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, a preparation method and application thereof, and halogenated branched butyl rubber, a preparation method and application thereof. The multi-component copolymer has a general formula shown in formula (I): R1, R2 and R3 are polymer chain segments, and the terminal contains a structural unit from a conjugated diene; R1 contains a styrene structural unit and a butadiene structural unit; R2 contains the chain segment shown in the formula; R3 contains the chain segment shown in the formula; wherein, is a styrene chain segment, and X is halogen. The multi-component copolymer is used as a grafting agent to prepare halogenated branched butyl rubber, the saturation degree of the halogenated branched butyl rubber can be improved, the extrusion swelling effect can be significantly reduced, the vulcanization speed, the ozone aging resistance and the air tightness can be improved, and the balance among the aging resistance, the product size stability and the vulcanization processing performance of the high-branched and high-saturation halogenated branched butyl rubber is achieved.

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 halogenated branched butyl rubber and its preparation method and application. Background Technology

[0002] Butyl rubber (IIR) is a cationic copolymer made from isobutylene and a small amount of isoprene. It possesses excellent airtightness and damping properties, and is widely used in the manufacture of inner tubes, airtight layers, and vulcanizing bladders for automotive tires, making it one of the most important synthetic rubber varieties. High-saturation butyl rubber's molecular chains are mainly composed of carbon-carbon single bonds, with low unsaturation (only about 0.5-1.5%), resulting in extremely low air permeability and excellent ozone resistance. This allows it to be used in the airtight layers of heavy-duty tires operating in harsh environments and under demanding conditions, as well as in medical applications. However, high-saturation butyl rubber also suffers from drawbacks such as high molecular chain isotacticity, high crystallinity, poor viscoelasticity, and slow vulcanization speed. These drawbacks lead to low vulcanization efficiency, poor vulcanization performance, and a tendency for excessive flow and deformation during processing, which has become a bottleneck restricting its entry into high-end applications.

[0003] Therefore, it is urgent to solve the problems of significant extrusion swelling effect, long vulcanization scorch time, low vulcanization speed and poor ozone aging resistance of butyl rubber during processing. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems of existing butyl rubber, such as significant extrusion swelling effect, long vulcanization scorch time, low vulcanization speed and poor ozone aging resistance, and to provide a multi-component copolymer and its preparation method and application, as well as halogenated branched butyl rubber and its preparation method and application.

[0005] To achieve the above objectives, a first aspect of the present invention provides a multi-component copolymer having the general formula shown in formula (I):

[0006]

[0007] R1, R2 and R3 are polymer chain segments, and their ends contain structural units from conjugated dienes.

[0008] R1 contains styrene structural units and butadiene structural units;

[0009] R2 contains the chain segment shown in equation (II), wherein, The connection position between the chain segment and the benzene ring shown in formula (II) is indicated;

[0010]

[0011] R3 contains the chain segment shown in equation (III), wherein, The connection position between the chain segment and the benzene ring shown in formula (III);

[0012]

[0013] In equations (II) and (III), X is a styrene segment, and X is a halogen.

[0014] A second aspect of the present invention provides a method for preparing a multi-component copolymer, wherein the preparation method includes:

[0015] (1-1) In the presence of a first initiator, isoprene undergoes a first polymerization reaction, the resulting first polymerization product undergoes a second polymerization reaction with styrene, and the resulting second polymerization product undergoes a first halogenation reaction in the presence of a second initiator and a halogenating agent to obtain product a;

[0016] (1-2) Butadiene undergoes a third polymerization reaction in the presence of a first initiator. The resulting third polymerization product undergoes a fourth polymerization reaction with styrene. The resulting fourth polymerization product undergoes a second halogenation reaction in the presence of a second initiator and a halogenating agent to obtain product b.

[0017] (1-3) In the presence of the first initiator, styrene and butadiene undergo a fifth polymerization reaction to obtain product c;

[0018] (2) In the presence of a coupling agent, the products a, b and c are subjected to a coupling reaction, and the coupling reaction products are subjected to a capping reaction with a conjugated diene to obtain the multi-component copolymer;

[0019] The coupling agent has the general formula described in formula (IV):

[0020]

[0021] Among them, R 1 R 2 and R 3 Each is independently selected from F, Cl, or Br.

[0022] A third aspect of the present invention provides a multi-component copolymer prepared by the method described in the second aspect above.

[0023] The fourth aspect of the present invention provides the application of the multi-component copolymer described in the first or third aspect above as a grafting agent in the preparation of diene rubber.

[0024] The fifth aspect of the present invention provides a halogenated branched butyl rubber, wherein the halogenated branched butyl rubber comprises: a structural unit A derived from isobutylene, a structural unit B derived from isoprene, and a structural unit C derived from a grafting agent;

[0025] The grafting agent is a multi-component copolymer as described in the first or third aspect above.

[0026] The sixth aspect of the present invention provides a method for preparing halogenated branched butyl rubber, wherein the method comprises: subjecting isobutylene, isoprene and grafting agent to cationic polymerization in the presence of a diluent, a solvent and a co-initiator to obtain the halogenated branched butyl rubber;

[0027] The grafting agent is a multi-component copolymer as described in the first or third aspect above.

[0028] The seventh aspect of the present invention provides a halogenated branched butyl rubber prepared by the method described in the sixth aspect above.

[0029] The eighth aspect of the present invention provides the application of the halogenated branched butyl rubber described in the fifth or seventh aspect above in tires and medical stoppers.

[0030] Through the above technical solution, the present invention can achieve the following beneficial effects:

[0031] (1) The multi-component copolymer provided by the present invention combines -BR- segments, -IR- segments, -PS- segments and -SBR- segments with different structures on a macromolecular chain to form a "tri-hetero-arm" star structure with a stable secondary halogen substitution structure. The secondary halogen substitution structure is obtained by adding halogenating agent to the unsaturated "double bonds" in the -BR- segments and -IR- segments, and significantly reduces the content of unsaturated "double bonds". When this multi-component copolymer is used as a grafting agent to prepare halogenated branched butyl rubber, its different segment properties, "tri-hetero-arm" star structure and stable secondary halogen substitution structure work together to improve the saturation of butyl rubber, significantly reduce the extrusion swelling effect, greatly improve the vulcanization speed, ozone aging resistance and air tightness, and achieve a balance between the aging properties, product dimensional stability and vulcanization processing performance of highly branched and highly saturated halogenated branched butyl rubber.

[0032] (2) The multi-component copolymer provided by the present invention has no volatile organic compounds (VOCs) and by-product hydrogen halide emissions during the preparation process. It has the characteristics of green and environmentally friendly preparation method, short process flow, controllable secondary halogen substitution structure, and suitability for industrial production. As a grafting agent in the preparation of diene rubber, it can significantly broaden the application range of halogenated branched butyl rubber. Detailed Implementation

[0033] 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.

[0034] A first aspect of the present invention provides a multi-component copolymer having the general formula shown in formula (I):

[0035]

[0036] R1, R2 and R3 are polymer chain segments, and their ends contain structural units from conjugated dienes.

[0037] R1 contains styrene structural units and butadiene structural units;

[0038] R2 contains the chain segment shown in equation (II), wherein, The connection position between the chain segment and the benzene ring shown in formula (II) is indicated;

[0039]

[0040] R3 contains the chain segment shown in equation (III), wherein, The connection position between the chain segment and the benzene ring shown in formula (III);

[0041]

[0042] In equations (II) and (III), X is a styrene segment, and X is a halogen.

[0043] According to the present invention, in the multi-component copolymer, the styrene structural unit and butadiene structural unit contained in R1 can be obtained by random copolymerization of styrene and 1,3-butadiene; the segment represented by R2 contains a block obtained by halogenating isoprene homopolymer block with a halogenating agent and a styrene homopolymer block; the segment represented by R3 contains a block obtained by halogenating 1,3-butadiene homopolymer block with a halogenating agent and a styrene homopolymer block. The above-mentioned segments with different structures are respectively connected to the 1, 3, and 5 positions of the benzene ring structure to form a "tri-hetero-arm" star structure, while having a stable secondary halogen substitution structure. Furthermore, the ends of the copolymer contain structural units from the conjugated diene, which makes the multi-component copolymer have high polymerization activity and can be used as a grafting agent to prepare branched diene rubber. In particular, when used to prepare halogenated branched diene rubber, it can improve the saturation of butyl rubber, significantly reduce the extrusion swell effect, and greatly improve the vulcanization speed, ozone aging resistance, and air tightness.

[0044] According to the present invention, in formulas (II) and (III), n and m represent repeated blocks, and the present invention does not impose any particular limitation on the values ​​of n and m.

[0045] According to the present invention, in the multi-component copolymer, the molar ratio of R1:R2:R3:phenyl is (1-4):(2-9):(2-9):0.1. When the molar ratio of the above structures in the multi-component copolymer meets this range, a multi-component copolymer having the "tri-hetero-arm" star structure can be synthesized.

[0046] According to the present invention, the content of structural units derived from conjugated dienes at the ends of the multi-component copolymer is 0.25-1 wt%, preferably 0.3-0.9 wt%. When the content of structural units derived from conjugated dienes in the multi-component copolymer meets the above range, the multi-component copolymer can have high polymerization activity, which is beneficial for use as a grafting agent to polymerize with diene monomers such as isobutylene and isoprene to obtain halogenated branched diene rubber.

[0047] In this invention, the proportion and content of each of the above-mentioned structures in the multi-component copolymer can be determined by infrared spectroscopy or nuclear magnetic resonance, or calculated based on the feeding relationship during the preparation process.

[0048] According to the present invention, the halogen content in the multi-component copolymer is 10-30 wt%, preferably 15-25 wt%. When the halogen content in the multi-component copolymer meets the above range, the halogenated branched diene rubber obtained by polymerization using the multi-component copolymer as a grafting agent can have a high halogen content.

[0049] In this invention, the halogen content in the multi-component copolymer is determined using a thermogravimetric analyzer.

[0050] According to the present invention, in the chain segments shown in formula (II) and formula (III), X is selected from F, Cl or Br, preferably Cl or Br, and more preferably Br.

[0051] According to the present invention, the conjugated diene is selected from butadiene and / or isoprene.

[0052] According to the present invention, the number average molecular weight of the multi-component copolymer is 80,000-90,000 g / mol, preferably 83,000-87,000 g / mol.

[0053] According to the present invention, the molecular weight distribution index (Mw / Mn) of the multi-component copolymer is 9-11, preferably 9.3-10.3.

[0054] In this invention, the number-average molecular weight and molecular weight distribution index are determined by gel chromatography.

[0055] A second aspect of the present invention provides a method for preparing a multi-component copolymer, wherein the preparation method includes:

[0056] (1-1) In the presence of a first initiator, isoprene undergoes a first polymerization reaction, the resulting first polymerization product undergoes a second polymerization reaction with styrene, and the resulting second polymerization product undergoes a first halogenation reaction in the presence of a second initiator and a halogenating agent to obtain product a;

[0057] (1-2) Butadiene undergoes a third polymerization reaction in the presence of a first initiator. The resulting third polymerization product undergoes a fourth polymerization reaction with styrene. The resulting fourth polymerization product undergoes a second halogenation reaction in the presence of a second initiator and a halogenating agent to obtain product b.

[0058] (1-3) In the presence of the first initiator, styrene and butadiene undergo a fifth polymerization reaction to obtain product c;

[0059] (2) In the presence of a coupling agent, the products a, b and c are subjected to a coupling reaction, and the coupling reaction products are subjected to a capping reaction with a conjugated diene to obtain the multi-component copolymer;

[0060] The coupling agent has the general formula described in formula (IV):

[0061]

[0062] Among them, R 1 R 2 and R 3 Each is independently selected from F, Cl, or Br.

[0063] In this invention, the above-mentioned preparation method is used to combine -BR-, -IR-, -PS-, and -SBR- segments with different structures onto a macromolecular chain using a coupling agent 1,3,5-trihalobenzene, forming a "tri-hetero-arm" star structure. During the preparation process, a stable secondary halogen-substituted structure is obtained by halogenation with a halogenating agent. Finally, a conjugated diene structural unit is introduced to end-cap the copolymer, giving it high polymerization activity. It can be used as a high-performance grafting agent for the preparation of halogenated branched butyl rubber. The preparation method of the multi-component copolymer has no by-product hydrogen halide emission during implementation, making it green and environmentally friendly with a simple process flow.

[0064] According to the present invention, in the method for preparing the multi-component copolymer, the first polymerization reaction, the second polymerization reaction, the third polymerization reaction, the fourth polymerization reaction, the first halogenation reaction, the second halogenation reaction, the coupling reaction, and the end-capping reaction are all carried out in the presence of a solvent. Further, the first polymerization reaction, the third polymerization reaction, and the fifth polymerization reaction are preferably carried out in the presence of a structure-regulating agent; the first halogenation reaction and the second halogenation reaction are preferably carried out in the presence of a molecular weight regulator.

[0065] According to the present invention, a three-reactor polymerization method is preferably adopted, that is, steps (1-1), (1-2) and (1-3) are carried out in three separate reactors, as detailed below:

[0066] According to the present invention, in step (1-1), based on a total amount of halogenating agent of 100 parts by weight in the preparation method of the multi-component copolymer, the amount of each raw material fed in step (1-1) satisfies the following: solvent 100-200 parts by weight, isoprene 30-40 parts by weight, styrene 20-30 parts by weight, structure modifier 0.1-0.3 parts by weight, first initiator 0.05-0.2 parts by weight, halogenating agent 50-60 parts by weight, molecular weight modifier 0.2-0.5 parts by weight, and second initiator 0.1-0.4 parts by weight.

[0067] According to the present invention, in step (1-1), for the operation of the first polymerization reaction, the second polymerization reaction and the first halogenation reaction, the raw materials are prepared according to the proportions described above. Inert gas is introduced into the first reaction vessel to remove oxygen. Then, solvent, isoprene and structure modifier are added. The temperature is raised to the temperature required for the first polymerization reaction and the first initiator is added to carry out the first polymerization reaction. After the first polymerization reaction is completed, styrene and structure modifier are added to the first reaction vessel. The temperature is raised to the temperature required for the second polymerization reaction and the second polymerization reaction is carried out. After the second polymerization reaction is completed, halogenating agent and molecular weight modifier are added to the first reaction vessel. The temperature is raised to the temperature required for the first halogenation reaction and the second initiator is added to initiate the first halogenation reaction. After the reaction is completed, product a is obtained.

[0068] According to the present invention, the temperature of the first polymerization reaction is 40-50°C, preferably 43-47°C. If the temperature of the first polymerization reaction is too low, the polymerization will be incomplete, resulting in a low molecular weight of the first polymerization product; if the temperature of the first polymerization reaction is too high, the molecular structure of the first polymerization product will change. The time of the first polymerization reaction is 20-30 min, preferably 23-27 min. If the time of the first polymerization reaction is too short, the polymerization will be incomplete, resulting in a low molecular weight of the first reaction product; if the time of the first polymerization reaction is too long, the preparation cost will increase.

[0069] According to the present invention, the temperature of the second polymerization reaction is 60-70°C, preferably 63-67°C. If the temperature of the second polymerization reaction is too low, the polymerization will be incomplete, resulting in a low molecular weight of the second polymerization product; if the temperature of the second polymerization reaction is too high, the molecular structure of the second polymerization product will change. The time of the second polymerization reaction is 40-50 min, preferably 43-47 min. If the time of the second polymerization reaction is too short, the polymerization will be incomplete, resulting in a low molecular weight of the second reaction product; if the time of the second polymerization reaction is too long, the preparation cost will increase.

[0070] According to the present invention, the temperature of the first halogenation reaction is 70-80°C, preferably 73-77°C. If the temperature of the first halogenation reaction is too low, incomplete halogenation will result in an excessively low halogen content in product a; if the temperature of the first halogenation reaction is too high, the molecular weight of product a will be too large, and the molecular weight distribution will be too wide. The time of the first halogenation reaction is 2-4 hours, preferably 2.5-3.5 hours. If the time of the first halogenation reaction is too short, the molecular weight of product a will be too small; if the time of the first halogenation reaction is too long, the preparation cost will increase.

[0071] According to the present invention, in step (1-2), based on a total amount of halogenating agent of 100 parts by weight in the preparation method of the multi-component copolymer, the amount of each raw material fed in step (1-1) satisfies the following: solvent 100-200 parts by weight, butadiene 20-30 parts by weight, styrene 30-40 parts by weight, structure modifier 0.1-0.3 parts by weight, first initiator 0.05-0.2 parts by weight, halogenating agent 40-50 parts by weight, molecular weight modifier 0.1-0.3 parts by weight, and second initiator 0.1-0.3 parts by weight.

[0072] According to the present invention, in steps (1-2), for the operation of the third polymerization reaction, the fourth polymerization reaction, and the second halogenation reaction, the raw materials are prepared according to the proportions described above. Inert gas is introduced into the second reactor to remove oxygen. Then, solvent, butadiene, and structure modifier are added. The temperature is raised to the temperature required for the third polymerization reaction, and the first initiator is added to carry out the third polymerization reaction. After the third polymerization reaction is completed, styrene is added to the second reactor, and the temperature is raised to the temperature required for the fourth polymerization reaction to carry out the fourth polymerization reaction. After the fourth polymerization reaction is completed, halogenating agent and molecular weight modifier are added to the second reactor, and the temperature is raised to the temperature required for the second halogenation reaction. The second initiator is added to initiate the second halogenation reaction. After the reaction is completed, product b is obtained.

[0073] According to the present invention, the temperature of the third polymerization reaction is 40-50°C, preferably 43-47°C. If the temperature of the third polymerization reaction is too low, the polymerization will be incomplete, resulting in a low molecular weight of the product; if the temperature of the third polymerization reaction is too high, the molecular structure of the product will change. The time of the third polymerization reaction is 30-40 min, preferably 33-37 min. If the time of the third polymerization reaction is too short, the polymerization will be incomplete, resulting in a low molecular weight of the product; if the time of the third polymerization reaction is too long, the preparation cost will increase.

[0074] According to the present invention, the temperature of the fourth polymerization reaction is 50-60°C, preferably 53-57°C. If the temperature of the fourth polymerization reaction is too low, the polymerization will be incomplete, resulting in a low molecular weight of the fourth polymerization product; if the temperature of the fourth polymerization reaction is too high, the molecular structure of the fourth polymerization product will change. The time of the fourth polymerization reaction is 50-60 min, preferably 53-57 min. If the time of the fourth polymerization reaction is too short, the polymerization will be incomplete, resulting in a low molecular weight of the fourth polymerization product; if the time of the fourth polymerization reaction is too long, the preparation cost will increase.

[0075] According to the present invention, the temperature of the second halogenation reaction is 70-80°C, preferably 73-77°C. If the temperature of the second halogenation reaction is too low, incomplete halogenation will result in an excessively low halogen content in product b; if the temperature of the second halogenation reaction is too high, the molecular weight of product b will be too large, and the molecular weight distribution will be too wide. The time of the second halogenation reaction is 2-3 hours, preferably 2.3-2.7 hours. If the time of the second halogenation reaction is too short, the molecular weight of product b will be too small; if the time of the second halogenation reaction is too long, the preparation cost will increase.

[0076] According to the present invention, in steps (1-1) and (1-2), the unsaturated double bonds in the -BR- and -IR- segments generated by the second polymerization reaction and the fourth polymerization reaction are subjected to free radical addition by a halogenating agent under the initiation of a specific second initiator. This significantly reduces the content of unsaturated double bonds, avoiding the introduction of unsaturated double bonds in the subsequent branching process of butyl rubber, thereby increasing the saturation of butyl rubber and greatly improving its resistance to bromine oxidation and its gas tightness. Furthermore, the secondary halogen structure formed by halogenation with the halogenating agent differs from the ion substitution generation method in the prior art, avoiding the generation of byproduct hydrogen halides and blocking the isomerization conditions from the secondary halogen structure to the primary structure. This improves the stability of the secondary halogen structure in the halogenated branched butyl rubber, thereby increasing the vulcanization rate of the halogenated branched butyl rubber and solving the problem of slow vulcanization rate of butyl rubber during processing.

[0077] According to the present invention, in steps (1-3), based on a total amount of halogenating agent of 100 parts by weight in the preparation method of the multi-component copolymer, the amount of each raw material fed in steps (1-3) satisfies the following: 100-200 parts by weight of solvent, 5-10 parts by weight of butadiene, 10-20 parts by weight of styrene, 0.1-0.3 parts by weight of structure modifier, and 0.03-0.16 parts by weight of first initiator.

[0078] According to the present invention, in step (1-3), for the operation process of the fifth polymerization reaction, the raw materials are prepared in the proportions described above, an inert gas is introduced into the third reaction vessel to remove oxygen, and then a solvent, styrene, butadiene, and a structure modifier are added. The temperature is raised to the temperature required for the fifth polymerization reaction and a first initiator is added to carry out the fifth polymerization reaction to obtain product c.

[0079] According to the present invention, the temperature of the fifth polymerization reaction is 60-70°C, preferably 63-67°C. If the temperature of the fifth polymerization reaction is too low, the polymerization will be incomplete, resulting in a low molecular weight of product c; if the temperature of the fifth polymerization reaction is too high, abnormal polymerization or explosive polymerization will occur. The time of the fifth polymerization reaction is 30-40 min, preferably 33-37 min. If the time of the fifth polymerization reaction is too short, the polymerization will be incomplete, resulting in a low molecular weight of product c; if the time of the fifth polymerization reaction is too long, the preparation cost will increase.

[0080] According to the present invention, in steps (1-1), (1-2), and (1-3), the -PS- and -SBR- segments generated by the second, fourth, and fifth polymerization reactions contain a large number of benzene rings. The benzene rings have high rigidity and large steric hindrance, which can obtain high strength and can compensate for the decrease in strength of butyl rubber caused by the increase in the disorder of molecular chain segments.

[0081] According to the present invention, in step (2), based on the total amount of halogenating agent in the preparation method of the multi-component copolymer being 100 parts by weight, the amount of each raw material fed in step (2) satisfies the following: coupling agent is 0.5-5 parts by weight, conjugated diene is 1-2 parts by weight, and product a, product b and product c are respectively obtained by the quantities of products obtained in steps (1-1), (1-2) and (1-3).

[0082] According to the present invention, in step (2), for the operation process of the coupling reaction and the end-capping reaction, the raw materials are prepared in the proportions described above, the product b obtained from the second reaction vessel and the product c obtained from the third reaction vessel are placed in the first reaction vessel and mixed with product a, the temperature is raised to the temperature required for the coupling reaction and the coupling reaction is carried out; after the coupling reaction is completed, the temperature required for the coupling reaction is maintained, and a conjugated diene is added to the first reaction vessel for the end-capping reaction, and the reaction product is wet-coagulated and dried to obtain the multi-component copolymer.

[0083] According to the present invention, the coupling reaction temperature is 80-90°C, preferably 83-87°C. If the coupling reaction temperature is too low, the coupling effect will be poor, the chain segment distribution of the resulting multi-component copolymer will be narrower, and consequently, the viscoelasticity and dimensional stability of the rubber made from the multi-component copolymer will be worse. If the coupling reaction temperature is too high, the coupling effect will also be affected. The coupling reaction time is 150-170 min, preferably 155-165 min. Both excessively short and excessively long coupling reaction times will affect the coupling reaction effect.

[0084] According to the present invention, the temperature of the end-capping reaction is 80-90°C, preferably 83-87°C. If the end-capping reaction temperature is too low, the end-capping effect will be poor; if the end-capping reaction temperature is too high, the conjugated diene will easily undergo self-polymerization, failing to achieve the end-capping effect. The end-capping reaction time is 20-30 min, preferably 23-27 min. If the end-capping reaction time is too short, the end-capping will be incomplete, resulting in a poor end-capping effect; if the end-capping reaction time is too long, the product will not change significantly after complete end-capping, leading to increased preparation costs.

[0085] According to the present invention, in step (2), the obtained "tri-arm" star structure can effectively destroy the regularity of the molecular chain in the copolymerization of isobutylene and isoprene during the preparation of halogenated branched butyl rubber, increase the disorder of the chain segments, so that butyl rubber can obtain good viscoelastic properties, reduce the extrusion swelling effect, and ensure the processing dimensional stability of butyl rubber.

[0086] According to the present invention, in the method for preparing the multi-component copolymer, the solvent is selected from at least one of straight-chain alkanes, aromatics, and cycloalkanes, more preferably at least one of pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, and ethylbenzene, and more preferably hexane. In the present invention, the solvents used in different steps may be the same or different, but are preferably the same.

[0087] According to the present invention, in the method for preparing the multi-component copolymer, the first initiator is a hydrocarbon-based monolithium compound, preferably RLi, wherein R is a saturated aliphatic hydrocarbon group containing 1-20 carbon atoms, an alicyclic hydrocarbon group containing 3-20 carbon atoms, an aromatic hydrocarbon group containing 6-20 carbon atoms, or a complex group of the above groups. More preferably, the first initiator is selected from at least one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthium lithium, cyclohexyllithium, and dodecyllithium. In the present invention, the first initiator used in different steps can be the same or different, but preferably the same.

[0088] According to the present invention, in the method for preparing the multi-component copolymer, the second initiator is an organic peroxide, more preferably at least one selected from di-tert-butyl hydroperoxide (TBHP), 2,5-dimethyl-2,5-di-tert-butylperoxide (BPDH), di-tert-butyl peroxide (DTBP), and dicumyl peroxide (DCP), and more preferably di-tert-butyl peroxide. In the present invention, the second initiator used in different steps may be the same or different, but is preferably the same.

[0089] According to the present invention, in the method for preparing the multi-component copolymer, the halogenating agent is preferably an organic halogenating agent. More preferably, the halogenating agent is selected from at least one of N-bromosuccinimide, dimethyl bromide thiobromide, N-bromosuccinimide, N-chlorosuccinimide, N-chlorosuccinimide, and dimethyl chloride thiobromide, and more preferably at least one of N-bromosuccinimide, dimethyl bromide thiobromide, and N-bromosuccinimide. In the present invention, the halogenating agents used in different steps can be the same or different, but are preferably the same.

[0090] According to the present invention, in the method for preparing the multi-component copolymer, the structure modifier is a polar organic compound, more preferably at least one selected from diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, and triethylamine, and more preferably tetrahydrofuran. In the present invention, the structure modifiers used in different steps may be the same or different, but are preferably the same.

[0091] According to the present invention, in the method for preparing the multi-component copolymer, the molecular weight regulator is selected from at least one of tert-decanethiols, tert-dodecanethiols, tert-tetradecanethiols, and tert-hexadecanethiols, and is more preferably tert-dodecanethiols. In the present invention, the molecular weight regulators used in different steps may be the same or different, but are preferably the same.

[0092] According to the present invention, in the method for preparing the multi-component copolymer, the conjugated diene is selected from butadiene and / or isoprene.

[0093] A third aspect of the present invention provides a multi-component copolymer prepared by the method described in the second aspect above.

[0094] According to the present invention, the multi-component copolymers prepared by the method described in the second aspect above have the same structural composition, performance indicators and effects as the multi-component copolymers described in the first aspect above, and will not be repeated here.

[0095] The fourth aspect of the present invention provides the application of the multi-component copolymer described in the first or third aspect above as a grafting agent in the preparation of diene rubber.

[0096] According to the present invention, preferably, the diene rubber is butyl rubber.

[0097] The fifth aspect of the present invention provides a halogenated branched butyl rubber, wherein the halogenated branched butyl rubber comprises: a structural unit A derived from isobutylene, a structural unit B derived from isoprene, and a structural unit C derived from a grafting agent;

[0098] The grafting agent is a multi-component copolymer as described in the first or third aspect above.

[0099] According to the present invention, based on the total weight of the halogenated branched butyl rubber, the weight ratio of structural unit A, structural unit B, and structural unit C is (6-15):(0.05-0.5):1, preferably (8-10):(0.1-0.3):1. In the present invention, by controlling the weight ratio of structural unit A, structural unit B, and structural unit C within a specific range, a halogenated branched butyl rubber with suitable halogen content can be obtained.

[0100] The halogenated branched butyl rubber provided by this invention contains structural units from the aforementioned specific grafting agent. This grafting agent combines -BR-, -IR-, -PS-, and -SBR- segments of different structures onto a macromolecular chain to form a "tri-hetero-arm" star structure with a stable secondary halogen substitution structure. The aforementioned different segments, the "tri-hetero-arm" star structure, and the stable secondary halogen substitution structure are introduced into the structure of the butyl rubber through graft polymerization and work synergistically to give the halogenated branched butyl rubber high saturation, high branching degree, significantly reduced extrusion swell effect, fast vulcanization speed, strong ozone aging resistance, and good air tightness.

[0101] The sixth aspect of the present invention provides a method for preparing halogenated branched butyl rubber, wherein the method comprises: subjecting isobutylene, isoprene and grafting agent to cationic polymerization in the presence of a diluent, a solvent and a co-initiator to obtain the halogenated branched butyl rubber;

[0102] The grafting agent is a multi-component copolymer as described in the first or third aspect above.

[0103] According to the present invention, in the preparation method of the halogenated branched butyl rubber, based on a total amount of 100 parts by weight of isobutylene and isoprene, the solvent is 30-80 parts by weight, the diluent is 30-80 parts by weight, the grafting agent is 6-15 parts by weight, and the co-initiator is 0.1-0.6 parts by weight.

[0104] According to the present invention, in the preparation method of the halogenated branched butyl rubber, the weight ratio of isobutylene to isoprene is (25-95):1.

[0105] In this invention, by controlling the amounts of isobutylene, isoprene, and grafting agent within the specific range mentioned above, halogenated branched butyl rubber with excellent aging properties, product dimensional stability, and vulcanization processing performance can be obtained.

[0106] According to the present invention, the cationic polymerization reaction can be carried out using a conventional reaction process in the art for preparing butyl rubber using a grafting agent. Preferably, the raw materials can be prepared according to the proportions described above, and an inert gas is introduced into the reactor to purge oxygen. Then, a mixture of solvent and a first portion of diluent (the volume ratio of diluent to solvent is 70-30:30-70) and the grafting agent are added. After the grafting agent is fully dissolved, the temperature is lowered to -95 to -85°C. Then, a second portion of diluent, isobutylene, and isoprene are added, and the temperature is adjusted to the temperature required for the cationic polymerization reaction. Then, the remaining portion of diluent and co-initiator (which are pre-mixed and aged at -95 to -85°C) are added to the reaction system to carry out the cationic polymerization reaction. After the reaction is completed, a terminator is added to terminate the reaction. The product is then coagulated, washed, and dried to obtain the halogenated branched butyl rubber.

[0107] According to the present invention, the temperature of the cationic polymerization reaction is -100°C to -90°C. If the temperature of the cationic polymerization reaction is too low, the reaction time will be prolonged, and the molecular weight of the rubber product may be too low; if the temperature of the cationic polymerization reaction is too high, the molecular structure of the rubber product may change. The time of the cationic polymerization reaction is 2-4 hours. If the time of the cationic polymerization reaction is too short, the reaction will be incomplete, resulting in a low molecular weight of the rubber product; if the time of the cationic polymerization reaction is too long, the molecular structure of the rubber product may change.

[0108] According to the present invention, in the method for preparing the halogenated branched butyl rubber, the solvent is selected from at least one of straight-chain alkanes, aromatics and cycloalkanes, more preferably at least one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, and more preferably hexane.

[0109] According to the present invention, in the preparation method of the halogenated branched butyl rubber, the diluent is a haloalkane, and the halogen in the haloalkane is F, Cl or Br; preferably, the haloalkane is a haloalkane with 1-4 carbon atoms.

[0110] In this invention, preferably, the diluent is selected from at least one of chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, fluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.

[0111] In this invention, the ratio of the first diluent, the second diluent, and the remaining diluent can be chosen using conventional methods in the art, and this invention does not impose any particular limitation on this.

[0112] According to the present invention, the co-initiator comprises an alkyl aluminum halide and a protic acid. Preferably, in the co-initiator, the molar ratio of the alkyl aluminum halide to the protic acid is (10-100):1.

[0113] According to 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.

[0114] According to the present invention, the protic acid is selected from at least one of HCl, HF, HBr, H2SO4, H2CO3, H3PO4 and HNO3.

[0115] According to the present invention, the terminating agent is selected from at least one of methanol, ethanol and butanol.

[0116] The seventh aspect of the present invention provides a halogenated branched butyl rubber prepared by the method described in the sixth aspect above.

[0117] According to the present invention, the halogenated branched butyl rubber prepared by the method described in the sixth aspect above has the same structural composition, performance indicators and effects as the halogenated branched butyl rubber described in the fifth aspect above above, and will not be repeated here.

[0118] The eighth aspect of the present invention provides the application of the halogenated branched butyl rubber described in the fifth or seventh aspect above in tires and medical stoppers.

[0119] The halogenated branched butyl rubber of this invention has high saturation and high branching degree, low extrusion swell effect, fast vulcanization speed, strong ozone aging resistance, and good air tightness. It can be well applied to the requirements of butyl rubber aging resistance, product dimensional stability and vulcanization processing performance in tire inner tubes, tire air tightness layers and medical rubber stoppers.

[0120] The present invention will be described in detail below through embodiments.

[0121] In the following examples and comparative examples, unless otherwise specified, conventional conditions or conditions recommended by the manufacturer were followed. Reagents or instruments used, unless otherwise specified, are all commercially available products. The weight ratios of the structural units in the resulting multi-component copolymer product and the halogenated branched butyl rubber were determined based on the amount of raw materials fed.

[0122] (1) Source of raw materials:

[0123] Styrene, 1,3-butadiene: Polymer grade, China Petroleum Lanzhou Petrochemical Company;

[0124] Isobutylene and isoprene: Polymer grade, Zhejiang Xinhui New Material Co., Ltd.;

[0125] N-Bromosuccinimide: Polymer grade, Jiangsu Runfeng Synthetic Technology Co., Ltd.;

[0126] N-Chlorosuccinimide: Polymer grade, Wuhan Shuer Biotechnology Co., Ltd.;

[0127] Di-tert-butyl peroxide (DTBP): Lanzhou Additives Factory;

[0128] n-Butyllithium: 98% purity, Nanjing Tonglian Chemical Co., Ltd.;

[0129] Sesquiethylaluminum chloride: 98% purity, Bailingwei Technology Co., Ltd.

[0130] 1,3,5-Trichlorobenzene: 99% purity, Yangzhou Haichen Chemical Co., Ltd.;

[0131] All other reagents are commercially available industrial products.

[0132] (2) Analysis and testing methods:

[0133] 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 on the sample. The first stage of thermal degradation is 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. The calculation formula is as follows:

[0134]

[0135] 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.

[0136] Number-average molecular weight and molecular weight distribution index 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.

[0137] Unsaturation degree determination: The Bruker AVANCE 300 nuclear magnetic resonance spectrometer with a magnetic field strength of 9.20 Tesla was used, with CDCl3 as solvent and TMS as internal standard, and the determination was performed at room temperature (25℃).

[0138] Branching degree determination: Branching degree = molecular weight of polymer after branching / molecular weight of polymer before branching.

[0139] Static ozone performance testing: A TD-401A thermal aging tester was used. The test parameters were: 25% tensile strength, ozone mass fraction 50 × 10⁻⁶. -8 Temperature 40℃, time 1000h.

[0140] Vulcanization characteristics determination: Tested according to the method specified in GB / T 16584-1996.

[0141] Air tightness test: The air permeability number was determined using an automated air tightness tester according to ISO 2782:1995. The test gas was N2, the test temperature was 23℃, and the test sample was an 8cm diameter circular sea sheet with a thickness of 1mm.

[0142] Extrusion swell ratio determination: A Malvern RH2000 capillary rheometer (UK) was used at a temperature of 100℃, an aspect ratio of 16:1, and a shear rate of 10-1000 s. -1 Measurement within the interval.

[0143] Preparation Example 1

[0144] This preparation example illustrates the preparation of multi-component copolymers.

[0145] (1-1) In a 15L stainless steel first reactor with a jacket, argon gas was purged twice. Then, 1000g of hexane, 300g of isoprene, and 1.3g of tetrahydrofuran were added to the first reactor in sequence. After heating to 40℃, 13.5mmol of n-butyllithium was added to start the reaction for 20min. Next, 200g of styrene and 1.1g of tetrahydrofuran were added to the first reactor in sequence. After heating to 60℃, the reaction was carried out for 40min to form -PS-IR- segments. Finally, 500g of N-bromosuccinimide and 2.0g of tert-dodecyl mercaptan were added to the first reactor in sequence. After heating to 70℃, 1.5g of DTBP was added and the reaction was carried out for 2.0h to obtain product a.

[0146] (1-2) In a 15L stainless steel second reactor, the system was purged twice with argon gas. Then, 1000g of hexane, 200g of 1,3-butadiene, and 1.0g of tetrahydrofuran were added sequentially. After heating to 40℃, 11.5mmol of n-butyllithium was added to start the reaction for 30min. Next, 300g of styrene was added to the second reactor, and the temperature was raised to 50℃. The reaction was carried out for 50min to form -BR-PS- segments. Finally, 500g of N-bromosuccinimide and 1.0g of tert-dodecyl mercaptan were added to the second reactor sequentially. The temperature was raised to 70℃, and 1.2g of DTBP was added to react for 2.0h to obtain product b.

[0147] (1-3) In a 15L stainless steel third reactor, the system was purged twice with argon gas. Then, 1000g of hexane, 100g of styrene, 50g of 1,3-butadiene, and 1.0g of tetrahydrofuran were added sequentially. After heating to 60℃, 8.5mmol of n-butyllithium was added to start the reaction for 30min, forming the -SBR- segment, and product c was obtained.

[0148] (2) Add all of product b from the second reactor and all of product c from the third reactor to the first reactor and mix with product a. Heat to 80°C and add 100 mmol of 1,3,5-trichlorobenzene for coupling reaction. After reacting for 150 min, add 10 g of 1,3-butadiene to the first reactor for end-capping activation. React for 20 min until no free monomers are present. The adhesive solution is wet coagulated and dried to obtain a multi-component copolymer, denoted as P1 (Mn is 81000, Mw / Mn is 9.16).

[0149] Calculations show that in P1, the molar ratio of R1:R2:R3:phenyl is 1.9:5.8:6.3:0.1, the Br content in P1 is 20.9 wt%, and the content of the terminal structural units of P1 derived from conjugated dienes is 0.46 wt%.

[0150] Preparation Example 2

[0151] This preparation example illustrates the preparation of multi-component copolymers.

[0152] (1-1) In a 15L stainless steel first reactor with a jacket, argon gas was purged twice. Then, 1200g of hexane, 330g of isoprene, and 1.9g of tetrahydrofuran were added to the first reactor in sequence. After heating to 43℃, 15.5mmol of n-butyllithium was added to start the reaction for 23min. Next, 220g of styrene and 1.5g of tetrahydrofuran were added to the first reactor in sequence. After heating to 63℃, the reaction was carried out for 43min to form -PS-IR- segments. Finally, 520g of N-bromosuccinimide and 2.5g of tert-dodecyl mercaptan were added to the first reactor in sequence. After heating to 73℃, 2.1g of DTBP was added and the reaction was carried out for 2.6h to obtain product a.

[0153] (1-2) In a 15L stainless steel second reactor, the system was purged twice with argon gas. Then, 1300g of hexane, 220g of 1,3-butadiene, and 1.4g of tetrahydrofuran were added sequentially. After heating to 43℃, 12.5mmol of n-butyllithium was added to start the reaction for 33min. Next, 320g of styrene was added to the second reactor, and the temperature was raised to 56℃. The reaction was carried out for 56min to form -BR-PS- segments. Finally, 480g of N-bromosuccinimide and 1.5g of tert-dodecyl mercaptan were added to the second reactor sequentially. The temperature was raised to 73℃, and 1.7g of DTBP was added to react for 2.5h to obtain product b.

[0154] (1-3) In a 15L stainless steel third reactor, the system was purged twice with argon gas. Then, 1200g of hexane, 120g of styrene, 60g of 1,3-butadiene, and 1.4g of tetrahydrofuran were added sequentially. After heating to 66℃, 10.5mmol of n-butyllithium was added to start the reaction for 33min, forming -SBR- segments to obtain product c.

[0155] (2) Add all of product b from the second reactor and all of product c from the third reactor to the first reactor and mix with product a. Heat to 83°C and add 100 mmol of 1,3,5-trichlorobenzene for coupling reaction. After reacting for 155 min, add 12 g of 1,3-butadiene to the first reactor for end-capping activation. React for 23 min until no free monomers are present. The adhesive solution is wet coagulated and dried to obtain a multi-component copolymer, denoted as P2 (Mn is 83000, Mw / Mn is 9.48).

[0156] Calculations show that in P2, the molar ratio of R1:R2:R3:phenyl is 2.3:6.3:6.8:0.1, the Br content in P2 is 19.8 wt%, and the content of the terminal structural units of P2 derived from conjugated dienes is 0.53 wt%.

[0157] Preparation Example 3

[0158] This preparation example illustrates the preparation of multi-component copolymers.

[0159] (1-1) In a 15L stainless steel first reactor with a jacket, argon gas was purged three times. Then, 1400g of hexane, 350g of isoprene, and 2.2g of tetrahydrofuran were added to the first reactor in sequence. After heating to 45℃, 17.5mmol of n-butyllithium was added to start the reaction for 25min. Next, 240g of styrene and 1.8g of tetrahydrofuran were added to the first reactor in sequence. After heating to 64℃, the reaction was carried out for 45min to form -PS-IR- segments. Finally, 540g of N-bromosuccinimide and 3.0g of tert-dodecyl mercaptan were added to the first reactor in sequence. After heating to 75℃, 2.4g of DTBP was added and the reaction was carried out for 3.0h to obtain product a.

[0160] (1-2) In a 15L stainless steel second reactor, the system was purged with argon gas three times. Then, 1500g of hexane, 240g of 1,3-butadiene, and 1.7g of tetrahydrofuran were added sequentially. After heating to 44℃, 14.2mmol of n-butyllithium was added to start the reaction for 35min. Next, 340g of styrene was added to the second reactor, the temperature was raised to 54℃, and the reaction was carried out for 55min to form -BR-PS- segments. Finally, 460g of N-bromosuccinimide and 1.8g of tert-dodecyl mercaptan were added to the second reactor sequentially, the temperature was raised to 74℃, and 2.2g of DTBP was added to react for 2.5h to obtain product b.

[0161] (1-3) In a 15L stainless steel third reactor, the system was purged twice with argon gas. Then, 1500g of hexane, 150g of styrene, 70g of 1,3-butadiene, and 2.0g of tetrahydrofuran were added sequentially. After heating to 64℃, 11.6 mmol of n-butyllithium was added to start the reaction for 35 min, forming the -SBR- segment, and product c was obtained.

[0162] (2) Add all of product b from the second reactor and all of product c from the third reactor to the first reactor and mix with product a. Heat to 85°C and add 100 mmol of 1,3,5-trichlorobenzene for coupling reaction. After reacting for 160 min, add 15 g of 1,3-butadiene to the first reactor for end-capping activation. React for 25 min until no free monomers are present. The adhesive solution is wet coagulated and dried to obtain a multi-component copolymer, denoted as P3 (Mn is 85000, Mw / Mn is 9.79).

[0163] Calculations show that in P3, the molar ratio of R1:R2:R3:phenyl is 2.8:6.9:7.3:0.1, the Br content in P3 is 18.8 wt%, and the content of structural units from conjugated dienes at the end of P3 is 0.62 wt%.

[0164] Preparation Example 4

[0165] This preparation example illustrates the preparation of multi-component copolymers.

[0166] (1-1) In a 15L stainless steel first reactor with a jacket, argon gas was purged three times. Then, 1600g of hexane, 370g of isoprene, and 2.5g of tetrahydrofuran were added to the first reactor in sequence. After heating to 47℃, 19.2 mmol of n-butyllithium was added to start the reaction for 26 min. Next, 260g of styrene and 2.1g of tetrahydrofuran were added to the first reactor in sequence. After heating to 66℃, the reaction was carried out for 47 min to form -PS-IR- segments. Finally, 560g of N-chlorosuccinimide and 3.5g of tert-dodecyl mercaptan were added to the first reactor in sequence. After heating to 76℃, 2.6g of DTBP was added and the reaction was carried out for 3.3 h to obtain product a.

[0167] (1-2) In a 15L stainless steel second reactor, the system was purged with argon gas three times. Then, 1600g of hexane, 260g of 1,3-butadiene, and 2.0g of tetrahydrofuran were added sequentially. After heating to 46℃, 15.6mmol of n-butyllithium was added to start the reaction for 36min. Next, 360g of styrene was added to the second reactor, and the temperature was raised to 56℃. The reaction was carried out for 57min to form -BR-PS- segments. Finally, 440g of N-chlorosuccinimide and 2.1g of tert-dodecyl mercaptan were added to the second reactor sequentially. The temperature was raised to 76℃, and 2.5g of DTBP was added to react for 2.7h to obtain product b.

[0168] (1-3) In a 15L stainless steel third reactor, the system was purged twice with argon gas. Then, 1700g of hexane, 170g of styrene, 80g of 1,3-butadiene, and 2.2g of tetrahydrofuran were added sequentially. After heating to 66℃, 13.5mmol of n-butyllithium was added to start the reaction for 36min, forming the -SBR- segment, and product c was obtained.

[0169] (2) Add all of product b from the second reactor and all of product c from the third reactor to the first reactor and mix with product a. Heat to 86°C and add 100 mmol of 1,3,5-trichlorobenzene for coupling reaction. After reacting for 164 min, add 16 g of 1,3-butadiene to the first reactor for end-capping activation. React for 26 min until no free monomers are present. The adhesive solution is wet coagulated and dried to obtain a multi-component copolymer, denoted as P4 (Mn is 87000, Mw / Mn is 9.97).

[0170] Calculations show that in P4, the molar ratio of R1:R2:R3:phenyl is 3.2:7.3:7.8:0.1, the Cl content in P4 is 10.6 wt%, and the content of terminal structural units from conjugated dienes in P4 is 0.63 wt%.

[0171] Preparation Example 5

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

[0173] (1-1) In a 15L stainless steel first reactor with a jacket, argon gas was purged four times. Then, 1800g of hexane, 390g of isoprene, and 2.8g of tetrahydrofuran were added to the first reactor in sequence. After heating to 49℃, 21.5mmol of n-butyllithium was added to start the reaction for 28min. Next, 280g of styrene and 2.6g of tetrahydrofuran were added to the first reactor in sequence. After heating to 68℃, the reaction was carried out for 49min to form -PS-IR- segments. Finally, 580g of N-bromosuccinimide and 3.8g of tert-dodecyl mercaptan were added to the first reactor in sequence. After heating to 78℃, 2.8g of DTBP was added and the reaction was carried out for 3.6h to obtain product a.

[0174] (1-2) In a 15L stainless steel second reactor, the system was purged with argon gas four times. Then, 1800g of hexane, 290g of 1,3-butadiene, and 2.6g of tetrahydrofuran were added sequentially. After heating to 48℃, 16.5mmol of n-butyllithium was added to start the reaction for 38min. Next, 380g of styrene was added to the second reactor, and the temperature was raised to 58℃. The reaction was carried out for 59min to form -BR-PS- segments. Finally, 420g of N-bromosuccinimide and 2.3g of tert-dodecyl mercaptan were added to the second reactor sequentially. The temperature was raised to 78℃, and 2.7g of DTBP was added to react for 2.9h to obtain product b.

[0175] (1-3) In a 15L stainless steel third reactor, the system was purged twice with argon gas. Then, 1900g of hexane, 180g of styrene, 90g of 1,3-butadiene, and 2.6g of tetrahydrofuran were added sequentially. After heating to 68℃, 15.5mmol of n-butyllithium was added to start the reaction for 38min, forming the -SBR- segment, and product c was obtained.

[0176] (2) Add all of product b from the second reactor and all of product c from the third reactor to the first reactor and mix with product a. Heat to 88°C and add 100 mmol of 1,3,5-trichlorobenzene for coupling reaction. After reacting for 167 min, add 18 g of 1,3-butadiene to the first reactor for end-capping activation. React for 28 min until no free monomers are present. The adhesive solution is wet coagulated and dried to obtain a multi-component copolymer, denoted as P5 (Mn is 89000, Mw / Mn is 10.21).

[0177] Calculations show that in P5, the molar ratio of R1:R2:R3:phenyl is 3.4:7.8:8.5:0.1, the Br content in P5 is 17.2 wt%, and the content of structural units from conjugated dienes at the end of P5 is 0.68 wt%.

[0178] Preparation Example 6

[0179] This preparation example illustrates the preparation of multi-component copolymers.

[0180] (1-1) In a 15L stainless steel first reactor with a jacket, argon gas was purged four times. Then, 2000g of hexane, 400g of isoprene, and 3.0g of tetrahydrofuran were added to the first reactor in sequence. After heating to 50℃, 22.5mmol of n-butyllithium was added to start the reaction for 30min. Next, 300g of styrene and 3.0g of tetrahydrofuran were added to the first reactor in sequence. After heating to 70℃, the reaction was carried out for 50min to form -PS-IR- segments. Finally, 600g of N-bromosuccinimide and 4.0g of tert-dodecyl mercaptan were added to the first reactor in sequence. After heating to 80℃, 3.0g of DTBP was added and the reaction was carried out for 4.0h to obtain product a.

[0181] (1-2) In a 15L stainless steel second reactor, the system was purged with argon gas four times. Then, 2000g of hexane, 300g of 1,3-butadiene, and 3.0g of tetrahydrofuran were added sequentially. After heating to 50℃, 17.5mmol of n-butyllithium was added to start the reaction for 40min. Next, 400g of styrene was added to the second reactor, the temperature was raised to 60℃, and the reaction was carried out for 60min to form -BR-PS- segments. Finally, 400g of N-bromosuccinimide and 2.7g of tert-dodecyl mercaptan were added sequentially to the second reactor, the temperature was raised to 80℃, and 3.0g of DTBP was added to react for 3.0h to obtain product b.

[0182] (1-3) In a 15L stainless steel third reactor, the system was purged twice with argon gas. Then, 2000g of hexane, 200g of styrene, 100g of 1,3-butadiene, and 3.0g of tetrahydrofuran were added sequentially. After heating to 70℃, 16.5mmol of n-butyllithium was added to start the reaction for 40min, forming -SBR- segments to obtain product c.

[0183] (2) Add all of product b from the second reactor and all of product c from the third reactor to the first reactor and mix with product a. Heat to 88°C and add 100 mmol of 1,3,5-trichlorobenzene for coupling reaction. After reacting for 170 min, add 20 g of 1,3-butadiene to the first reactor for end-capping activation. React for 30 min until no free monomers are present. The adhesive solution is wet coagulated and dried to obtain a multi-component copolymer, denoted as P6 (Mn is 90000, Mw / Mn is 10.35).

[0184] Calculations show that in P6, the molar ratio of R1:R2:R3:phenyl is 3.8:8.1:8.8:0.1, the Br content in P6 is 16.7wt%, and the content of structural units from conjugated dienes at the end of P6 is 0.74wt%.

[0185] Preparation Example 7

[0186] This preparation example illustrates the preparation of multi-component copolymers.

[0187] The method of Preparation Example 1 was followed, except that in the steps involving the use of N-bromosuccinimide, an equal weight of the inorganic brominating agent hydrogen bromide was used instead of N-bromosuccinimide. All other conditions were the same as in Preparation Example 1. A multi-component copolymer was obtained, denoted as P7 (Mn = 78000, Mw / Mn = 8.52).

[0188] Calculations show that in P7, the molar ratio of R1:R2:R3:phenyl is 1.9:5.8:6.3:0.1, the Br content in P7 is 45.9 wt%, and the content of structural units from conjugated dienes at the end of P7 is 0.46 wt%.

[0189] Preparation Example 8

[0190] This preparation example illustrates the preparation of multi-component copolymers.

[0191] The method of Preparation Example 2 was followed, except that in the steps involving the use of DTBP, equal weights of hydrogen peroxide (H2O2) were used instead of DTBP. All other conditions were the same as in Preparation Example 2. A multi-component copolymer was obtained, denoted as P8 (Mn = 71000, Mw / Mn = 7.58).

[0192] Calculations show that in P8, the molar ratio of R1:R2:R3:phenyl is 2.3:6.3:6.8:0.1, the Br content in P8 is 19.8 wt%, and the content of structural units from conjugated dienes at the end of P8 is 0.53 wt%.

[0193] Preparation Example 9

[0194] This preparation example illustrates the preparation of multi-component copolymers.

[0195] The method of Preparation Example 3 was followed, except that the amount of N-bromosuccinimide added to the first reaction vessel was 200 g. All other conditions were the same as in Preparation Example 3. A multi-component copolymer was obtained, denoted as P9 (Mn = 78000, Mw / Mn = 9.05).

[0196] Calculations show that in P9, the molar ratio of R1:R2:R3:phenyl is 2.8:6.9:7.3:0.1, the Br content in P9 is 12.4 wt%, and the content of the terminal structural units of P9 derived from conjugated dienes is 0.73 wt%.

[0197] Comparative Preparation Example 1

[0198] This preparation example illustrates the preparation of multi-component copolymers.

[0199] The method of Preparation Example 5 was followed, except that the coupling agent 1,3,5-trichlorobenzene was not added during the preparation process. All other conditions were the same as in Preparation Example 5. A multi-component copolymer was obtained, denoted as DP1 (Mn = 52000, Mw / Mn = 2.26).

[0200] Calculations show that the molar ratio of R1:R2:R3 in DP1 is 3.4:7.8:8.5, the Br content in DP1 is 17.2 wt%, and the content of the terminal structural units of DP1 derived from conjugated dienes is 0.46 wt%.

[0201] Comparative Preparation Example 2

[0202] This preparation example illustrates the preparation of multi-component copolymers.

[0203] (1-1) In a 15L stainless steel first reactor with a jacket, argon gas was purged four times. Then, 2000g of hexane, 400g of isoprene, and 3.0g of tetrahydrofuran were added to the polymerization reactor in sequence. After heating to 50℃, 22.5mmol of n-butyllithium was added to start the reaction for 30min. Next, 300g of styrene and 3.0g of tetrahydrofuran were added to the first reactor in sequence. The temperature was raised to 70℃ and the reaction was carried out for 50min to form -PS-IR- segments. Finally, 600g of N-bromosuccinimide and 4.0g of tert-dodecyl mercaptan were added to the first reactor in sequence. The temperature was raised to 80℃ and 3.0g of DTBP was added to react for 4.0h to obtain product a.

[0204] (1-2) In a 15L stainless steel second reactor, the system was purged with argon gas four times. Then, 2000g of hexane, 300g of 1,3-butadiene, and 3.0g of tetrahydrofuran were added sequentially. After heating to 50℃, 17.5mmol of n-butyllithium was added to start the reaction for 40min. Next, 400g of styrene was added to the second reactor, the temperature was raised to 60℃, and the reaction was carried out for 60min to form -BR-PS- segments. Finally, 400g of N-bromosuccinimide and 2.7g of tert-dodecyl mercaptan were added sequentially to the second reactor, the temperature was raised to 80℃, and 3.0g of DTBP was added to react for 3.0h to obtain product b.

[0205] (2) Add all of product b from the second reactor to the first reactor and mix with product a. Heat to 88°C and add 100 mmol of 1,3,5-trichlorobenzene for coupling reaction. After reacting for 170 min, add 20 g of 1,3-butadiene to the first reactor for end-capping activation. React for 30 min until no free monomers are present. The adhesive solution is wet-coagulated and dried to obtain a multi-component copolymer, denoted as DP2 (Mn is 65000, Mw / Mn is 5.12).

[0206] Calculations show that the molar ratio of R2:R3:phenyl in DP2 is 8.1:8.8:0.1 (DP2 does not contain R1), the Br content in DP2 is 18.8 wt%, and the content of structural units from conjugated dienes at the end of DP2 is 0.83 wt%.

[0207] Example 1

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

[0209] In a jacketed 4L stainless steel reactor, nitrogen was purged three times. 300g of chloromethane, 700g of hexane, and 35g of the multi-component copolymer (P1) prepared in Example 1 were added to the polymerization reactor. The mixture was stirred and dissolved for 60 minutes until P1 was completely dissolved. The temperature was then lowered to -85°C, and 500g of chloromethane, 460g of isobutylene, and 5g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -90°C. Then, 50g of chloromethane, 1.075g of sesquiethylaluminum chloride, and 0.007g of HCl (mixed and aged at -85°C for 30 minutes) were added to the polymerization system and stirred for 2.0 hours. Finally, 25g of ethanol was added, the mixture was discharged, coagulated, washed, and dried to obtain halogenated branched butyl rubber, denoted as S1 (bromine content 2.36 wt%).

[0210] Based on the total weight of S1, the weight ratio of structural unit A from isobutylene, structural unit B from isoprene, and structural unit C from grafting agent is 13:0.14:1.

[0211] S1 was made into a standard sample, and its performance is shown in Table 1.

[0212] Example 2

[0213] This embodiment illustrates the preparation of halogenated branched butyl rubber.

[0214] In a 4L stainless steel reactor with a jacket, nitrogen was purged three times. 400g of chloromethane, 600g of hexane, and 38g of the multi-component copolymer (P2) prepared in Example 2 were added to the polymerization reactor. The mixture was stirred and dissolved for 65 minutes until P2 was completely dissolved. The temperature was then lowered to -88°C, and 600g of chloromethane, 455g of isobutylene, and 7g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -92°C. Then, 60g of chloromethane, 1.189g of sesquiethylaluminum chloride, and 0.011g of HCl (mixed and aged at -85°C for 32 minutes) were added to the polymerization system and stirred for 2.6 hours. Finally, 30g of ethanol was added, the mixture was discharged, coagulated, washed, and dried to obtain halogenated branched butyl rubber, denoted as S2 (bromine content 2.45 wt%).

[0215] Based on the total weight of S2, the weight ratio of structural unit A from isobutylene, structural unit B from isoprene, and structural unit C from grafting agent is 12:0.18:1.

[0216] S2 was made into a standard sample, and its performance is shown in Table 1.

[0217] Example 3

[0218] This embodiment illustrates the preparation of halogenated branched butyl rubber.

[0219] In a 4L stainless steel reactor with a jacket, nitrogen was purged three times. 500g of chloromethane and 500g of hexane were added to the polymerization reactor to prepare 41g of the multi-component copolymer (P3) obtained in Example 3. The mixture was stirred and dissolved for 70min until P3 was completely dissolved. Then, the temperature was lowered to -90℃, and 700g of chloromethane, 449g of isobutylene, and 10g of isoprene were added sequentially. The mixture was stirred and mixed until the polymerization system temperature dropped to -94℃. Then, 70g of chloromethane, 1.203g of sesquiethylaluminum chloride, and 0.031g of HCl (mixed and aged at -88℃ for 34min) were added to the polymerization system and stirred for 3.0h. Finally, 35g of ethanol was added, the mixture was discharged, coagulated, washed, and dried to obtain halogenated branched butyl rubber, denoted as S3 (bromine content 2.65wt%).

[0220] Based on the total weight of S3, the weight ratio of structural unit A from isobutylene, structural unit B from isoprene, and structural unit C from grafting agent is 11:0.24:1.

[0221] S3 was made into a standard sample, and its performance is shown in Table 1.

[0222] Example 4

[0223] This embodiment illustrates the preparation of halogenated branched butyl rubber.

[0224] In a 4L stainless steel reactor with a jacket, nitrogen was purged three times. 600g of chloromethane and 400g of hexane were added to the polymerization reactor to prepare 44g of the multi-component copolymer (P4) obtained in Example 4. The mixture was stirred and dissolved for 74 minutes until P4 was completely dissolved. Then, the temperature was lowered to -91°C, and 800g of chloromethane, 444g of isobutylene, and 12g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -95°C. Then, 80g of chloromethane, 1.315g of sesquiethylaluminum chloride, and 0.048g of HCl (mixed and aged at -90°C for 36 minutes) were added to the polymerization system and stirred for 3.3 hours. Finally, 40g of ethanol was added, the mixture was discharged, coagulated, washed, and dried to obtain halogenated branched butyl rubber, denoted as S4 (chlorine content 2.72 wt%).

[0225] Based on the total weight of S4, the weight ratio of structural unit A from isobutylene, structural unit B from isoprene, and structural unit C from grafting agent is 10:0.27:1.

[0226] S4 was made into a standard sample, and its performance is shown in Table 1.

[0227] Example 5

[0228] This embodiment illustrates the preparation of halogenated branched butyl rubber.

[0229] In a 4L stainless steel reactor with a jacket, nitrogen was purged three times. 650g of chloromethane, 350g of hexane, and 48g of the multi-component copolymer (P5) prepared in Example 5 were added to the polymerization reactor. The mixture was stirred and dissolved for 78 minutes until P5 was completely dissolved. The temperature was then lowered to -93°C, and 900g of chloromethane, 438g of isobutylene, and 14g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -97°C. Then, 90g of chloromethane, 1.425g of sesquiethylaluminum chloride, and 0.057g of HCl (mixed and aged at -93°C for 38 minutes) were added to the polymerization system and stirred for 3.7 hours. Finally, 45g of ethanol was added, the mixture was discharged, coagulated, washed, and dried to obtain halogenated branched butyl rubber, designated S5 (bromine content 2.86 wt%).

[0230] Based on the total weight of S5, the weight ratio of structural unit A from isobutylene, structural unit B from isoprene, and structural unit C from grafting agent is 9:0.29:1.

[0231] S5 was made into a standard sample, and its performance is shown in Table 1.

[0232] Example 6

[0233] This embodiment illustrates the preparation of halogenated branched butyl rubber.

[0234] In a jacketed 4L stainless steel reactor, nitrogen was purged five times. 700g of chloromethane, 300g of hexane, and 50g of the multi-component copolymer (P6) prepared in Example 6 were added to the polymerization reactor. The mixture was stirred and dissolved for 80 minutes until the grafting agent was completely dissolved. The temperature was then lowered to -95°C, and 1000g of chloromethane, 435g of isobutylene, and 15g of isoprene were added sequentially. The mixture was stirred until the polymerization system temperature dropped to -100°C. Then, 100g of chloromethane, 1.564g of sesquiethylaluminum chloride, and 0.074g of HCl (mixed and aged at -95°C for 40 minutes) were added to the polymerization system and stirred for 4.0 hours. Finally, 50g of ethanol was added, the mixture was discharged, coagulated, washed, and dried to obtain halogenated branched butyl rubber, designated S6 (bromine content 2.97 wt%).

[0235] Based on the total weight of S6, the weight ratio of structural unit A from isobutylene, structural unit B from isoprene, and structural unit C from grafting agent is 9:0.3:1.

[0236] S6 was made into a standard sample, and its performance is shown in Table 1.

[0237] Example 7

[0238] This embodiment illustrates the preparation of halogenated branched butyl rubber.

[0239] The method of Example 6 was followed, except that 50g of the multi-component copolymer (P2) obtained in Preparation Example 2 was used instead of 50g of the multi-component copolymer (P6) obtained in Preparation Example 6. All other conditions were the same as in Example 6. Halogenated branched butyl rubber was obtained, denoted as S7 (bromine content 3.16 wt%).

[0240] Based on the total weight of S7, the weight ratio of structural unit A from isobutylene, structural unit B from isoprene, and structural unit C from grafting agent is 9:0.3:1.

[0241] S7 was made into a standard sample, and its performance is shown in Table 1.

[0242] Example 8

[0243] This embodiment illustrates the preparation of halogenated branched butyl rubber.

[0244] The method of Example 6 was followed, except that 50g of the multi-component copolymer (P3) obtained in Preparation Example 3 was used instead of 50g of the multi-component copolymer (P6) obtained in Preparation Example 6. All other conditions were the same as in Example 6. Halogenated branched butyl rubber was obtained, denoted as S8 (bromine content 3.08wt%).

[0245] Based on the total weight of S8, the weight ratio of structural unit A from isobutylene, structural unit B from isoprene, and structural unit C from grafting agent is 9:0.3:1.

[0246] S8 was made into a standard sample, and its performance is shown in Table 1.

[0247] Example 9

[0248] The method of Example 1 was followed, except that an equal weight of the multi-component polymer P7 was used instead of the multi-component polymer P1. All other conditions were the same as in Example 1. A halogenated branched butyl rubber, designated S9 (bromine content 1.85 wt%), was obtained.

[0249] S9 was made into a standard sample, and its performance is shown in Table 1.

[0250] Example 10

[0251] The method of Example 2 was followed, except that an equal weight of the multi-component polymer P8 was used instead of the multi-component polymer P2. All other conditions were the same as in Example 2. A halogenated branched butyl rubber, designated S10 (bromine content 1.89 wt%), was obtained.

[0252] S10 was made into a standard sample, and its performance is shown in Table 1.

[0253] Example 11

[0254] The method of Example 3 was followed, except that an equal weight of the multi-component polymer P9 was used instead of the multi-component polymer P3. All other conditions were the same as in Example 3. A halogenated branched butyl rubber, designated S11 (bromine content 1.97 wt%), was obtained.

[0255] S11 was made into a standard sample, and its performance is shown in Table 1.

[0256] Comparative Example 1

[0257] The method of Example 5 was followed, except that an equal weight of the multi-component polymer DP1 was used instead of the multi-component polymer P5. All other conditions were the same as in Example 5. A halogenated branched butyl rubber, denoted as D1 (bromine content 0.58 wt%), was obtained.

[0258] D1 was made into a standard sample, and its performance is shown in Table 1.

[0259] Comparative Example 2

[0260] The method of Example 6 was followed, except that an equal weight of the multi-component polymer DP2 was used instead of the multi-component polymer P6. All other conditions were the same as in Example 6. A halogenated branched butyl rubber, denoted as D2 (bromine content 0.76 wt%), was obtained.

[0261] D2 was made into a standard sample, and its performance is shown in Table 1.

[0262] Table 1

[0263]

[0264] Note: In Table 1, T 10 T represents the scorching time, reflecting the size of the scorching safety window. 90 The positive vulcanization time reflects the speed of vulcanization.

[0265] As shown in Table 1, the halogenated branched butyl rubbers S1-S11 prepared using the multi-component copolymer of the present invention as grafting agents have a high halogen content, high saturation, high branching degree, low extrusion swell ratio, and short scorch time (T). 10 ) and positive vulcanization time (T 90 The S7 and S8 varieties exhibit short striations, low air permeability, and long static ozone cracking time, demonstrating excellent vulcanization characteristics, aging resistance, dimensional stability during product processing, and extremely high airtightness. Among these, S7 and S8 possess particularly outstanding comprehensive performance advantages. This invention achieves a balance between the aging resistance, dimensional stability, and vulcanization processing performance of highly saturated, highly branched halogenated branched butyl rubber. In contrast, Comparative Examples 1-2, which did not use the multi-component copolymer of this invention as a grafting agent, resulted in halogenated branched butyl rubber products D1-D2 with significantly inferior comprehensive performance compared to S1-S11.

[0266] 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 has the general formula shown in formula (I): Equation (I) R1, R2 and R3 are polymer chain segments, and their ends contain structural units from conjugated dienes. R1 contains styrene structural units and butadiene structural units; R2 contains the chain segment shown in equation (II), wherein, The connection position between the chain segment and the benzene ring shown in formula (II); Equation (II) R3 contains the chain segment shown in equation (III), wherein, The connection position between the chain segment and the benzene ring shown in formula (III); Equation (III) In equations (II) and (III), X is a styrene segment, and X is a halogen.

2. The multi-component copolymer according to claim 1, wherein, The halogen content in the multi-component copolymer is 10-30 wt%.

3. The multi-component copolymer according to claim 2, wherein, The halogen content in the multi-component copolymer is 15-25 wt%.

4. The multi-component copolymer according to claim 1, wherein, The content of structural units at the ends of the multi-component copolymer derived from conjugated dienes is 0.25-1 wt%.

5. The multi-component copolymer according to claim 4, wherein, The content of structural units at the ends of the multi-component copolymer derived from conjugated dienes is 0.3-0.9 wt%.

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

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

8. The multi-component copolymer according to claim 1, wherein, The number-average molecular weight of the multi-component copolymer is 80,000-90,000 g / mol.

9. The multi-component copolymer according to claim 8, wherein, The number-average molecular weight of the multi-component copolymer is 83,000-87,000 g / mol.

10. The multi-component copolymer according to claim 1, wherein, The molecular weight distribution index of the multi-component copolymer is 9-11.

11. The multi-component copolymer according to claim 10, wherein, The molecular weight distribution index of the multi-component copolymer is 9.3-10.

3.

12. A method for preparing a multi-component copolymer, characterized in that, The preparation method includes: (1-1) In the presence of a first initiator, isoprene undergoes a first polymerization reaction, the resulting first polymerization product undergoes a second polymerization reaction with styrene, and the resulting second polymerization product undergoes a first halogenation reaction in the presence of a second initiator and a halogenating agent to obtain product a; (1-2) Butadiene undergoes a third polymerization reaction in the presence of a first initiator. The resulting third polymerization product undergoes a fourth polymerization reaction with styrene. The resulting fourth polymerization product undergoes a second halogenation reaction in the presence of a second initiator and a halogenating agent to obtain product b. (1-3) In the presence of the first initiator, styrene and butadiene undergo a fifth polymerization reaction to obtain product c; (2) In the presence of a coupling agent, the products a, b and c are coupled together, and the coupling reaction products are capped with a conjugated diene to obtain the multi-component copolymer; The coupling agent has the general formula described in formula (IV): Formula (IV) Among them, R 1 R 2 and R 3 Each is independently selected from F, Cl, or Br.

13. The method according to claim 12, wherein, The first polymerization reaction, the second polymerization reaction, the third polymerization reaction, the fourth polymerization reaction, the first halogenation reaction, the second halogenation reaction, the coupling reaction, and the end-capping reaction are carried out in the presence of a solvent.

14. The method according to claim 13, wherein, The first, third, and fifth polymerization reactions are carried out in the presence of a structure modifier.

15. The method according to claim 14, wherein, The first halogenation reaction and the second halogenation reaction are carried out in the presence of a molecular weight regulator.

16. The method according to claim 15, wherein, Based on a total halogenating agent of 100 parts by weight in the method, the amount of each raw material fed in step (1-1) is as follows: 30-40 parts by weight of isoprene, 20-30 parts by weight of styrene, 0.1-0.3 parts by weight of structure modifier, 0.05-0.2 parts by weight of first initiator, 50-60 parts by weight of halogenating agent, 0.2-0.5 parts by weight of molecular weight modifier, and 0.1-0.4 parts by weight of second initiator.

17. The method according to claim 15, wherein, In steps (1-2), the amount of each raw material fed is as follows: 20-30 parts by weight of butadiene, 30-40 parts by weight of styrene, 0.1-0.3 parts by weight of structure modifier, 0.05-0.2 parts by weight of first initiator, 40-50 parts by weight of halogenating agent, 0.1-0.3 parts by weight of molecular weight modifier and 0.1-0.3 parts by weight of second initiator.

18. The method according to claim 14, wherein, In steps (1-3), the amount of each raw material fed is as follows: 5-10 parts by weight of butadiene, 10-20 parts by weight of styrene, 0.1-0.3 parts by weight of structure modifier, and 0.03-0.16 parts by weight of first initiator.

19. The method according to claim 12, wherein, In step (2), the coupling agent is 0.5-5 parts by weight and the conjugated diene is 1-2 parts by weight.

20. The method according to claim 13, wherein, The solvent is selected from at least one of straight-chain alkanes, aromatics, and cycloalkanes.

21. The method according to claim 20, wherein, The solvent is at least one selected from pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.

22. The method according to claim 21, wherein, The solvent is hexane.

23. The method according to claim 12, wherein, The first initiator is a hydrocarbon-based monolithium compound.

24. The method according to claim 23, wherein, The first initiator is RLi, wherein R is a saturated aliphatic hydrocarbon group containing 1-20 carbon atoms, an alicyclic hydrocarbon group containing 3-20 carbon atoms, an aromatic hydrocarbon group containing 6-20 carbon atoms, or a complex group of the above groups.

25. The method according to claim 24, wherein, The first initiator is at least one selected from n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthalenelithium, cyclohexyllithium, and dodecyllithium.

26. The method according to claim 12, wherein, The second initiator is an organic peroxide.

27. The method according to claim 26, wherein, The second initiator is at least one of di-tert-butyl hydroperoxide, 2,5-dimethyl-2,5-di-tert-butylhexane peroxide, di-tert-butyl peroxide, and dicumyl peroxide.

28. The method according to claim 27, wherein, The second initiator is di-tert-butyl peroxide.

29. The method according to claim 12, wherein, The halogenating agent is selected from at least one of N-bromosuccinimide, dimethyl thiobromobromo, N-bromosuccinimide, N-chlorosuccinimide, N-chlorosuccinimide, and dimethyl thiochloride chloride.

30. The method according to claim 29, wherein, The halogenating agent is at least one of N-bromosuccinimide, dimethyl bromide thiobromide, and N-bromosuccinimide.

31. The method according to claim 14, wherein, The structure modifier is a polar organic compound.

32. The method according to claim 31, wherein, The structure modifier is at least one selected from diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, and triethylamine.

33. The method according to claim 32, wherein, The structure modifier is tetrahydrofuran.

34. The method according to claim 15, wherein, The molecular weight regulator is selected from at least one of tert-decanethiol, tert-dodecanethiol, tert-tetradecanethiol, and tert-hexadecanethiol.

35. The method according to claim 15, wherein, The molecular weight regulator is tert-dodecyl mercaptan.

36. The method according to claim 12, wherein, The conjugated diene is selected from butadiene and / or isoprene.

37. The preparation method according to any one of claims 13-36, wherein, The conditions for the first polymerization reaction include: a temperature of 40-50℃ and a time of 20-30 min.

38. The preparation method according to claim 37, wherein, The conditions for the first polymerization reaction include: a temperature of 43-47°C and a time of 23-27 min.

39. The preparation method according to any one of claims 13-36, wherein, The conditions for the second polymerization reaction include: a temperature of 60-70℃ and a time of 40-50 min.

40. The preparation method according to claim 39, wherein, The conditions for the second polymerization reaction include: a temperature of 63-67°C and a time of 43-47 min.

41. The preparation method according to any one of claims 13-36, wherein, The conditions for the first halogenation reaction include: a temperature of 70-80℃ and a time of 2-4 hours.

42. The preparation method according to claim 41, wherein, The conditions for the first halogenation reaction include: a temperature of 73-77°C and a time of 2.5-3.5 h.

43. The preparation method according to any one of claims 13-36, wherein, The conditions for the third polymerization reaction include: a temperature of 40-50℃ and a time of 30-40 min.

44. The preparation method according to claim 43, wherein, The conditions for the third polymerization reaction include: a temperature of 43-47°C and a time of 33-37 min.

45. The preparation method according to any one of claims 13-36, wherein, The conditions for the fourth polymerization reaction include: a temperature of 50-60℃ and a time of 50-60 min.

46. ​​The preparation method according to claim 45, wherein, The conditions for the fourth polymerization reaction include: a temperature of 53-57°C and a time of 53-57 min.

47. The preparation method according to any one of claims 13-36, wherein, The conditions for the second halogenation reaction include: a temperature of 70-80℃ and a time of 2-3 hours.

48. The preparation method according to claim 47, wherein, The conditions for the second halogenation reaction include: a temperature of 73-77°C and a time of 2.3-2.7 h.

49. The preparation method according to any one of claims 13-36, wherein, The conditions for the fifth polymerization reaction include: a temperature of 60-70℃ and a time of 30-40 min.

50. The preparation method according to claim 49, wherein, The conditions for the fifth polymerization reaction include: a temperature of 63-67°C and a time of 33-37 min.

51. The preparation method according to any one of claims 13-36, wherein, The conditions for the coupling reaction include: a temperature of 80-90℃ and a time of 150-170 min.

52. The preparation method according to claim 51, wherein, The conditions for the coupling reaction include: a temperature of 83-87℃ and a time of 155-165 min.

53. The preparation method according to any one of claims 13-36, wherein, The conditions for the end-capping reaction include: a temperature of 80-90℃ and a time of 20-30 min.

54. The preparation method according to claim 53, wherein, The conditions for the end-capping reaction include: a temperature of 83-87℃ and a time of 23-27 min.

55. A multi-component copolymer prepared by the method of any one of claims 12-54.

56. The use of a multi-component copolymer according to any one of claims 1-11 and 55 as a grafting agent in the preparation of diene rubber.

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

58. A halogenated branched butyl rubber, characterized in that, The halogenated branched butyl rubber comprises: structural unit A from isobutylene, structural unit B from isoprene, and structural unit C from a grafting agent; The grafting agent is a multi-component copolymer as described in any one of claims 1-11 and 55.

59. The halogenated branched butyl rubber according to claim 58, wherein, Based on the total weight of the halogenated branched butyl rubber, the weight ratio of structural unit A, structural unit B and structural unit C is (6-15):(0.05-0.5):

1.

60. The halogenated branched butyl rubber according to claim 59, wherein, Based on the total weight of the halogenated branched butyl rubber, the weight ratio of structural unit A, structural unit B and structural unit C is (8-10):(0.1-0.3):

1.

61. A method for preparing halogenated branched butyl rubber, characterized in that, The method includes: In the presence of a diluent, a solvent, and a co-initiator, isobutylene, isoprene, and a grafting agent are subjected to a cationic polymerization reaction to obtain the halogenated branched butyl rubber. The grafting agent is a multi-component copolymer as described in any one of claims 1-11 and 55.

62. The method according to claim 61, wherein, Based on a total of 100 parts by weight of isobutylene and isoprene, the diluent is 30-80 parts by weight, the grafting agent is 6-15 parts by weight, and the co-initiator is 0.1-0.6 parts by weight.

63. The method according to claim 61, wherein, The weight ratio of isobutylene to isoprene is (25-95):

1.

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

65. The method according to claim 64, wherein, The haloalkane is a haloalkane with 1-4 carbon atoms.

66. The method according to claim 64, wherein, The diluent is selected from at least one of chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, fluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.

67. The method according to claim 61, wherein, The co-initiators include alkyl aluminum halides and protic acids.

68. The method according to claim 67, 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.

69. The method according to claim 67, wherein, The protic acid is selected from at least one of HCl, HF, HBr, H2SO4, H2CO3, H3PO4, and HNO3.

70. The method of claim 67, wherein, In the co-initiator, the molar ratio of the alkyl aluminum halide to the protic acid is (10-100):

1.

71. The method according to any one of claims 61-70, wherein, The conditions for the cationic polymerization include: a temperature of -100°C to -90°C and a time of 2-4 hours.

72. A halogenated branched butyl rubber prepared by the method according to any one of claims 61-71.

73. The use of the halogenated branched butyl rubber according to any one of claims 58-60 and 72 in tires and medical stoppers.

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