Multipolymer, method for producing the same and use thereof, and halogenated branched butyl rubber, method for producing the same 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 of related applications) This application claims the benefits of Chinese Patent Application No. 202211173618.9, filed on September 26, 2022, with the title "Multicomponent Copolymer, Method for Producing the Same and Use thereof, and Halogenated Branched Butyl Rubber, Method for Producing the Same and Use thereof," the contents of which are incorporated herein by reference.

[0002] The present invention relates to the technical field of rubber manufacturing, and more specifically to polypolymers, methods for producing the same and their use, as well as halogenated branched butyl rubber, methods for producing the same and its use. [Background technology]

[0003] Butyl rubber (IIR) is copolymerized from isobutylene and a small amount of isoprene via cationic polymerization. It possesses excellent airtightness and damping properties and is widely used as the most important synthetic rubber in fields such as manufacturing inner tubes and airtight layers for automobile tires and vulcanization capsules. The molecular chains of high-saturation butyl rubber are mainly composed of carbon-carbon single bonds and have a low degree of unsaturation (only about 0.5-1.5%), resulting in extremely low permeability and excellent ozone resistance. It is used in airtight layers of load-bearing tires in harsh environments and working conditions, as well as in the medical field.

[0004] Furthermore, highly saturated butyl rubber has drawbacks such as high polymer chain isotacticity, high crystallinity, low viscoelasticity, and slow vulcanization rate. As a result, highly saturated butyl rubber has low vulcanization efficiency and poor vulcanization performance during processing, and is prone to excessive flow and deformation, thus becoming a bottleneck that limits the use of butyl rubber in high-end applications.

[0005] Therefore, it is urgent to address the problems of significant die swell effect during butyl rubber processing, long vulcanization scorch time, slow vulcanization rate, and poor ozone aging resistance. [Overview of the project] [Problems that the invention aims to solve]

[0006] The object of the present invention is to provide a multi-component copolymer, a method for producing the same, and its use, as well as halogenated branched butyl rubber, a method for producing the same, in order to solve the problems that exist in conventional butyl rubber, such as a prominent die-well 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 objective, a first aspect of the present invention provides a multicomponent copolymer having a general formula represented by formula (I). TIFF0007911624000001.tif39170 (where R1, R2, and R3 are polymer segments, each containing a structural unit derived from a conjugated diene at its terminal, R1 contains styrene structural units and butadiene structural units. R2 includes the segment shown by equation (II), where, TIFF0007911624000002.tif6170 represents the linkage position of the segment shown in formula (II) to the benzene ring, TIFF0007911624000003.tif23170R3 contains the segment shown by equation (III), where, TIFF0007911624000004.tif6170 represents the linkage position of the segment shown in formula (III) to the benzene ring, In formulas (II) and (III) of TIFF0007911624000005.tif18170, TIFF0007911624000006.tif9170 is a styrene segment, and X is a halogen.

[0008] A second aspect of the present invention is: Step (1-1) involves subjecting isoprene to a first polymerization reaction in the presence of a first initiator, subjecting the obtained first polymerization reaction product and styrene to a second polymerization reaction, and subjecting the obtained second polymerization reaction product to a first halogenation reaction in the presence of a second initiator and a halogenating agent to obtain product a. Steps (1-2) include: (1) In the presence of a first initiator, butadiene is subjected to a third polymerization reaction; (2) The obtained third polymerization reaction product and styrene are subjected to a fourth polymerization reaction; (3) In the presence of a second initiator and a halogenating agent, the obtained fourth polymerization reaction product is subjected to a second halogenation reaction to obtain product b; Steps (1-3) involve subjecting styrene and butadiene to a fifth polymerization reaction in the presence of a first initiator to obtain product c, The process includes step (2) of coupling product a, product b, and product c in the presence of a coupling agent, and carrying out a capping reaction between the coupling reaction product and the conjugated diene to obtain the multi-component copolymer, The coupling agent provides a method for producing a multi-component copolymer having the general formula shown in formula (IV). TIFF0007911624000007.tif40170(here, R 1 , R 2 , and R 3 Each of these is independently selected from F, Cl, or Br.

[0009] A third aspect of the present invention provides a multi-component copolymer produced by the method described in the second aspect above.

[0010] A fourth aspect of the present invention provides the use of the multi-component copolymer described in the first or third aspect above as a grafting agent in the production of diene rubber.

[0011] A fifth aspect of the present invention comprises structural unit A derived from isobutylene, structural unit B derived from isoprene, and structural unit C derived from a grafting agent, The grafting agent is a halogenated branched butyl rubber, which is a multi-component copolymer as described in the first or third embodiment above.

[0012] A sixth aspect of the present invention includes the step of causing a cationic polymerization reaction of isobutylene, isoprene, and a grafting agent in the presence of a diluent, a solvent, and a co-initiator to obtain the halogenated branched butyl rubber, The present invention provides a method for producing halogenated branched butyl rubber, wherein the graft agent is a multi-component copolymer as described in the first or third embodiment above.

[0013] A seventh aspect of the present invention provides halogenated branched butyl rubber manufactured by the method described in the sixth aspect above.

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

[0015] According to the above technical proposal, the present invention provides the following beneficial effects.

[0016] (1) The multi-component copolymer according to the present invention combines structurally different -BR-segments, -IR-segments, -PS-segments, and -SBR-segments in a polymer chain to form a "three-armed" star structure and has a stable 2-position halogen substitution structure. The 2-position halogen substitution structure is obtained by adding a halogenating agent to the unsaturated "double bonds" of the -BR-segments and -IR-segments, significantly reducing the content of unsaturated "double bonds". This multi-component copolymer is used as a grafting agent for producing halogenated branched butyl rubber. Its different segment characteristics, "three-armed" star structure, and stable 2-position halogen substitution structure work synergistically to increase the saturation of the butyl rubber, significantly reduce the die swell effect, greatly increase the vulcanization rate, and greatly improve ozone aging resistance and airtightness, thus balancing the aging resistance, dimensional stability of the product, and vulcanization processability of highly branched, highly saturated halogenated branched butyl rubber.

[0017] (2) The multi-component copolymer according to the present invention has no emission of volatile organic compounds (VOCs) and hydrogen halide as a by-product during the manufacturing process. The manufacturing method is environmentally friendly, has a short process flow, enables control of the 2-position halogen substitution structure, and is 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.

Embodiments for Carrying Out the Invention

[0018] The endpoints and any values within the ranges disclosed in this specification are not limited to 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, by combining between the endpoint values of each range, between the endpoint value of each range and an individual point value, and between individual point values, one or more new numerical ranges can be obtained, and these numerical ranges should be regarded as specifically disclosed in this specification.

[0019] The first aspect of the present invention provides a multi-component copolymer having a general formula represented by formula (I). TIFF0007911624000008.tif39170 (Here, R1, R2, and R3 are each polymer segments, containing a structural unit derived from a conjugated diene at the end, R1 includes a styrene structural unit and a butadiene structural unit, R2 includes a segment represented by formula (II), where TIFF0007911624000009.tif6170 represents the connection position with the benzene ring of the segment represented by formula (II), TIFF0007911624000010.tif23170R3 includes a segment represented by formula (III), where TIFF0007911624000011.tif6170 represents the connection position with the benzene ring of the segment represented by formula (III), TIFF0007911624000012.tif18170In formula (II) and formula (III), TIFF0007911624000013.tif9170 is a styrene segment, and X is a halogen.

[0020] In this invention, "bonding position to the benzene ring" refers to the bonding position to the benzene ring in formula (I).

[0021] According to the present invention, in the multi-component 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 indicated by R2 includes a block of isoprene homopolymer block halogenated with a halogenating agent and a styrene homopolymer block. The segment indicated by R3 includes a block of 1,3-butadiene homopolymer block halogenated with a halogenating agent and a styrene homopolymer block. The multi-component copolymer has a "three-armed" star structure in which the above-mentioned structurally different segments are linked at the 1,3, and 5 positions of the benzene ring structure, and also has a stable 2-position halogen substitution structure, containing structural units derived from conjugated dienes at its ends, thereby having high polymerization activity and being useful as a graft agent in the production of branched diene rubber, in particular in the production of halogenated branched diene rubber, which can increase the saturation of butyl rubber, significantly reduce the die swell effect, significantly increase the vulcanization rate, and significantly improve ozone aging resistance and airtightness.

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

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

[0024] According to the present invention, the content of structural units derived from conjugated dienes at the terminals of the multi-component copolymer is 0.25 to 1 wt%, preferably 0.3 to 0.9 wt%. When the content of structural units derived from conjugated dienes in the multi-component copolymer satisfies the above range, the multi-component copolymer can be given high polymerization activity, which is advantageous for polymerizing with diene monomers such as isobutylene and isoprene as a graft agent to produce halogenated branched diene rubber.

[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 raw material input relationship during the manufacturing process.

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

[0027] In this invention, the halogen content in the multi-component copolymer is measured by a thermogravimetric analyzer.

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

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

[0030] According to the present invention, the number-average molecular weight of the multi-component 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 multi-component copolymer is 9 to 11, preferably 9.3 to 10.3.

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

[0033] A second aspect of the present invention is: Step (1-1) involves subjecting isoprene to a first polymerization reaction in the presence of a first initiator, subjecting the obtained first polymerization reaction product and styrene to a second polymerization reaction, and subjecting the obtained second polymerization reaction product to a first halogenation reaction in the presence of a second initiator and a halogenating agent to obtain product a. Steps (1-2) include: (1) In the presence of a first initiator, butadiene is subjected to a third polymerization reaction; (2) The obtained third polymerization reaction product and styrene are subjected to a fourth polymerization reaction; (3) In the presence of a second initiator and a halogenating agent, the obtained fourth polymerization reaction product is subjected to a second halogenation reaction to obtain product b; Steps (1-3) involve subjecting styrene and butadiene to a fifth polymerization reaction in the presence of a first initiator to obtain product c, The process includes step (2) of coupling product a, product b, and product c in the presence of a coupling agent, and carrying out a capping reaction between the coupling reaction product and the conjugated diene to obtain the multi-component copolymer, The coupling agent provides a method for producing a multi-component copolymer having the general formula shown in formula (IV). TIFF0007911624000014.tif40170(here, R 1 , R 2 , and R 3 Each of these is independently selected from F, Cl, or Br.

[0034] In the present invention, according to the above manufacturing method, a coupling agent, 1,3,5-trihalobenzene, is used to combine structurally different -BR-segments, -IR-segments, -PS-segments, and -SBR-segments in the polymer chain to form a "three-armed" star structure. During the manufacturing process, halogenation with a halogenating agent is performed to obtain a stable 2-position halogen-substituted structure. Finally, conjugated diene structural units are introduced and capped. The resulting multi-component copolymer has high polymerization activity and excellent performance as a graft agent in the production of halogenated branched butyl rubber. Furthermore, the manufacturing method for the multi-component copolymer does not produce hydrogen halogens as by-products during the process, making it environmentally friendly and simple.

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

[0036] According to the present invention, a three-vessel polymerization method is employed in which steps (1-1), (1-2), and (1-3) are carried out in three separate reaction vessels, which will be explained in detail below.

[0037] According to the present invention, in step (1-1), with respect to 100 parts by weight of the total amount 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 structural 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), regarding the operation process of the first polymerization reaction, the second polymerization reaction, and the first halogenation reaction, each raw material is prepared in the above proportions, an inert gas is introduced into the first reaction vessel to remove oxygen gas, then the solvent, isoprene, and a structural modifier are added, the temperature is raised to the temperature required for the first polymerization reaction, the first initiator is added, and the first polymerization reaction is carried out. After the first polymerization reaction is completed, styrene and a structural modifier are added to the first reaction vessel, the temperature is raised to the temperature required for the second polymerization reaction, and the second polymerization reaction is carried out. After the second polymerization reaction is completed, a halogenating agent and a molecular weight modifier are further added to the first reaction vessel, the temperature is raised to the temperature required for the first halogenation reaction, the second initiator is added to start the first halogenation reaction, and after the reaction is completed, product a is obtained.

[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, polymerization will be insufficient, and the molecular weight of the first polymerization reaction product will be too low. If the temperature of the first polymerization reaction is too high, the molecular structure of the first polymerization reaction product will change. 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, polymerization will be insufficient, and the molecular weight of the first reaction product will be too low. If the time of the first polymerization reaction is too long, the manufacturing cost will increase.

[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, polymerization will be insufficient, and furthermore, the molecular weight of the second polymerization reaction product will be too low. If the temperature of the second polymerization reaction is too high, the molecular structure of the second polymerization reaction product will change. 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, polymerization will be insufficient, and furthermore, the molecular weight of the second reaction product will be too low. If the time of the second polymerization reaction is too long, the manufacturing cost will increase.

[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 product a is too low. If the temperature of the first halogenation reaction is too high, the molecular weight of product a is too high and the molecular weight distribution is too broad. The duration of the first halogenation reaction is 2 to 4 hours, preferably 2.5 to 3.5 hours. If the duration of the first halogenation reaction is too short, the molecular weight of product a is too small. If the duration of the first halogenation reaction is too long, the manufacturing cost increases.

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

[0043] According to the present invention, in step (1-2), regarding the operation process of the third polymerization reaction, the fourth polymerization reaction, and the second halogenation reaction, each raw material is prepared in the above proportions, an inert gas is introduced into the second reaction vessel to remove oxygen gas, then the solvent, butadiene, and a structural modifier are added, the temperature is raised to the temperature required for the third polymerization reaction, the first initiator is added, and the third polymerization reaction is carried out. After the third polymerization reaction is completed, styrene is added to the second reaction vessel, the temperature is raised to the temperature required for the fourth polymerization reaction, and the fourth polymerization reaction is carried out. After the fourth polymerization reaction is completed, a halogenating agent and a molecular weight modifier are further added to the second reaction vessel, the temperature is raised to the temperature required for the second halogenation reaction, the second initiator is added to develop the second halogenation reaction, and after the reaction is completed, product b is obtained.

[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, polymerization will be insufficient, and the molecular weight of the third polymerization reaction product will be too low. If the temperature of the third polymerization reaction is too high, the molecular structure of the third polymerization reaction product will change. 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, polymerization will be insufficient, and the molecular weight of the third polymerization reaction product will be too low. If the time of the third polymerization reaction is too long, the manufacturing cost will increase.

[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, polymerization will be insufficient, and furthermore, the molecular weight of the fourth polymerization reaction product will be too low. If the temperature of the fourth polymerization reaction is too high, the molecular structure of the fourth polymerization reaction product will change. The time of the fourth polymerization reaction is 50 to 60 min, preferably 53 to 57 min. If the time of the fourth polymerization reaction is too short, polymerization will be insufficient, and furthermore, the molecular weight of the fourth polymerization reaction product will be too low. If the time of the fourth polymerization reaction is too long, the manufacturing cost will increase.

[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 will be insufficient and the halogen content of product b will be too low. If the temperature of the second halogenation reaction is too high, the molecular weight of product b will be too high and the molecular weight distribution will be too broad. The duration of the second halogenation reaction is 2 to 3 hours, preferably 2.3 to 2.7 hours. If the duration of the second halogenation reaction is too short, the molecular weight of product b will be too low, and if the duration of the second halogenation reaction is too long, the manufacturing cost will increase.

[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 initiated by a specific second initiator are subjected to free radical addition with a halogenating agent, significantly reducing the content of unsaturated "double bonds." This prevents the introduction of unsaturated "double bonds" by subsequent butyl rubber branching, further increasing the 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 conventional method of generation by ion substitution, avoids the generation of hydrogen halide as a byproduct, eliminates the conditions for isomerization from the 2-position halogen structure to the 1-position structure, improves the stability of the 2-position halogen structure in halogenated branched butyl rubber, further accelerates the vulcanization rate of halogenated branched butyl rubber, and solves the problem of slow vulcanization rate of butyl rubber in the processing process.

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

[0050] According to the present invention, in step (1-3), regarding the operation process of the fifth polymerization reaction, each raw material is prepared in the above proportions, an inert gas is introduced into the third reaction vessel to remove oxygen gas, then the solvent, styrene, butadiene, and structural modifier are added, the temperature is raised to the temperature required for the fifth polymerization reaction, the first initiator is added, and the fifth polymerization reaction is carried out 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, polymerization will be insufficient, and the molecular weight of product c will be too low. If the temperature of the fifth polymerization reaction is too high, abnormal polymerization or flash polymerization will occur. 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, polymerization will be insufficient, and the molecular weight of product c will be too low. If the time of the fifth polymerization reaction is too long, the manufacturing cost will increase.

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

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

[0054] According to the present invention, in step (2), regarding the operation process of the coupling reaction and capping reaction, each raw material is prepared in the above proportions, product b produced in the second reaction vessel and product c produced in the third reaction vessel are placed in the first reaction vessel and mixed with product a, the temperature is raised to the temperature required for the coupling reaction and the coupling reaction is carried out, after the coupling reaction is completed the temperature required for the coupling reaction is maintained, a conjugated diene is added to the first reaction vessel and the capping reaction is carried out, wet agglomeration and baking are performed on the reaction product to obtain the multicomponent 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 decreases, the distribution of segments in the produced multi-component copolymer becomes narrower, and as a result, the rubber produced using the multi-component copolymer deteriorates in viscoelasticity and dimensional stability. If the temperature of the coupling reaction is too high, the coupling effect is affected. The duration of the coupling reaction is 150 to 170 min, preferably 155 to 165 min. If the duration 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 deteriorates, and if the temperature of the capping reaction is too high, the conjugated diene self-polymerizes and fails to perform its capping function. The duration of the capping reaction is 20 to 30 minutes, preferably 23 to 27 minutes. If the duration of the capping reaction is too short, capping is insufficient and the capping effect deteriorates, and if the duration of the capping reaction is too long, there is no clear change in the product after capping is completed, resulting in increased manufacturing costs.

[0057] According to the present invention, in step (2), the obtained "three-armed" star structure effectively disrupts the regularity of the molecular chains during copolymerization of isobutylene and isoprene in the production of halogenated branched butyl rubber, improves segment disorder, imparts excellent viscoelasticity to the butyl rubber, reduces the die swell effect, and ensures the processing dimensional stability of the butyl rubber.

[0058] According to the present invention, in the method for producing the multi-component 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, and more preferably hexane. In the present invention, the solvents used in each step may be the same or different, but preferably they are the same.

[0059] According to the present invention, in the method for producing the multi-component copolymer, the first initiator is a hydrocarbyl monolithium compound, preferably RLi, where R includes 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 initiator used in each step may be the same or different, but preferably they are the same.

[0060] According to the present invention, in the method for producing the multi-component 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-butyl hexaneperoxide (BPDH), di-tert-butyl peroxide (DTBP), and dicumyl peroxide (DCP), more preferably di-tert-butyl peroxide. In the present invention, the second initiator used in each step may be the same or different, but preferably the same.

[0061] According to the present invention, in the method for producing the multi-component copolymer, it is preferable to use an organic halogenating agent as the halogenating agent, and more preferably, the halogenating agent is at least one selected from N-bromosuccinimide, bromodimethylsulfonium bromide, N-bromosuccinimide, N-chlorosuccinimide, N-chlorosuccinimide, and chlorodimethylsulfonium chloride, and more preferably, at least one of 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 multi-component copolymer, the structural modifier 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 structural modifiers used in each step may be the same or different, but preferably they are the same.

[0064] According to the present invention, in the method for producing the multi-component 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 preferably they are the same.

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

[0066] A third aspect of the present invention provides a multi-component copolymer produced by the method described in the second aspect above.

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

[0068] A fourth aspect of the present invention provides the use of the multi-component copolymer described in the first or third aspect above as a grafting agent in the production of diene rubber.

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

[0070] A fifth aspect of the present invention comprises structural unit A derived from isobutylene, structural unit B derived from isoprene, and structural unit C derived from a grafting agent, The grafting agent is a halogenated branched butyl rubber, which is a multi-component copolymer as described in the first or third embodiment above.

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

[0072] The halogenated branched butyl rubber according to the present invention contains structural units derived from the aforementioned specific grafting agent, which combines structurally different -BR-segments, -IR-segments, -PS-segments, and -SBR-segments with polymer chains to form a "three-armed" star structure, and also obtains a stable 2-position halogen substitution structure. Each of the above segments, the "three-armed" star structure, and the stable 2-position halogen substitution structure are introduced into the structure of the butyl rubber by graft polymerization and perform a synergistic effect. As a result, the halogenated branched butyl rubber has high saturation and branching, a significantly reduced die swell effect, a fast vulcanization rate, high ozone aging resistance, and good airtightness.

[0073] A sixth aspect of the present invention includes the step of causing a cationic polymerization reaction of isobutylene, isoprene, and a grafting agent in the presence of a diluent, a solvent, and a co-initiator to obtain the halogenated branched butyl rubber, The present invention provides a method for producing halogenated branched butyl rubber, wherein the graft agent is a multi-component copolymer as described in the first or third embodiment above.

[0074] According to the present invention, in the method for producing 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 co-initiator is 0.1 to 0.6 parts by weight, relative to 100 parts by weight of isobutylene and isoprene in total.

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

[0076] In this invention, by controlling the amounts of isobutylene, isoprene, and grafting agent to the above-mentioned specific range, halogenated branched butyl rubber with excellent aging resistance, dimensional stability of the product, and vulcanization processability can be obtained.

[0077] According to the present invention, the cationic polymerization reaction can employ a reaction process for producing butyl rubber using a conventional grafting agent in the art. Preferably, each raw material is prepared in the above proportions, an inert gas is introduced into the reaction vessel to remove oxygen gas, a mixture of the solvent and the first part of the diluent (the volume ratio of diluent:solvent is 70-30:30-70), and the grafting agent are added to thoroughly dissolve the grafting agent, and the temperature is lowered to -95 to -85°C. Then, the second part of the diluent, isobutylene, and isoprene are added to adjust the temperature to the temperature required for the cationic polymerization reaction. The remaining diluent and co-initiator (both of which are pre-mixed and aged at -95 to -85°C) are added to the reaction system to carry out the cationic polymerization reaction. After the reaction is complete, a termination agent is added to stop the reaction, the product is aggregated and washed, dried, and the halogenated branched butyl rubber is obtained.

[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 will be long and the molecular weight of the rubber product will be too low. If the temperature of the cationic polymerization reaction is too high, the molecular structure of the rubber product may change. The duration of the cationic polymerization reaction is 2 to 4 hours. If the duration of the cationic polymerization reaction is too short, the reaction will be insufficient and the molecular weight of the rubber product will be too low. If the duration of the cationic polymerization reaction is too long, the molecular structure of the rubber product 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 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, 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, preferably, the diluent is 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 proportions of the first part of the diluent, the second part of the diluent, and the remaining diluent may be those of the art, and are not particularly limited in the present invention.

[0083] According to the present invention, the co-initiator comprises an alkylaluminum halide and a protonic acid. Preferably, in the co-initiator, the molar ratio of the alkylaluminum halide to the protonic acid is (10 to 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 inhibitor is at least one selected from methanol, ethanol, and butanol.

[0087] A seventh aspect of the present invention provides halogenated branched butyl rubber manufactured by the method described in the sixth aspect above.

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

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

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

[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 stated, conventional conditions or conditions proposed by the manufacturer shall be followed. Unless the manufacturer is specified for the reagents or equipment used, they are all commonly available commercially. The weight ratio relationship between the obtained multi-component copolymer product and each structural unit contained in the halogenated branched butyl rubber was calculated and determined 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-butylperoxide (DTBP): Lanzhou Pharmacy n-Butyllithium: 98% purity, Nanjing Tonglian Chemical Industry Co., Ltd. Ethyl aluminum sesquichloride: 98% purity, Bailingwei 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 testing method: Measurement of bromine content: A 10 mg sample is weighed and the sample is thermally decomposed using a Q600 TG / DTG thermogravimetric analyzer at a heating rate of 10°C / min, under a nitrogen atmosphere, and at a flow rate of 50 mL / min. In the first stage of thermal decomposition, HBr is generated by the debromination of bromine-containing units in the sample. The bromine content (X) in the sample is estimated from the percentage of HBr removed, and the calculation formula is as follows. In formula TIFF0007911624000015.tif11170, 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: These are measured using a Waters 2414 gel permeation chromatograph (GPC) manufactured in the USA. A polystyrene standard sample is used for the calibration curve, the mobile phase is tetrahydrofuran, the column temperature is 40°C, the sample concentration is 1 mg / mL, the injection volume is 50 μL, the elution time is 40 min, and the flow rate is 1 mL / min.

[0096] Measurement of unsaturation: A Bruker AVANCE300 nuclear magnetic resonance spectrometer is used, with a magnetic field strength of 9.20 Tesla, CDC13 as the solvent, and TMS as the internal standard, and measurements are taken at room temperature (25°C).

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

[0098] Measurement of static ozone performance: A TD-401A thermal aging tester was used, with test parameters of 25% elongation and 50 × 10⁻¹ ozone mass fraction. -8 The temperature is 40°C and the time is 1000h.

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

[0100] Airtightness measurement: An automated 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] Dicewell ratio measurement: Using a Malvern RH2000 capillary rheometer (UK), temperature 100°C, aspect ratio 16:1, shear rate 10-1000S. -1 Next, we measure the die swell ratio.

[0102] Manufacturing Example 1 This manufacturing example describes the production of a multi-component copolymer. (1-1) Argon gas was introduced into a 15L stainless steel first reaction vessel with a jacket and purged twice. 1000g of hexane, 300g of isoprene, and 1.3g of tetrahydrofuran were added sequentially to the first reaction vessel, and the temperature was raised to 40°C. Then, 13.5mmo1 of n-butyllithium was added and the reaction was carried out for 20 minutes. Next, 200g of styrene and 1.1g of tetrahydrofuran were added sequentially to the first reaction vessel, and the temperature was raised to 60°C and the reaction was carried out for 40 minutes to form the -PS-IR-segment. Finally, 500g of N-bromosuccinimide and 2.0g of tert-dodecyl mercaptan were added sequentially to the first reaction vessel, and the temperature was raised to 70°C. 1.5g of DTBP was added and the reaction was carried out for 2.0 hours to obtain product a.

[0103] (1-2) In a 15L stainless steel second reaction vessel, the system was purged twice by introducing argon gas, and 1000g of hexane, 200g of 1,3-butadiene, and 1.0g of tetrahydrofuran were added in sequence. After raising the temperature to 40°C, 11.5mmo1 of n-butyllithium was added and the reaction was carried out for 30 minutes. Next, 300g of styrene was added to the second reaction vessel, the temperature was raised to 50°C, and the reaction was carried out for 50 minutes to form the -BR-PS- segment. Finally, 500g of N-bromosuccinimide and 1.0g of tert-dodecyl mercaptan were added in sequence to the second reaction vessel, the temperature was raised to 70°C, and 1.2g of DTBP was added and the reaction was carried out for 2.0 hours to obtain product b.

[0104] (1-3) In a 15L stainless steel third reaction vessel, the system was purged twice by introducing argon gas, and 1000g of hexane, 100g of styrene, 50g of 1,3-butadiene, and 1.0g of tetrahydrofuran were added in sequence. After raising the temperature to 60°C, 8.5mm of n-butyllithium was added and the reaction was carried out for 30 minutes to form an -SBR- segment and obtain product c.

[0105] (2) All of product b from the second reaction vessel and all of product c from the third reaction vessel were added to the first reaction vessel 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 the coupling reaction. After 150 minutes of reaction, 10 g of 1,3-butadiene was added to the first reaction vessel to perform capping activation. After 20 minutes of reaction until the free monomers were gone, the gel solution was subjected to wet flocculation and baking to obtain a multi-component copolymer, which was P1 (Mn = 81000, Mw / Mn = 9.16).

[0106] The calculations show that in P1, the molar ratio of R1:R2:R3:phenyl is 1.9:5.8:6.3:0.1, the Br content in P1 is 20.9 wt%, and the content of structural units derived from the conjugated diene at the end of P1 is 0.46 wt%.

[0107] Manufacturing Example 2 This manufacturing example describes the production of a multi-component copolymer. (1-1) Argon gas was introduced into a 15L stainless steel first reaction vessel with a jacket and purged twice. 1200g of hexane, 330g of isoprene, and 1.9g of tetrahydrofuran were added sequentially to the first reaction vessel, and the temperature was raised to 43°C. Then, 15.5m of n-butyllithium was added and the reaction was carried out for 23 minutes. Next, 220g of styrene and 1.5g of tetrahydrofuran were added sequentially to the first reaction vessel, and the temperature was raised to 63°C and the reaction was carried out for 43 minutes to form the -PS-IR-segment. Finally, 520g of N-bromosuccinimide and 2.5g of tert-dodecyl mercaptan were added sequentially to the first reaction vessel, and the temperature was raised to 73°C. 2.1g of DTBP was added and the reaction was carried out for 2.6 hours to obtain product a.

[0108] (1-2) In a 15L stainless steel second reaction vessel, the system was purged twice by introducing argon gas, and 1300g of hexane, 220g of 1,3-butadiene, and 1.4g of tetrahydrofuran were added in sequence. After raising the temperature to 43°C, 12.5mmo1 of n-butyllithium was added and the reaction was carried out for 33 minutes. Next, 320g of styrene was added to the second reaction vessel, the temperature was raised to 56°C, and the reaction was carried out for 56 minutes to form the -BR-PS- segment. Finally, 480g of N-bromosuccinimide and 1.5g of tert-dodecyl mercaptan were added in sequence to the second reaction vessel, the temperature was raised to 73°C, and 1.7g of DTBP was added and the reaction was carried out for 2.5 hours to obtain product b.

[0109] (1-3) In a 15L stainless steel third reaction vessel, the system was purged twice by introducing argon gas. 1200g of hexane, 120g of styrene, 60g of 1,3-butadiene, and 1.4g of tetrahydrofuran were added in sequence, and after raising the temperature to 66°C, 10.5mm of n-butyllithium was added and the reaction was carried out for 33 minutes to form an -SBR- segment and obtain product c.

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

[0111] Manufacturing Example 3 This manufacturing example describes the production of a multi-component copolymer. (1-1) Argon gas was introduced into a 15L stainless steel first reaction vessel with a jacket and purged three times. 1400g of hexane, 350g of isoprene, and 2.2g of tetrahydrofuran were added sequentially to the first reaction vessel, and the temperature was raised to 45°C. Then, 17.5mmo1 of n-butyllithium was added and the reaction was carried out for 25 minutes. Next, 240g of styrene and 1.8g of tetrahydrofuran were added sequentially to the first reaction vessel, and the temperature was raised to 64°C and the reaction was carried out for 45 minutes to form the -PS-IR-segment. Finally, 540g of N-bromosuccinimide and 3.0g of tert-dodecyl mercaptan were added sequentially to the first reaction vessel, and the temperature was raised to 75°C. 2.4g of DTBP was added and the reaction was carried out for 3.0 hours to obtain product a.

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

[0113] (1-3) In a 15L stainless steel third reaction vessel, the system was purged twice by introducing argon gas, and 1500g of hexane, 150g of styrene, 70g of 1,3-butadiene, and 2.0g of tetrahydrofuran were added in sequence. After raising the temperature to 64°C, 11.6mmo1 of n-butyllithium was added and the reaction was carried out for 35 minutes to form an -SBR- segment and obtain product c.

[0114] (2) All of product b from the second reaction vessel and all of product c from the third reaction vessel were added to the first reaction vessel and mixed with product a. The temperature was raised to 85°C, and 100 mmol of 1,3,5-trichlorobenzene was added to carry out the coupling reaction. After 160 minutes of reaction, 15 g of 1,3-butadiene was added to the first reaction vessel to perform capping activation. The reaction was carried out for 25 minutes until the free monomers were gone. The gel solution was subjected to wet aggregation and baking to obtain a multi-component copolymer, which was P3 (Mn = 85000, Mw / Mn = 9.79).

[0115] The calculations show that in P3, the molar ratio of R1:R2:R3:phenyl is 2.8:6.9:7.3:0.1, the Br content in P3 is 18.8 wt%, and the content of structural units derived from the conjugated diene at the end of P3 is 0.62 wt%.

[0116] Manufacturing Example 4 This manufacturing example describes the production of a multi-component copolymer. (1-1) Argon gas was introduced into a 15L stainless steel first reaction vessel with a jacket and purged three times. 1600g of hexane, 370g of isoprene, and 2.5g of tetrahydrofuran were added sequentially to the first reaction vessel, and the temperature was raised to 47°C. Then, 19.2m of n-butyllithium was added and the reaction was carried out for 26 minutes. Next, 260g of styrene and 2.1g of tetrahydrofuran were added sequentially to the first reaction vessel, and the temperature was raised to 66°C and the reaction was carried out for 47 minutes to form the -PS-IR-segment. Finally, 560g of N-chlorosuccinimide and 3.5g of tert-dodecyl mercaptan were added sequentially to the first reaction vessel, and the temperature was raised to 76°C. 2.6g of DTBP was added and the reaction was carried out for 3.3 hours to obtain product a.

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

[0118] (1-3) In a 15L stainless steel third reaction vessel, the system was purged twice by introducing argon gas. 1700g of hexane, 170g of styrene, 80g of 1,3-butadiene, and 2.2g of tetrahydrofuran were added in sequence, and after raising the temperature to 66°C, 13.5mmo1 of n-butyllithium was added and the reaction was carried out for 36 minutes to form an -SBR- segment and obtain product c.

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

[0120] Manufacturing Example 5 This manufacturing example describes the production of a multi-component copolymer. (1-1) Argon gas was introduced into a 15L stainless steel first reaction vessel with a jacket and purged four times. 1800g of hexane, 390g of isoprene, and 2.8g of tetrahydrofuran were added sequentially to the first reaction vessel, and the temperature was raised to 49°C. Then, 21.5mmo1 of n-butyllithium was added and the reaction was carried out for 28 minutes. Next, 280g of styrene and 2.6g of tetrahydrofuran were added sequentially to the first reaction vessel, and the temperature was raised to 68°C and the reaction was carried out for 49 minutes to form the -PS-IR-segment. Finally, 580g of N-bromosuccinimide and 3.8g of tert-dodecyl mercaptan were added sequentially to the first reaction vessel, and the temperature was raised to 78°C. 2.8g of DTBP was added and the reaction was carried out for 3.6 hours to obtain product a.

[0121] (1-2) In a 15L stainless steel second reaction vessel, argon gas was introduced and the system was purged four times. 1800g of hexane, 290g of 1,3-butadiene, and 2.6g of tetrahydrofuran were added in sequence, and the temperature was raised to 48°C. Then, 16.5mmo1 of n-butyllithium was added and the reaction was carried out for 38 minutes. Next, 380g of styrene was added to the second reaction vessel, the temperature was raised to 58°C, and the reaction was carried out for 59 minutes to form the -BR-PS- segment. Finally, 420g of N-bromosuccinimide and 2.3g of tert-dodecyl mercaptan were added in sequence to the second reaction vessel, the temperature was raised to 78°C, and 2.7g of DTBP was added and the reaction was carried out for 2.9 hours to obtain product b.

[0122] (1-3) In a 15L stainless steel third reaction vessel, the system was purged twice by introducing argon gas, and 1900g of hexane, 180g of styrene, 90g of 1,3-butadiene, and 2.6g of tetrahydrofuran were added in sequence. After raising the temperature to 68°C, 15.5 mmol of n-butyllithium was added and the reaction was carried out for 38 minutes to form an -SBR- segment and obtain product c.

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

[0124] The calculations show that in P5, the molar ratio of R1:R2:R3:phenyl is 3.4:7.8:8.5:0.1, the Br content in P5 is 17.2 wt%, and the content of structural units derived from the conjugated diene at the end of P5 is 0.68 wt%.

[0125] Manufacturing Example 6 This manufacturing example describes the production of a multi-component copolymer. (1-1) Argon gas was introduced into a 15L stainless steel first reaction vessel with a jacket and purged four times. 2000g of hexane, 400g of isoprene, and 3.0g of tetrahydrofuran were added sequentially to the first reaction vessel, and the temperature was raised to 50°C. Then, 22.5mmo1 of n-butyllithium was added and the mixture was reacted for 30 minutes. Next, 300g of styrene and 3.0g of tetrahydrofuran were added sequentially to the first reaction vessel, and the temperature was raised to 70°C and the mixture was reacted for 50 minutes to form the -PS-IR-segment. Finally, 600g of N-bromosuccinimide and 4.0g of tert-dodecyl mercaptan were added sequentially to the first reaction vessel, and the temperature was raised to 80°C. 3.0g of DTBP was added and the mixture was reacted for 4.0 hours to obtain product a.

[0126] (1-2) In a 15L stainless steel second reaction vessel, argon gas was introduced and the system was purged four times. 2000g of hexane, 300g of 1,3-butadiene, and 3.0g of tetrahydrofuran were added in sequence, and the temperature was raised to 50°C. Then, 17.5mmo1 of n-butyllithium was added and the reaction was carried out for 40 minutes. Next, 400g of styrene was added to the second reaction vessel, the temperature was raised to 60°C, and the reaction was carried out for 60 minutes to form the -BR-PS- segment. Finally, 400g of N-bromosuccinimide and 2.7g of tert-dodecyl mercaptan were added in sequence to the second reaction vessel, the temperature was raised to 80°C, and 3.0g of DTBP was added and the reaction was carried out for 3.0 hours to obtain product b.

[0127] (1-3) In a 15L stainless steel third reaction vessel, the system was purged twice by introducing argon gas, and 2000g of hexane, 200g of styrene, 100g of 1,3-butadiene, and 3.0g of tetrahydrofuran were added in sequence. After raising the temperature to 70°C, 16.5mmo1 of n-butyllithium was added and the reaction was carried out for 40 minutes to form an -SBR- segment and obtain product c.

[0128] (2) All of product b from the second reaction vessel and all of product c from the third reaction vessel were added to the first reaction vessel and mixed with product a. The temperature was raised to 88°C, and 100 mmol of 1,3,5-trichlorobenzene was added to carry out the coupling reaction. After 170 minutes of reaction, 20 g of 1,3-butadiene was added to the first reaction vessel to perform capping activation. After 30 minutes of reaction until the free monomers were gone, the gel solution was subjected to wet flocculation and baking to obtain a multi-component copolymer, which was P6 (Mn = 90000, Mw / Mn = 10.35).

[0129] The calculations show that in P6, the molar ratio of R1:R2:R3:phenyl is 3.8:8.1:8.8:0.1, the Br content in P6 is 16.7 wt%, and the content of structural units derived from the conjugated diene at the end of P6 is 0.74 wt%.

[0130] Manufacturing example 7 This manufacturing example describes the production of a multi-component copolymer. In the step using N-bromosuccinimide, the remaining conditions were the same as in Production Example 1, except that the same weight of an inorganic brominating agent, hydrogen bromide, was used instead of N-bromosuccinimide in each step, to obtain a polypolymer with P7 (Mn = 78000, Mw / Mn = 8.52).

[0131] The calculations show that in P7, the molar ratio of R1:R2:R3:phenyl is 1.9:5.8:6.3:0.1, the Br content in P7 is 45.9 wt%, and the content of structural units derived from the conjugated diene at the end of P7 is 0.46 wt%.

[0132] Manufacturing Example 8 This manufacturing example describes the production of a multi-component copolymer. In the step using DTBP, the same weight of hydrogen peroxide (H2O2) was used instead of DTBP in each step, but the remaining conditions were the same as in Production Example 2 to obtain a multicomponent copolymer with P8 (Mn = 71000, Mw / Mn = 7.58).

[0133] The calculations show that in P8, the molar ratio of R1:R2:R3:phenyl is 2.3:6.3:6.8:0.1, the Br content in P8 is 19.8 wt%, and the content of structural units derived from the conjugated diene at the end of P8 is 0.53 wt%.

[0134] Manufacturing Example 9 This manufacturing example describes the production of a multi-component copolymer. Except for adding 200 g of N-bromosuccinimide to the first reaction vessel, the remaining conditions were the same as in Production Example 3 to obtain a multicomponent copolymer with P9 (Mn = 78000, Mw / Mn = 9.05).

[0135] The calculations show that in P9, the molar ratio of R1:R2:R3:phenyl is 2.8:6.9:7.3:0.1, the Br content in P9 is 12.4 wt%, and the content of structural units derived from the conjugated diene at the end of P9 is 0.73 wt%.

[0136] Comparative Manufacturing Example 1 This manufacturing example describes the production of a multi-component copolymer. Except for the fact that the coupling was performed without adding 1,3,5-trichlorobenzene as a coupling agent in the manufacturing process, the remaining conditions were the same as in Manufacturing Example 5 to obtain a multi-component copolymer, which was named DP1 (Mn = 52000, Mw / Mn = 2.26).

[0137] The calculations show that in DP1, the molar ratio of R1:R2:R3 is 3.4:7.8:8.5, the Br content in DP1 is 17.2 wt%, and the content of structural units derived from the conjugated diene at the end of DP1 is 0.46 wt%.

[0138] Comparative Manufacturing Example 2 This manufacturing example describes the production of a multi-component copolymer. (1-1) Argon gas was introduced into a 15L stainless steel reactor with a jacket and purged four times. 2000g of hexane, 400g of isoprene, and 3.0g of tetrahydrofuran were added sequentially to the polymerization vessel, and the temperature was raised to 50°C. Then, 22.5mmo1 of n-butyllithium was added and the mixture was reacted for 30 minutes. Next, 300g of styrene and 3.0g of tetrahydrofuran were added sequentially to the reactor, and the temperature was raised to 70°C and the mixture was reacted for 50 minutes to form the -PS-IR segment. Finally, 600g of N-bromosuccinimide and 4.0g of tert-dodecyl mercaptan were added sequentially to the reactor, and the temperature was raised to 80°C. 3.0g of DTBP was added and the mixture was reacted for 4.0 hours to obtain product a.

[0139] (1-2) In a 15L stainless steel second reaction vessel, argon gas was introduced and the system was purged four times. 2000g of hexane, 300g of 1,3-butadiene, and 3.0g of tetrahydrofuran were added in sequence, and the temperature was raised to 50°C. Then, 17.5mmo1 of n-butyllithium was added and the reaction was carried out for 40 minutes. Next, 400g of styrene was added to the second reaction vessel, the temperature was raised to 60°C, and the reaction was carried out for 60 minutes to form the -BR-PS- segment. Finally, 400g of N-bromosuccinimide and 2.7g of tert-dodecyl mercaptan were added in sequence to the second reaction vessel, the temperature was raised to 80°C, and 3.0g of DTBP was added and the reaction was carried out for 3.0 hours to obtain product b.

[0140] (2) All of product b from the second reaction vessel was added to the first reaction vessel and mixed with product a. The temperature was raised to 88°C, and 100 mmol of 1,3,5-trichlorobenzene was added to carry out the coupling reaction. After 170 minutes of reaction, 20 g of 1,3-butadiene was added to the first reaction vessel to perform capping activation. The reaction was carried out for 30 minutes until the free monomers were gone. The gel solution was subjected to wet aggregation and baking to obtain a multi-component copolymer, which was DP2 (Mn = 65000, Mw / Mn = 5.12).

[0141] The calculations show that in DP2, the molar ratio of R2:R3:phenyl is 8.1:8.8:0.1 (DP2 does not contain R1), the Br content in DP2 is 18.8 wt%, and the content of structural units derived from conjugated dienes at the ends of DP2 is 0.83 wt%.

[0142] Example 1 This embodiment describes the production of halogenated branched butyl rubber. In a 4L stainless steel reaction vessel with a jacket, nitrogen was introduced and purged three times. 300g of methyl chloride, 700g of hexane, and 35g of the multi-component copolymer (P1) produced in Production Example 1 were added to the polymerization vessel 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 sequence and stirred to mix. When the temperature of the polymerization system dropped to -90°C, 50g of methyl chloride, 1.075g of ethylaluminum sesquichloride, and 0.007g of HCl (aged by mixing at -85°C for 30 minutes) were added together to the polymerization system and stirred for 2.0 hours to react. Finally, 25g of ethanol was added, the discharged material was agglomerated and washed, dried, and halogenated branched butyl rubber was obtained, designated as S1 (bromine content 2.36 wt%).

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

[0144] Standard samples were prepared using S1, and the test performance is shown in Table 1.

[0145] Example 2 This embodiment describes the production of halogenated branched butyl rubber.

[0146] In a 4L stainless steel reaction vessel with a jacket, nitrogen was introduced and purged three times. 400g of methyl chloride, 600g of hexane, and 38g of the multi-component copolymer (P2) produced in Production Example 2 were added to the polymerization vessel and stirred for 65 minutes until dissolved. 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 sequence and stirred to mix. When the temperature of the polymerization system dropped to -92°C, 60g of methyl chloride, 1.189g of ethylaluminum sesquichloride, and 0.011g of HCl (aged for 32 minutes under conditions of -85°C) were added together to the polymerization system and stirred for 2.6 hours to react. Finally, 30g of ethanol was added, the discharged material was agglomerated and washed, dried, and halogenated branched butyl rubber was obtained, which was designated as S2 (bromine content 2.45 wt%).

[0147] Based on the total weight of S2, the weight ratio of structural unit A derived from isobutylene, structural unit B derived from isoprene, and structural unit C derived from the graft agent is 12:0.18:1. Standard samples were prepared using S2, and the test performance is shown in Table 1.

[0148] Example 3 This embodiment describes the production of halogenated branched butyl rubber.

[0149] In a 4L stainless steel reaction vessel with a jacket, nitrogen was introduced and purged three times. 500g of methyl chloride, 500g of hexane, and 41g of the multicomponent copolymer (P3) produced in Production Example 3 were added to the polymerization vessel and stirred for 70 minutes to dissolve. After P3 was completely dissolved, the temperature was lowered to -90°C, and 700g of methyl chloride, 449g of isobutylene, and 10g of isoprene were added in sequence and stirred to mix. When the temperature of the polymerization system dropped to -94°C, 70g of methyl chloride, 1.203g of ethylaluminum sesquichloride, and 0.031g of HCl (aged for 34 minutes under conditions of -88°C) were added together to the polymerization system and stirred for 3.0 hours to react. Finally, 35g of ethanol was added, the discharged material was agglomerated and washed, dried, and halogenated branched butyl rubber was obtained, which was designated as S3 (bromine content 2.65 wt%).

[0150] Based on the total weight of S3, the weight ratio of structural unit A derived from isobutylene, structural unit B derived from isoprene, and structural unit C derived from the graft agent is 11:0.24:1. Standard samples were prepared using S3, and the test performance is shown in Table 1.

[0151] Example 4 This embodiment describes the production of halogenated branched butyl rubber. In a 4L stainless steel reaction vessel with a jacket, nitrogen was introduced and purged three times. 600g of methyl chloride, 400g of hexane, and 44g of the multi-component copolymer (P4) produced in Production Example 4 were added to the polymerization vessel and stirred for 74 minutes until dissolved. After P4 was completely dissolved, the temperature was lowered to -91°C, and 800g of methyl chloride, 444g of isobutylene, and 12g of isoprene were added in sequence and stirred to mix. When the temperature of the polymerization system dropped to -95°C, 80g of methyl chloride, 1.315g of ethylaluminum sesquichloride, and 0.048g of HCl (aged for 36 minutes under conditions of -90°C) were added together to the polymerization system and stirred for 3.3 hours to react. Finally, 40g of ethanol was added, the discharged material was agglomerated and washed, dried, and halogenated branched butyl rubber was obtained, which was S4 (nitrogen content 2.72 wt%).

[0152] Based on the total weight of S4, the weight ratio of structural unit A derived from isobutylene, structural unit B derived from isoprene, and structural unit C derived from the graft agent is 10:0.27:1. Standard samples were prepared using S4, and the test performance is shown in Table 1.

[0153] Example 5 This embodiment describes the production of halogenated branched butyl rubber. In a 4L stainless steel reaction vessel with a jacket, nitrogen was introduced and purged three times. 650g of methyl chloride, 350g of hexane, and 48g of the multi-component copolymer (P5) produced in Production Example 5 were added to the polymerization vessel and stirred for 78 minutes until dissolved. 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 sequence and stirred to mix. When the temperature of the polymerization system dropped to -97°C, 90g of methyl chloride, 1.425g of ethylaluminum sesquichloride, and 0.057g of HCl (aged for 38 minutes under -93°C conditions) were added together to the polymerization system and stirred for 3.7 hours to react. Finally, 45g of ethanol was added, the discharged material was agglomerated and washed, dried, and halogenated branched butyl rubber was obtained, which was designated as S5 (bromine content 2.86 wt%).

[0154] Based on the total weight of S5, the weight ratio of structural unit A derived from isobutylene, structural unit B derived from isoprene, and structural unit C derived from the graft agent is 9:0.29:1. Standard samples were prepared using S5, and the test performance is shown in Table 1.

[0155] Example 6 This embodiment describes the production of halogenated branched butyl rubber.

[0156] In a 4L stainless steel reaction vessel with a jacket, nitrogen was introduced and purged five times. 700g of methyl chloride, 300g of hexane, and 50g of the multi-component copolymer (P6) produced in Production Example 6 were added to the polymerization vessel 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 sequence and stirred to mix. When the polymerization system temperature dropped to -100°C, 100g of methyl chloride, 1.564g of ethylaluminum sesquichloride, and 0.074g of HCl (aged for 40 minutes under -95°C conditions) were added together to the polymerization system and stirred for 4.0 hours to react. Finally, 50g of ethanol was added, the discharged material was agglomerated and washed, dried, and halogenated branched butyl rubber was obtained, which was designated as S6 (bromine content 2.97 wt%).

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

[0158] Example 7 This embodiment describes the production of halogenated branched butyl rubber. The method of Example 6 was followed, except that 50g of the multi-component copolymer (P2) produced in Production Example 2 was used instead of "50g of the multi-component copolymer (P6) produced in Production Example 6," and the remaining conditions were the same as in Example 6.

[0159] Halogenated branched butyl rubber was obtained and classified as S7 (bromine content 3.16 wt%).

[0160] Based on the total weight of S7, the weight ratio of structural unit A derived from isobutylene, structural unit B derived from isoprene, and structural unit C derived from the graft agent is 9:0.3:1. Standard samples were prepared using S7, and the test performance is shown in Table 1.

[0161] Example 8 This embodiment describes the production of halogenated branched butyl rubber.

[0162] The method of Example 6 was followed, except that 50g of the multi-component copolymer (P3) produced in Production Example 3 was used instead of "50g of the multi-component copolymer (P6) produced in Production Example 6," and the remaining conditions were the same as in Example 6.

[0163] Halogenated branched butyl rubber was obtained and classified as S8 (bromine content 3.08 wt%).

[0164] Based on the total weight of S8, the weight ratio of structural unit A derived from isobutylene, structural unit B derived from isoprene, and structural unit C derived from the graft agent is 9:0.3:1. Standard samples were 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 and given the value S9 (bromine content 1.85 wt%).

[0166] Standard samples were 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 the multi-component polymer P8 was used instead of the multi-component polymer P2, with the remaining conditions being the same as in Example 2. A halogenated branched butyl rubber was obtained and was classified as S10 (bromine content 1.89 wt%).

[0168] Standard samples were 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 the multipolymer P9 was used instead of the multipolymer P3, with the remaining conditions being the same as in Example 3. A halogenated branched butyl rubber was obtained and was given the S11 (bromine content of 1.97 wt%).

[0170] Standard samples were 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 the multi-component polymer DP1 was used instead of the multi-component polymer P5, with the remaining conditions being the same as in Example 5. A halogenated branched butyl rubber was obtained and designated as D1 (bromine content 0.58 wt%).

[0172] Standard samples were prepared using D1, and the test performance is shown in Table 1.

[0173] Comparative Example 2 According to the method of Example 6, except that the same weight of the copolymer DP2 was used instead of the copolymer P6, the remaining conditions were the same as those in Example 6. A halogenated branched butyl rubber was obtained and designated as D2 (bromine content: 0.76 wt%). Standard samples were 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 copolymer of the present invention as a grafting agent have a high halogen content, high saturation and high branching degree, a low die swell ratio, a short scorch time (T 10 ), and an optimum vulcanization time (T 90 ), a low air permeability, a long crack generation time as static ozone performance, and exhibit good vulcanization characteristics, anti-aging properties, product processing dimensional stability, and extremely high airtightness. Among them, S7 and S8 have particularly excellent comprehensive performance. In the present invention, it was found that a balance was achieved among the aging properties, product dimensional stability, and vulcanization processability of the high-saturation / high-branching halogenated branched butyl rubber.

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

[0177] As described above, the preferred embodiments of the present invention have been described in detail, but 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 appropriate manner. These simple modifications and combinations should be regarded as the disclosure content of the present invention as well, and all belong to the protection scope of the present invention.

Claims

1. Step (1-1) involves subjecting isoprene to a first polymerization reaction in the presence of a first initiator, subjecting the obtained first polymerization reaction product and styrene to a second polymerization reaction, and subjecting the obtained second polymerization reaction product to a first halogenation reaction in the presence of a second initiator and a halogenating agent to obtain product a. Steps (1-2) include: (1) In the presence of a first initiator, butadiene is subjected to a third polymerization reaction; (2) The obtained third polymerization reaction product and styrene are subjected to a fourth polymerization reaction; (3) In the presence of a second initiator and a halogenating agent, the obtained fourth polymerization reaction product is subjected to a second halogenation reaction to obtain product b; Steps (1-3) include subjecting styrene and butadiene to a fifth polymerization reaction in the presence of a first initiator to obtain product c, The process includes (2) a coupling reaction of product a, product b, and product c in the presence of a coupling agent, and a capping reaction between the coupling reaction product and the conjugated diene to obtain a multi-component copolymer. The coupling agent has the general formula shown in formula (IV), A method for producing a multi-component copolymer. (Here, R 1 , R 2 , and R 3 Each of these is independently selected from F, Cl, or Br.

2. The first polymerization reaction, second polymerization reaction, third polymerization reaction, fourth polymerization reaction, first halogenation reaction, second halogenation reaction, coupling reaction, and capping reaction are carried out in the presence of a solvent. The method according to claim 1.

3. The first polymerization reaction, the third polymerization reaction, and the fifth polymerization reaction are carried out in the presence of a structural modifier. and / or, the first halogenation reaction, the second halogenation reaction, is carried out in the presence of a molecular weight adjusting agent. The method according to claim 2.

4. In step (1-1), the amount of each raw material added to 100 parts by weight of the total amount of halogenating agent in the above method is such that: isoprene 30-40 parts by weight, styrene 20-30 parts by weight, structural modifier 0.1-0.3 parts by weight, first initiator 0.05-0.2 parts by weight, halogenating agent 50-60 parts by weight, molecular weight modifier 0.2-0.5 parts by weight, and second initiator 0.1-0.4 parts by weight. And / or, in step (1-2), the amount of each raw material added is such that it satisfies 20-30 parts by weight of butadiene, 30-40 parts by weight of styrene, 0.1-0.3 parts by weight of a structural 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 step (1 to 3), the amount of each raw material added is such that it satisfies 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 structural modifier, and 0.03 to 0.16 parts by weight of 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. The method according to claim 2.

5. The solvent is at least one selected from linear alkanes, aromatic hydrocarbons, and cycloalkanes. 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 structural modifier is a polar organic compound, and / or, the molecular weight adjusting agent 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 according to claim 4.

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

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