Halogenated grafting agent, halogenated branched butyl rubber, and production methods and uses thereof

Abstract

The present invention relates to the field of rubber damping materials, and discloses a halogenated grafting agent, a halogenated branched butyl rubber, and their production methods and uses. The halogenated grafting agent contains a structural unit A, an optional structural unit B, a structural unit C, and a structural unit D. The structural unit A has a structure represented by formula (1), the structural unit C has a structure represented by formula (2), the structural unit B is connected to the structural unit A and the structural unit C respectively, the structural unit D is a terminal capping structural unit, and the structural unit B and the structural unit D are each independently derived from a conjugated diene. The method of the present invention solves the problem of isomerization rearrangement of the halogenated structure with low damping properties in butyl rubber, and not only avoids damage to the mechanical properties and air permeability of butyl rubber by the damping brominated grafting agent, but also improves the damping performance and tensile strength of butyl rubber. 【Chemical 1】 JPEG2025516734000010.jpg48170

Description

Cross - reference to related applications

[0001] This application claims the benefit of Chinese Patent Application No. 202211183875.0, filed on September 27, 2022, the content of which is incorporated herein by reference.

Technical Field

[0002] The present invention relates to the field of rubber damping materials, specifically to halogenated grafting agents and halogenated branched butyl rubber, and their manufacturing methods and uses.

Background Art

[0003] Due to the unique viscoelasticity of polymers, rubber damping materials have an obvious damping effect of reducing vibration and noise and improving the working environment of humans and machines. They are widely used in many fields such as high - speed railways, aerospace, naval vessels and ships, mechanical engineering, automobiles, and electronic and electrical appliances. In particular, in the data storage systems of IT devices such as various servers, computers, workstations, and switches, the rotation of the fan generates vibration and noise in the cabinet, which has a significant impact on the service life of the hard drive. Therefore, the demand for efficient damping and vibration - control products is very high. In addition, the usage environment of electronic devices faces complex usage environments such as further low temperatures and further high temperatures, and the requirements for rubber damping materials are very high.

[0004] Diene rubbers are widely used in various fields of daily production and life. Their main industrial products include butadiene rubber, isoprene rubber, butyl rubber, halogenated butyl rubber, etc. Brominated butyl rubber (BIIR) is an important type of halogenated butyl rubber, which has excellent damping performance and is one of the most widely used basic damping rubbers. However, conventional brominated butyl rubber has drawbacks such as insufficient damping value, insufficient stability of damping performance, insufficient effective damping temperature range, and inferior mechanical properties, and cannot meet the requirements for the damping performance of materials by large - scale equipment and precision equipment. This has become a bottleneck in the expansion of the application of brominated butyl rubber materials.

[0005] CN103113682A discloses a high-performance damping rubber and its manufacturing method. This high-performance damping rubber is obtained by blending and polymerizing a first precursor and a second precursor. The first precursor has a molecular chain with a cationic group, the second precursor has a molecular chain with an anionic group, the molar ratio of the cationic group to the anionic group in the rubber is 1:1, the breaking strength is 5 - 20 MPa, the breaking elongation is 200% - 300%, the repair efficiency is as high as 90%, and a high-performance damping rubber with a wide damping temperature range of 20 - 100 °C and a high repair efficiency is obtained.

[0006] CN103113682A discloses a high-damping material with a wide temperature range for electronic products and its manufacturing method. By forming a supramolecular network structure through the interaction between non-polar butyl rubber, brominated p-tert-octylphenol formaldehyde resin, and polar small molecule hindered phenol A060, the temperature range reaches -60 - 100 °C.

[0007] Liao Mingyi et al. (Journal of Dalian Maritime University, 2008, 34(2): 83 - 86) disclose a step-by-step method to improve the damping performance of butyl rubber (IIR). Using IIR as the polymer network and poly(styrene-methyl methacrylate) [P(St-MMA)] as the polymer network II, a butyl rubber / poly(styrene-methyl methacrylate) interpenetrating polymer network [IIR / P(St-MMA)] is manufactured by graft polymerization to produce a butyl rubber material with a wide temperature range and high damping performance.

[0008] In the prior art, by using methods such as the blending method, copolymerization method, and interpenetrating network polymer method, the effective damping temperature range of the rubber can be broadened and the damping performance of the rubber can be improved to a certain extent. However, these methods still have certain limitations, leading to a decrease in the mechanical properties of the modified material.

Summary of the Invention

Problems to be Solved by the Invention

[0009] An object of the present invention is to obtain a halogenated branched butyl rubber having a high maximum attenuation rate, which is used in the production of halogenated branched butyl rubber, in order to solve the problems of the prior art that the attenuation characteristics and mechanical properties of rubber materials are not high, and to provide a halogenated grafting agent, a halogenated branched butyl rubber, and their production methods and uses. The method of the present invention solves the problem of isomerization rearrangement of the halogenated structure in butyl rubber, which has low attenuation, and not only avoids damage to the mechanical properties and air permeability of butyl rubber by the attenuation brominated grafting agent, but also improves the attenuation performance and tensile strength of butyl rubber.

Means for Solving the Problems

[0010] To achieve the above object, a first aspect of the present invention contains a structural unit A, an arbitrary structural unit B, a structural unit C, and a structural unit D. The structural unit A has a structure represented by the formula (1), the structural unit C has a structure represented by the formula (2), the structural unit B is connected to the structural unit A and the structural unit C respectively, the structural unit D is a terminal capping structural unit, and the structural unit B and the structural unit D each independently provide a halogenated grafting agent derived from a conjugated diene.

Chemical formula

[0011] A second aspect of the present invention is Under polymerization reaction conditions, in the presence of an initiator, a monomer represented by formula (I) and a monomer represented by formula (II) are subjected to a polymerization reaction to obtain a polymerization product. Or, (1) in the presence of a molecular weight regulator, a first solvent, and a first initiator, a first polymerization reaction of the monomer represented by formula (I) is carried out, and a second conjugated diene is optionally added to carry out a first capping reaction to obtain a first product. (2) In the presence of a structure regulator, a second solvent, and a second initiator, a second polymerization reaction of the monomer represented by formula (II) is carried out to obtain a second product, and then the first product is added thereto to carry out a third polymerization reaction to obtain a third product, step S1; A second capping reaction is carried out between the polymerization product obtained in step S1 or the third product obtained in step (2) and a first conjugated diene to obtain the halogenated grafting agent, step S2. A method for producing a halogenated grafting agent is provided.

Chemical formula

[0012] A third aspect of the present invention provides a halogenated grafting agent produced by the aforementioned production method.

[0013] A fourth aspect of the present invention provides the use of the aforementioned halogenated grafting agent as a grafting agent for producing diene rubber.

[0014] The fifth aspect of the present invention provides a halogenated branched butyl rubber comprising a structural unit E derived from isobutylene, a structural unit F derived from isoprene, and a structural unit G derived from a halogenated grafting agent, wherein the halogenated grafting agent is the aforementioned halogenated grafting agent.

[0015] The sixth aspect of the present invention is A method for producing a halogenated branched butyl rubber, comprising the step of cationically polymerizing isobutylene, isoprene, and the aforementioned halogenated grafting agent in the presence of a diluent, an organic solvent, and a co-initiator to obtain the halogenated branched butyl rubber.

[0016] The seventh aspect of the present invention provides a halogenated branched butyl rubber obtained by the aforementioned production method.

[0017] The eighth aspect of the present invention provides the use of the aforementioned halogenated branched butyl rubber in automobiles and electronic and electrical devices.

Advantages of the Invention

[0018] According to the above technical solution, the beneficial technical effects obtained by the present invention are as follows.

[0019] (1) The halogenated grafting agent according to the present invention is one in which a p-alkylphenyl structural unit and a haloalkyl structural unit are bonded on a polymer chain, and its molecular chain has the characteristics of high rigidity, large steric hindrance, strong adsorption force, and many active sites. Thereby, the p-alkylphenyl and the halogen atom can produce a remarkable "synergistic effect" when improving the damping property of the material. When this halogenated grafting agent is used as a halogenated grafting agent to produce a halogenated branched butyl rubber, the damping performance of the halogenated branched butyl rubber can be greatly improved, and a high-damping halogenated branched butyl rubber with a high maximum damping rate can be produced.

[0020] (2) In the present invention, the halogenated grafting agent produced by free radical polymerization and anionic polymerization contains a non-polar p-alkylbenzene ring structure. The benzene ring has the characteristics of high rigidity and large steric hindrance. It not only avoids the problem that the molecular weight distribution of butyl rubber broadens due to branching and the mechanical properties and airtightness of butyl rubber decrease, but also improves the tensile strength of butyl rubber.

[0021] (3) The halogenated branched butyl rubber produced by the present invention is generated by addition polymerization using a polymer attenuation halogenated grafting agent instead of ionic substitution. The p-alkylphenyl and s-position bromine-halogen structures in the grafting agent are embedded in the main segment of butyl rubber, blocking the isomerization conditions of the molecular structure, improving the stability of the attenuation performance of the halogenated branched butyl rubber, and expanding the application range of the high attenuation halogenated branched butyl rubber.

[0022] (4) In the production process of the high attenuation halogenated branched butyl rubber, the present invention eliminates the emissions of volatile organic compounds (VOC) and by-product HBr, reduces the harm to the human body and the environment, omits the recovery process of by-product HBr by alkali washing. Its production method is environmentally friendly, has a short process, low production cost, and is suitable for industrial production.

Brief Description of the Drawings

[0023]

Figure 1

Embodiments for Carrying out the Invention

[0024] The endpoints and any values disclosed in this specification are not limited to exact 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, between the endpoint values of individual ranges, between the endpoint values of individual ranges and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in this specification.

[0025] The first aspect of the present invention contains structural unit A, optional structural unit B, structural unit C, and structural unit D. The structural unit A has a structure represented by formula (1), the structural unit C has a structure represented by formula (2), the structural unit B is connected to the structural unit A and the structural unit C respectively, the structural unit D is a terminal capping structural unit, and the structural unit B and the structural unit D each independently provide a halogenated grafting agent derived from a conjugated diene.

Chemical formula

[0026] The halogenated grafting agent of the present invention has a p-alkylphenyl structural unit and a haloalkyl structural unit bonded to a polymer chain. Its molecular chain is characterized by high rigidity, large steric hindrance, strong adsorption force, and a large number of active sites. In addition, since the conjugated diene structural unit is included at the end of the copolymer, this multi-component copolymer has high polymerization activity and can be used as a grafting agent for the production of branched diene rubber, particularly halogenated branched diene rubber.

[0027] The grafting agent of the present invention contains a large number of regularly arranged benzene ring structures and can fully exhibit the characteristics of high rigidity and large steric hindrance, significantly improving the elastic modulus and barrier properties of the halogenated grafting agent. The halogenated branched diene rubber produced using this grafting agent has high damping performance while maintaining excellent mechanical strength and airtightness.

[0028] The stability of the bromine structure in the grafting agent of the present invention not only improves the damping performance of the halogenated branched diene rubber but also solves the problem of butyl rubber that it is difficult to vulcanize due to few double bonds caused by high saturation, helps to accelerate the vulcanization rate, and can improve the vulcanization processability of the halogenated branched diene rubber.

[0029] Therefore, the grafting agent of the present invention has the characteristics of a large number of benzene ring structures, a stable halogen structure, and high isotacticity. The halogenated branched diene rubber produced using this grafting agent not only has high damping performance but also has excellent airtightness, mechanical strength, and vulcanization processability, meeting the requirements of various applications.

[0030] In the present invention, the above C 1 ~C 8Examples of the linear or branched alkyl may be any one of, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, 2-methylhexyl, 2-ethylhexyl, 1-methylheptyl, 2-methylheptyl, n-octyl, and isooctyl.

[0031] In some embodiments, R 1 and R 2 are each independently hydrogen or a linear or branched alkyl of C 1 to C 3 , preferably hydrogen, methyl, ethyl, or propyl.

[0032] In some embodiments, R 3 is a linear or branched alkyl of C 1 to C 5 , preferably methyl, ethyl, n-propyl, or isopropyl.

[0033] In some embodiments, R 4 and R 5 are each independently hydrogen or an alkyl of C 1 to C 2 , preferably hydrogen, methyl, or ethyl.

[0034] In some embodiments, X is at least one selected from Cl and Br, preferably Br.

[0035] In some embodiments, the conjugated diene is butadiene and / or isoprene.

[0036] In some preferred embodiments of the present invention, the structural unit represented by formula (1) may be a structural unit derived from p-alkylstyrene, such as p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-n-butylstyrene, p-isobutylstyrene, or p-isopentylstyrene.

[0037] In some preferred embodiments of the present invention, the structural unit represented by formula (2) may be a structural unit derived from a halogenated olefin, such as vinyl bromide, vinyl chloride, 1-bromo-1-propene, 2-bromo-1-propene, 1-bromo-1-butene, or 2-bromo-1-butene. Preferably, it is a structural unit derived from vinyl bromide or 2-bromo-1-butene.

[0038] In order to improve the maximum attenuation rate, air permeability, and tensile strength of the halogenated branched butyl rubber, in some embodiments, the mass ratio of the structural unit A, structural unit B, structural unit C, and structural unit D is 100:0 to 2:15 to 70:3 to 7, for example, 100:0.3:30:4, 100:0.5:40:5, 100:0.6:50:6, 100:0.8:60:7, 100:0.9:70:5, 100:1:65:4, 100:1.2:50:5, 100:1.3:55:6, 100:1.4:45:3, 100:1.5:80:5, 100:1.8:78:5, and any value within the range consisting of any two of the above numerical values. Preferably, it is 100:0.3 to 1.5:30 to 68:4 to 6. When the mass ratio of each structural unit satisfies this range, the obtained halogenated branched butyl rubber has a maximum attenuation rate tanδ max of 1.5 or more, an air permeability of 20.215 to 21.251 cm 3 , and a tensile strength of 17.6 MPa to 20.6 MPa.

[0039] In the present invention, the mass ratio of each structural unit may be represented by the input mass ratio of the monomers corresponding to each structural unit.

[0040] In some embodiments, the structural unit B is derived from butadiene, and the structural unit D is derived from isoprene.

[0041] As a preferred embodiment, the structure of the halogenated grafting agent of the present invention is represented by the general formula I1-A1-B1-C-B2-A2-I2, where I1 and I2 are structural units derived from isoprene, A1 and A2 are structural units represented by formula (1), B1 and B2 are structural units derived from butadiene, and C is a structural unit represented by formula (2).

[0042] In some embodiments, the halogen content in the halogenated grafting agent is 3 to 7 wt%, preferably 4 to 6 wt% by mass percentage.

[0043] In the present invention, the halogen content is measured using a Q600 type TG / DTG thermogravimetric analyzer.

[0044] In some embodiments, the number average molecular weight of the halogenated grafting agent is 25,000 to 50,000 g / mol, preferably 30,000 to 40,000 g / mol.

[0045] In some embodiments, the molecular weight distribution index (Mw / Mn) of the halogenated grafting agent is 1.5 to 4, for example, 1.6, 1.9, 2, 2.5, 2.8, 3, 3.5, 3.7, and any value within the range consisting of any two of the above numerical values, preferably 2 to 3.5.

[0046] In some embodiments, the halogenated grafting agent is a block copolymer or a random copolymer.

[0047] In some embodiments, the halogenated grafting agent has an apparent viscosity of 5 to 35 mPa·s at 25°C.

[0048] In the present invention, the apparent viscosity of the halogenated grafting agent is tested using an Ubbelohde viscometer in accordance with the GB / T 10247-2008 viscosity measurement method.

[0049] The second aspect of the present invention is Under the coincidence reaction conditions, in the presence of an initiator, a monomer represented by the formula (I) and a monomer represented by the formula (II) are subjected to a polymerization reaction to obtain a polymerization product. Or, (1) in the presence of a molecular weight regulator, a first solvent, and a first initiator, a first polymerization reaction of the monomer represented by the formula (I) is carried out, and a second conjugated diene is optionally added to carry out a first capping reaction. After obtaining a first product, (2) in the presence of a structure regulator, a second solvent, and a second initiator, a second polymerization reaction of the monomer represented by the formula (II) is carried out. After obtaining a second product, the first product is added thereto, and a third polymerization reaction is carried out to obtain a third product, step S1; A second capping reaction is carried out between the polymerization product obtained in step S1 or the third product obtained in step (2) and a first conjugated diene to obtain the halogenated grafting agent, step S2. A method for producing a halogenated grafting agent is provided. [Chemical formula] (Here, R 1 and R 2 are each independently hydrogen or a linear or branched alkyl of C 1 to C 5 , R 3 is a linear or branched alkyl of C 1 to C 8 , R 4 and R 5 are each independently hydrogen or a linear or branched alkyl of C 1 to C 4 , and X is a halogen.)

[0050] In some embodiments, R 1 and R 2 are each independently hydrogen or a linear or branched alkyl of C 1 to C 3 , preferably hydrogen, methyl, ethyl, or propyl.

[0051] In some embodiments, R 3 is a linear or branched alkyl of C 1 to C 5is a linear or branched alkyl, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, or isopentyl.

[0052] In some embodiments, R 4 and R 5 are each independently hydrogen or C 1 ~C 2 alkyl, preferably hydrogen, methyl, or ethyl.

[0053] In some embodiments, X is at least one selected from Cl and Br, preferably Br.

[0054] The present invention first synthesizes a polymer halogenating agent having anionic reactivity, and then uses an alkyllithium as an initiator to synthesize a polymer attenuation halogenated grafting agent from p-alkylstyrene and this polymer halogenating agent. Using this polymer attenuation halogenated grafting agent, isobutylene, and isoprene, cationic polymerization is carried out in the presence of a composite catalyst system of an alkylaluminum halide and a protonic acid to produce a highly attenuated halogenated branched butyl rubber. In the grafting agent of the present invention, due to the introduction of the benzene ring and the halogen atom and the use of the anionic polymerization method, the benzene ring and the halogen atom are regularly arranged, the steric hindrance effect of the molecular chain is increased, the polarity of the grafting agent is strengthened, and as a result, the movement resistance of the segment is increased, the internal friction is increased, and the relaxation tension of the segment is increased. In this way, during the production process of grafting butyl rubber, damage to the mechanical properties and air permeability of butyl rubber by the attenuation halogenated grafting agent is avoided, and the attenuation performance and tensile strength of butyl rubber are improved.

[0055] According to the method of the present invention, it is possible to produce a highly attenuated halogenated branched butyl rubber having a high maximum attenuation rate and a tanδ max of 1.5 or more.

[0056] In some embodiments, the mass ratio of the monomer represented by formula (I), the second conjugated diene, the monomer represented by formula (II), and the first conjugated diene is 100:0 to 2:15 to 70:3 to 7, for example, 100:0.3:30:4, 100:0.5:40:5, 100:0.6:50:6, 100:0.8:60:7, 100:0.9:70:5, 100:1:65:4, 100:1.2:50:5, 100:1.3:55:6, 100:1.4:45:3, 100:1.5:80:5, 100:1.8:78:5, and any value within the range consisting of any two of the above numerical values, preferably 100:0.3 to 1.5:30 to 68:4 to 6.

[0057] In the present invention, when the mass ratio of the monomer represented by formula (I), the second conjugated diene, the monomer represented by formula (II), and the first conjugated diene is controlled within a specific range, a normal reaction for producing a polymer grafting agent and a grafted butyl rubber can be ensured.

[0058] In the present invention, the second conjugated diene and the first conjugated diene are used as a terminal capping agent, and their usage amounts have an important influence on the polymerization reaction. If there is too much, the flexibility of the segments of the grafting agent increases, and the damping performance and mechanical strength of the butyl rubber are impaired. If there is too little, the terminal capping becomes insufficient, the number of reactive sites decreases, the grafting rate decreases, and when it becomes butyl rubber, the modification effect of the damping performance and mechanical strength of the rubber decreases.

[0059] In some embodiments, the monomer represented by the formula (II) is a halogenated olefin, preferably at least one selected from vinyl bromide, vinyl chloride, 1-bromo-1-propene, 2-bromo-1-propene, 1-bromo-1-butene, and 2-bromo-1-butene, preferably vinyl bromide or 2-bromo-1-butene.

[0060] In some embodiments, the monomer represented by the formula (I) is p-alkylstyrene, preferably at least one selected from p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-n-butylstyrene, p-isobutylstyrene, and p-isopentylstyrene, preferably p-methylstyrene.

[0061] In some embodiments, the second conjugated diene is butadiene and / or isoprene, preferably isoprene.

[0062] In some embodiments, the first conjugated diene is butadiene and / or isoprene, preferably 1,3-butadiene.

[0063] In some embodiments, the first initiator is an organic peroxide, preferably at least one selected from dicumyl peroxide (DCP), cumene hydroperoxide, and benzoyl peroxide (BPO), more preferably benzoyl peroxide (BPO).

[0064] In some embodiments, the second initiator is a hydrocarbyl monolithium compound R-Li, where R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or a composite group of the above groups containing 1 to 20 carbon atoms, preferably at least one selected from n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium, and dodecyllithium, more preferably n-butyllithium.

[0065] In some embodiments, the molecular weight regulator is at least one selected from tert-decyl mercaptan, tert-dodecyl mercaptan, tert-tetradecyl mercaptan, and tert-hexadecyl mercaptan, preferably tert-dodecyl mercaptan.

[0066] In some embodiments, the structure regulator is a polar organic compound, preferably at least one selected from diethylene glycol dimethyl ether (DGE), tetrahydrofuran (THF), ethyl ether, ethyl methyl ether, anisole, diphenyl ether, glycol dimethyl ether (DME), and triethylamine, more preferably tetrahydrofuran (THF).

[0067] The structure regulator of the present invention is a polar organic compound that generates a solvation effect in the polymerization system, is used to adjust the ionic reactivity, can adjust the reactivity ratio of p-alkylstyrene and isoprene, and can randomly copolymerize both of them.

[0068] In some embodiments, the first solvent and the second solvent are each independently a hydrocarbon solvent, preferably 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.

[0069] In the present invention, the usage amounts of the molecular weight regulator, the structure regulator, the solvent, etc. are not particularly limited, and they may be added in the normal usage amounts in the art.

[0070] In some embodiments, the conditions of the first polymerization reaction include a reaction temperature of 50 to 60°C and a reaction time of 4 to 6 h.

[0071] In some embodiments, the conditions of the first capping reaction include a reaction temperature of 50 to 60°C and a reaction time of 20 to 40 min.

[0072] In some embodiments, the conditions of the second polymerization reaction include a reaction temperature of 60 to 70°C and a reaction time of 70 to 90 min.

[0073] In some embodiments, the conditions of the third polymerization reaction include a reaction temperature of 80 to 90°C and a reaction time of 80 to 100 min.

[0074] In some embodiments, the conditions of the second capping reaction include a reaction temperature of 80 to 90 °C and a reaction time of 30 to 40 min.

[0075] The method of the present invention further includes a step of adding a terminator to terminate the reaction after the polymerization is completed, and the terminator may be one or more selected from methanol, ethanol, and ethanol.

[0076] In the present invention, the polymerization reaction is carried out without oxygen and water, preferably in an inert gas environment. Both the polymerization process and the dissolution process are carried out in a hydrocarbon solvent.

[0077] In the present invention, vinyl bromide and p-methylstyrene are directly polymerized without adding an intermediate capping agent. Since vinyl bromide cannot undergo an anionic polymerization reaction, only free radical polymerization using an organic peroxide such as BPO to initiate the reaction can be used for this polymerization.

[0078] The third aspect of the present invention provides a halogenated grafting agent produced by the aforementioned production method.

[0079] The fourth aspect of the present invention provides the use of the aforementioned halogenated grafting agent as a grafting agent for producing diene rubber.

[0080] The fifth aspect of the present invention provides a halogenated branched butyl rubber containing a structural unit E derived from pre-isobutylene, a structural unit F derived from isoprene, and a structural unit G derived from a halogenated grafting agent, and the halogenated grafting agent is the aforementioned halogenated grafting agent.

[0081] In some embodiments, based on the total weight of the halogenated branched butyl rubber, the mass ratio of the structural unit E, the structural unit F, and the structural unit G is 100:2 to 6:3 to 8, preferably 100:3 to 5:4 to 7.

[0082] The sixth aspect of the present invention is Provided is a method for producing a halogenated branched butyl rubber, which includes a step of subjecting isobutylene, isoprene, and the aforementioned halogenated grafting agent to cationic polymerization in the presence of a diluent, an organic solvent, and a co-initiator to obtain the halogenated branched butyl rubber.

[0083] In some embodiments, the mass ratio of isobutylene, isoprene, and the halogenated grafting agent is 100:2 to 6:3 to 8, preferably 100:3 to 5:4 to 7.

[0084] In some embodiments, the diluent is a halogenated alkane, the halogen atom in the halogenated alkane is F, Cl, or Br, the number of carbon atoms in the halogenated alkane is 1 to 4, and preferably, the diluent is at least one selected from monochloromethane, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, and carbon tetrafluoride.

[0085] In some embodiments, the solvent is a hydrocarbon solvent, preferably at least one of a linear alkane, an aromatic hydrocarbon, and a cycloalkane, and more preferably at least one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.

[0086] In some embodiments, the co-initiator includes a protonic acid and an alkylaluminum halide. Preferably, in the co-initiator, the molar ratio of the protonic acid to the alkylaluminum halide is 1:10 to 100. Preferably, the protonic acid is HCI, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 、and HNO 3It is at least one selected from the group consisting of, and the alkyl aluminum halide is at least one selected from diethyl aluminum monochloride, diisobutyl aluminum monochloride, methyl aluminum dichloride, ethyl aluminum sesquichloride, isobutyl aluminum sesquichloride, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride, and ethyl aluminum chloride.

[0087] In some embodiments, the mass ratio of the isobutylene to the co-initiator is 100:0.01 to 0.5.

[0088] In some embodiments, the conditions for the cationic polymerization include a polymerization temperature of -100°C to -80°C and a cationic polymerization time of 3 to 4 h.

[0089] The seventh aspect of the present invention provides a halogenated branched butyl rubber obtained by the aforementioned production method. The halogenated branched butyl rubber of the present invention is preferably a brominated branched butyl rubber.

[0090] The eighth aspect of the present invention provides the use of the aforementioned halogenated branched butyl rubber in many fields such as automobiles and electronic and electrical devices.

[0091] In a preferred embodiment of the present invention, the halogenated grafting agent is a linear block copolymer obtained by polymerizing isoprene, 1,3-butadiene, p-alkylstyrene, and vinyl bromide.

[0092] In a particularly preferred embodiment of the present invention, the production method of the above-mentioned halogenated grafting agent specifically includes the following steps. S1: Based on 100 parts by mass of vinyl bromide, first, introduce an inert gas into a 15 L stainless steel reaction kettle with a jacket and replace it 2 to 4 times. Then, add 100 to 200 parts of a solvent, 100 parts of vinyl bromide, and 0.2 to 0.5 parts of a molecular weight regulator to the reaction kettle in sequence, stir and mix them, and heat. When the temperature of the reaction kettle reaches 50 to 60 °C, add 0.01 to 0.15 parts of the first initiator and react for 4 to 6 h. Then, further add 1 to 4 parts of 1,3-butadiene to the polymerization kettle for capping and react for 20 to 40 min until there is no free monomer left. After the reaction is completed, wash and bake to obtain a high molecular weight brominating agent. S2: Taking the total mass of the reaction monomers as 100%, first, introduce argon into a 15 L stainless steel reaction kettle with a jacket and replace it 2 to 4 times. Then, add 200% to 300% of a solvent, 60% to 80% of p-alkylstyrene, and 0.3% to 0.5% of a structure regulator to the polymerization kettle in sequence. After heating to 60 to 70 °C, add the second initiator and react for 70 to 90 min. Then, further add 20% to 40% of the high molecular weight brominating agent and 0.1% to 0.2% of the structure regulator to the polymerization kettle, heat to 80 to 90 °C, and react for 80 to 100 min. Finally, further add 3 to 5 parts of isoprene to the polymerization kettle for capping and react for 30 to 40 min until there is no free monomer left. Coagulate the paste solution by the wet method and bake to obtain a halogenated grafting agent.

[0093] According to a particularly preferred embodiment of the present invention, the method for producing a halogenated branched butyl rubber with the above-mentioned halogenated grafting agent specifically includes the following steps.

[0094] Taking the mass of isobutylene, which is the reaction monomer, as 100%, first, nitrogen is introduced into a 4L stainless steel reaction kettle with a jacket and replaced 3 to 5 times. Then, 100% - 200% of a mixed solvent (the V:V ratio of the diluent / solvent is 70 - 30 / 30 - 70) and 4% - 7% of the halogenated grafting agent prepared above are added to the polymerization kettle, and stirred for 40 - 60 min to dissolve, completely dissolving the grafting agent. Then, when the temperature is lowered to -80~-70°C, 100% - 200% of the diluent, 100% of isobutylene, and 3% - 5% of isoprene are further added, and stirred and mixed until the temperature of the polymerization system drops to -90~-80°C. Then, 10% - 20% of the diluent and 0.01% - 0.5% of the co-initiator are mixed under the condition of -100~-90°C and aged for 40 - 50 min, then added to the polymerization system and stirred for 3 - 4 h to react. Finally, 4% - 7% of the terminator is added, the material is taken out, aggregated, washed, and dried to obtain a high-damping halogenated branched butyl rubber product.

[0095] Hereinafter, the present invention will be described in detail by way of examples.

[0096] If specific conditions are not specified in the following examples and comparative examples, they are carried out according to normal conditions or the conditions proposed by the manufacturer. When the manufacturer of the reagents or instruments used is not specified, all are ordinary products that can be obtained as commercially available products. The mass ratio relationship between the multi-component copolymer products produced and each structural unit contained in the halogenated branched butyl rubber is determined according to the raw material input amount.

[0097] (1) Origin of raw materials: 1,3-butadiene: polymerization grade, purchased from PetroChina Lanzhou Petrochemical Company Isobutylene, isoprene: polymerization grade, purchased from Zhejiang Xinhui New Materials Co., Ltd. p-methylstyrene: polymerization grade, purchased from Jiande Bofeng Chemical Co., Ltd. p-n-butylstyrene: polymerization grade, purchased from Luoyang Boyuan Energy Technology Co., Ltd. Vinyl bromide: polymerization grade, purchased from Wuhan Fuyuan Technology Co., Ltd. Benzoyl peroxide (BPO): purchased from Lanzhou Auxiliary Agent Company n-Butyllithium: 98% purity, purchased from Nanjing Tonglian Chemical Co., Ltd. Ethyl aluminum sesquichloride: 98% purity, purchased from Bilingwei Technology Co., Ltd. Other reagents are commercially available industrial products.

[0098] (2) Analytical test method Bromine content measurement: Weigh out 10 mg of sample, and use a Q600 TG / DTG thermogravimetric analyzer to pyrolyze the sample under nitrogen atmosphere at a heating rate of 10°C / min and a flow rate of 50 mL / min. In the first pyrolysis step, the bromine-containing units in the sample are debrominated to form HBr, and the percentage of the formed HBr content is used to estimate the bromine content (X) in the sample, which is calculated using the following formula:

number

[0099] In the examples and comparative examples of the present invention, the mass ratio of the monomer input amount is equal to the mass ratio of each corresponding structural unit in the produced halogenated grafting agent. Production Example 1

[0100] (1) Production of polymer brominating agent: First, introduce argon into a 15L stainless steel reaction kettle with a jacket and replace it twice. Add 1000 g of cyclohexane, 1000 g of vinyl bromide, and 2 g of tert-dodecyl mercaptan to the reaction kettle in sequence, stir and mix, heat, and when the temperature of the reaction kettle reaches 50°C, add 0.1 g of BPO and react for 4 h. Then, add 10 g of 1,3-butadiene to the polymerization kettle for capping and react for 20 min until there is no free monomer. After the reaction is completed, wash and bake to obtain 1010 g of a polymer brominating agent containing 10 g of structural unit B (1,3-butadiene). (2) Production of halogenated grafting agent: First, introduce argon into a 15L stainless steel reaction kettle with a jacket and replace it twice. Add 2000 g of cyclohexane, 600 g of p-methylstyrene, and 3 g of THF to the polymerization kettle in sequence, heat to 60°C, add 14.6 mmol of n-butyllithium and react for 70 min. Then, add 400 g of polymer brominating agent (containing 4 g of structural unit B) and 1 g of THF to the polymerization kettle, further heat to 80°C, and react for 80 min. Finally, add 30 g of isoprene to the polymerization kettle and perform a capping reaction for 30 min until there is no free monomer. Coagulate the paste solution by the wet method and bake to obtain a halogenated grafting agent S1 with a mass ratio of structural units derived from vinyl bromide, 1,3-butadiene, p-methylstyrene, and isoprene of 100:0.67:67:5. As a result of detection, for the halogenated grafting agent S1, Mn was 30350, Mw / Mn was 2, the bromine content was 5.97%, and the apparent viscosity at 25°C was 8 mPa·s. As can be seen from Fig. 1, the asymmetric stretching vibration doublet absorption peak of the benzene ring appears at a wave number of 3005-3100 cm -1 , and the stretching vibration absorption peak of methyl (CH -1 ) appears at a wave number of 2950-2800 cm 3 . The stretching vibration absorption peak of "carbon-carbon double bond" appears at a wave number of 1680-1500 cm -1 . The stretching vibration single absorption peak of para-position substitution of the benzene ring appears at a wave number of 900-850 cm -1 . The stretching vibration single absorption peak of the bromine atom appears at a wave number of 700-650 cm -1 . From this, it is clear that the halogenated grafting agent produced from vinyl bromide, 1,3-butadiene, p-methylstyrene, and isoprene contains a para-methylbenzene structure and a bromine substitution structure. Production Example 2

[0101] (1) Production of the polymer brominating agent: First, introduce argon into a 15 L stainless steel reaction kettle with a jacket and replace it twice. Then, add 1200 g of cyclohexane, 1000 g of vinyl bromide, and 2.5 g of tert-dodecyl mercaptan to the reaction kettle in sequence, stir and mix them, heat them. When the temperature of the reaction kettle reaches 52 °C, add 0.4 g of BPO and react for 4.5 h. Then, add 15 g of 1,3-butadiene to the polymerization kettle for capping and react for 26 min until there is no free monomer left. After the reaction is completed, wash and bake to obtain 1015 g of the polymer brominating agent. (2) Production of the halogenated grafting agent: First, introduce argon into a 15 L stainless steel reaction kettle with a jacket and replace it twice. Add 2100 g of cyclohexane, 650 g of p-methylstyrene, and 3.5 g of THF to the polymerization kettle in sequence, heat up to 62 °C, add 14.9 mmol of n-butyllithium, and react for 74 min. Then, further add 350 g of the polymer brominating agent and 1.2 g of THF to the polymerization kettle, heat up to 82 °C, and react for 85 min. Finally, further add 35 g of isoprene to the polymerization kettle and perform a capping reaction for 32 min until there is no free monomer left. Coagulate the paste solution by the wet method and bake it to obtain a halogenated grafting agent S2 in which the mass ratio of the structural units derived from vinyl bromide, 1,3-butadiene, p-methylstyrene, and isoprene is 100:0.77:54:5.4. As a result of detection, for the halogenated grafting agent S2, Mn was 31500, Mw / Mn was 2.3, the bromine content was 5.63%, and the apparent viscosity at 25 °C was 12 mPa·s. Production Example 3

[0102] (1) Production of the polymer brominating agent: First, introduce argon into a 15 L stainless steel reaction kettle with a jacket and replace it three times. Add 1500 g of cyclohexane, 1000 g of vinyl bromide, and 3 g of tert-dodecyl mercaptan to the reaction kettle in sequence, stir and mix, heat, and when the temperature of the reaction kettle reaches 54 °C, add 0.7 g of BPO and react for 5 h. Then, further add 20 g of 1,3-butadiene to the polymerization kettle for capping and react for 30 min until there is no free monomer left. After the reaction is completed, wash and bake to obtain 1020 g of the polymer brominating agent. (2) Production of Halogenated Grafting Agent: First, introduce argon into a 15 L stainless steel reactor with a jacket and replace it three times. Then, add 2300 g of cyclohexane, 700 g of p-methylstyrene, and 4 g of THF to the polymerization reactor in sequence, heat up to 64 °C, add 15.5 mmol of n-butyllithium, and react for 78 min. After that, further add 300 g of polymer brominating agent and 1.4 g of THF to the polymerization reactor, heat up to 85 °C, and react for 90 min. Finally, further add 40 g of isoprene to the polymerization reactor and perform a capping reaction for 34 min until there is no free monomer left. Coagulate the paste solution by the wet method and bake it to obtain a halogenated grafting agent S3 with a mass ratio of structural units derived from vinyl bromide, 1,3-butadiene, p-methylstyrene, and isoprene of 100:0.86:43:5.7. As a result of detection, for the halogenated grafting agent S3, Mn was 33600, Mw / Mn was 2.7, bromine content was 5.03%, and the apparent viscosity at 25 °C was 17 mPa·s. Production Example 4

[0103] (1) Production of Polymer Brominating Agent: First, introduce argon into a 15 L stainless steel reactor with a jacket and replace it three times. Then, add 1700 g of cyclohexane, 1000 g of vinyl bromide, and 4 g of tert-dodecyl mercaptan to the reaction kettle in sequence, stir and mix, heat, and when the temperature of the reaction kettle reaches 56 °C, add 0.9 g of BPO and react for 5.3 h. After that, further add 30 g of 1,3-butadiene to the polymerization kettle for capping and react for 30 min until there is no free monomer left. After the reaction is completed, wash and bake to obtain 1030 g of polymer brominating agent. (2) Production of Halogenated Grafting Agent: First, introduce argon into a 15L stainless steel reaction kettle with a jacket and replace it three times. Then, add 2500 g of cyclohexane, 730 g of p-methylstyrene, and 4.4 g of THF to the polymerization kettle in sequence, heat up to 66°C, add 16.1 mmol of n-butyllithium, and react for 80 min. After that, further add 270 g of polymer brominating agent and 1.7 g of THF to the polymerization kettle, heat up to 87°C, and react for 93 min. Finally, further add 43 g of isoprene to the polymerization kettle and carry out a capping reaction for 36 min until there is no free monomer left. Coagulate the paste solution by the wet method and bake it to obtain a halogenated grafting agent S4 with a mass ratio of structural units derived from vinyl bromide, 1,3-butadiene, p-methylstyrene, and isoprene of 100:1.1:38:5.9. As a result of detection, for the halogenated grafting agent S4, Mn was 36100, Mw / Mn was 3, the bromine content was 4.68%, and the apparent viscosity at 25°C was 23 mPa·s. Production Example 5

[0104] (1) Production of Polymer Brominating Agent: First, introduce argon into a 15L stainless steel reaction kettle with a jacket and replace it four times. Then, add 1800 g of cyclohexane, 1000 g of 2-bromo-1-propene, and 4.5 g of tert-dodecyl mercaptan to the reaction kettle in sequence, stir and mix, heat, and when the temperature of the reaction kettle reaches 58°C, add 1.2 g of BPO and react for 5.6 h. After that, further add 35 g of 1,3-butadiene to the polymerization kettle for capping and react for 35 min until there is no free monomer left. After the reaction is completed, wash and bake to obtain 1035 g of polymer brominating agent. (2) Production of Halogenated Grafting Agent: First, introduce argon into a 15L stainless steel reaction kettle with a jacket and replace it 4 times. Then, add 2700 g of cyclohexane, 760 g of p-ethylstyrene, and 4.8 g of THF to the polymerization kettle in sequence. Heat up to 68 °C, add 16.8 mmol of n-butyllithium, and react for 85 min. Then, further add 240 g of polymer brominating agent and 1.9 g of THF to the polymerization kettle, heat up to 88 °C, and react for 96 min. Finally, further add 45 g of isoprene to the polymerization kettle and carry out a capping reaction for 38 min until there is no free monomer left. Coagulate the paste solution by the wet method and bake it to obtain a halogenated grafting agent S5 with a mass ratio of structural units derived from 2-bromo-1-propene, 1,3-butadiene, p-ethylstyrene, and isoprene of 100:1.1:38:5.9. As a result of detection, for the halogenated grafting agent S5, Mn was 38200, Mw / Mn was 3.3, the bromine content was 4.45%, and the apparent viscosity at 25 °C was 26 mPa·s. Production Example 6

[0105] (1) Production of Polymer Brominating Agent: First, introduce argon into a 15L stainless steel reaction kettle with a jacket and replace it 4 times. Then, add 2000 g of cyclohexane, 1000 g of 2-bromo-1-butene, and 5 g of tert-dodecyl mercaptan to the reaction kettle in sequence, stir and mix, heat, and when the temperature of the reaction kettle reaches 60 °C, add 1.5 g of DCP and react for 6 h. Then, further add 40 g of 1,3-butadiene to the polymerization kettle for capping and react for 40 min until there is no free monomer left. After the reaction is completed, wash and bake to obtain 1040 g of polymer brominating agent. (2) Production of Halogenated Grafting Agent: First, introduce argon into a 15L stainless steel reactor with a jacket and replace it 4 times. Then, add 3000g of cyclohexane, 800g of p-n-butylstyrene, and 5g of THF to the polymerization kettle in sequence, heat up to 70°C, add 17.3 mmol of n-butyllithium, and react for 90 minutes. Subsequently, add 200g of polymer brominating agent and 2g of THF to the polymerization kettle, further heat up to 90°C, and react for 100 minutes. Finally, add 50g of isoprene to the polymerization kettle and perform a capping reaction for 40 minutes until there is no free monomer left. Coagulate the paste solution by the wet method and bake it to obtain a halogenated grafting agent S6 with a mass ratio of structural units derived from 2-bromo-1-butene, 1,3-butadiene, p-n-butylstyrene, and isoprene of 100:1:25:6.25. As a result of detection, for the halogenated grafting agent S6, Mn was 39600, Mw / Mn was 3.5, bromine content was 4.12%, and apparent viscosity at 25°C was 30 mPa·s. Production Example 7

[0106] A halogenated grafting agent was produced in the same manner as in the method of Production Example 1 except that the addition amount of 1,3-butadiene during the production process was 20g, and a halogenated grafting agent S7 with a mass ratio of structural units derived from vinyl bromide, 1,3-butadiene, p-methylstyrene, and isoprene of 100:1.34:67:5 was obtained. As a result of detection, for the halogenated grafting agent S7, Mn was 30600, Mw / Mn was 2.1, bromine content was 5.92%, and apparent viscosity at 25°C was 9.2 mPa·s. Production Example 8

[0107] A halogenated grafting agent was produced according to the method of Production Example 1 except that the addition amount of 1,3-butadiene during the production process was 30g, and a halogenated grafting agent S8 with a mass ratio of structural units derived from vinyl bromide, 1,3-butadiene, p-methylstyrene, and isoprene of 100:1.94:67:5 was obtained. As a result of the detection, for the halogenated grafting agent S8, Mn was 31,000, Mw / Mn was 2.2, the bromine content was 5.91%, and the apparent viscosity at 25 °C was 11.2 mPa·s. Production Example 9

[0108] A halogenated grafting agent was produced in the same manner as in Production Example 1 except that the addition amount of p-methylstyrene during the production process was 700 g, and a halogenated grafting agent S9 having a mass ratio of structural units derived from vinyl bromide, 1,3-butadiene, p-methylstyrene, and isoprene of 100:0.57:57:4 was obtained. As a result of the detection, for the halogenated grafting agent S9, Mn was 33,000, Mw / Mn was 2.5, the bromine content was 5.23%, and the apparent viscosity at 25 °C was 16 mPa·s. Production Example 10

[0109] A halogenated grafting agent was produced in the same manner as in Production Example 1 except that the addition amount of p-methylstyrene during the production process was 800 g, and a halogenated grafting agent S10 having a mass ratio of structural units derived from vinyl bromide, 1,3-butadiene, p-methylstyrene, and isoprene of 100:0.49:50:4 was obtained. As a result of the detection, for the halogenated grafting agent S10, Mn was 35,000, Mw / Mn was 2.9, the bromine content was 4.76%, and the apparent viscosity at 25 °C was 26 mPa·s. Production Example 11

[0110] A halogenated grafting agent was produced in the same manner as in Production Example 1 except that vinyl bromide in Production Example 1 was changed to vinyl chloride during the production process, and a halogenated grafting agent S11 having a mass ratio of structural units derived from vinyl chloride, 1,3-butadiene, p-methylstyrene, and isoprene of 100:0.67:67:5 was obtained. As a result of the detection, for the halogenated grafting agent S11, Mn was 30,100, Mw / Mn was 2.1, the chlorine content was 5.72%, and the apparent viscosity at 25 °C was 5.7 mPa·s. Production Example 12

[0111] Into a 15 L stainless steel reactor with a jacket, argon was introduced and replaced twice. 1000 g of cyclohexane, 1000 g of vinyl bromide, 600 g of p-methylstyrene, and 2 g of tert-dodecyl mercaptan were sequentially added to the reactor, stirred and mixed, heated, and when the temperature of the reactor reached 50 °C, 0.1 g of BPO was added and reacted for 4 h. Finally, 30 g of isoprene was further added to the polymerization kettle, and the capping reaction was carried out for 30 min until there was no free monomer. The paste liquid was aggregated by the wet method and baked to obtain a halogenated grafting agent S12 in which the mass ratio of the structural units derived from vinyl bromide, p-methylstyrene, and isoprene was 100:17:5. As a result of detection, for the halogenated grafting agent S12, Mn was 50000, Mw / Mn was 4, the bromine content was 12.1%, and the apparent viscosity at 25 °C was 35 mPa·s. Production Example 13

[0112] During the production process of the halogenated grafting agent in step (2), except that the addition amount of the polymer brominating agent was 200 g, the halogenated grafting agent was produced in the same manner as in the method of Production Example 1, and a halogenated grafting agent S13 in which the mass ratio of the structural units derived from vinyl bromide, 1,3-butadiene, p-methylstyrene, and isoprene was 100:0.34:33:5 was obtained. As a result of detection, for the halogenated grafting agent S13, Mn was 25000, Mw / Mn was 1.5, the bromine content was 4.91%, and the apparent viscosity at 25 °C was 5 mPa·s. Production Example 14

[0113] During the production process of the halogenated grafting agent in step (2), except that the addition amount of the polymer brominating agent was 300 g, the halogenated grafting agent was produced in the same manner as in the method of Production Example 1, and a halogenated grafting agent S14 in which the mass ratio of the structural units derived from vinyl bromide, 1,3-butadiene, p-methylstyrene, and isoprene was 100:0.5:50:5 was obtained. As a result of the detection, for the halogenated grafting agent S14, Mn was 28,000, Mw / Mn was 1.7, the bromine content was 5.38%, and the apparent viscosity at 25°C was 7 mPa·s. Production Comparative Example 1

[0114] During the production process of the halogenated grafting agent in step (2), except that p-methylstyrene was changed to styrene, the halogenated grafting agent was produced in the same manner as in the method of Production Example 1, and a halogenated grafting agent D1 with a mass ratio of structural units derived from vinyl bromide, 1,3-butadiene, styrene, and isoprene of 100:0.67:67:5 was obtained. As a result of the detection, for the halogenated grafting agent D1, Mn was 23,000, Mw / Mn was 1.9, the bromine content was 5.98%, and the apparent viscosity at 25°C was 3.8 mPa·s. Production Comparative Example 2

[0115] During the production process of the polymer brominating agent in step (1), except that vinyl bromide was changed to ethylene, the halogenated grafting agent was produced in the same manner as in the method of Production Example 1, and a halogenated grafting agent D2 with a mass ratio of structural units derived from ethylene, 1,3-butadiene, p-methylstyrene, and isoprene of 100:0.67:67:5 was obtained. As a result of the detection, for the halogenated grafting agent D2, Mn was 21,000, Mw / Mn was 2.4, the bromine content was 0%, and the apparent viscosity at 25°C was 3.1 mPa·s. Example 1

[0116] First, nitrogen was introduced into a 4L stainless steel reaction kettle with a jacket and replaced three times. 700 g of monochloromethane and 300 g of cyclohexane were added to the polymerization kettle, and 20 g of the halogenated grafting agent S1 obtained in Production Example 1 was added. The mixture was stirred for 40 min to dissolve and completely dissolved. Then, after cooling to -70°C, 500 g of monochloromethane, 500 g of isobutylene, and 15 g of isoprene were added in sequence, and the mixture was stirred and mixed until the temperature of the polymerization system dropped to -80°C. Then, 50 g of monochloromethane, 1.05 g of ethylaluminum sesquichloride, and 0.011 g of HCl were mixed and aged under the condition of -90°C for 40 min, and then added to the polymerization system all at once and stirred for 3 h to react. Finally, after adding 20 g of methanol, the material was taken out and subjected to aggregation, washing, and drying to obtain a brominated branched butyl rubber product in which the mass ratio of the structural units derived from isobutylene, isoprene, and the halogenated grafting agent S1 was 100:3:4. Sample collection and analysis: A standard sample was prepared, and the test characteristics are shown in Table 1. Examples 2 to 14

[0117] A brominated branched butyl rubber product was produced in the same manner as in Example 1 except that the halogenated grafting agent S1 was changed to any one of the halogenated grafting agents S2 to S14, and a brominated branched butyl rubber product was obtained. Sample collection and analysis: A standard sample was prepared, and the test characteristics are shown in Table 1. Example 15

[0118] A brominated branched butyl rubber product was produced in the same manner as in Example 1 except that the addition amount of the halogenated grafting agent S1 during the production process was 25 g, and a brominated branched butyl rubber product in which the mass ratio of the structural units derived from isobutylene, isoprene, and the halogenated grafting agent S1 was 100:3:5 was obtained. Sample collection and analysis: A standard sample was prepared, and the test characteristics are shown in Table 1. Example 16

[0119] A brominated branched butyl rubber product was produced in the same manner as in Example 1 except that the addition amount of the halogenated grafting agent S1 during the manufacturing process was 30 g, and a brominated branched butyl rubber product having a mass ratio of structural units derived from isobutylene, isoprene, and the halogenated grafting agent S1 of 100:3:6 was obtained. Sample collection and analysis: A standard sample was produced, and the test characteristics are shown in Table 1. Example 17

[0120] A brominated branched butyl rubber product was produced in the same manner as in Example 1 except that the addition amount of the halogenated grafting agent S1 during the manufacturing process was 35 g, and a brominated branched butyl rubber product having a mass ratio of structural units derived from isobutylene, isoprene, and the halogenated grafting agent S1 of 100:3:7 was obtained. Sample collection and analysis: A standard sample was produced, and the test characteristics are shown in Table 1. Example 18

[0121] A brominated branched butyl rubber product was produced in the same manner as in Example 1 except that the addition amount of isoprene during the manufacturing process was 20 g, and a brominated branched butyl rubber product having a mass ratio of structural units derived from isobutylene, isoprene, and the halogenated grafting agent S1 of 100:4:4 was obtained. Sample collection and analysis: A standard sample was produced, and the test characteristics are shown in Table 1. Example 19

[0122] A brominated branched butyl rubber product was produced in the same manner as in Example 1 except that the addition amount of isoprene during the manufacturing process was 25 g, and a brominated branched butyl rubber product having a mass ratio of structural units derived from isobutylene, isoprene, and the halogenated grafting agent S1 of 100:5:4 was obtained. Sample collection and analysis: A standard sample was produced, and the test characteristics are shown in Table 1. Example 20

[0123] A brominated branched butyl rubber product was produced in the same manner as in Example 1 except that 1.05 g of ethylaluminum sesquichloride and 0.011 g of HCl were changed to 1.05 g of aluminum trichloride, and a brominated branched butyl rubber product was obtained. Sample collection and analysis: A standard sample was produced, and the test characteristics are shown in Table 1. Comparative Example 1

[0124] A brominated branched butyl rubber product was produced in the same manner as in Example 1 except that the halogenated grafting agent S1 was changed to the halogenated grafting agent D1, and a brominated branched butyl rubber product was obtained. Sample collection and analysis: A standard sample was produced, and the test characteristics are shown in Table 1. Comparative Example 2

[0125] A brominated branched butyl rubber product was produced in the same manner as in Example 1 except that the halogenated grafting agent S1 was changed to the halogenated grafting agent D2, and a brominated branched butyl rubber product was obtained. Sample collection and analysis: A standard sample was produced, and the test characteristics are shown in Table 1.

[0126]

Table 1

[0127] From the results in Table 1, it was found that the halogenated branched butyl rubber product produced in the examples of the present invention has better damping performance, better airtightness, and better mechanical properties compared with the comparative examples.

[0128] 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, various simple modifications can be made to the technical solutions of the present invention, including combining each technical feature in other appropriate ways. These simple modifications and combinations should also be regarded as the disclosed content of the present invention and all belong to the protection scope of the present invention.

Claims

1. It contains structural unit A, optional structural unit B, structural unit C, and structural unit D, wherein the structural unit A has a structure represented by formula (1), the structural unit C has a structure represented by formula (2), the structural unit B is connected to the structural unit A and the structural unit C respectively, the structural unit D is a terminal capping structural unit, and the structural unit B and the structural unit D are each independently derived from a conjugated diene, and it is a halogenated grafting agent characterized by this. 【Chemical 1】 (Here, R １ and R ２ are each independently hydrogen or a linear or branched alkyl of C １ to C ５ ; R ３ is a linear or branched alkyl of C １ to C ８ ; R ４ and R ５ are each independently hydrogen or a linear or branched alkyl of C １ to C ４ ; and X is a halogen.)

2. R １ and R ２ are each independently hydrogen or a straight-chain or branched alkyl having C １ to C ３ and R ３ is a straight-chain or branched alkyl having C １ to C ５ and R ４ and R ５ are each independently hydrogen or an alkyl having C １ to C ２ and X is at least one selected from Cl and Br And / or, the conjugated diene is butadiene and / or isoprene, and the halogenated grafting agent according to claim 1.

3. The mass ratio of the structural unit A, the structural unit B, the structural unit C, and the structural unit D is 100:0 to 2:15 to 70:3 to 7, And / or, the structural unit B is derived from butadiene, and the structural unit D is derived from isoprene, and the halogenated grafting agent according to claim 1 or 2.

4. The halogen content in the halogenated grafting agent is 3 wt% to 7 wt% by mass percentage, And / or, the number average molecular weight of the halogenated grafting agent is 25,000 to 50,000 g / mol, And / or, the molecular weight distribution index of the halogenated grafting agent is 1.5 to 4, And / or, the halogenated grafting agent is a block copolymer or a random copolymer, And / or, the apparent viscosity of the halogenated grafting agent at 25°C is 5 to 35 mPa·s, and the halogenated grafting agent according to claim 1 or 2.

5. Under polymerization reaction conditions, in the presence of an initiator, a monomer represented by formula (I) and a monomer represented by formula (II) are subjected to a polymerization reaction to obtain a polymerization product, Or, (1) in the presence of a molecular weight regulator, a first solvent, and a first initiator, a first polymerization reaction of the monomer represented by formula (I) is carried out, and a second conjugated diene is optionally added to carry out a first capping reaction. After obtaining a first product, (2) in the presence of a structure regulator, a second solvent, and a second initiator, a second polymerization reaction of the monomer represented by formula (II) is carried out. After obtaining a second product, the first product is added thereto, and a third polymerization reaction is carried out to obtain a third product, step S1, Performing a second capping reaction of the polymerization product obtained in step S1 or the third product obtained in step (2) with the first conjugated diene to obtain the halogenated grafting agent, step S2, 【Chemical Formula 2】 (Here, R １ and R ２ are each independently hydrogen or a linear or branched alkyl of C １ to C ５ ; R ３ is a linear or branched alkyl of C １ to C ８ ; R ４ and R ５ are each independently hydrogen or a linear or branched alkyl of C １ to C ４ ; and X is a halogen.) A method for producing a halogenated grafting agent, characterized by including this.

6. The mass ratio of the monomer represented by formula (I), the second conjugated diene, the monomer represented by formula (II), and the first conjugated diene is 100:0 to 2:15 to 70:3 to 7. The production method according to claim 5.

7. The monomer represented by the formula (II) is a halogenated olefin, and / or the monomer represented by the formula (I) is p-alkylstyrene, and / or the first conjugated diene and the second conjugated olefin are each independently butadiene and / or isoprene, and / or, the second initiator is a hydrocarbyl monolithium compound R-Li, where R is C １ to C ２０ saturated aliphatic hydrocarbon group of, C ３ to C ２０ alicyclic hydrocarbon group of, C ６ to C ２０ aromatic hydrocarbon group of, or a composite group of the above groups, and / or the first initiator is an organic peroxide, and / or the molecular weight regulator is at least one selected from tert-decyl mercaptan, tert-dodecyl mercaptan, tert-tetradecyl mercaptan, and tert-hexadecyl mercaptan, and / or the structure regulator is a polar organic compound, and / or the first solvent and the second solvent are each independently a hydrocarbon solvent. The production method according to claim 5 or 6.

8. The monomer represented by the formula (II) is at least one selected from vinyl bromide, vinyl chloride, 1-bromo-1-propene, 2-bromo-1-propene, 1-bromo-1-butene, and 2-bromo-1-butene, and / or the monomer represented by the formula (I) is at least one selected from p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-n-butylstyrene, p-isobutylstyrene, and p-isopentylstyrene, and / or the first initiator is at least one selected from dicumyl peroxide, cumene hydroperoxide, and benzoyl peroxide, and / or the second initiator is at least one selected from n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium, and dodecyllithium, And / or, the structure modifier is at least one selected from diethylene glycol dimethyl ether, tetrahydrofuran, ethyl ether, ethyl methyl ether, anisole, diphenyl ether, glycol dimethyl ether, and triethylamine, And / or, each of the first solvent and the second solvent is independently at least one selected from pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene, The production method according to claim 7.

9. The conditions of the first polymerization reaction include a reaction temperature of 50 to 60 ° C and a reaction time of 4 to 6 h, And / or, the conditions of the first capping reaction include a reaction temperature of 50 to 60 ° C and a reaction time of 20 to 40 min, And / or, the conditions of the second polymerization reaction include a reaction temperature of 60 to 70 ° C and a reaction time of 70 to 90 min, And / or, the conditions of the third polymerization reaction include a reaction temperature of 80 to 90 ° C and a reaction time of 80 to 100 min, And / or, the conditions of the second capping reaction include a reaction temperature of 80 to 90 ° C and a reaction time of 30 to 40 min, The production method according to claim 5 or 6.

10. A halogenated grafting agent produced by the production method according to any one of claims 5 to 9.

11. Use of the halogenated grafting agent according to any one of claims 1 to 4 and 10 as a grafting agent for producing diene rubber.

12. The use according to claim 11, wherein the diene rubber is butyl rubber.

13. An isobutylene-derived structural unit E, an isoprene-derived structural unit F, and a halogenated grafting agent-derived structural unit G are included, and the halogenated grafting agent is the halogenated grafting agent according to any one of claims 1 to 4 and 10. A halogenated branched butyl rubber characterized by that.

14. Based on the total weight of the halogenated branched butyl rubber, the mass ratio of the structural unit E, the structural unit F, and the structural unit G is 100: 2 to 6: 3 to 8. The halogenated branched butyl rubber according to claim 13.

15. A step of cationically polymerizing isobutylene, isoprene, and the halogenated grafting agent according to any one of claims 1 to 4 and 10 in the presence of a diluent, an organic solvent, and a co-initiator to obtain a halogenated branched butyl rubber. A method for producing a halogenated branched butyl rubber, characterized by including.

16. The mass ratio of isobutylene, isoprene, and the halogenated grafting agent is 100:2 to 6:3 to 8, and / or, the diluent is a halogenated alkane, the halogen atom in the halogenated alkane is Cl or Br, and the number of carbon atoms in the halogenated alkane is 1 to 4, and / or, the co-initiator contains a protonic acid and an alkylaluminum halide, and the molar ratio of the protonic acid to the alkylaluminum halide is 1:10 to 100, and / or, the mass ratio of the isobutylene to the co-initiator is 100:0.01 to 0.5, and / or, the conditions for the cationic polymerization include a polymerization temperature of -100°C to -80°C and a cationic polymerization time of 3 to 4 h. The production method according to claim 15.

17. The protonic acid is at least one selected from HCI, HF, HBr, H ２ SO ４ 、H ２ CO ３ 、H ３ PO ４ 、and HNO ３ and is at least one selected therefrom. 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. The production method according to claim 16.

18. The halogenated branched butyl rubber obtained by the production method according to any one of claims 15 to 17.

19. Use of the halogenated branched butyl rubber according to claim 13, 14 or 18 in automobiles and electronic and electrical devices.

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