Multicomponent copolymer, its manufacturing method and use thereof, and halogenated branched butyl rubber, its manufacturing method and use thereof

Abstract

The present invention relates to the technical field of rubber production and discloses a multicomponent copolymer, its production method, and use, as well as a halogenated branched butyl rubber, its production method, and use. The multicomponent copolymer has the general formula shown in Formula (I). By using the multicomponent copolymer as a grafting agent to produce halogenated branched butyl rubber, the saturation degree of the halogenated branched butyl rubber is increased, the die swelling effect is significantly reduced, the vulcanization rate is increased, and the ozone aging resistance and airtightness are improved, thereby achieving a balance between the aging resistance of the highly branched, highly saturated halogenated branched butyl rubber, the dimensional stability of the product, and vulcanization processability. TIFF2025528184000025.tif39170 (R1, R2, and R3 are each a polymer segment containing a structural unit derived from a conjugated diene at the end, R1 contains a styrene structural unit and a butadiene structural unit, and R2 contains a segment represented by formula (II), TIFF2025528184000026.tif23170R3 contains a segment represented by formula (III), TIFF2025528184000027.tif18170 where, TIFF2025528184000028.tif9170 is a styrene segment, and X is a halogen.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of Chinese Patent Application No. 202211173618.9, filed on September 26, 2022, entitled "Multicomponent copolymer, its manufacturing method and use, and halogenated branched butyl rubber, its manufacturing method and use," the contents of which are incorporated herein by reference.

[0002] The present invention relates to the technical field of rubber production, and in particular to a multicomponent copolymer, its preparation method and use thereof, and a halogenated branched butyl rubber, its preparation method and use thereof. [Background technology]

[0003] Butyl rubber (IIR) is a copolymer of isobutylene and a small amount of isoprene through cationic polymerization. Its excellent airtightness and damping properties make it the most important synthetic rubber, widely used in the manufacture of inner tubes, airtight layers, and vulcanized capsules for automobile tires. The molecular chain of highly saturated butyl rubber is primarily composed of carbon-carbon single bonds, and its low degree of unsaturation (only about 0.5-1.5%) gives it extremely low breathability and excellent ozone resistance. It is used in the airtight layers of load-bearing tires in harsh environments and working conditions, as well as in the medical field.

[0004] In addition, highly saturated butyl rubber has drawbacks such as polymer chain isotacticity, high crystallinity, low viscoelasticity, and slow vulcanization speed. As a result, highly saturated butyl rubber has low vulcanization efficiency during processing, poor vulcanization performance, and is prone to excessive flow and deformation, which are bottlenecks that limit the use of butyl rubber in high-end applications.

[0005] Therefore, there is an urgent need to solve the problems of significant die swelling effect during processing of butyl rubber, long vulcanization scorch time, slow vulcanization rate, and poor ozone aging resistance. Summary of the Invention [Problem to be solved by the invention]

[0006] The object of the present invention is to provide a multicomponent copolymer, a method for producing the same and a use thereof, as well as a halogenated branched butyl rubber, a method for producing the same and a use thereof, in order to solve the problems existing in conventional butyl rubber, such as a significant die swelling effect, a long vulcanization scorch time, a slow vulcanization rate, and poor ozone aging resistance. [Means for solving the problem]

[0007] To achieve the above object, a first aspect of the present invention provides a multicomponent copolymer having the general formula shown in formula (I). TIFF2025528184000002.tif39170 (wherein R1, R2, and R3 are each a polymer segment containing a structural unit derived from a conjugated diene at the end, R1 comprises a styrene structural unit and a butadiene structural unit, R2 comprises a segment of formula (II), wherein: TIFF2025528184000003.tif6170 represents the linking position of the segment represented by formula (II) with the benzene ring, TIFF2025528184000004.tif23170R3 comprises a segment represented by formula (III), wherein: TIFF2025528184000005.tif6170 represents the linking position of the segment represented by formula (III) with the benzene ring, TIFF2025528184000006.tif18170In formula (II) and formula (III), TIFF2025528184000007.tif9170 is a styrene segment, and X is a halogen.

[0008] A second aspect of the present invention is a step (1-1) of subjecting isoprene to a first polymerization reaction in the presence of a first initiator, subjecting the resulting first polymerization reaction product and styrene to a second polymerization reaction, and subjecting the resulting second polymerization reaction product to a first halogenation reaction in the presence of a second initiator and a halogenating agent to obtain a product a; a step (1-2) of subjecting butadiene to a third polymerization reaction in the presence of a first initiator, subjecting the obtained third polymerization reaction product and styrene to a fourth polymerization reaction, and subjecting the obtained fourth polymerization reaction product to a second halogenation reaction in the presence of a second initiator and a halogenating agent to obtain a product b; (1-3) subjecting styrene and butadiene to a fifth polymerization reaction in the presence of a first initiator to obtain product c; and step (2) of coupling the product a, the product b, and the product c in the presence of a coupling agent, and then capping the coupling reaction product with a conjugated diene to obtain the multicomponent copolymer; The coupling agent has the general formula (IV), which provides a method for producing a multi-component copolymer. TIFF2025528184000008.tif40170 (where R 1 , R 2 , and R 3 are each independently selected from F, Cl, or Br.

[0009] A third aspect of the present invention provides a multicomponent copolymer produced by the method according to the second aspect.

[0010] A fourth aspect of the present invention provides use of the multicomponent copolymer according to the first or third aspect as a grafting agent in the production of a diene rubber.

[0011] A fifth aspect of the present invention is a polymer comprising structural units A derived from isobutylene, structural units B derived from isoprene, and structural units C derived from a grafting agent, The grafting agent provides a halogenated branched butyl rubber that is the multicomponent copolymer according to the first or third aspect.

[0012] A sixth aspect of the present invention is a method for producing a halogenated branched butyl rubber, comprising the steps of: cationic polymerization of isobutylene, isoprene, and a grafting agent in the presence of a diluent, a solvent, and a coinitiator to obtain the halogenated branched butyl rubber; The present invention provides a method for producing a halogenated branched butyl rubber, wherein the grafting agent is the multicomponent copolymer according to the first or third aspect.

[0013] A seventh aspect of the present invention provides a halogenated branched butyl rubber produced by the method according to the sixth aspect.

[0014] An eighth aspect of the present invention provides use of the halogenated branched butyl rubber according to the fifth or seventh aspect in tires and medical rubber stoppers. [Effects of the Invention]

[0015] According to the above technical solution, the present invention can achieve the following beneficial effects:

[0016] (1) The multicomponent copolymer of the present invention combines structurally distinct -BR, -IR, -PS, and -SBR segments in the polymer chain to form a "three-arm" star structure and possesses a stable 2-position halogen-substituted structure. The 2-position halogen-substituted structure is obtained by adding a halogenating agent to the unsaturated "double bonds" of the -BR and -IR segments, significantly reducing the content of unsaturated "double bonds." This multicomponent copolymer is used as a grafting agent for producing halogenated branched butyl rubber. The synergistic effects of its distinct segment characteristics, "three-arm" star structure, and stable 2-position halogen-substituted structure increase the degree of saturation of the butyl rubber, significantly reduce the die swelling effect, greatly accelerate the vulcanization rate, and significantly improve the ozone aging resistance and airtightness. This balances the aging resistance, dimensional stability, and vulcanization processability of the highly branched, highly saturated halogenated branched butyl rubber.

[0017] (2) The multicomponent copolymer of the present invention does not emit volatile organic compounds (VOCs) or hydrogen halide by-products during the production process, and the production method is environmentally friendly, has a short process flow, and the 2-position halogen substitution structure is controllable, making it suitable for industrial production. When used as a grafting agent in the production of diene rubber, it can significantly expand the application range of halogenated branched butyl rubber. DETAILED DESCRIPTION OF THE INVENTION

[0018] The endpoints of ranges and any values ​​disclosed herein are not intended to be limiting to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. In the case of numerical ranges, the endpoints of each range, the endpoints of each range and the individual point values, and the individual point values ​​can be combined to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0019] A first aspect of the present invention provides a multicomponent copolymer having the general formula shown in formula (I). TIFF2025528184000009.tif39170 (wherein R1, R2, and R3 are each a polymer segment containing a structural unit derived from a conjugated diene at its end, R1 comprises a styrene structural unit and a butadiene structural unit, R2 comprises a segment of formula (II), wherein: TIFF2025528184000010.tif6170 represents the linking position of the segment represented by formula (II) with the benzene ring, TIFF2025528184000011.tif23170R3 comprises a segment represented by formula (III), wherein: TIFF2025528184000012.tif6170 represents the linking position of the segment represented by formula (III) with the benzene ring, TIFF2025528184000013.tif18170In formula (II) and formula (III), TIFF2025528184000014.tif9170 is a styrene segment, and X is a halogen.

[0020] In the present invention, the "position of attachment to a benzene ring" refers to the position of attachment to a benzene ring in formula (I).

[0021] According to the present invention, in the multicomponent copolymer, the styrene structural units and butadiene structural units contained in R1 are obtained by random copolymerization of styrene and 1,3-butadiene. The segment represented by R2 includes a block obtained by halogenating an isoprene homopolymer block with a halogenating agent and a styrene homopolymer block. The segment represented by R3 includes a block obtained by halogenating a 1,3-butadiene homopolymer block with a halogenating agent and a styrene homopolymer block. In the multicomponent copolymer, the above structurally different segments are linked at the 1, 3, and 5 positions of the benzene ring structure to form a "three-arm" star structure. The multicomponent copolymer also has a stable 2-position halogen-substituted structure and contains structural units derived from conjugated dienes at its terminals. This makes it highly polymerizable and useful as a grafting agent for the production of branched diene rubber, particularly halogenated branched diene rubber. It can increase the degree of saturation of butyl rubber, significantly reduce the die swelling effect, significantly increase the vulcanization rate, and significantly improve ozone aging resistance and airtightness.

[0022] According to the present invention, in formula (II) and formula (III), n and m represent repeating blocks, and the numerical values ​​of n and m are not particularly limited in the present invention.

[0023] According to the present invention, the molar ratio of R1:R2:R3:phenyl in the multicomponent copolymer is (1-4):(2-9):(2-9):0.1. When the molar ratio of the above structures in the multicomponent copolymer satisfies this range, a multicomponent copolymer having the "three-arm" star structure can be synthesized.

[0024] According to the present invention, the content of the structural units derived from the conjugated diene at the terminals of the multicomponent copolymer is 0.25 to 1 wt%, preferably 0.3 to 0.9 wt%. When the content of the structural units derived from the conjugated diene in the multicomponent copolymer satisfies the above range, the multicomponent copolymer can have high polymerization activity, which is advantageous for producing a halogenated branched diene rubber by polymerizing the multicomponent copolymer with a diene monomer such as isobutylene or isoprene as a grafting agent.

[0025] In the present invention, the proportion and content of each of the above structures in the multi-component copolymer may be measured by infrared spectroscopy or nuclear magnetic resonance, or calculated according to the relationship between raw material inputs during the production process.

[0026] According to the present invention, the halogen content in the multicomponent copolymer is 10 to 30 wt%, preferably 15 to 25 wt%. When the halogen content in the multicomponent copolymer satisfies the above range, the halogenated branched diene rubber obtained by polymerizing the multicomponent copolymer as a grafting agent has a high halogen content.

[0027] In the present invention, the halogen content in the multicomponent copolymer is measured by a thermogravimetric analyzer.

[0028] According to the present invention, in the segments of formula (II) and formula (III), X is selected from F, Cl or Br, preferably Cl or Br, more preferably Br.

[0029] According to the invention, the conjugated diene is selected from butadiene and / or isoprene.

[0030] According to the present invention, the number average molecular weight of the multicomponent copolymer is 80,000 to 90,000 g / mol, preferably 83,000 to 87,000 g / mol.

[0031] According to the present invention, the molecular weight distribution index (Mw / Mn) of the multicomponent copolymer is 9 to 11, preferably 9.3 to 10.3.

[0032] In the present invention, the number average molecular weight and the molecular weight distribution index are measured by gel chromatography.

[0033] A second aspect of the present invention is a step (1-1) of subjecting isoprene to a first polymerization reaction in the presence of a first initiator, subjecting the resulting first polymerization reaction product and styrene to a second polymerization reaction, and subjecting the resulting second polymerization reaction product to a first halogenation reaction in the presence of a second initiator and a halogenating agent to obtain a product a; a step (1-2) of subjecting butadiene to a third polymerization reaction in the presence of a first initiator, subjecting the obtained third polymerization reaction product and styrene to a fourth polymerization reaction, and subjecting the obtained fourth polymerization reaction product to a second halogenation reaction in the presence of a second initiator and a halogenating agent to obtain a product b; (1-3) subjecting styrene and butadiene to a fifth polymerization reaction in the presence of a first initiator to obtain product c; and step (2) of coupling the product a, the product b, and the product c in the presence of a coupling agent, and then capping the coupling reaction product with a conjugated diene to obtain the multicomponent copolymer; The coupling agent has the general formula (IV), which provides a method for producing a multi-component copolymer. TIFF2025528184000015.tif40170 (where R 1 , R 2 , and R 3 are each independently selected from F, Cl, or Br.

[0034] According to the above-mentioned preparation method of the present invention, the coupling agent 1,3,5-trihalobenzene is used to combine the structurally different -BR-, -IR-, -PS-, and -SBR- segments in the polymer chain to form a "three-arm" star structure, which is then halogenated with a halogenating agent during the preparation process to obtain a stable 2-position halogen-substituted structure. Finally, a conjugated diene structural unit is introduced for capping. As a result, the resulting multicomponent copolymer has high polymerization activity and excellent performance as a grafting agent in the production of halogenated branched butyl rubber. The preparation method of the multicomponent copolymer does not emit hydrogen halide as a by-product during the implementation process, making it environmentally friendly and simple.

[0035] According to the present invention, in the method for producing the multicomponent 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 capping reaction are all carried out in the presence of a solvent. Furthermore, the first polymerization reaction, the third polymerization reaction, and the fifth polymerization reaction are preferably carried out in the presence of a structure modifier, and the first halogenation reaction and the second halogenation reaction are preferably carried out in the presence of a molecular weight modifier.

[0036] According to the present invention, a three-kettle polymerization method is adopted in which step (1-1), step (1-2), and step (1-3) are carried out in three reaction vessels, respectively, as will be specifically described below.

[0037] According to the present invention, in step (1-1), relative to a total amount of 100 parts by weight of halogenating agent in the method for producing the multi-component copolymer, the amounts of each raw material added in step (1-1) are 100 to 200 parts by weight of solvent, 30 to 40 parts by weight of isoprene, 20 to 30 parts by weight of styrene, 0.1 to 0.3 parts by weight of structure modifier, 0.05 to 0.2 parts by weight of first initiator, 50 to 60 parts by weight of halogenating agent, 0.2 to 0.5 parts by weight of molecular weight modifier, and 0.1 to 0.4 parts by weight of second initiator.

[0038] According to the present invention, in step (1-1), the operation process of the first polymerization reaction, the second polymerization reaction, and the first halogenation reaction is as follows: prepare the raw materials in the above-mentioned proportions; introduce an inert gas into the first reactor to remove oxygen; add a solvent, isoprene, and a structure modifier; heat the mixture to a temperature required for the first polymerization reaction; add a first initiator; and carry out the first polymerization reaction; after the first polymerization reaction is completed, add styrene and a structure modifier into the first reactor; heat the mixture to a temperature required for the second polymerization reaction; and carry out the second polymerization reaction; after the second polymerization reaction is completed, add a halogenating agent and a molecular weight modifier into the first reactor; heat the mixture to a temperature required for the first halogenation reaction; add a second initiator to start the first halogenation reaction; and after the reaction is completed, obtain product a.

[0039] According to the present invention, the temperature of the first polymerization reaction is 40 to 50°C, preferably 43 to 47°C. If the temperature of the first polymerization reaction is too low, the polymerization is insufficient and the molecular weight of the first polymerization reaction product is too low, while if the temperature of the first polymerization reaction is too high, the molecular structure of the first polymerization reaction product changes. The time of the first polymerization reaction is 20 to 30 minutes, preferably 23 to 27 minutes. If the time of the first polymerization reaction is too short, the polymerization is insufficient and the molecular weight of the first reaction product is too low, while the time of the first polymerization reaction is too long, resulting in increased production costs.

[0040] According to the present invention, the temperature of the second polymerization reaction is 60 to 70°C, preferably 63 to 67°C. If the temperature of the second polymerization reaction is too low, the polymerization is insufficient and the molecular weight of the second polymerization reaction product is too low, while if the temperature of the second polymerization reaction is too high, the molecular structure of the second polymerization reaction product changes. The time of the second polymerization reaction is 40 to 50 minutes, preferably 43 to 47 minutes. If the time of the second polymerization reaction is too short, the polymerization is insufficient and the molecular weight of the second reaction product is too low, while if the time of the second polymerization reaction is too long, the production cost increases.

[0041] According to the present invention, the temperature of the first halogenation reaction is 70 to 80°C, preferably 73 to 77°C. If the temperature of the first halogenation reaction is too low, halogenation is insufficient and the halogen content of the product a is too low. If the temperature of the first halogenation reaction is too high, the molecular weight of the product a is too high and the molecular weight distribution is too broad. The time for the first halogenation reaction is 2 to 4 hours, preferably 2.5 to 3.5 hours. If the time for the first halogenation reaction is too short, the molecular weight of the product a is too low. If the time for the first halogenation reaction is too long, the production cost increases.

[0042] According to the present invention, in step (1-2), relative to a total amount of 100 parts by weight of halogenating agent in the multicomponent copolymer production method, the amounts of each raw material added in step (1-1) are 100 to 200 parts by weight of solvent, 20 to 30 parts by weight of butadiene, 30 to 40 parts by weight of styrene, 0.1 to 0.3 parts by weight of structure modifier, 0.05 to 0.2 parts by weight of first initiator, 40 to 50 parts by weight of halogenating agent, 0.1 to 0.3 parts by weight of molecular weight modifier, and 0.1 to 0.3 parts by weight of second initiator.

[0043] According to the present invention, in step (1-2), the operation process of the third polymerization reaction, the fourth polymerization reaction, and the second halogenation reaction is as follows: prepare the raw materials in the above-mentioned proportions; introduce an inert gas into the second reactor to remove oxygen gas; then add the solvent, butadiene, and structure modifier; heat the temperature to the required temperature for the third polymerization reaction; add the first initiator; carry out the third polymerization reaction; after the third polymerization reaction is completed, add styrene into the second reactor; heat the temperature to the required temperature for the fourth polymerization reaction; carry out the fourth polymerization reaction; after the fourth polymerization reaction is completed, add the halogenating agent and molecular weight modifier into the second reactor; heat the temperature to the required temperature for the second halogenation reaction; add the second initiator; carry out the second halogenation reaction; after the reaction is completed, obtain product b.

[0044] According to the present invention, the temperature of the third polymerization reaction is 40 to 50°C, preferably 43 to 47°C. If the temperature of the third polymerization reaction is too low, the polymerization is insufficient and the molecular weight of the third polymerization reaction product is too low, while if the temperature of the third polymerization reaction is too high, the molecular structure of the third polymerization reaction product changes. The time of the third polymerization reaction is 30 to 40 minutes, preferably 33 to 37 minutes. If the time of the third polymerization reaction is too short, the polymerization is insufficient and the molecular weight of the third polymerization reaction product is too low, while if the time of the third polymerization reaction is too long, the production cost increases.

[0045] According to the present invention, the temperature of the fourth polymerization reaction is 50 to 60°C, preferably 53 to 57°C. If the temperature of the fourth polymerization reaction is too low, the polymerization is insufficient and the molecular weight of the fourth polymerization reaction product is too low, while if the temperature of the fourth polymerization reaction is too high, the molecular structure of the fourth polymerization reaction product changes. The time of the fourth polymerization reaction is 50 to 60 minutes, preferably 53 to 57 minutes. If the time of the fourth polymerization reaction is too short, the polymerization is insufficient and the molecular weight of the fourth polymerization reaction product is too low, while if the time of the fourth polymerization reaction is too long, the production cost increases.

[0046] According to the present invention, the temperature of the second halogenation reaction is 70 to 80°C, preferably 73 to 77°C. If the temperature of the second halogenation reaction is too low, halogenation is insufficient and the halogen content of the product b is too low. If the temperature of the second halogenation reaction is too high, the molecular weight of the product b is too high and the molecular weight distribution is too broad. The time for the second halogenation reaction is 2 to 3 hours, preferably 2.3 to 2.7 hours. If the time for the second halogenation reaction is too short, the molecular weight of the product b is too low, and the time for the second halogenation reaction is too long, resulting in increased production costs.

[0047] According to the present invention, in steps (1-1) and (1-2), the unsaturated "double bonds" in the -BR- and -IR- segments produced by the second and fourth polymerization reactions are subjected to free radical addition with a halogenating agent under initiation with a specific second initiator, significantly reducing the content of unsaturated "double bonds." This prevents the introduction of unsaturated "double bonds" in the subsequent branching of the butyl rubber, further increasing the degree of saturation of the butyl rubber, and significantly improving the ozone resistance and airtightness of the butyl rubber.

[0048] Furthermore, the 2-position halogen structure formed by halogenation with a halogenating agent, unlike the ion substitution method used in conventional technologies, avoids the production of hydrogen halide as a by-product and eliminates the condition for isomerization from the 2-position halogen structure to the 1-position structure, improving the stability of the 2-position halogen structure in halogenated branched butyl rubber and further accelerating the vulcanization rate of halogenated branched butyl rubber, thereby resolving the problem of the slow vulcanization rate of butyl rubber during processing.

[0049] According to the present invention, in step (1-3), relative to a total amount of 100 parts by weight of the halogenating agent in the method for producing the multi-component copolymer, the amounts of the raw materials added in step (1-3) are 100 to 200 parts by weight of solvent, 5 to 10 parts by weight of butadiene, 10 to 20 parts by weight of styrene, 0.1 to 0.3 parts by weight of structure modifier, and 0.03 to 0.16 parts by weight of first initiator.

[0050] According to the present invention, in step (1-3), the operation process of the fifth polymerization reaction is as follows: prepare each raw material in the above-mentioned ratio; introduce inert gas into the third reactor to remove oxygen gas; add solvent, styrene, butadiene, and structure modifier; heat to a temperature required for the fifth polymerization reaction; add the first initiator; and carry out the fifth polymerization reaction to obtain product c.

[0051] According to the present invention, the temperature of the fifth polymerization reaction is 60 to 70°C, preferably 63 to 67°C. If the temperature of the fifth polymerization reaction is too low, the polymerization is insufficient and the molecular weight of the product c is too low, while if the temperature of the fifth polymerization reaction is too high, abnormal polymerization or flash polymerization occurs. The time of the fifth polymerization reaction is 30 to 40 minutes, preferably 33 to 37 minutes. If the time of the fifth polymerization reaction is too short, the polymerization is insufficient and the molecular weight of the product c is too low, while if the time of the fifth polymerization reaction is too long, the production cost increases.

[0052] According to the present invention, the -PS- segment and -SBR- segment produced by the second polymerization reaction, the fourth polymerization reaction, and the fifth polymerization reaction in steps (1-1), (1-2), and (1-3) contain a large amount of benzene rings, and the benzene rings have high rigidity, large steric hindrance, and high strength, which can compensate for the decrease in strength of butyl rubber caused by improved disorder of molecular segments.

[0053] According to the present invention, in step (2), the amounts of each raw material added in step (2) are 0.5 to 5 parts by weight of coupling agent and 1 to 2 parts by weight of conjugated diene relative to 100 parts by weight of the total amount of halogenating agent in the multi-component copolymer production method, and product a, product b, and product c are the amounts of products obtained in step (1-1), step (1-2), and step (1-3), respectively.

[0054] According to the present invention, in step (2), the operation process of the coupling reaction and capping reaction is as follows: prepare each raw material in the above-mentioned ratio; put the product b produced in the second reactor and the product c produced in the third reactor into the first reactor and mix with the product a; heat the mixture to a temperature required for the coupling reaction; carry out the coupling reaction; after the coupling reaction is completed, maintain the temperature required for the coupling reaction; add a conjugated diene to the first reactor to carry out the capping reaction; and then wet-coagulate and bake the reaction product to obtain the multi-component copolymer.

[0055] According to the present invention, the temperature of the coupling reaction is 80 to 90°C, preferably 83 to 87°C. If the temperature of the coupling reaction is too low, the coupling effect is reduced and the segment distribution of the produced multicomponent copolymer becomes narrow. As a result, the viscoelasticity and dimensional stability of the rubber produced using the multicomponent copolymer deteriorate. If the temperature of the coupling reaction is too high, the coupling effect is affected. The time of the coupling reaction is 150 to 170 minutes, preferably 155 to 165 minutes. If the time of the coupling reaction is too short or too long, the coupling reaction effect is affected.

[0056] According to the present invention, the temperature of the capping reaction is 80 to 90°C, preferably 83 to 87°C. If the temperature of the capping reaction is too low, the capping effect will be deteriorated, and if the temperature of the capping reaction is too high, the conjugated diene will self-polymerize and will not be able to perform the capping function. The time of the capping reaction is 20 to 30 minutes, preferably 23 to 27 minutes. If the time of the capping reaction is too short, the capping will be insufficient and the capping effect will be deteriorated, and if the time of the capping reaction is too long, there will be no obvious change in the product after capping is completed, resulting in increased production costs.

[0057] According to the present invention, in step (2), the resulting "three-arm" star structure can effectively disrupt the molecular chain regularity during copolymerization of isobutylene and isoprene during the preparation of halogenated branched butyl rubber, improve segment disorder, impart excellent viscoelasticity to the butyl rubber, reduce the die swelling effect, and ensure the processing dimensional stability of the butyl rubber.

[0058] According to the present invention, in the method for producing the multicomponent copolymer, the solvent is at least one selected from linear alkanes, aromatic hydrocarbons, and cycloalkanes, more preferably at least one selected from pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, and ethylbenzene, more preferably hexane. In the present invention, the solvents used in each step may be the same or different, but are preferably the same.

[0059] According to the present invention, in the method for producing a multicomponent copolymer, the first initiator is a hydrocarbyl monolithium compound, preferably RLi, where R comprises a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a composite group of the above groups. More preferably, the first initiator is at least one selected from n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium, and dodecyllithium. In the present invention, the first initiators used in each step may be the same or different, but are preferably the same.

[0060] According to the present invention, in the method for producing the multicomponent copolymer, the second initiator is an organic peroxide, more preferably at least one of di-tert-butyl hydroperoxide (TBHP), 2,5-dimethyl-2,5-di-tert-butylhexane peroxide (BPDH), di-tert-butyl peroxide (DTBP), and dicumyl peroxide (DCP), more preferably di-tert-butyl peroxide. In the present invention, the second initiators used in each step may be the same or different, but are preferably the same.

[0061] According to the present invention, in the method for producing the multicomponent copolymer, the halogenating agent is preferably an organic halogenating agent, and the halogenating agent is preferably at least one selected from N-bromosuccinimide, bromodimethylsulfonium bromide, N-bromosuccinimide, N-chlorosuccinimide, N-chlorosuccinimide, and chlorodimethylsulfonium chloride, more preferably at least one selected from N-bromosuccinimide, bromodimethylsulfonium bromide, and N-bromosuccinimide. In the present invention, the halogenating agents used in each step may be the same or different, but are preferably the same.

[0062] According to the present invention, in the method for producing the multicomponent copolymer, the structure control agent is a polar organic compound, more preferably at least one of diethylene glycol dimethyl ether, tetrahydrofuran, ethyl ether, ethyl methyl ether, anisole, diphenyl ether, glycol dimethyl ether, and triethylamine, and more preferably tetrahydrofuran.

[0063] In the present invention, the structure-controlling agents used in each step may be the same or different, but are preferably the same.

[0064] According to the present invention, in the method for producing a multicomponent copolymer, the molecular weight modifier is at least one selected from tert-decyl mercaptan, tert-dodecyl mercaptan, tert-tetradecyl mercaptan, and tert-hexadecyl mercaptan, more preferably tert-dodecyl mercaptan. In the present invention, the molecular weight modifiers used in each step may be the same or different, but are preferably the same.

[0065] According to the present invention, in the method for producing a multicomponent copolymer, the conjugated diene is selected from butadiene and / or isoprene.

[0066] A third aspect of the present invention provides a multicomponent copolymer produced by the method according to the second aspect.

[0067] According to the present invention, the multicomponent copolymer produced by the method described in the second aspect of the present invention has the same structural composition, performance index and functions as the multicomponent copolymer described in the first aspect of the present invention, and therefore will not be described in detail here.

[0068] A fourth aspect of the present invention provides use of the multicomponent copolymer according to the first or third aspect as a grafting agent in the production of a diene rubber.

[0069] According to the present invention, preferably, the diene rubber is a butyl rubber.

[0070] A fifth aspect of the present invention is a polymer comprising structural units A derived from isobutylene, structural units B derived from isoprene, and structural units C derived from a grafting agent, The grafting agent provides a halogenated branched butyl rubber that is the multicomponent copolymer according to the first or third aspect.

[0071] According to the present invention, the weight ratio of the structural units A, B, and C, based on the total weight of the halogenated branched butyl rubber, is (6-15):(0.05-0.5):1, preferably (8-10):(0.1-0.3):1. In the present invention, by adjusting the weight ratio of the structural units A, B, and C to a specific range, a halogenated branched butyl rubber having an appropriate halogen content can be obtained.

[0072] The halogenated branched butyl rubber according to the present invention contains structural units derived from the specific grafting agent described above. The grafting agent combines structurally different -BR-, -IR-, -PS-, and -SBR- segments in the polymer chain to form a "three-arm" star structure, and also results in a stable 2-position halogen-substituted structure. The above-mentioned segments, the "three-arm" star structure, and the stable 2-position halogen-substituted structure are introduced into the butyl rubber structure by graft polymerization, and act synergistically. As a result, the halogenated branched butyl rubber has a high degree of saturation and branching, a significantly reduced die swelling effect, a fast vulcanization rate, excellent ozone aging resistance, and good airtightness.

[0073] A sixth aspect of the present invention is a method for producing a halogenated branched butyl rubber, comprising the steps of: cationic polymerization of isobutylene, isoprene, and a grafting agent in the presence of a diluent, a solvent, and a coinitiator to obtain the halogenated branched butyl rubber; The present invention provides a method for producing a halogenated branched butyl rubber, wherein the grafting agent is the multicomponent copolymer according to the first or third aspect.

[0074] According to the present invention, in the method for producing the halogenated branched butyl rubber, the solvent is 30 to 80 parts by weight, the diluent is 30 to 80 parts by weight, the grafting agent is 6 to 15 parts by weight, and the coinitiator is 0.1 to 0.6 parts by weight, relative to 100 parts by weight of the total amount of isobutylene and isoprene.

[0075] According to the present invention, in the method for producing the halogenated branched butyl rubber, the weight ratio of isobutylene:isoprene is (25-95):1.

[0076] In the present invention, by controlling the amounts of isobutylene, isoprene, and grafting agent added within the above-mentioned specific ranges, a halogenated branched butyl rubber excellent in aging resistance, dimensional stability of the product, and vulcanization processability can be obtained.

[0077] According to the present invention, the cationic polymerization reaction can be carried out using a reaction process for producing butyl rubber using a conventional grafting agent. Preferably, the raw materials are prepared in the above-mentioned proportions, an inert gas is introduced into a reactor to remove oxygen, a mixture of a solvent and a first portion of a diluent (diluent:solvent volume ratio of 70-30:30-70) is added, and the grafting agent is added. The grafting agent is fully dissolved, and the temperature is lowered to -95 to -85°C. Then, the second portion of the diluent, isobutylene, and isoprene are added, and the temperature is adjusted to the temperature required for the cationic polymerization reaction. The remaining diluent and coinitiator (both of which are premixed and aged at -95 to -85°C) are then 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, and the product is coagulated, washed, and dried to obtain the halogenated branched butyl rubber.

[0078] 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 becomes long and the molecular weight of the rubber product becomes too low, while 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 to 4 hours. If the time of the cationic polymerization reaction is too short, the reaction is insufficient and the molecular weight of the rubber product becomes too low, while if the time of the cationic polymerization reaction is too long, the molecular structure of the product rubber may change.

[0079] According to the present invention, in the method for producing halogenated branched butyl rubber, the solvent is at least one selected from linear alkanes, aromatic hydrocarbons, and cycloalkanes, more preferably at least one selected from pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene, and more preferably hexane.

[0080] According to the present invention, in the method for producing halogenated branched butyl rubber, the diluent is a haloalkane, and the halogen in the haloalkane is F, Cl, or Br, and preferably, the haloalkane is a haloalkane having 1 to 4 carbon atoms.

[0081] In the present invention, the diluent is preferably at least one selected from methyl chloride, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.

[0082] In the present invention, the ratio of the first part of the diluent, the second part of the diluent, and the remaining diluent may be selected according to the ordinary skill in the art, and is not particularly limited in the present invention.

[0083] According to the present invention, the coinitiator includes an alkylaluminum halide and a protonic acid. Preferably, in the coinitiator, the molar ratio of the alkylaluminum halide to the protonic acid is (10-100):1.

[0084] According to the present invention, the alkylaluminum halide is at least one selected from diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, dimethylaluminum chloride, and ethylaluminum chloride.

[0085] According to the present invention, the protonic acid is at least one selected from HCl, HF, HBr, H2SO4, H2CO3, H3PO4, and HNO3.

[0086] According to the present invention, the terminator is at least one selected from methanol, ethanol, and butanol.

[0087] A seventh aspect of the present invention provides a halogenated branched butyl rubber produced by the method according to the sixth aspect.

[0088] According to the present invention, the halogenated branched butyl rubber produced by the method according to the sixth aspect of the present invention has the same structural composition, performance indicators and functions as the halogenated branched butyl rubber according to the fifth aspect of the present invention, and therefore will not be described in detail here.

[0089] An eighth aspect of the present invention provides use of the halogenated branched butyl rubber according to the fifth or seventh aspect in tires and medical rubber stoppers.

[0090] The halogenated branched butyl rubber described in the present invention has a high degree of saturation and branching, a low die swelling effect, a fast vulcanization rate, high resistance to ozone aging, and excellent airtightness, and can meet the requirements for butyl rubber aging resistance, product dimensional stability, and vulcanization processability required for tire inner tubes, tire airtight layers, and medical rubber stoppers.

[0091] The present invention will be described in detail below with reference to examples.

[0092] In the following examples and comparative examples, unless specific conditions are described, conventional conditions or conditions proposed by the manufacturer are followed. Reagents or equipment used without a manufacturer's name are all commercially available products. The weight ratio relationship between the resulting multicomponent copolymer product and each structural unit contained in the halogenated branched butyl rubber was determined by calculation based on the input amounts.

[0093] (1) Origin of raw materials: Styrene, 1,3-butadiene: Polymerization grade, China Petroleum Lanzhou Petrochemical Corporation Isobutylene, Isoprene: Polymerization Grade, Zhejiang Xinhui New Materials Co., Ltd. N-Bromosuccinimide: Polymerization grade, Jiangsu Runfeng Synthetic Technology Co., Ltd. N-chlorosuccinimide: Polymerization grade, Wuhan Shuer Biotechnology Co., Ltd. Di-tert-butyl peroxide (DTBP): Lanzhou Auxiliary Agent Plant n-Butyllithium: 98% purity, Nanjing Tonglian Chemical Industry Co., Ltd. Ethyl aluminum sesquichloride: 98% purity, manufactured by Bai Lingwei Technology Co., Ltd. 1,3,5-Trichlorobenzene: 99% purity, Yangzhou Haichen Chemical Co., Ltd. All other reagents are commercially available industrial products.

[0094] (2) Analytical test method: Bromine content measurement: Weigh out 10 mg of sample and pyrolyze it using a Q600 TG / DTG thermogravimetric analyzer at a heating rate of 10°C / min under a nitrogen atmosphere at a flow rate of 50 mL / min. In the first stage of pyrolysis, HBr is produced by debromination of bromine-containing units in the sample. The bromine content (X) in the sample is estimated from the proportion of HBr removed, using the following formula: TIFF2025528184000016.tif11170In the formula, Y is the content of the sample at 220°C, 79.904 is the relative atomic weight of bromine, and 1.008 is the relative atomic weight of hydrogen.

[0095] Measurement of number average molecular weight and molecular weight distribution index: Measured using a Waters 2414 gel permeation chromatograph (GPC) manufactured by the U.S.A. Polystyrene standard samples were used for the calibration curve, the mobile phase was tetrahydrofuran, the column temperature was 40°C, the sample concentration was 1 mg / mL, the injection volume was 50 μL, the elution time was 40 min, and the flow rate was 1 mL / min.

[0096] Measurement of unsaturation degree: Measurement is performed using a Bruker AVANCE300 nuclear magnetic resonance apparatus at a magnetic field strength of 9.20 tesla, CDC13 as a solvent, and TMS as an internal standard at room temperature (25°C).

[0097] Measurement of branching degree: Branching degree = molecular weight of polymer after branching / molecular weight of polymer before branching.

[0098] Measurement of static ozone performance: Using a TD-401A model heat aging tester, the test parameters were elongation 25%, ozone mass fraction 50 × 10 -8 The temperature was 40°C and the time was 1000 hours.

[0099] Measurement of vulcanization properties: Test according to the method specified in GB / T16584-1996.

[0100] Airtightness measurement: An automatic airtightness tester is used to measure the air permeability value according to ISO 2782:1995. The test gas is N2, the test temperature is 23°C, and the test sample is a round sheet with a diameter of 8 cm and a thickness of 1 mm.

[0101] Measurement of die swell ratio: Using a Malvern RH2000 capillary rheometer manufactured by the UK, the temperature was 100°C, the aspect ratio was 16:1, and the shear rate was 10 to 1000 s. -1 The die swell ratio is measured.

[0102] Manufacturing Example 1 This production example illustrates the production of a multicomponent copolymer. (1-1) Argon gas was introduced into a 15L jacketed stainless steel first reactor, and the atmosphere was replaced twice. 1000g of hexane, 300g of isoprene, and 1.3g of tetrahydrofuran were added in that order, and the temperature was raised to 40°C. 13.5mmol of n-butyllithium was added and the reaction was allowed to proceed for 20 minutes. Next, 200g of styrene and 1.1g of tetrahydrofuran were added in that order, and the temperature was raised to 60°C. The reaction was allowed to proceed for 40 minutes to form the -PS-IR- segment. Finally, 500g of N-bromosuccinimide and 2.0g of tert-dodecyl mercaptan were added in that order, and the temperature was raised to 70°C. 1.5g of DTBP was added and the reaction was allowed to proceed for 2.0 hours to obtain product a.

[0103] (1-2) Argon gas was introduced into a 15-liter stainless steel second reactor, and the system was purged twice. 1000 g of hexane, 200 g of 1,3-butadiene, and 1.0 g of tetrahydrofuran were added in that order, and the temperature was raised to 40°C. 11.5 mmol of n-butyllithium was added and the reaction was continued for 30 minutes. Next, 300 g of styrene was added to the second reactor, and the temperature was raised to 50°C. The reaction was continued for 50 minutes to form the -BR-PS- segment. Finally, 500 g of N-bromosuccinimide and 1.0 g of tert-dodecyl mercaptan were added in that order to the second reactor, and the temperature was raised to 70°C. 1.2 g of DTBP was added and the reaction was continued for 2.0 hours to obtain product b.

[0104] (1-3) Argon gas was introduced into a 15 L stainless steel third reaction vessel, and the system was purged twice. 1000 g of hexane, 100 g of styrene, 50 g of 1,3-butadiene, and 1.0 g of tetrahydrofuran were added in that order, and the temperature was raised to 60°C. 8.5 mmol of n-butyllithium was then added and reacted for 30 minutes to form an -SBR- segment, yielding product c.

[0105] (2) All of the product b from the second reactor and all of the product c from the third reactor were added to the first reactor and mixed with product a. The temperature was raised to 80°C, and 100 mmol of 1,3,5-trichlorobenzene was added to carry out a coupling reaction. After 150 minutes of reaction, 10 g of 1,3-butadiene was added to the first reactor for capping activation. After 20 minutes of reaction, when the free monomer disappeared, the gel liquid was subjected to wet coagulation and baking to obtain a multi-component copolymer, designated P1 (Mn is 81,000, Mw / Mn is 9.16).

[0106] As a result of calculation, the molar ratio of R1:R2:R3:phenyl in P1 was 1.9:5.8:6.3:0.1, the Br content in P1 was 20.9 wt%, and the content of structural units derived from conjugated dienes at the terminals of P1 was 0.46 wt%.

[0107] Manufacturing Example 2 This production example illustrates the production of a multicomponent copolymer. (1-1) Argon gas was introduced into a 15L jacketed stainless steel first reactor, and the atmosphere was purged twice. 1200g of hexane, 330g of isoprene, and 1.9g of tetrahydrofuran were added in that order, and the temperature was raised to 43°C. After that, 15.5mmol of n-butyllithium was added and the reaction was allowed to proceed for 23 minutes. Next, 220g of styrene and 1.5g of tetrahydrofuran were added in that order, and the temperature was raised to 63°C. The reaction was allowed to proceed for 43 minutes to form the -PS-IR- segment. Finally, 520g of N-bromosuccinimide and 2.5g of tert-dodecyl mercaptan were added in that order, and the temperature was raised to 73°C. 2.1g of DTBP was added and the reaction was allowed to proceed for 2.6 hours to obtain product a.

[0108] (1-2) Argon gas was introduced into a 15-liter stainless steel second reactor, and the system was purged twice. 1300 g of hexane, 220 g of 1,3-butadiene, and 1.4 g of tetrahydrofuran were added in that order, and the temperature was raised to 43°C. 12.5 mmol of n-butyllithium was added and the reaction was carried out for 33 minutes. Next, 320 g of styrene was added to the second reactor, and the temperature was raised to 56°C. The reaction was carried out for 56 minutes to form the -BR-PS- segment. Finally, 480 g of N-bromosuccinimide and 1.5 g of tert-dodecyl mercaptan were added in that order to the second reactor, and the temperature was raised to 73°C. 1.7 g of DTBP was added and the reaction was carried out for 2.5 hours, yielding product b.

[0109] (1-3) Argon gas was introduced into a 15 L stainless steel third reaction vessel, and the system was purged twice. 1200 g of hexane, 120 g of styrene, 60 g of 1,3-butadiene, and 1.4 g of tetrahydrofuran were added in that order, and the temperature was raised to 66°C. 10.5 mmol of n-butyllithium was then added and reacted for 33 minutes to form an -SBR- segment, yielding product c.

[0110] (2) All of the product b from the second reactor and all of the product c from the third reactor were added to the first reactor and mixed with product a. The temperature was raised to 83°C, and 100mmol of 1,3,5-trichlorobenzene was added to carry out a coupling reaction. After 155 minutes of reaction, 12g of 1,3-butadiene was added to the first reactor for capping activation. After 23 minutes of reaction, when the free monomer was gone, the gel solution was subjected to wet coagulation and baking to obtain a multi-component copolymer, designated P2 (Mn is 83000, Mw / Mn is 9.48). As a result of calculation, the molar ratio of R1:R2:R3:phenyl in P2 was 2.3:6.3:6.8:0.1, the Br content in P2 was 19.8 wt%, and the content of structural units derived from the conjugated diene at the terminal of P2 was 0.53 wt%.

[0111] Manufacturing Example 3 This production example illustrates the production of a multicomponent copolymer. (1-1) A 15L jacketed stainless steel first reactor was purged with argon gas three times. 1400g of hexane, 350g of isoprene, and 2.2g of tetrahydrofuran were added in that order and heated to 45°C. 17.5mmol of n-butyllithium was added and reacted for 25 minutes. Next, 240g of styrene and 1.8g of tetrahydrofuran were added in that order and heated to 64°C. The reaction was continued for 45 minutes to form the -PS-IR- segment. Finally, 540g of N-bromosuccinimide and 3.0g of tert-dodecyl mercaptan were added in that order and heated to 75°C. 2.4g of DTBP was added and reacted for 3.0 hours to obtain product a.

[0112] (1-2) Argon gas was introduced into a 15-liter stainless steel second reactor, and the system was purged three times. 1500 g of hexane, 240 g of 1,3-butadiene, and 1.7 g of tetrahydrofuran were added in that order, and the temperature was raised to 44°C. 14.2 mmol of n-butyllithium was added and the reaction was carried out for 35 minutes. Next, 340 g of styrene was added to the second reactor, and the temperature was raised to 54°C. The reaction was carried out for 55 minutes to form the -BR-PS- segment. Finally, 460 g of N-bromosuccinimide and 1.8 g of tert-dodecyl mercaptan were added in that order to the second reactor, and the temperature was raised to 74°C. 2.2 g of DTBP was added and the reaction was carried out for 2.5 hours to obtain product b.

[0113] (1-3) Argon gas was introduced into a 15 L stainless steel third reaction vessel, and the system was purged twice. 1500 g of hexane, 150 g of styrene, 70 g of 1,3-butadiene, and 2.0 g of tetrahydrofuran were added in that order, and the temperature was raised to 64°C. 11.6 mmol of n-butyllithium was then added and reacted for 35 minutes to form an -SBR- segment, yielding product c.

[0114] (2) All of the product b from the second reactor and all of the product c from the third reactor were added to the first reactor and mixed with product a. The temperature was raised to 85°C, and 100mmol of 1,3,5-trichlorobenzene was added to carry out a coupling reaction. After 160 minutes of reaction, 15g of 1,3-butadiene was added to the first reactor for capping activation. After 25 minutes of reaction, when the free monomer was gone, the gel solution was subjected to wet coagulation and baking to obtain a multi-component copolymer, designated P3 (Mn is 85,000, Mw / Mn is 9.79).

[0115] As a result of calculation, the molar ratio of R1:R2:R3:phenyl in P3 was 2.8:6.9:7.3:0.1, the Br content in P3 was 18.8 wt%, and the content of structural units derived from the conjugated diene at the terminal of P3 was 0.62 wt%.

[0116] Manufacturing Example 4 This production example illustrates the production of a multicomponent copolymer. (1-1) A 15L jacketed stainless steel first reactor was purged with argon gas three times. 1600g of hexane, 370g of isoprene, and 2.5g of tetrahydrofuran were added in that order, and the temperature was raised to 47°C. After that, 19.2mmol of n-butyllithium was added and the reaction was allowed to proceed for 26 minutes. Next, 260g of styrene and 2.1g of tetrahydrofuran were added in that order, and the temperature was raised to 66°C. The reaction was allowed to proceed for 47 minutes to form the -PS-IR- segment. Finally, 560g of N-chlorosuccinimide and 3.5g of tert-dodecyl mercaptan were added in that order, and the temperature was raised to 76°C. 2.6g of DTBP was added and the reaction was allowed to proceed for 3.3 hours to obtain product a.

[0117] (1-2) Argon gas was introduced into a 15-liter stainless steel second reactor, and the system was purged three times. 1600 g of hexane, 260 g of 1,3-butadiene, and 2.0 g of tetrahydrofuran were added in that order, and the temperature was raised to 46°C. 15.6 mmol of n-butyllithium was added and the reaction was carried out for 36 minutes. Next, 360 g of styrene was added to the second reactor, and the temperature was raised to 56°C. The reaction was carried out for 57 minutes to form the -BR-PS- segment. Finally, 440 g of N-chlorosuccinimide and 2.1 g of tert-dodecyl mercaptan were added in that order to the second reactor, and the temperature was raised to 76°C. 2.5 g of DTBP was added and the reaction was carried out for 2.7 hours to obtain product b.

[0118] (1-3) Argon gas was introduced into a 15 L stainless steel third reaction vessel, and the system was purged twice. 1700 g of hexane, 170 g of styrene, 80 g of 1,3-butadiene, and 2.2 g of tetrahydrofuran were added in that order, and the temperature was raised to 66°C. 13.5 mmol of n-butyllithium was then added and reacted for 36 minutes to form an -SBR- segment, yielding product c.

[0119] (2) All of the product b from the second reactor and all of the product c from the third reactor were added to the first reactor and mixed with product a. The temperature was raised to 86°C, and 100mmol of 1,3,5-trichlorobenzene was added to carry out a coupling reaction. After 164 minutes of reaction, 16g of 1,3-butadiene was added to the first reactor for capping activation. After 26 minutes of reaction, when the free monomer was gone, the gel solution was subjected to wet coagulation and baking to obtain a multi-component copolymer, designated P4 (Mn is 87000, Mw / Mn is 9.97). As a result of calculation, the molar ratio of R1:R2:R3:phenyl in P4 was 3.2:7.3:7.8:0.1, the Cl content in P4 was 10.6 wt%, and the content of structural units derived from conjugated dienes at the terminals of P4 was 0.63 wt%.

[0120] Manufacturing Example 5 This production example illustrates the production of a multicomponent copolymer. (1-1) A 15L jacketed stainless steel first reactor was purged with argon gas four times. 1800g of hexane, 390g of isoprene, and 2.8g of tetrahydrofuran were added in that order and heated to 49°C. 21.5mmol of n-butyllithium was added and reacted for 28 minutes. Next, 280g of styrene and 2.6g of tetrahydrofuran were added in that order and heated to 68°C. The reaction was continued for 49 minutes to form the -PS-IR- segment. Finally, 580g of N-bromosuccinimide and 3.8g of tert-dodecyl mercaptan were added in that order and heated to 78°C. 2.8g of DTBP was added and reacted for 3.6 hours to obtain product a.

[0121] (1-2) Argon gas was introduced into a 15-liter stainless steel second reactor, and the system was purged four times. 1800 g of hexane, 290 g of 1,3-butadiene, and 2.6 g of tetrahydrofuran were added in that order, and the temperature was raised to 48°C. 16.5 mmol of n-butyllithium was added and the reaction was carried out for 38 minutes. Next, 380 g of styrene was added to the second reactor, and the temperature was raised to 58°C. The reaction was carried out for 59 minutes to form the -BR-PS- segment. Finally, 420 g of N-bromosuccinimide and 2.3 g of tert-dodecyl mercaptan were added in that order to the second reactor, and the temperature was raised to 78°C. 2.7 g of DTBP was added and the reaction was carried out for 2.9 hours to obtain product b.

[0122] (1-3) Argon gas was introduced into a 15 L stainless steel third reaction vessel, and the system was purged twice. 1900 g of hexane, 180 g of styrene, 90 g of 1,3-butadiene, and 2.6 g of tetrahydrofuran were added in that order, and the temperature was raised to 68°C. 15.5 mmol of n-butyllithium was then added and reacted for 38 minutes to form an -SBR- segment, yielding product c.

[0123] (2) All of the product b from the second reactor and all of the product c from the third reactor were added to the first reactor and mixed with product a. The temperature was raised to 88°C, and 100mmol of 1,3,5-trichlorobenzene was added to carry out a coupling reaction. After 167 minutes of reaction, 18g of 1,3-butadiene was added to the first reactor for capping activation. After 28 minutes of reaction, when the free monomer was gone, the gel solution was subjected to wet coagulation and baking to obtain a multi-component copolymer, designated P5 (Mn is 89000, Mw / Mn is 10.21).

[0124] As a result of calculation, the molar ratio of R1:R2:R3:phenyl in P5 was 3.4:7.8:8.5:0.1, the Br content in P5 was 17.2 wt%, and the content of structural units derived from the conjugated diene at the terminal of P5 was 0.68 wt%.

[0125] Manufacturing Example 6 This production example illustrates the production of a multicomponent copolymer. (1-1) A 15L jacketed stainless steel first reactor was purged with argon gas four times. 2000g of hexane, 400g of isoprene, and 3.0g of tetrahydrofuran were added in that order and heated to 50°C. 22.5mmol of n-butyllithium was added and reacted for 30 minutes. Next, 300g of styrene and 3.0g of tetrahydrofuran were added in that order and heated to 70°C. The reaction was continued for 50 minutes to form the -PS-IR- segment. Finally, 600g of N-bromosuccinimide and 4.0g of tert-dodecyl mercaptan were added in that order and heated to 80°C. 3.0g of DTBP was added and reacted for 4.0 hours to obtain product a.

[0126] (1-2) Argon gas was introduced into a 15-liter stainless steel second reactor, and the system was purged four times. 2000 g of hexane, 300 g of 1,3-butadiene, and 3.0 g of tetrahydrofuran were added in that order, and the temperature was raised to 50°C. 17.5 mmol of n-butyllithium was added and the reaction was continued for 40 minutes. Next, 400 g of styrene was added to the second reactor, and the temperature was raised to 60°C. The reaction was continued for 60 minutes to form the -BR-PS- segment. Finally, 400 g of N-bromosuccinimide and 2.7 g of tert-dodecyl mercaptan were added in that order to the second reactor, and the temperature was raised to 80°C. 3.0 g of DTBP was added and the reaction was continued for 3.0 hours to obtain product b.

[0127] (1-3) Argon gas was introduced into a 15 L stainless steel third reaction vessel, and the system was purged twice. 2000 g of hexane, 200 g of styrene, 100 g of 1,3-butadiene, and 3.0 g of tetrahydrofuran were added in that order, and the temperature was raised to 70°C. 16.5 mmol of n-butyllithium was then added and the reaction was carried out for 40 minutes to form an -SBR- segment, yielding product c.

[0128] (2) All of the product b from the second reactor and all of the product c from the third reactor were added to the first reactor and mixed with product a. The temperature was raised to 88°C, and 100mmol of 1,3,5-trichlorobenzene was added to carry out a coupling reaction. After 170 minutes of reaction, 20g of 1,3-butadiene was added to the first reactor for capping activation. After 30 minutes of reaction, when the free monomer was gone, the gel liquid was subjected to wet coagulation and baking to obtain a multi-component copolymer, designated P6 (Mn is 90,000, Mw / Mn is 10.35).

[0129] As a result of calculation, the molar ratio of R1:R2:R3:phenyl in P6 was 3.8:8.1:8.8:0.1, the Br content in P6 was 16.7 wt%, and the content of structural units derived from the conjugated diene at the terminal of P6 was 0.74 wt%.

[0130] Manufacturing Example 7 This production example illustrates the production of a multicomponent copolymer. In the step using N-bromosuccinimide, the same weight of inorganic brominating agent, hydrogen bromide, was used instead of N-bromosuccinimide. The remaining conditions were the same as in Production Example 1, and a multicomponent copolymer, designated P7 (Mn: 78,000, Mw / Mn: 8.52), was obtained.

[0131] As a result of calculation, the molar ratio of R1:R2:R3:phenyl in P7 was 1.9:5.8:6.3:0.1, the Br content in P7 was 45.9 wt%, and the content of structural units derived from the conjugated diene at the terminal of P7 was 0.46 wt%.

[0132] Manufacturing Example 8 This production example illustrates the production of a multicomponent copolymer. In the steps using DTBP, the same weight of hydrogen peroxide (H2O2) was used instead of DTBP, and the remaining conditions were the same as in Production Example 2 to obtain a multicomponent copolymer designated P8 (Mn: 71,000, Mw / Mn: 7.58).

[0133] As a result of calculation, the molar ratio of R1:R2:R3:phenyl in P8 was 2.3:6.3:6.8:0.1, the Br content in P8 was 19.8 wt%, and the content of structural units derived from the conjugated diene at the terminal of P8 was 0.53 wt%.

[0134] Manufacturing Example 9 This production example illustrates the production of a multicomponent copolymer. Except for changing the amount of N-bromosuccinimide added to the first reaction vessel to 200 g, the remaining conditions were the same as in Production Example 3 to obtain a multicomponent copolymer designated P9 (Mn: 78,000, Mw / Mn: 9.05).

[0135] As a result of calculation, the molar ratio of R1:R2:R3:phenyl in P9 was 2.8:6.9:7.3:0.1, the Br content in P9 was 12.4 wt%, and the content of structural units derived from the conjugated diene at the terminal of P9 was 0.73 wt%.

[0136] Comparative Manufacturing Example 1 This production example illustrates the production of a multicomponent copolymer. In the production process, coupling was performed without adding 1,3,5-trichlorobenzene as a coupling agent, but the remaining conditions were the same as in Production Example 5, and a multi-component copolymer was obtained, designated DP1 (Mn: 52,000, Mw / Mn: 2.26).

[0137] As a result of calculation, the molar ratio of R1:R2:R3 in DP1 was 3.4:7.8:8.5, the Br content in DP1 was 17.2 wt%, and the content of structural units derived from conjugated dienes at the ends of DP1 was 0.46 wt%.

[0138] Comparative Manufacturing Example 2 This production example illustrates the production of a multicomponent copolymer. (1-1) A 15L jacketed stainless steel first reactor was purged with argon gas four times. 2000g of hexane, 400g of isoprene, and 3.0g of tetrahydrofuran were added to the reactor in that order, and the temperature was raised to 50°C. 22.5mmol of n-butyllithium was added and the reaction was allowed to proceed for 30 minutes. Next, 300g of styrene and 3.0g of tetrahydrofuran were added in that order, and the temperature was raised to 70°C. The reaction was allowed to proceed for 50 minutes to form the -PS-IR- segment. Finally, 600g of N-bromosuccinimide and 4.0g of tert-dodecyl mercaptan were added in that order, and the temperature was raised to 80°C. 3.0g of DTBP was added and the reaction was allowed to proceed for 4.0 hours to obtain product a.

[0139] (1-2) Argon gas was introduced into a 15-liter stainless steel second reactor, and the system was purged four times. 2000 g of hexane, 300 g of 1,3-butadiene, and 3.0 g of tetrahydrofuran were added in that order, and the temperature was raised to 50°C. 17.5 mmol of n-butyllithium was added and the reaction was continued for 40 minutes. Next, 400 g of styrene was added to the second reactor, and the temperature was raised to 60°C. The reaction was continued for 60 minutes to form the -BR-PS- segment. Finally, 400 g of N-bromosuccinimide and 2.7 g of tert-dodecyl mercaptan were added in that order to the second reactor, and the temperature was raised to 80°C. 3.0 g of DTBP was added and the reaction was continued for 3.0 hours to obtain product b.

[0140] (2) All of the product b from the second reactor was added to the first reactor and mixed with product a. The temperature was raised to 88°C, and 100mmol of 1,3,5-trichlorobenzene was added to carry out a coupling reaction. After 170 minutes of reaction, 20g of 1,3-butadiene was added to the first reactor for capping activation. After 30 minutes of reaction, when the free monomer disappeared, the gel liquid was subjected to wet coagulation and baking to obtain a multi-component copolymer, DP2 (Mn is 65,000, Mw / Mn is 5.12).

[0141] As a result of calculation, the molar ratio of R2:R3:phenyl in DP2 was 8.1:8.8:0.1 (DP2 does not contain R1), the Br content in DP2 was 18.8 wt%, and the content of structural units derived from conjugated dienes at the terminals of DP2 was 0.83 wt%.

[0142] Example 1 This example illustrates the preparation of halogenated branched butyl rubber. A 4L jacketed stainless steel reactor was purged with nitrogen three times. 300g of methyl chloride, 700g of hexane, and 35g of the multicomponent copolymer (P1) prepared in Preparation Example 1 were added to the reactor and stirred for 60 minutes to dissolve. After P1 was completely dissolved, the temperature was lowered to -85°C, and 500g of methyl chloride, 460g of isobutylene, and 5g of isoprene were added in that order and stirred to mix. When the temperature of the polymerization system was lowered to -90°C, 50g of methyl chloride, 1.075g of ethyl aluminum sesquichloride, and 0.007g of HCl (aged by mixing for 30 minutes at -85°C) were added to the polymerization system and stirred for 2.0 hours. Finally, 25g of ethanol was added, and the discharged material was flocculated, washed, and dried to obtain a halogenated branched butyl rubber, designated S1 (bromine content 2.36wt%).

[0143] Based on the total weight of S1, the weight ratio of structural units A derived from isobutylene, structural units B derived from isoprene, and structural units C derived from the grafting agent is 13:0.14:1.

[0144] A standard sample was prepared using S1, and the test performance is shown in Table 1.

[0145] Example 2 This example illustrates the preparation of halogenated branched butyl rubber.

[0146] A 4L jacketed stainless steel reactor was purged with nitrogen three times. 400g of methyl chloride, 600g of hexane, and 38g of the multicomponent copolymer (P2) prepared in Preparation Example 2 were added to the reactor and stirred for 65 minutes to dissolve. After P2 was completely dissolved, the temperature was lowered to -88°C, and 600g of methyl chloride, 455g of isobutylene, and 7g of isoprene were added in that order and stirred to mix. When the temperature of the polymerization system dropped to -92°C, 60g of methyl chloride, 1.189g of ethyl aluminum sesquichloride, and 0.011g of HCl (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, and the discharged material was flocculated, washed, and dried to obtain a halogenated branched butyl rubber, designated S2 (bromine content 2.45wt%).

[0147] Based on the total weight of S2, the weight ratio of structural units A derived from isobutylene, structural units B derived from isoprene, and structural units C derived from the grafting agent is 12:0.18:1. A standard sample was prepared using S2, and the test performance is shown in Table 1.

[0148] Example 3 This example illustrates the preparation of halogenated branched butyl rubber.

[0149] A 4L jacketed stainless steel reactor was purged with nitrogen three times. 500g of methyl chloride, 500g of hexane, and 41g of the multicomponent copolymer (P3) prepared in Preparation Example 3 were added to the reactor and stirred for 70 minutes to dissolve. After P3 was completely dissolved, the temperature was lowered to -90°C. 700g of methyl chloride, 449g of isobutylene, and 10g of isoprene were added in that order and stirred to mix. When the temperature of the polymerization system dropped to -94°C, 70g of methyl chloride, 1.203g of ethyl aluminum sesquichloride, and 0.031g of HCl (aged at -88°C for 34 minutes) were added to the polymerization system and stirred for 3.0 hours. Finally, 35g of ethanol was added, and the discharged material was flocculated, washed, and dried to obtain a halogenated branched butyl rubber, designated S3 (bromine content 2.65wt%).

[0150] Based on the total weight of S3, the weight ratio of structural units A derived from isobutylene, structural units B derived from isoprene, and structural units C derived from the grafting agent is 11:0.24:1. A standard sample was prepared using S3, and the test performance is shown in Table 1.

[0151] Example 4 This example illustrates the preparation of halogenated branched butyl rubber. A 4L jacketed stainless steel reactor was purged with nitrogen three times. 600g of methyl chloride, 400g of hexane, and 44g of the multicomponent copolymer (P4) prepared in Preparation Example 4 were added to the reactor and stirred for 74 minutes to dissolve. After P4 was completely dissolved, the temperature was lowered to -91°C. 800g of methyl chloride, 444g of isobutylene, and 12g of isoprene were added in that order and stirred to mix. When the temperature of the polymerization system dropped to -95°C, 80g of methyl chloride, 1.315g of ethyl aluminum sesquichloride, and 0.048g of HCl (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, and the discharged material was flocculated, washed, and dried to obtain a halogenated branched butyl rubber, designated S4 (nitrogen content 2.72wt%).

[0152] Based on the total weight of S4, the weight ratio of structural units A derived from isobutylene, structural units B derived from isoprene, and structural units C derived from the grafting agent is 10:0.27:1. A standard sample was prepared using S4, and the test performance is shown in Table 1.

[0153] Example 5 This example illustrates the preparation of halogenated branched butyl rubber. A 4L jacketed stainless steel reactor was purged with nitrogen three times. 650g of methyl chloride, 350g of hexane, and 48g of the multicomponent copolymer (P5) prepared in Preparation Example 5 were added to the reactor and stirred for 78 minutes to dissolve. After P5 was completely dissolved, the temperature was lowered to -93°C, and 900g of methyl chloride, 438g of isobutylene, and 14g of isoprene were added in that order and stirred to mix. When the temperature of the polymerization system dropped to -97°C, 90g of methyl chloride, 1.425g of ethyl aluminum sesquichloride, and 0.057g of HCl (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, and the discharged material was flocculated, washed, and dried to obtain a halogenated branched butyl rubber, designated S5 (bromine content 2.86wt%).

[0154] Based on the total weight of S5, the weight ratio of structural units A derived from isobutylene, structural units B derived from isoprene, and structural units C derived from the grafting agent is 9:0.29:1. A standard sample was prepared using S5, and the test performance is shown in Table 1.

[0155] Example 6 This example illustrates the preparation of halogenated branched butyl rubber.

[0156] A 4L jacketed stainless steel reactor was purged with nitrogen five times. 700g of methyl chloride, 300g of hexane, and 50g of the multicomponent copolymer (P6) prepared in Preparation Example 6 were added to the reactor and stirred for 80 minutes to dissolve. After the grafting agent was completely dissolved, the temperature was lowered to -95°C. 1000g of methyl chloride, 435g of isobutylene, and 15g of isoprene were added in that order and stirred to mix. When the temperature of the polymerization system was lowered to -100°C, 100g of methyl chloride, 1.564g of ethyl aluminum sesquichloride, and 0.074g of HCl (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, and the discharged material was flocculated, washed, and dried to obtain a halogenated branched butyl rubber, designated S6 (bromine content 2.97wt%).

[0157] Based on the total weight of S6, the weight ratio of the structural unit A derived from isobutylene, the structural unit B derived from isoprene, and the structural unit C derived from the grafting agent was 9:0.3:1. A standard sample was prepared using S6, and the test performance is shown in Table 1.

[0158] Example 7 This example illustrates the preparation of halogenated branched butyl rubber. The method of Example 6 was followed, except that 50 g of the multicomponent copolymer (P2) prepared in Preparation Example 2 was used instead of 50 g of the multicomponent copolymer (P6) prepared in Preparation Example 6, and the remaining conditions were the same as in Example 6.

[0159] A halogenated branched butyl rubber was obtained and designated S7 (bromine content: 3.16 wt%).

[0160] Based on the total weight of S7, the weight ratio of structural units A derived from isobutylene, structural units B derived from isoprene, and structural units C derived from the grafting agent was 9:0.3:1. A standard sample was prepared using S7, and the test performance is shown in Table 1.

[0161] Example 8 This example illustrates the preparation of halogenated branched butyl rubber.

[0162] The method of Example 6 was followed, except that 50 g of the multicomponent copolymer (P3) prepared in Preparation Example 3 was used instead of 50 g of the multicomponent copolymer (P6) prepared in Preparation Example 6, and the remaining conditions were the same as in Example 6.

[0163] A halogenated branched butyl rubber was obtained and designated S8 (bromine content: 3.08 wt%).

[0164] Based on the total weight of S8, the weight ratio of structural units A derived from isobutylene, structural units B derived from isoprene, and structural units C derived from the grafting agent is 9:0.3:1. A standard sample was prepared using S8, and the test performance is shown in Table 1.

[0165] Example 9 The method of Example 1 was followed, except that the same weight of multipolymer P7 was used instead of multipolymer P1, and the remaining conditions were the same as in Example 1. A halogenated branched butyl rubber was obtained, designated S9 (bromine content: 1.85 wt%).

[0166] A standard sample was prepared using S9, and the test performance is shown in Table 1.

[0167] Example 10 The method of Example 2 was followed, except that the same weight of multipolymer P8 was used instead of multipolymer P2, and the remaining conditions were the same as in Example 2. A halogenated branched butyl rubber was obtained, designated S10 (bromine content: 1.89 wt%).

[0168] A standard sample was prepared using S10, and the test performance is shown in Table 1.

[0169] Example 11 The method of Example 3 was followed, except that the same weight of multipolymer P9 was used instead of multipolymer P3, and the remaining conditions were the same as in Example 3. A halogenated branched butyl rubber was obtained, designated S11 (bromine content: 1.97 wt%).

[0170] A standard sample was prepared using S11, and the test performance is shown in Table 1.

[0171] Comparative Example 1 The method of Example 5 was followed, except that the same weight of multipolymer DP1 was used instead of multipolymer P5, and the remaining conditions were the same as in Example 5. A halogenated branched butyl rubber was obtained, designated D1 (bromine content 0.58 wt%).

[0172] A standard sample was prepared using D1, and the test performance is shown in Table 1.

[0173] Comparative Example 2 The method of Example 6 was followed, except that the same weight of multipolymer DP2 was used instead of multipolymer P6, and the remaining conditions were the same as in Example 6. A halogenated branched butyl rubber was obtained, designated D2 (bromine content 0.76 wt%). A standard sample was prepared using D2, and the test performance is shown in Table 1.

[0174] [Table 1]

[0175] From the results in Table 1, the halogenated branched butyl rubbers S1 to S11 produced using the multicomponent copolymer of the present invention as a grafting agent have a high halogen content, a high degree of saturation and branching, a low die swelling ratio, and a short scorch time (T 10 ) and optimum vulcanization time (T 90 ) and low air permeability, long static ozone cracking time, good vulcanization properties, anti-aging properties, product processing dimensional stability, and extremely high airtightness. Among them, S7 and S8 have particularly excellent overall performance, and it has been found that the present invention achieves a balance between the anti-aging properties, product dimensional stability, and vulcanization processability of the highly saturated, highly branched halogenated branched butyl rubber.

[0176] On the other hand, in Comparative Examples 1 and 2 in which the multicomponent copolymer of the present invention was not used as a grafting agent, the obtained halogenated branched butyl rubber products D1 and D2 were significantly inferior in overall performance to S1 to S11.

[0177] Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, multiple simple modifications can be made to the technical solution of the present invention, including combining each technical feature in any other suitable manner, and these simple modifications and combinations should also be considered as the disclosure content of the present invention, and all fall within the protection scope of the present invention.

Claims

1. having the general formula (I): Multi-component copolymer. (where R 1 , R 2 , and R 3 are polymer segments each containing a structural unit derived from a conjugated diene at its terminal, R 1 contains styrene structural units and butadiene structural units, R 2 comprises a segment of formula (II), wherein: represents the position at which the segment represented by formula (II) is linked to the benzene ring, R 3 comprises a segment of formula (III), wherein: represents the position at which the segment represented by formula (III) is linked to the benzene ring, In formula (II) and formula (III), is a styrene segment and X is a halogen.

2. R 1 :R 2 :R 3 the molar ratio of phenyl to phenyl is (1-4):(2-9):(2-9):0.1, and / or the halogen content in the multicomponent copolymer is 10 to 30 wt %, and / or the content of the structural unit derived from the conjugated diene at the terminal of the multi-component copolymer is 0.25 to 1 wt %, and / or X is selected from F, Cl or Br, and / or the conjugated diene is selected from butadiene and / or isoprene; The multicomponent copolymer according to claim 1 .

3. The number average molecular weight of the multicomponent copolymer is 80,000 to 90,000 g / mol; and / or the molecular weight distribution index of the multicomponent copolymer is 9 to 11; The multicomponent copolymer according to claim 1 or 2.

4. A step (1-1) of subjecting isoprene to a first polymerization reaction in the presence of a first initiator, subjecting the resulting first polymerization reaction product and styrene to a second polymerization reaction, and subjecting the resulting second polymerization reaction product to a first halogenation reaction in the presence of a second initiator and a halogenating agent to obtain product a; a step (1-2) of subjecting butadiene to a third polymerization reaction in the presence of a first initiator, subjecting the obtained third polymerization reaction product and styrene to a fourth polymerization reaction, and subjecting the obtained fourth polymerization reaction product to a second halogenation reaction in the presence of a second initiator and a halogenating agent to obtain a product b; (1-3) subjecting styrene and butadiene to a fifth polymerization reaction in the presence of a first initiator to obtain product c; and step (2) of coupling the product a, the product b, and the product c in the presence of a coupling agent, and then capping the coupling reaction product with a conjugated diene to obtain a multi-component copolymer; The coupling agent has the general formula shown in formula (IV): Method for producing multicomponent copolymers. (where R 1 , R 2 , and R 3 are each independently selected from F, Cl, or Br.

5. 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 capping reaction are carried out in the presence of a solvent; The method of claim 4.

6. the first polymerization reaction, the third polymerization reaction, and the fifth polymerization reaction are carried out in the presence of a structure-controlling agent; and / or the first halogenation reaction and the second halogenation reaction are carried out in the presence of a molecular weight modifier. The method of claim 5.

7. In the method, relative to 100 parts by weight of the total amount of the halogenating agent, in step (1-1), the input amounts of each raw material are 30 to 40 parts by weight of isoprene, 20 to 30 parts by weight of styrene, 0.1 to 0.3 parts by weight of structure modifier, 0.05 to 0.2 parts by weight of a first initiator, 50 to 60 parts by weight of a halogenating agent, 0.2 to 0.5 parts by weight of a molecular weight modifier, and 0.1 to 0.4 parts by weight of a second initiator; and / or, in steps (1-2), the amounts of the raw materials added are 20-30 parts by weight of butadiene, 30-40 parts by weight of styrene, 0.1-0.3 parts by weight of a structure modifier, 0.05-0.2 parts by weight of a first initiator, 40-50 parts by weight of a halogenating agent, 0.1-0.3 parts by weight of a molecular weight modifier, and 0.1-0.3 parts by weight of a second initiator; And / or, in steps (1 to 3), the amounts of each raw material added are 5 to 10 parts by weight of butadiene, 10 to 20 parts by weight of styrene, 0.1 to 0.3 parts by weight of a structure modifier, and 0.03 to 0.16 parts by weight of a first initiator; and / or, in step (2), the coupling agent is 0.5 to 5 parts by weight, and the conjugated diene is 1 to 2 parts by weight; 7. The method according to claim 5 or 6.

8. the solvent is at least one selected from a linear alkane, an aromatic hydrocarbon, and a cycloalkane; and / or the first initiator is a hydrocarbyl monolithium compound; and / or the second initiator is an organic peroxide; and / or the halogenating agent is at least one selected from N-bromosuccinimide, bromodimethylsulfonium bromide, N-bromosuccinimide, N-chlorosuccinimide, N-chlorosuccinimide, and chlorodimethylsulfonium chloride; and / or the structure-controlling agent is a polar organic compound; and / or the molecular weight modifier is at least one selected from tert-decyl mercaptan, tert-dodecyl mercaptan, tert-tetradecyl mercaptan, and tert-hexadecyl mercaptan; and / or the conjugated diene is selected from butadiene and / or isoprene; 7. The method according to claim 5 or 6.

9. the solvent is at least one selected from a linear alkane, an aromatic hydrocarbon, and a cycloalkane; and / or the first initiator is a hydrocarbyl monolithium compound; and / or the second initiator is an organic peroxide; and / or the halogenating agent is at least one selected from N-bromosuccinimide, bromodimethylsulfonium bromide, N-bromosuccinimide, N-chlorosuccinimide, N-chlorosuccinimide, and chlorodimethylsulfonium chloride; and / or the structure-controlling agent is a polar organic compound; and / or the molecular weight modifier is at least one selected from tert-decyl mercaptan, tert-dodecyl mercaptan, tert-tetradecyl mercaptan, and tert-hexadecyl mercaptan; and / or the conjugated diene is selected from butadiene and / or isoprene; The method of claim 7.

10. The conditions of the first polymerization reaction include a temperature of 40 to 50°C and a time of 20 to 30 minutes; and / or the conditions of the second polymerization reaction include a temperature of 60 to 70°C and a time of 40 to 50 minutes; and / or the conditions of the first halogenation reaction include a temperature of 70 to 80°C and a time of 2 to 4 hours; and / or the conditions of the third polymerization reaction include a temperature of 40 to 50°C and a time of 30 to 40 minutes; and / or the conditions of the fourth polymerization reaction include a temperature of 50 to 60°C and a time of 50 to 60 minutes; and / or the conditions of the second halogenation reaction include a temperature of 70 to 80°C and a time of 2 to 3 hours; and / or the conditions of the fifth polymerization reaction include a temperature of 60 to 70°C and a time of 30 to 40 minutes; and / or the coupling reaction conditions include a temperature of 80 to 90°C and a time of 150 to 170 min; and / or the capping reaction conditions include a temperature of 80 to 90°C and a time of 20 to 30 minutes; The method of any one of claims 5, 6 and 9.

11. The conditions of the first polymerization reaction include a temperature of 40 to 50°C and a time of 20 to 30 minutes; and / or the conditions of the second polymerization reaction include a temperature of 60 to 70°C and a time of 40 to 50 minutes; and / or the conditions of the first halogenation reaction include a temperature of 70 to 80°C and a time of 2 to 4 hours; and / or the conditions of the third polymerization reaction include a temperature of 40 to 50°C and a time of 30 to 40 minutes; and / or the conditions of the fourth polymerization reaction include a temperature of 50 to 60°C and a time of 50 to 60 minutes; and / or the conditions of the second halogenation reaction include a temperature of 70 to 80°C and a time of 2 to 3 hours; and / or the conditions of the fifth polymerization reaction include a temperature of 60 to 70°C and a time of 30 to 40 minutes; and / or the coupling reaction conditions include a temperature of 80 to 90°C and a time of 150 to 170 min; and / or the capping reaction conditions include a temperature of 80 to 90°C and a time of 20 to 30 minutes; The method of claim 7.

12. The conditions of the first polymerization reaction include a temperature of 40 to 50°C and a time of 20 to 30 minutes; and / or the conditions of the second polymerization reaction include a temperature of 60 to 70°C and a time of 40 to 50 minutes; and / or the conditions of the first halogenation reaction include a temperature of 70 to 80°C and a time of 2 to 4 hours; and / or the conditions of the third polymerization reaction include a temperature of 40 to 50°C and a time of 30 to 40 minutes; and / or the conditions of the fourth polymerization reaction include a temperature of 50 to 60°C and a time of 50 to 60 minutes; and / or the conditions of the second halogenation reaction include a temperature of 70 to 80°C and a time of 2 to 3 hours; and / or the conditions of the fifth polymerization reaction include a temperature of 60 to 70°C and a time of 30 to 40 minutes; and / or the coupling reaction conditions include a temperature of 80 to 90°C and a time of 150 to 170 min; and / or the capping reaction conditions include a temperature of 80 to 90°C and a time of 20 to 30 minutes; The method of claim 8.

13. A multicomponent copolymer produced by the method according to any one of claims 4 to 12.

14. 14. Use of the multicomponent copolymer according to any one of claims 1 to 3 and 13 as a grafting agent in the production of diene rubber.

15. The diene rubber is a butyl rubber.

15. The use according to claim 14.

16. The halogenated branched butyl rubber comprises structural units A derived from isobutylene, structural units B derived from isoprene, and structural units C derived from a grafting agent, The grafting agent is a multicomponent copolymer according to any one of claims 1 to 3 and 13. Halogenated branched butyl rubber.

17. a weight ratio of the structural unit A, the structural unit B, and the structural unit C based on the total weight of the halogenated branched butyl rubber is (6 to 15):(0.05 to 0.5):1; 17. The halogenated branched butyl rubber of claim 16.

18. subjecting isobutylene, isoprene, and a grafting agent to a cationic polymerization reaction in the presence of a diluent, a solvent, and a coinitiator to obtain the halogenated branched butyl rubber; The grafting agent is a multicomponent copolymer according to any one of claims 1 to 3 and 13. Method for producing halogenated branched butyl rubber.

19. the diluent is 30 to 80 parts by weight, the grafting agent is 6 to 15 parts by weight, and the coinitiator is 0.1 to 0.6 parts by weight, relative to 100 parts by weight of the total amount of isobutylene and isoprene; and / or the weight ratio of isobutylene:isoprene is (25-95):1; 20. The method of claim 18.

20. the diluent is a haloalkane, and the halogen in the haloalkane is F, Cl, or Br; and / or the coinitiator comprises an alkylaluminum halide and a protonic acid; 20. The method of claim 18 or 19.

21. In the coinitiator, the molar ratio of the alkylaluminum halide to the protonic acid is (10-100):1; 21. The method of claim 20.

22. The cationic polymerization conditions include a temperature of −100° C. to −90° C. and a time of 2 to 4 hours.

22. The method of any one of claims 18, 19, and 21.

23. The cationic polymerization conditions include a temperature of −100° C. to −90° C. and a time of 2 to 4 hours.

21. The method of claim 20.

24. A halogenated branched butyl rubber produced by the method according to any one of claims 18 to 23.

25. Use of the halogenated branched butyl rubber according to any one of claims 16, 17 and 24 in tires and medical rubber stoppers.

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