, the temperature was lowered to -77℃, and then 600g of monochloromethane, 500g of isobutylene, and 22g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -86℃. Then, 60g of monochloromethane, 1.13g of sesquiethylaluminum chloride, and 0.015g of HCl were mixed and aged at -92℃ for 52 minutes, and then added to the polymerization system. The mixture was stirred and reacted for 3.2 hours. Finally, 17g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain the brominated branched butyl rubber product. The mass ratio of isobutylene, isoprene, and multi-component copolymer S-2 in the raw materials was 100:4.4:7.4.

[0194] Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0195] Example 13

[0196] This embodiment illustrates the preparation of halogenated branched butyl rubber.

[0197] First, in a jacketed 4L stainless steel reactor, nitrogen was purged four times. Then, 200g of dichloromethane, 300g of hexane, and 40g of the multi-component copolymer S-3 were added to the polymerization reactor and stirred for 64 minutes until completely dissolved. Next, the temperature was lowered to -80℃, and then 700g of monochloromethane, 500g of isobutylene, and 24g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -87℃. Then, 70g of monochloromethane, 1.24g of sesquiethylaluminum chloride, and 0.021g of HCl were mixed and aged at -94℃ for 54 minutes, and then added to the polymerization system. The mixture was stirred and reacted for 3.4 hours. Finally, 19g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain the brominated branched butyl rubber product. The mass ratio of isobutylene, isoprene, and multi-component copolymer S-3 in the raw materials was 100:4.8:8.

[0198] Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0199] Example 14

[0200] This embodiment illustrates the preparation of halogenated branched butyl rubber.

[0201] First, in a jacketed 4L stainless steel reactor, nitrogen was purged four times. Then, 700g of dichloromethane, 300g of hexane, and 43g of the multi-component copolymer S-4 were added to the polymerization reactor and stirred for 65 minutes until completely dissolved. Next, the temperature was lowered to -81℃, and then 800g of monochloromethane, 500g of isobutylene, and 26g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -88℃. Then, 80g of monochloromethane, 1.36g of sesquiethylaluminum chloride, and 0.035g of HCl were mixed and aged at -96℃ for 56 minutes, and then added to the polymerization system. The mixture was stirred and reacted for 3.6 hours. Finally, 20g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain the brominated branched butyl rubber product. The mass ratio of isobutylene, isoprene, and multi-component copolymer S-4 in the raw materials was 100:5.5:8.6.

[0202] Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0203] Example 15

[0204] This embodiment illustrates the preparation of halogenated branched butyl rubber.

[0205] First, in a jacketed 4L stainless steel reactor, nitrogen was purged five times. Then, 500g of dichloromethane, 500g of hexane, and 48g of the multi-component copolymer S-5 were added to the polymerization reactor and stirred for 67 minutes until completely dissolved. Next, the temperature was lowered to -83℃, and then 900g of monochloromethane, 500g of isobutylene, and 28g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -89℃. Then, 90g of monochloromethane, 1.41g of sesquiethylaluminum chloride, and 0.042g of HCl were mixed and aged at -98℃ for 58 minutes, and then added to the polymerization system. The mixture was stirred and reacted for 3.9 hours. Finally, 23g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain the brominated branched butyl rubber product. The mass ratio of isobutylene, isoprene, and multi-component copolymer S-5 in the raw materials was 100:5.6:9.6.

[0206] Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0207] Example 16

[0208] This embodiment illustrates the preparation of halogenated branched butyl rubber.

[0209] First, in a jacketed 4L stainless steel reactor, nitrogen was purged five times. Then, 300g of dichloromethane, 700g of hexane, and 50g of the multi-component copolymer S-6 were added to the polymerization reactor and stirred for 70 minutes until completely dissolved. Next, the temperature was lowered to -85℃, and then 1000g of monochloromethane, 500g of isobutylene, and 30g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -90℃. Then, 100g of monochloromethane, 1.50g of sesquiethylaluminum chloride, and 0.065g of HCl were mixed and aged at -100℃ for 60 minutes, and then added to the polymerization system. The mixture was stirred and reacted for 4.0 hours. Finally, 25g of methanol was added, and the mixture was discharged, coagulated, washed, and dried to obtain the brominated branched butyl rubber product. The mass ratio of isobutylene, isoprene, and multi-component copolymer S-6 in the raw materials was 100:6:10.

[0210] Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0211] Example 17

[0212] Halogenated branched butyl rubber was prepared according to the method of Example 11, except that the multi-component copolymer S-1 was replaced with multi-component copolymer S-7 to obtain the brominated branched butyl rubber product.

[0213] Example 18

[0214] Halogenated branched butyl rubber was prepared according to the method of Example 11, except that the multi-component copolymer S-1 was replaced with multi-component copolymer S-8 to obtain the brominated branched butyl rubber product.

[0215] Example 19

[0216] Halogenated branched butyl rubber was prepared according to the method of Example 11, except that the multi-component copolymer S-1 was replaced with multi-component copolymer S-9 to obtain the brominated branched butyl rubber product.

[0217] Example 20

[0218] Halogenated branched butyl rubber was prepared according to the method of Example 11, except that the multi-component copolymer S-1 was replaced with multi-component copolymer S-10 to obtain the brominated branched butyl rubber product.

[0219] Comparative Example 1

[0220] The multi-component copolymer was prepared according to the method of Example 1, except that p-bromomethylstyrene was replaced with methylallyl bromide to obtain multi-component copolymer D-1.

[0221] Halogenated branched butyl rubber was prepared according to the method of Example 11, except that the multi-component copolymer S-1 was replaced with multi-component copolymer D-1 to obtain the brominated branched butyl rubber product.

[0222] Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0223] Comparative Example 2

[0224] The multi-component copolymer was prepared according to the method of Example 3, except that p-bromomethylstyrene was not added during the preparation process to obtain multi-component copolymer D-2.

[0225] Halogenated branched butyl rubber was prepared according to the method of Example 13, except that the multi-component copolymer S-3 was replaced with multi-component copolymer D-2 to obtain the brominated branched butyl rubber product.

[0226] Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0227] Comparative Example 3

[0228] The multi-component copolymer was prepared according to the method of Example 4, except that MMA was not added during the preparation process to obtain multi-component copolymer D-3.

[0229] Halogenated branched butyl rubber was prepared according to the method of Example 14, except that the multi-component copolymer S-4 was replaced with multi-component copolymer D-3 to obtain the brominated branched butyl rubber product.

[0230] Sampling and analysis: Standard samples were prepared, and the test performance is shown in Table 1.

[0231] Table 1

[0232]

[0233] As can be seen from the results in Table 1, the monomers used to prepare the multi-component copolymers in Comparative Examples 1-3 are different from those in this invention, resulting in poor performance in terms of effective damping temperature range, damping performance, airtightness, and mechanical properties. The brominated branched butyl rubber products prepared in Examples 11-20 of this invention have a wider effective damping temperature range, better damping performance, better airtightness, and better mechanical properties compared to Comparative Examples 1-3.

[0234] Figure 1 The dynamic mechanical spectra of the brominated branched butyl rubber product (curve #1) prepared in Example 11 of the present invention and the existing brominated butyl rubber (BIIR) 2302 (curve #2) are shown.

[0235] Depend on Figure 1 It can be seen that the brominated branched butyl rubber product prepared in Example 11 of the present invention has a larger damping factor in a wider effective damping temperature range compared with the existing brominated butyl rubber (BIIR) 2302.

[0236] The halogenated branched butyl rubber prepared by this invention is generated by addition polymerization using a multi-component copolymer as a grafting agent, rather than by ionic substitution. This blocks the conditions for halogen structural isomerization, improves the effective damping temperature range and the stability of damping performance of the halogenated branched butyl rubber, and broadens the application range of the halogenated branched butyl rubber.

[0237] The present invention produces no volatile organic compounds (VOCs) or byproduct HBr during the preparation of halogenated branched butyl rubber. The preparation method is green and environmentally friendly, with a short process flow, low production cost, and is suitable for industrial production.

[0238] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A multi-component copolymer, characterized in that, The multi-component copolymer includes: structural unit A, structural unit B, and structural unit C; wherein structural unit A has the structure shown in formula (1), structural unit B has the structure shown in formula (2), and structural unit C has the structure shown in formula (3). Equation (1) Equation (2) Equation (3) Among them, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently hydrogen or C1-C. 10 Straight-chain or branched alkyl groups; X is a halogen, and n is any integer from 1 to 10; The ends of the multi-component copolymer contain structural units derived from conjugated dienes.

2. The multi-component copolymer according to claim 1, wherein, R1, R2, R3, R4, R5, R6, R7 and R8 are each independently hydrogen or C1-C6 straight-chain or branched alkyl groups.

3. The multi-component copolymer according to claim 2, wherein, R1, R2, R3, R4, R5, R6, R7 and R8 are each independently hydrogen or C1-C4 straight-chain or branched alkyl groups.

4. The multi-component copolymer according to claim 2, wherein, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently hydrogen, methyl, or ethyl.

5. The multi-component copolymer according to claim 2, wherein, R6 is a methyl group.

6. The multi-component copolymer according to claim 1, wherein, X is selected from Cl and / or Br.

7. The multi-component copolymer according to claim 1, wherein, n is any integer from 1 to 5.

8. The multi-component copolymer according to claim 7, wherein, n is any integer from 1 to 3.

9. The multi-component copolymer according to claim 1, wherein, The conjugated diene is butadiene and / or isoprene.

10. The multi-component copolymer according to claim 1, wherein, The mass ratio of structural unit A, structural unit B, structural unit C and structural unit from conjugated diene is 100:20-50:10-25:1-5.

11. The multi-component copolymer according to claim 10, wherein, The mass ratio of structural unit A, structural unit B, structural unit C and structural unit from conjugated diene is 100:30-40:15-20:2-3.

12. The multi-component copolymer according to claim 1, wherein, The mass percentage of halogen in the multi-component copolymer is 2.5-5.5%.

13. The multi-component copolymer according to claim 1, wherein, The halogen content in the multi-component copolymer is 4-5% by mass.

14. The multi-component copolymer according to claim 1 or 2, wherein, The number-average molecular weight of the multi-component copolymer is 25,000-60,000 g / mol.

15. The multi-component copolymer according to claim 1 or 2, wherein, The number-average molecular weight of the multi-component copolymer is 40,000-50,000 g / mol.

16. The multi-component copolymer according to claim 1 or 2, wherein, The molecular weight distribution index of the multi-component copolymer is 1.2-2.

17. The multi-component copolymer according to claim 16, wherein, The molecular weight distribution index of the multi-component copolymer is 1.45-1.

95.

18. The multi-component copolymer according to claim 1 or 2, wherein, The apparent viscosity of the multi-component copolymer at 25°C is 8-40 cps.

19. A method for preparing a multi-component copolymer, characterized in that, The preparation method includes: under polymerization reaction conditions, in the presence of an initiator, an optional structure modifier and an organic solvent, performing a polymerization reaction on the monomers shown in formula (I), formula (II) and formula (III) to obtain a polymer solution; Formula (I) Equation (II) Equation (III) The multi-component copolymer is obtained by adding a conjugated diene monomer to the polymer solution and carrying out an end-capping reaction. Among them, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently hydrogen or C1-C. 10 Straight-chain or branched alkyl groups; X is a halogen, and n is any integer from 1 to 10.

20. The preparation method according to claim 19, wherein, R1, R2, R3, R4, R5, R6, R7 and R8 are each independently hydrogen or C1-C6 straight-chain or branched alkyl groups.

21. The preparation method according to claim 20, wherein, R1, R2, R3, R4, R5, R6, R7 and R8 are each independently hydrogen or C1-C4 straight-chain or branched alkyl groups.

22. The preparation method according to claim 21, wherein, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently hydrogen, methyl, or ethyl.

23. The preparation method according to claim 19, wherein, R6 is a methyl group.

24. The preparation method according to claim 19, wherein, X is selected from Cl and / or Br.

25. The preparation method according to claim 19, wherein, n is any integer from 1 to 5.

26. The preparation method according to claim 25, wherein, n is any integer from 1 to 3.

27. The preparation method according to any one of claims 19-26, wherein, The conjugated diene is butadiene and / or isoprene.

28. The preparation method according to any one of claims 19-26, wherein, The mass ratio of the monomer shown in formula (I), the monomer shown in formula (II), the monomer shown in formula (III), and the conjugated diene is 100:20-50:10-25:1-5.

29. The preparation method according to claim 28, wherein, The mass ratio of the monomer shown in formula (I), the monomer shown in formula (II), the monomer shown in formula (III), and the conjugated diene is 100:30-40:15-20:2-3.

30. The preparation method according to any one of claims 19-26, wherein, The polymerization reaction is carried out under a protective atmosphere, which is an inert atmosphere.

31. The preparation method according to any one of claims 19-26, wherein, The initiator is a hydrocarbon-based monolithium compound.

32. The preparation method according to claim 31, wherein, The initiator is RLi, wherein R is selected from C1-C. 20 saturated aliphatic hydrocarbon groups, C3-C 20 Alicyclic hydrocarbon groups and C6-C 20 At least one of the aromatic groups.

33. The preparation method according to claim 32, wherein, The initiator is selected from at least one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthalenelithium, cyclohexyllithium, and dodecyllithium.

34. The preparation method according to any one of claims 19-26, wherein, The amount of the initiator is 16-30 mmol relative to 1000 g of the monomer shown in formula (I).

35. The preparation method according to claim 34, wherein, The amount of the initiator is 18-25 mmol relative to 1000 g of the monomer shown in formula (I).

36. The preparation method according to any one of claims 19-26, wherein, The structure modifier is a polar organic compound.

37. The preparation method according to claim 36, wherein, The structure modifier is selected from at least one of diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, and triethylamine.

38. The preparation method according to any one of claims 19-26, wherein, The organic solvent is a hydrocarbon solvent.

39. The preparation method according to claim 38, wherein, The organic solvent is at least one of straight-chain alkanes, aromatics, and cycloalkanes.

40. The preparation method according to claim 39, wherein, The organic solvent is at least one selected from pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.

41. The preparation method according to any one of claims 19-26, wherein, The conditions for the polymerization reaction include: a polymerization temperature of 50-80℃ and a polymerization time of 220-270 min.

42. The preparation method according to any one of claims 19-26, wherein, The end-capping reaction temperature is 60-90℃, and the end-capping reaction time is 10-45 min.

43. The preparation method according to claim 42, wherein, The end-capping reaction temperature is 70-80℃; the end-capping reaction time is 20-30 min.

44. The preparation method according to any one of claims 19-26, wherein, The method includes the following steps: (1) The monomer, structure modifier, organic solvent and initiator shown in formula (I) are mixed to carry out the first polymerization reaction to obtain the first polymerization product; (2) Add the monomer and structure modifier shown in formula (II) to the first polymerization product and mix to carry out a second polymerization reaction to obtain the second polymerization product; (3) Add the monomer and structure modifier shown in formula (III) to the second polymerization product and mix to carry out the third polymerization reaction to obtain the third polymerization product; (4) Add a conjugated diene to the third polymerization product to carry out the end-capping reaction to obtain the multi-component copolymer.

45. The preparation method according to claim 44, wherein, In step (1), the mass ratio of the monomer to the structure modifier shown in formula (I) is 100:0.5-0.

7.

46. ​​The preparation method according to claim 44, wherein, In step (2), the mass ratio of the monomer to the structure modifier shown in formula (II) is 30-40:0.3-0.

5.

47. The preparation method according to claim 44, wherein, In step (3), the mass ratio of the monomer to the structure modifier shown in formula (III) is 15-20:0.2-0.

3.

48. The preparation method according to claim 44, wherein, The first polymerization reaction temperature is 40-80℃, and the first polymerization reaction time is 80-150 min.

49. The preparation method according to claim 48, wherein, The first polymerization reaction temperature is 50-60℃; the first polymerization reaction time is 100-120 min.

50. The preparation method according to claim 44, wherein, The second polymerization reaction temperature is 60-90℃; the second polymerization reaction time is 50-80 min.

51. The preparation method according to claim 50, wherein, The second polymerization reaction temperature is 70-80℃; the second polymerization reaction time is 60-70 min.

52. The preparation method according to claim 44, wherein, The third polymerization reaction temperature is 60-90℃; the third polymerization reaction time is 30-60 min.

53. The preparation method according to claim 52, wherein, The third polymerization reaction temperature is 70-80℃; the third polymerization reaction time is 40-50 min.

54. A multi-component copolymer obtained by the preparation method according to any one of claims 19-53.

55. The use of the multi-component copolymer according to any one of claims 1-18 and 54 as a grafting agent in the preparation of diene rubber.

56. The application according to claim 55, wherein, The diene rubber is butyl rubber.

57. A halogenated branched butyl rubber, characterized in that, The halogenated branched butyl rubber comprises: structural unit I from isobutylene, structural unit II from isoprene, and structural unit III from a halogenated grafting agent; Wherein, the halogenated grafting agent is a multi-component copolymer as described in any one of claims 1-18 or 54.

58. The halogenated branched butyl rubber according to claim 57, wherein, Based on the total weight of the halogenated branched butyl rubber, the mass ratio of structural unit I, structural unit II, and structural unit III is 100:4-6:7-10.

59. A method for preparing halogenated branched butyl rubber according to claim 57 or 58, characterized in that, The method includes: In the presence of a diluent, an organic solvent, and a co-initiator, isobutylene, isoprene, and the multi-component copolymer described in any one of claims 1-18 and 54 are subjected to cationic polymerization to obtain the halogenated branched butyl rubber.

60. The preparation method according to claim 59, wherein, The mass ratio of isobutylene, isoprene, and the multi-component copolymer is 100:4-6:7-10.

61. The preparation method according to claim 59, wherein, The diluent is a haloalkane, wherein the halogen atom in the haloalkane is F, Cl or Br.

62. The preparation method according to claim 61, wherein, The haloalkane is a haloalkane with 1-4 carbon atoms.

63. The preparation method according to claim 62, wherein, The diluent is selected from at least one of chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, fluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.

64. The preparation method according to claim 59, wherein, The mass ratio of isobutylene to the diluent is 100:180-320.

65. The preparation method according to claim 59, wherein, The organic solvent is a hydrocarbon solvent.

66. The preparation method according to claim 65, wherein, The organic solvent is at least one of straight-chain alkanes, aromatics, and cycloalkanes.

67. The preparation method according to claim 66, wherein, The organic solvent is at least one selected from pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.

68. The preparation method according to claim 59, wherein, The co-initiators include alkyl aluminum halides and protic acids.

69. The preparation method according to claim 68, wherein, The molar ratio of the alkyl aluminum halide to the protic acid in the co-initiator is 10-100:

1.

70. The preparation method according to claim 68, wherein, The alkyl aluminum halide is selected from at least one of diethylaluminum chloride, diisobutylaluminum chloride, dichloromethylaluminum, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, dichloro-n-propylaluminum, dichloroisopropylaluminum, dimethylaluminum chloride, and ethylaluminum chloride.

71. The preparation method according to claim 68, wherein, The protic acid is selected from at least one of HCl, HF, HBr, H2SO4, H2CO3, H3PO4, and HNO3.

72. The preparation method according to claim 59, wherein, The mass ratio of isobutylene to the co-initiator is 100:0.1-0.

3.

73. The preparation method according to claim 59, wherein, The conditions for the cationic polymerization include: a cationic polymerization temperature of -100℃ to -75℃; and a cationic polymerization time of 3-4 hours.

74. A halogenated branched butyl rubber obtained by the preparation method according to any one of claims 59-73.

75. The use of the halogenated branched butyl rubber according to any one of claims 57, 58 and 74 in instrument dampers and electrical dampers.

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