CN116355158A

CN116355158A - Brominated grafting agent and preparation method and application thereof

Info

Publication number: CN116355158A
Application number: CN202111633804.1A
Authority: CN
Inventors: 徐典宏; 孟令坤; 李旭晖; 朱晶; 翟云芳; 燕鹏华; 魏绪玲
Original assignee: Petrochina Co Ltd
Current assignee: Petrochina Co Ltd
Priority date: 2021-12-28
Filing date: 2021-12-28
Publication date: 2023-06-30

Abstract

The invention provides a brominated grafting agent and a preparation method and application thereof, wherein the brominated grafting agent has a structure shown in a formula 1, wherein BR is a 1, 3-butadiene homo-polymer block, IR is an isoprene homo-polymer block, PS is a styrene homo-polymer block, SBR is a random copolymerization block of styrene and 1, 3-butadiene, SB/(S- & gtB) is a random gradual change block of styrene and 1, 3-butadiene, a is more than or equal to 1, B is more than or equal to 1, c is more than or equal to 1, d is more than or equal to 1, e is more than or equal to 1, f is more than or equal to 1, g is more than or equal to 1, and h is more than or equal to 1; in the brominated grafting agent, the mass percentage of bromine element is 12-17%. The brominated grafting agent can be used as a modifier for the butyl rubber to modify the butyl rubber into brominated butyl rubber, and the properties of the brominated butyl rubber including dimensional stability, vulcanization processability, mechanical strength and the like are obviously improved, so that the application range of the butyl rubber is widened.

Description

Brominated grafting agent and preparation method and application thereof

Technical Field

The invention relates to a grafting agent, in particular to a brominated grafting agent, a preparation method and application thereof, and belongs to the technical field of high polymer materials.

Background

As one of the most important synthetic Rubber varieties, butyl Rubber (IIR for short) produced by cationic polymerization and copolymerization of isobutylene and a small amount of isoprene as raw materials is widely used in the fields of inner tubes, inner liners, curing bladders, and the like for manufacturing tires for vehicles.

However, the molecular chain of the butyl rubber has higher unsaturation degree, and the substituent methyl groups are symmetrically arranged, so that the molecular structure determines the unavoidable problems of poor ozone aging resistance, remarkable extrusion swelling effect, long vulcanization scorching time, low vulcanization speed and the like, and the processability of the butyl rubber cannot meet the processing requirements and application scenes of gradual diversification, thus becoming the bottleneck of expanding the application of the butyl rubber material.

Therefore, how to modify butyl rubber to have more excellent application performance is a technical problem to be solved by the technicians in the field.

Disclosure of Invention

The invention provides a brominated grafting agent which is used as a modifier of p-butyl rubber, can modify butyl rubber into brominated butyl rubber, and can obviously improve properties of the brominated butyl rubber including dimensional stability, vulcanization processability, mechanical strength, air tightness and the like, thereby widening the application range of the butyl rubber.

The invention also provides a preparation method of the brominated grafting agent, which can modify butyl rubber and ensure that the modified brominated butyl rubber has excellent processability.

The invention also provides a brominated butyl rubber which comprises the brominated grafting agent, and therefore, has excellent processability, and is particularly characterized by lower Mooney viscosity, air permeability and extrusion swell ratio, shorter vulcanization scorch time and positive vulcanization time, higher mechanical strength and higher branching degree.

The invention also provides a rubber product which is obtained by processing the brominated butyl rubber, and has excellent performances in the aspects of mechanical strength, product dimensional stability and the like.

The first aspect of the present invention provides a brominated grafting agent, wherein the brominated grafting agent has a structure represented by formula 1:

wherein BR is a 1, 3-butadiene homo-block, IR is an isoprene homo-block, PS is a styrene homo-block, SBR is a random copolymer block of styrene and 1, 3-butadiene, SB/(S.fwdarw.B) is a random gradient block of styrene and 1, 3-butadiene, a is not less than 1, B is not less than 1, c is not less than 1, d is not less than 1, e is not less than 1, f is not less than 1, g is not less than 1, h is not less than 1;

in the brominated grafting agent, the mass percentage of bromine element is 12-17%.

The brominated grafting agent is used for carrying out bromination modification on butyl rubber to obtain brominated butyl rubber. The invention is not limited to the molecular weight of the brominated grafting agent, as long as the polymer satisfying the structure and the mass percentage of bromine element is the brominated grafting agent of the invention.

Wherein the SB block in the random gradual change block SB/(S.fwdarw.B) of the styrene and the 1, 3-butadiene refers to a block in which styrene molecular chains and 1, 3-butadiene molecular chains are randomly distributed, and (S.fwdarw.B) refers to a block in which one end of the block is used as a starting end and the other end is used as a terminal, the content of the styrene molecular chains gradually decreases from the starting end to the terminal, and the content of the 1, 3-butadiene molecular chains gradually increases.

The random gradual change block SB/(S-B) of the styrene and the 1, 3-butadiene can effectively destroy the regularity of the copolymer molecular chains of the butadiene and the isoprene, increase the disorder of the segments of the brominated grafting agent, and further increase the disorder of the segments of the modified brominated butyl rubber.

The bromination grafting agent is a five-membered four-heteroarm star-shaped bromination grafting agent, namely the grafting agent is obtained by cross connection of four different structural units, wherein the first structural unit is a segmented copolymer of isoprene and styrene, the second structural unit is a copolymer of random gradual change blocks of styrene and 1, 3-butadiene and p-bromomethyl styrene, the third structural unit is a copolymer of 2-bromovinylbenzene and 1, 3-butadiene homopolymerization blocks and isoprene homopolymerization blocks, and the fourth structural unit is a copolymer of 2-bromovinylbenzene and 1, 3-butadiene and random copolymerization blocks of styrene and 1, 3-butadiene.

The brominated grafting agent has higher mass percent of bromine element, so that the brominated grafting agent has excellent stability, has a mixed structure of primary bromine and secondary bromine, is beneficial to solving the problem that butyl rubber is less in double bonds and difficult to vulcanize due to high saturation, and is beneficial to improving vulcanization speed.

In addition, from the structure, the five-membered four-heteroarm star-shaped structure of the brominated grafting agent can destroy the regular molecular structure of butyl rubber, the modified brominated butyl rubber can obtain lower Mooney viscosity by increasing the disorder of chain segments, the processing energy consumption is greatly reduced, and meanwhile, the butyl rubber has good viscoelastic property, so that the extrusion swelling effect is reduced, and the modified brominated butyl rubber is ensured to have excellent processing dimensional stability.

The PS chain segment, the SBR chain segment, the p-bromomethylstyrene and the first brominating agent in the brominating grafting agent contain a large number of benzene ring structures with the characteristics of high rigidity and high steric hindrance, so that the modified brominated butyl rubber has excellent mechanical strength and air tightness.

Therefore, the brominated grafting agent has the characteristics of stable bromine structure and high disorder degree, and the brominated butyl rubber modified by the brominated grafting agent can be beneficial to improving the vulcanization processability, the extrusion swelling effect, the air tightness and the mechanical strength of the modified brominated butyl rubber, so that the modified brominated butyl rubber has excellent processability to meet various application requirements.

Further, the inventors found that the brominated butyl rubber processing property can be further promoted with higher economic benefit when the number average molecular weight of the brominated grafting agent is 110000 ～ 120000 and the molecular weight distribution is 19.05-20.32.

In a specific embodiment, the brominated grafting agent is prepared by a process comprising:

reacting 3, 9-dioxo [5.5] spiro undecane with a halogenating agent under the action of a catalyst to obtain a coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane;

mixing and heating 2-bromovinylbenzene and a molecular weight regulator to 70-90 ℃, adding a first initiator to react for 3-5 h, and then adding 1, 3-butadiene to end for 40-60 min to obtain a first brominating agent;

mixing a first structure regulator with a second initiator to obtain a mixed system, continuously decelerating and adding a mixture of styrene and 1, 3-butadiene into the mixed system at 50-60 ℃ to react for 50-70 min to form a-SB/(S- & gtB) -chain segment, and then adding p-bromomethylstyrene to react for 50-70 min at 60-70 ℃ to obtain a first block system;

mixing 1, 3-butadiene, a second structure regulator and a third initiator, reacting for 40-50 min at 40-50 ℃ to obtain a first reaction system, adding isoprene into the first reaction system, reacting for 60-70 min at 50-60 ℃ to form a-BR-IR-chain segment, adding the first brominating agent, and reacting for 100-120 min at 60-70 ℃ to obtain a second block system;

Mixing 1, 3-butadiene, a third structure regulator and a fourth initiator, reacting for 40-50 min at 40-50 ℃ to obtain a second reaction system, adding styrene and 1, 3-butadiene into the second reaction system, reacting for 50-70 min at 50-60 ℃ to form a-BR-SBR-chain segment, adding the first brominating agent, and reacting for 60-80 min at 60-70 ℃ to obtain a third block system;

mixing isoprene, a fifth structure regulator and a fifth initiator, reacting for 30-40 min at 40-50 ℃ to obtain a third reaction system, adding styrene and a sixth structure regulator into the third reaction system, and reacting for 30-40 min at 50-60 ℃ to obtain a fourth block system with an-IR-PS-chain segment structure;

and adding the second block system, the third block system and the fourth block system into the first block system, adding the coupling agent 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane, and reacting for 140-160 min at 80-90 ℃ to obtain the brominated grafting agent.

The preparation method comprises the steps of preparing a coupling agent, preparing a first brominating agent, preparing a first block system, preparing a second block system, preparing a third block system, preparing a fourth block system and coupling the first block system, the second block system, the third block system and the fourth block system through the coupling agent. It will be appreciated that the preparation steps of the first block system, the second block system, the third block system and the fourth block system are not related in any way, and can be prepared separately and are not sequential to each other.

Specifically, in the preparation process of the coupling agent, the halogenating agent is selected from one of liquid chlorine or liquid bromine, preferably liquid bromine. The catalyst is selected from mixed aqueous solution of hydrochloric acid and methanol, and the molar concentration of the hydrochloric acid in the mixed aqueous solution is 0.4-0.9 mo/L.

In a specific embodiment, the preparation process of the coupling agent comprises the steps of dissolving 100% of reactants and 1% -5% of catalyst in 100% -200% of solvent, reacting for 1-3 hours at 60-80 ℃, adding 20% -40% of sodium hydroxide solution with the mass concentration of 10% -20% to terminate the reaction, adding 200% -300% of chloromethane to extract, separating, washing and drying to obtain the coupling agent 1, 5-dihalo-3, 3-bis (2-haloethyl) pentane. Wherein the reactant comprises 10-30% of 3, 9-dioxy [5.5] spiro undecane and 70-90% of halogenating agent according to mass percent.

In the preparation process of the first brominating agent, a first initiator is added into a mixed system of 2-bromovinylbenzene and a molecular weight regulator to initiate the free radical addition reaction of the 2-bromovinylbenzene, so as to obtain the first brominating agent meeting the structural requirement of the formula 1. The free radical addition reaction is not only favorable for avoiding the generation of byproduct hydrogen bromide (HBr), but also can avoid the molecular rearrangement of a bromine structure, thereby realizing the high bromine content and high bromine structure stability of the brominated grafting agent, and simultaneously omitting the alkali washing recovery flow of the byproduct HBr, thereby shortening the process flow and reducing the production cost.

Specifically, the molecular weight regulator is one selected from tertiary dodecyl mercaptan, tertiary tetradecyl mercaptan and tertiary hexadecyl mercaptan, and preferably tertiary dodecyl mercaptan. The first initiator is selected from organic peroxides, and may specifically be at least one selected from dicumyl peroxide, cumene hydroperoxide, benzoyl peroxide and di-t-butyl peroxide, and is preferably benzoyl peroxide.

In the preparation of the first block system, after a mixed system of the first structure regulator and the second initiator is obtained, continuously decelerating and adding a mixture of styrene and 1, 3-butadiene into the mixed system, wherein the continuously decelerating and adding mode can lead the reaction to be a variable speed polymerization process, and the random gradual change block of the styrene and the 1, 3-butadiene can be obtained. Specifically, the initial feed rate is greater than 4.0% mixture/min, and the magnitude of the decrease in feed rate can be set according to the reaction time, so long as it is ensured that the mixture of styrene and 1, 3-butadiene can be completely added to the mixed system of the first structure regulator and the second initiator within the prescribed reaction time.

The continuous slow addition of the mixture of styrene and 1, 3-butadiene to the mixed system for 50-70 min means that the reaction is started for 50-70 min after the addition of the mixture of styrene and 1, 3-butadiene is completed.

It will be appreciated that in addition to the above components, solvents are added during the preparation of the coupling agent, the first brominating agent, the first block system, the second block system, the third block system, and the fourth block system.

Specifically, in the preparation process of the coupling agent, the addition amount of the solvent is 1-2 times of that of the 3, 9-dioxo [5.5] spiro undecane and the halogenating agent. In the preparation process of the first brominating agent, the addition amount of the solvent is 2-3 times of that of the bromovinylbenzene; the addition amount of the solvent in the preparation process of the first block system, the second block system, the third block system and the fourth block system is 1-2 times of that of the brominating agent.

In a specific embodiment, the solvent is selected from linear alkanes, aromatic hydrocarbons and cycloalkanes, and may be specifically selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably cyclohexane.

The second initiator, the third initiator, the fourth initiator and the fifth initiator used in the preparation process of the first block system, the second block system, the third block system and the fourth block system are all hydrocarbyl mono-lithium compounds, namely RLi, wherein R is saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or composite group of the above groups containing 1-20 carbon atoms. Specifically, the hydrocarbyl monolithium compound is one selected from n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium, and dodecyllithium, and preferably n-butyllithium. The amount of each of the above initiators added during the preparation is determined by the molecular weight of the target brominated grafting agent, for example, the amount of butyl lithium species is calculated by the formula:

Butyllithium molar mass (mol) =total gum mass M (g)/molecular weight M (g/mol)

Wherein, the total mass of the glue refers to the expected preparation mass of the target brominated grafting agent, and the molecular weight refers to the molecular weight of the target brominated grafting agent.

The first structure modifier, the second structure modifier, the third structure modifier, the fourth structure modifier, the fifth structure modifier and the sixth structure modifier used in the preparation of the first block system, the second block system, the third block system and the fourth block system are all polar organic compounds for generating solvation effect in polymerization reaction, and are each independently selected from one of diethylene glycol dimethyl ether (DGE), tetrahydrofuran (THF), diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME) and triethylamine, preferably Tetrahydrofuran (THF).

In addition, the brominated grafting agent of the invention is prepared in the whole process under the anhydrous and anaerobic condition, so that the reaction condition needs to be protected by inert gas at the beginning of the preparation.

In the preparation process, the preparation of the brominated grafting agent with the target molecular weight can be realized by further controlling the dosage of each raw material, the preparation time and other factors.

As a preferred embodiment, when in the preparation of the first brominating agent, the mass ratio of brominating agent to the 2-bromovinylbenzene, the molecular weight regulator, the first initiator, the 1, 3-butadiene is 1:1: (0.002-0.005): (0.0005-0.005): (0.01-0.05); and/or the number of the groups of groups,

in the preparation of the first block system, the mass ratio of brominating agent to the first structure regulator, the styrene and the 1, 3-butadiene is 1: (0:003-0.006): (0.5-0.7): (0.3 to 0.4); and/or the number of the groups of groups,

in the preparation of the second block system, the mass ratio of brominating agent to the 1, 3-butadiene, the second structure regulator and the isoprene is 1: (0.2-0.3): (0.001-0.003): (0.3 to 0.4); and/or the number of the groups of groups,

in the preparation of the third block system, the mass ratio of the brominating agent to the 1, 3-butadiene, the third structure regulator, the styrene, the 1, 3-butadiene and the fourth structure regulator is 1: (0.2-0.3): (0.001-0.003): (0.2-0.3): (0.1-0.2): (0.002-0.004); and/or the number of the groups of groups,

in the preparation of the fourth block system, the mass ratio of the brominating agent to the isoprene, the fifth structure regulator, the styrene and the sixth structure regulator is 1: (0.2-0.3): (0.001-0.003): (0.2-0.3): (0.001-0.003), the economic efficiency of the production process can be increased by increasing the yield of the product.

It is noted that the brominating agent comprises, in mass percent, 30 to 40% of p-bromomethylstyrene in the preparation of the first block system, 40 to 50% of the first brominating agent in the preparation of the second block system, and 20 to 30% of the first brominating agent in the preparation of the third block system.

Further, the molar ratio of the coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane to the polymerization initiator is (2-4): 1; the polymerization initiator is composed of the second initiator, the third initiator, the fourth initiator and the fifth initiator.

The brominated grafting agent is an organic combination of 1, 3-butadiene and isoprene copolymer block, a random copolymer block of styrene and 1, 3-butadiene, a random gradual change block of styrene and 1, 3-butadiene, 1, 5-dihalo-3, 3-di (2-haloethyl) pentane, primary bromine and secondary bromine, and the parts are combined together and cooperatively played, so that the brominated grafting agent can be finally used for modifying butyl rubber, and the modified brominated butyl rubber has excellent vulcanization processability, dimensional stability, air tightness and mechanical property.

The second aspect of the invention provides a method for preparing a brominated grafting agent, comprising the steps of:

adding the second block system, the third block system and the fourth block system into the first block system, adding the coupling agent 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane, and reacting for 140-160 min at 80-90 ℃ to obtain the brominated grafting agent;

the brominated grafting agent has a structure shown in a formula 1,

The specific description of the preparation method is the same as that mentioned in the first aspect, and is not repeated here.

The preparation method utilizes a coupling agent to combine BR chain segments, IR chain segments, PS chain segments, SBR chain segments, SB/(S-B) chain segments, p-bromomethylstyrene and a first brominating agent on one macromolecular chain, thereby obtaining the five-membered four-hetero-arm star polymer with primary bromine structure and secondary bromine structure. On one hand, the brominated grafting agent prepared by the method has the advantage of high hybridization degree. On the other hand, the first brominating agent structure in the method is obtained through free radical polymerization, and HBr is not generated in the whole reaction process, so that the loss of bromine content is reduced, the utilization rate of bromine in the brominated butyl rubber is improved, and the improvement of the bromine content in the brominated butyl rubber is facilitated.

In addition, the preparation method can omit the alkaline washing recovery process of the byproduct HBr, and has the advantages of environmental protection, short process flow and low production cost.

In a third aspect, the present invention provides a brominated butyl rubber obtained by polymerizing a brominated grafting agent as described in the first aspect or a brominated grafting agent prepared by the preparation method as described in the second aspect with a system comprising isobutylene and isoprene;

The mass ratio of the brominated grafting agent to the isobutene to the isoprene is (5-8): (85-90): (5-7).

The brominated butyl rubber obtained by modified grafting according to the proportion of the raw materials has the characteristics of low Mooney viscosity, excellent vulcanization processability, dimensional stability, air tightness and mechanical strength because the brominated grafting agent has the characteristics of high stability and high disorder degree.

The invention is not limited to a particular method of modifying butyl rubber using a brominated grafting agent.

In a specific embodiment, the brominated butyl rubber is prepared by a process comprising the following steps:

adding a first diluent, isobutene and isoprene into a solution system of the brominated grafting agent at the temperature of-90 to-80 ℃ and controlling the temperature to be-100 to-90 ℃ to obtain a first system;

mixing a second diluent and a co-initiator at the temperature of minus 95 ℃ to minus 85 ℃ and aging for 20 min to 30min, adding an aging system into the first system to react for 5 h to 7h, and stopping the reaction to obtain the brominated butyl rubber. The invention is not limited to the dissolution mode of the brominated grafting agent, for example, the brominated grafting agent is added into a mixed solvent with the volume ratio of the diluent to the solvent of 6:4-4:6, and stirred for 70-90 min until the brominated grafting agent is dissolved. The diluent is selected from halogenated alkane, wherein halogen atoms in the halogenated alkane can be chlorine, bromine or fluorine, and the number of carbon atoms in the halogenated alkane is C1-C4, for example, one selected from chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, and dichloromethane is preferred.

Further, the mass ratio of the brominated grafting agent to the isoprene, the isobutene, the first diluent, the second diluent and the co-initiator is (5-8): (85-90): (100-200): (10-20): (0.2-0.5). It should be noted that isobutylene and isoprene herein refer to the raw materials of the polymer for the preparation of butyl rubber.

In addition, termination of the reaction may be achieved by addition of a terminator. The terminator is, for example, one or more selected from methanol, ethanol and butanol, and after terminating the reaction, the reaction system is coagulated, washed and dried to obtain the brominated butyl rubber of the present invention.

In the above preparation process, the first diluent and the second diluent are each independently selected from one of methane chloride, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, methane fluoride, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane, preferably dichloromethane.

The co-initiator is a combination of an alkyl aluminum halide and a protic acid. The alkyl aluminum halide is selected from diethyl aluminum chloride, diisobutyl aluminum chloride, methyl aluminum dichloride, aluminum sesquichloride, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride and ethyl aluminum chloride At least one, preferably sesquiethylaluminum chloride. The protonic acid is selected from HCl, HF, HBr, H ₂ SO ₄ 、H ₂ CO ₃ 、H ₃ PO ₄ And HNO ₃ Preferably HCl. Wherein the total adding amount of the co-initiator is 0.2-0.7% of the mass of the added reaction monomer, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.05:1-0.2:1.

In a fourth aspect, the present invention provides a rubber article processed from the brominated butyl rubber of the third aspect.

The rubber product of the invention has the characteristics of excellent vulcanization processability, dimensional stability, air tightness and mechanical strength.

The brominated grafting agent is used for modifying butyl rubber, and the special structure and bromine content of the brominated butyl rubber can ensure that the modified brominated butyl rubber has the characteristics of stable bromine structure, high branching degree and low Mooney viscosity, thereby being beneficial to improving the vulcanization processing characteristics (shorter vulcanization scorch time and positive vulcanization time), the processing dimensional stability (lower extrusion expansion ratio), the mechanical strength (higher tensile strength) and the airtight performance (lower air permeability) of the brominated butyl rubber.

Therefore, the rubber product processed from the brominated butyl rubber has excellent performances in vulcanization processing characteristics, product dimensional stability, mechanical strength, air tightness and the like.

Detailed Description

For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

The specific sources of part of raw materials in the following preparation process are as follows:

example 1

The preparation method of the brominated grafting agent comprises the following steps:

1) Preparation of the coupling agent: in a 4L stainless steel polymerization kettle with a jacket, argon is introduced to replace for 2 times, 600g of deionized water, 70g of 3, 9-dioxy [5.5] spiro undecane, 350g of liquid bromine, 10g of HCl-CH3OH solution (molar concentration of HCl is 0.5 mol/L), heating to 65 ℃, reacting for 1.5 hours, adding 60g of 10% NaOH aqueous solution with mass concentration to terminate the reaction, finally adding 1200g of chloromethane to extract, separate, wash and dry to obtain the coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane (yield 91%).

2) Preparation of the first brominating agent: introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2000g of cyclohexane, 1000g of 2-bromovinylbenzene and 2.0g of tertiary dodecyl mercaptan into the reaction kettle, stirring, mixing and heating, adding 0.5g of BPO when the temperature of the reaction kettle reaches 70 ℃, and reacting for 3.0h; then adding 10g of 1, 3-butadiene into a polymerization kettle for end capping, reacting for 40min, washing and drying to obtain the first brominating agent.

3) Preparation of the first block System: in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 2 times, sequentially adding 1000g of cyclohexane and 3.0g THF,25.5mmo1 n-butyllithium into the polymerization kettle, heating to 50 ℃, stirring and mixing 500g of styrene and 300g of 1, 3-butadiene for 30min to form a mixed solution, and continuously injecting the mixed solution into the reaction kettle A at an initial feeding speed of 57 g/min within 50min reaction time, wherein the feeding speed reduction amplitude is 2g of the mixed solution per minute, so as to form a-SB/(S- & gtB) -chain segment; and then adding 300g of p-bromomethylstyrene into the polymerization kettle A, heating to 60 ℃, and reacting for 50min to obtain a first block system.

4) Preparation of the second Block System: in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 2 times, sequentially adding 1000g of cyclohexane, 200g of 1, 3-butadiene, heating to 40 ℃,1.0g of THF, then adding 23.0 mmol of n-butyllithium to react for 40min, then adding 300g of isoprene into the polymerization kettle B, heating to 50 ℃, and reacting for 60min to form a-BR-IR-chain segment; and finally, sequentially adding 400g of a first brominating agent into the polymerization kettle B, heating to 60 ℃, and reacting for 100min to obtain a second block system.

5) Preparation of the third Block System: in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1000g of cyclohexane, 200g of 1, 3-butadiene and 1.0g of THF, heating to 40 ℃, and then adding 24.0 mmol 1 of n-butyllithium to react for 40min to form a-BR-chain segment; then sequentially adding 200g of styrene, 100g of 1, 3-butadiene and 2.0g of THF into a polymerization kettle C, heating to 50 ℃, reacting for 50min to form a-BR-SBR-chain segment, finally sequentially adding 200g of a first brominating agent into the polymerization kettle C, heating to 60 ℃, and reacting for 60min to obtain a third block system.

6) Preparation of the fourth Block System: in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 2 times, sequentially adding 1000g of cyclohexane, 200g of isoprene and 1.0g of THF, heating to 40 ℃, and then adding 20.0 mmol 1 of n-butyllithium to react for 30min to form an-IR-segment; and then sequentially adding 100g of styrene and 1.0g of THF into the polymerization kettle D, heating to 50 ℃, and reacting for 30min to form an-IR-PS-chain segment to obtain a fourth block system.

7) Mixing the first block system, the second block system and the third block system with the fourth block system, heating to 80 ℃, adding 260mmo1 of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane for coupling reaction for 140min, then treating the coupled reaction mixture with water, and carrying out wet condensation and drying on the glue solution to obtain the brominated grafting agent A of the embodiment.

The preparation method of the brominated butyl rubber comprises the following steps:

1) Adding 300g of methylene dichloride, 200g of cyclohexane and 25.0g of brominated grafting agent A into a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times, stirring and dissolving for 70min until the brominated grafting agent A is completely dissolved, then sequentially adding 500g of methylene dichloride, 450g of isobutene and 25.0g of isoprene when the temperature is reduced to-80 ℃, and stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃ to obtain a first system;

2) 50g of methylene dichloride, 1.25g of sesquiethyl aluminum chloride and 0.015g of HCl are mixed and aged for 20min at the temperature of minus 85 ℃ to obtain a second system;

3) Adding the second system into the first system, stirring and reacting for 5.0h, finally adding 25g of methanol, discharging, condensing, washing and drying to obtain the brominated butyl rubber A of the embodiment.

Example 2

1) Preparation of the coupling agent: as in example 1.

2) Preparation of the first brominating agent: as in example 1.

3) Preparation of the first block System: in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 2 times, sequentially adding 1200g of cyclohexane and 3.5g THF,27.5mmo1 n-butyllithium into the polymerization kettle, heating to 52 ℃, stirring and mixing 550g of styrene and 320g of 1, 3-butadiene for 32min to form a mixed solution, and continuously injecting the mixed solution into the reaction kettle A at an initial feeding speed of 59 g/min within 50min of reaction time, wherein the feeding speed reduction amplitude is 2g of the mixed solution per minute, so as to form a-SB/(S- & gtB) -chain segment; and then adding 320g of p-bromomethylstyrene into the polymerization kettle A, heating to 62 ℃, and reacting for 55min to obtain a first block system.

4) Preparation of the second Block System: in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 2 times, sequentially adding 1200g of cyclohexane, 220g of 1, 3-butadiene, heating to 42 ℃,1.4g of THF, then adding 25.0 mmol 1 of n-butyllithium to react for 42min, then adding 320g of isoprene into the polymerization kettle B, heating to 52 ℃, and reacting for 62min to form a-BR-IR-chain segment; finally, 420g of a first brominating agent is added into the polymerization kettle B in sequence, the temperature is raised to 62 ℃, and the reaction is carried out for 105 minutes, thus obtaining a second block system.

5) Preparation of the third Block System: in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1200g of cyclohexane, 220g of 1, 3-butadiene and 1.5g of THF, heating to 42 ℃, and then adding 26.0 mmol 1 of n-butyllithium to react for 42min to form a-BR-chain segment; then sequentially adding 220g of styrene, 120g of 1, 3-butadiene and 2.6g of THF into a polymerization kettle C, heating to 52 ℃, reacting for 55min to form a-BR-SBR-chain segment, finally sequentially adding 220g of first brominating agent into the polymerization kettle C, heating to 62 ℃, and reacting for 65min to obtain a third block system.

6) Preparation of the fourth Block System: in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 2 times, sequentially adding 1200g of cyclohexane, 220g of isoprene and 1.3g of THF, heating to 42 ℃, and then adding 22.0 mmol 1 of n-butyllithium to react for 32min to form an-IR-segment; then 120g of styrene and 1.4g of THF are sequentially added into the polymerization kettle D, the temperature is raised to 52 ℃, and the reaction is carried out for 32min, so that an-IR-PS-chain segment is formed, and a fourth block system is obtained.

7) Mixing the first block system, the second block system and the third block system with the fourth block system, heating to 82 ℃, adding 290mmo1 of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane for coupling reaction for 145min, then treating the coupled reaction mixture with water, and carrying out wet condensation and drying on the glue solution to obtain the brominated grafting agent B of the embodiment.

1) In a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 270g of methylene dichloride, 230g of cyclohexane and 28.0g of brominated grafting agent B into the polymerization kettle, stirring and dissolving for 75min until the brominated grafting agent B is completely dissolved, then cooling to the temperature of minus 82 ℃, sequentially adding 600g of methylene dichloride, 446g of isobutene and 26.0g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to minus 92 ℃ to obtain a first system;

2) Mixing and aging 60g of methylene dichloride, 1.52g of sesquiethyl aluminum chloride and 0.028g of HCl at the temperature of minus 87 ℃ for 22min to obtain a second system;

3) Adding the second system into the first system, stirring and reacting for 5.5 hours, finally adding 30g of methanol, discharging, condensing, washing and drying to obtain the brominated butyl rubber B of the embodiment.

Example 3

1) Preparation of the coupling agent: as in example 1.

2) Preparation of the first brominating agent: as in example 1.

3) Preparation of the first block System: in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 3 times, sequentially adding 1400g of cyclohexane and 4.0g THF,30.5mmo1 n-butyllithium into the polymerization kettle, heating to 54 ℃, stirring and mixing 600g of styrene and 340g of 1, 3-butadiene for 34min to form a mixed solution, and continuously injecting the mixed solution into the reaction kettle A at an initial feeding speed of 78 g/min within a reaction time of 60min, wherein the feeding speed reduction amplitude is 3g of the mixed solution per minute, so as to form a-SB/(S- & gtB) -chain segment; then 340g of p-bromomethylstyrene is added into the polymerization kettle A, the temperature is raised to 64 ℃, and the reaction is carried out for 58 minutes, thus obtaining a first block system.

4) Preparation of the second Block System: in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1400g of cyclohexane, 240g of 1, 3-butadiene, heating to 44 ℃,1.8g of THF, then adding 28.0 mmol 1 of n-butyllithium to react for 44min, then adding 340g of isoprene into the polymerization kettle B, heating to 54 ℃, and reacting for 64min to form a-BR-IR-chain segment; finally, 440g of a first brominating agent is added into the polymerization kettle B in sequence, the temperature is raised to 64 ℃, and the reaction is carried out for 108min, thus obtaining a second block system.

5) Preparation of the third Block System: in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 1400g of cyclohexane, 240g of 1, 3-butadiene and 1.8g of THF, heating to 44 ℃, and then adding 28.0 mmol 1 of n-butyllithium to react for 44min to form a-BR-chain segment; then adding 240g of styrene, 140g of 1, 3-butadiene and 3.0g of THF into a polymerization kettle C in sequence, heating to 54 ℃, reacting for 58min to form a-BR-SBR-chain segment, finally adding 240g of first brominating agent into the polymerization kettle C in sequence, heating to 64 ℃, and reacting for 68min to obtain a third block system.

6) Preparation of the fourth Block System: in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 3 times, sequentially adding 1400g of cyclohexane, 240g of isoprene and 1.8g of THF, heating to 44 ℃, and then adding 24.0 mmol 1 of n-butyllithium to react for 34min to form an-IR-segment; and then sequentially adding 140g of styrene and 1.9g of THF into the polymerization kettle D, heating to 54 ℃, and reacting for 34min to form an-IR-PS-chain segment to obtain a fourth block system.

7) Mixing the first block system, the second block system and the third block system with the fourth block system, heating to 84 ℃, adding 320mmo1 of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane for coupling reaction for 149min, treating the coupled reaction mixture with water, condensing the glue solution by a wet method, and drying to obtain the brominated grafting agent C of the embodiment.

1) Introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 4 times, adding 480g of methylene dichloride, 320g of cyclohexane and 30.0g of brominated grafting agent C into the polymerization kettle, stirring and dissolving for 79min until the brominated grafting agent C is completely dissolved, then cooling to the temperature of minus 84 ℃, sequentially adding 700g of methylene dichloride, 441g of isobutene and 29.0g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to minus 94 ℃ to obtain a first system;

2) 70g of methylene dichloride, 1.72g of aluminum sesquichloride and 0.035g of HCl are mixed and aged for 24min at the temperature of minus 89 ℃ to obtain a second system;

3) Adding the second system into the first system, stirring and reacting for 6 hours, finally adding 35g of methanol, discharging, condensing, washing and drying to obtain the brominated butyl rubber C of the embodiment.

Example 4

1) Preparation of the coupling agent: as in example 1.

2) Preparation of the first brominating agent: as in example 1.

3) Preparation of the first block System: in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 3 times, sequentially adding 1600g of cyclohexane and 4.5g THF,33.5mmo1 n-butyllithium into the polymerization kettle, heating to 56 ℃, stirring and mixing 630g of styrene and 360g of 1, 3-butadiene for 36min to form a mixed solution, and continuously injecting the mixed solution into the reaction kettle A at an initial feeding speed of 80g of the mixed solution/min within a reaction time of 60min, wherein the feeding speed reduction amplitude is 3g of the mixed solution per minute, so as to form a-SB/(S- & gtB) -chain segment; and then adding 360g of p-bromomethylstyrene into the polymerization kettle A, heating to 66 ℃, and reacting for 61min to obtain a first block system.

4) Preparation of the second Block System: in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 2 times, sequentially adding 1600g of cyclohexane, 260g of 1, 3-butadiene, heating to 46 ℃,2.2g of THF, then adding 30.0 mmol 1 of n-butyllithium to react for 46min, then adding 360g of isoprene into the polymerization kettle B, heating to 56 ℃, and reacting for 66min to form a-BR-IR-chain segment; and finally, sequentially adding 460g of a first brominating agent into the polymerization kettle B, heating to 66 ℃, and reacting for 112min to obtain a second block system.

5) Preparation of the third Block System: in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1600g of cyclohexane, 260g of 1, 3-butadiene and 2.2g of THF, heating to 46 ℃, and then adding 31.0 mmol 1 of n-butyllithium to react for 46min to form a-BR-chain segment; then 260g of styrene, 160g of 1, 3-butadiene and 3.5g of THF are sequentially added into a polymerization kettle C, the temperature is raised to 56 ℃ for reaction for 61min, a-BR-SBR-chain segment is formed, and finally 260g of a first brominating agent is sequentially added into the polymerization kettle C, the temperature is raised to 66 ℃ for reaction for 72min, so that a third block system is obtained.

6) Preparation of the fourth Block System: in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 2 times, sequentially adding 1600g of cyclohexane, 260g of isoprene and 2.3g of THF, heating to 46 ℃, and then adding 26.0mm 1 of n-butyllithium to react for 36min to form an-IR-segment; then 160g of styrene and 2.2g of THF are sequentially added into the polymerization kettle D, the temperature is raised to 56 ℃, and the reaction is carried out for 36min, so that an-IR-PS-chain segment is formed, and a fourth block system is obtained.

7) Mixing the first block system, the second block system and the third block system with the fourth block system, heating to 86 ℃, adding 360mmo1 of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane for coupling reaction for 152min, treating the coupled reaction mixture with water, condensing the glue solution by a wet method, and drying to obtain the brominated grafting agent D of the embodiment.

1) Adding 400g of methylene dichloride, 400g of cyclohexane and 33.0g of brominated grafting agent D into a 4L stainless steel reaction kettle with a jacket, stirring and dissolving for 82min until the brominated grafting agent D is completely dissolved, then cooling to the temperature of-86 ℃, sequentially adding 800g of methylene dichloride, 437g of isobutene and 30.0g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to the temperature of-96 ℃ to obtain a first system;

2) Mixing and aging 80g of methylene dichloride, 1.92g of sesquiethyl aluminum chloride and 0.051g of HCl at the temperature of-91 ℃ for 26 minutes to obtain a second system;

3) Adding the second system into the first system, stirring and reacting for 6.3 hours, finally adding 40g of methanol, discharging, condensing, washing and drying to obtain the brominated butyl rubber D of the embodiment.

Example 5

1) Preparation of the coupling agent: as in example 1.

2) Preparation of the first brominating agent: as in example 1.

3) Preparation of the first block System: in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 4 times, sequentially adding 1800g of cyclohexane and 5.0g THF,36.5mmo1 n-butyllithium into the polymerization kettle, heating to 58 ℃, stirring and mixing 660g of styrene and 380g of 1, 3-butadiene for 38min to form a mixed solution, and continuously injecting the mixed solution into the reaction kettle A at an initial feeding speed of 90g of mixed solution/min within a reaction time of 70min, wherein the feeding speed reduction amplitude is that the feeding speed of the mixture is reduced by 4g per minute, so as to form a-SB/(S- & gtB) -chain segment; then adding 380g of p-bromomethylstyrene into the polymerization kettle A, heating to 68 ℃, and reacting for 65min to obtain a first block system.

4) Preparation of the second Block System: in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 4 times, sequentially adding 1800g of cyclohexane, 280g of 1, 3-butadiene, heating to 48 ℃,2.6g of THF, then adding 34.0 mmol 1 of n-butyllithium to react for 48min, then adding 380g of isoprene into the polymerization kettle B, heating to 58 ℃, and reacting for 68min to form a-BR-IR-chain segment; finally, 480g of a first brominating agent is added into the polymerization kettle B in sequence, the temperature is raised to 68 ℃, and the reaction is carried out for 115 minutes, thus obtaining a second block system.

5) Preparation of the third Block System: in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 4 times, sequentially adding 1800g of cyclohexane, 280g of 1, 3-butadiene and 2.6g of THF, heating to 48 ℃, and then adding 35.0 mmol 1 of n-butyllithium to react for 48min to form a-BR-chain segment; then adding 280g of styrene, 180g of 1, 3-butadiene and 3.7g of THF into a polymerization kettle C in sequence, heating to 58 ℃, reacting for 65min to form a-BR-SBR-chain segment, finally adding 280g of first brominating agent into the polymerization kettle C in sequence, heating to 68 ℃, and reacting for 75min to obtain a third block system.

6) Preparation of the fourth Block System: in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 4 times, sequentially adding 1800g of cyclohexane, 280g of isoprene and 2.6g of THF, heating to 48 ℃, and then adding 28.0mm 1 of n-butyllithium to react for 38min to form an-IR-segment; then 180g of styrene and 2.7g of THF are sequentially added into the polymerization kettle D, the temperature is raised to 58 ℃ and the reaction is carried out for 38min, so that an-IR-PS-chain segment is formed, and a fourth block system is obtained.

7) Mixing the first block system, the second block system and the third block system with the fourth block system, heating to 88 ℃, adding 400mmo1 of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane for coupling reaction for 155min, then treating the coupled reaction mixture with water, and carrying out wet condensation and drying on the glue solution to obtain the brominated grafting agent E of the embodiment.

1) Adding 400g of methylene dichloride, 600g of cyclohexane and 35.0g of brominated grafting agent E into a 4L stainless steel reaction kettle with a jacket, stirring and dissolving for 86min until the brominated grafting agent E is completely dissolved, then cooling to-88 ℃, sequentially adding 900g of methylene dichloride, 433g of isobutene and 32.0g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-98 ℃ to obtain a first system;

2) Mixing and aging 90g of methylene dichloride, 2.02g of sesquiethyl aluminum chloride and 0.065g of HCl at the temperature of minus 93 ℃ for 28min to obtain a second system;

3) Adding the second system into the first system, stirring and reacting for 6.6 hours, finally adding 40g of methanol, discharging, condensing, washing and drying to obtain the brominated butyl rubber E of the embodiment.

Example 6

1) Preparation of the coupling agent: as in example 1.

2) Preparation of the first brominating agent: as in example 1.

3) Preparation of the first block System: in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 4 times, sequentially adding 2000g of cyclohexane and 6.0g THF,32.5mmo1 n-butyllithium into the polymerization kettle, heating to 60 ℃, stirring and mixing 700g of styrene and 400g of 1, 3-butadiene for 40min to form a mixed solution, and continuously injecting the mixed solution into the reaction kettle A at an initial feeding speed of 95 g/min within a reaction time of 70min, wherein the feeding speed reduction amplitude is that the feeding speed of the mixture is reduced by 4g per minute, so as to form a-SB/(S- & gtB) -chain segment; then 400g of p-bromomethyl styrene is added into the polymerization kettle A, the temperature is raised to 70 ℃, and the reaction is carried out for 70min, thus obtaining a first block system.

4) Preparation of the second Block System: in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 4 times, sequentially adding 2000g of cyclohexane, 300g of 1, 3-butadiene, heating to 50 ℃,3.0g of THF, then adding 36.0 mmol 1 of n-butyllithium to react for 50min, then adding 400g of isoprene into the polymerization kettle B, heating to 60 ℃, and reacting for 70min to form a-BR-IR-chain segment; and finally, sequentially adding 500g of a first brominating agent into the polymerization kettle B, heating to 70 ℃, and reacting for 120min to obtain a second block system.

5) Preparation of the third Block System: in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 4 times, sequentially adding 2000g of cyclohexane, 300g of 1, 3-butadiene and 3.0g of THF, heating to 50 ℃, and then adding 37.0 mmol 1 of n-butyllithium to react for 50min to form a-BR-chain segment; then sequentially adding 300g of styrene, 200g of 1, 3-butadiene and 4.0g of THF into a polymerization kettle C, heating to 60 ℃, reacting for 70min to form a-BR-SBR-chain segment, finally sequentially adding 300g of a first brominating agent into the polymerization kettle C, heating to 70 ℃, and reacting for 80min to obtain a third block system.

6) Preparation of the fourth Block System: in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 4 times, sequentially adding 2000g of cyclohexane, 300g of isoprene and 3.0g of THF, heating to 50 ℃, and then adding 30.0mm 1 of n-butyllithium to react for 40min to form an-IR-segment; then 200g of styrene, 3.0g of THF are sequentially added into the polymerization kettle D, the temperature is raised to 60 ℃, and the reaction is carried out for 40min, so that an-IR-PS-chain segment is formed, and a fourth block system is obtained.

7) Mixing the first block system, the second block system and the third block system with the fourth block system, heating to 90 ℃, adding 500mmo1 of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane for coupling reaction for 160min, then treating the coupled reaction mixture with water, condensing the glue solution by a wet method, and drying to obtain the brominated grafting agent F of the embodiment.

1) Adding 500g of methylene dichloride, 500g of cyclohexane, 40.0g of brominated grafting agent F into a 4L stainless steel reaction kettle with a jacket, stirring and dissolving for 90min until the brominated grafting agent F is completely dissolved, then cooling to the temperature of minus 90 ℃, sequentially adding 1000g of methylene dichloride, 425g of isobutene and 35.0g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to minus 100 ℃ to obtain a first system;

2) Mixing and aging 100g of methylene dichloride, 2.22g of sesquiethyl aluminum chloride and 0.072g of HCl at the temperature of minus 95 ℃ for 30min to obtain a second system;

3) Adding the second system into the first system, stirring and reacting for 7.0h, finally adding 40g of methanol, discharging, condensing, washing and drying to obtain the brominated butyl rubber F of the embodiment.

Example 7

1) Preparation of the coupling agent: as in example 1.

2) Preparation of the first brominating agent: as in example 1.

3) Preparation of the first block System: in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 2 times, sequentially adding 1000g of cyclohexane and 3.0g THF,23.5mmo1 n-butyllithium into the polymerization kettle, heating to 50 ℃, stirring and mixing 490g of styrene and 300g of 1, 3-butadiene for 30min to form a mixed solution, and continuously injecting the mixed solution into the reaction kettle A at an initial feeding speed of 55g of the mixed solution/min within 50min of reaction time, wherein the feeding speed reduction amplitude is 2g of the mixed solution per minute, so as to form a-SB/(S- & gtB) -chain segment; then 280g of p-bromomethylstyrene is added into the polymerization kettle A, the temperature is raised to 60 ℃, and the reaction is carried out for 50min, thus obtaining a first block system.

4) Preparation of the second Block System: in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 2 times, sequentially adding 1000g of cyclohexane, 200g of 1, 3-butadiene, heating to 40 ℃,1.0g of THF, then adding 21.0 mmol 1 of n-butyllithium to react for 40min, then adding 290g of isoprene into the polymerization kettle B, heating to 50 ℃, and reacting for 60min to form a-BR-IR-chain segment; and finally, sequentially adding 380g of a first brominating agent into the polymerization kettle B, heating to 60 ℃, and reacting for 100min to obtain a second block system.

5) Preparation of the third Block System: in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1000g of cyclohexane, 200g of 1, 3-butadiene and 1.0g of THF, heating to 40 ℃, and then adding 23.0 mmol of 1-n-butyllithium to react for 40min to form a-BR-chain segment; then sequentially adding 200g of styrene, 100g of 1, 3-butadiene and 2.0g of THF into a polymerization kettle C, heating to 50 ℃, reacting for 50min to form a-BR-SBR-chain segment, finally sequentially adding 190g of a first brominating agent into the polymerization kettle C, heating to 60 ℃, and reacting for 60min to obtain a third block system.

6) Preparation of the fourth Block System: in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 2 times, sequentially adding 1000g of cyclohexane, 190g of isoprene and 1.0g of THF, heating to 40 ℃, and then adding 18.0mm 1 of n-butyllithium to react for 30min to form an-IR-segment; and then sequentially adding 100g of styrene and 1.0g of THF into the polymerization kettle D, heating to 50 ℃, and reacting for 30min to form an-IR-PS-chain segment to obtain a fourth block system.

7) Mixing the first block system, the second block system and the third block system with the fourth block system, heating to 80 ℃, adding 220mmo1 of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane for coupling reaction for 140min, then treating the coupled reaction mixture with water, and performing wet condensation and drying on the glue solution to obtain the brominated grafting agent G of the embodiment.

1) Adding 300G of methylene dichloride, 200G of cyclohexane and 25.0G of brominated grafting agent into a 4L stainless steel reaction kettle with a jacket, stirring and dissolving for 70min until the brominated grafting agent is completely dissolved, then cooling to the temperature of minus 80 ℃, sequentially adding 500G of methylene dichloride, 450G of isobutene and 25.0G of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to minus 90 ℃ to obtain a first system;

3) Adding the second system into the first system, stirring and reacting for 5.0h, finally adding 25G of methanol, discharging, condensing, washing and drying to obtain the brominated butyl rubber G of the embodiment.

Example 8

1) Preparation of the coupling agent: as in example 1.

2) Preparation of the first brominating agent: as in example 1.

3) Preparation of the first block System: in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 4 times, sequentially adding 2000g of cyclohexane and 6.0g THF,35.5mmo1 n-butyllithium into the polymerization kettle, heating to 60 ℃, stirring and mixing 710g of styrene and 420g of 1, 3-butadiene for 40min to form a mixed solution, and continuously injecting the mixed solution into the reaction kettle A at an initial feeding speed of 95 g/min within a reaction time of 70min, wherein the feeding speed reduction amplitude is that the feeding speed of the mixture is reduced by 4g per minute, so as to form a-SB/(S- & gtB) -chain segment; and then adding 430g of p-bromomethylstyrene into the polymerization kettle A, heating to 70 ℃, and reacting for 70min to obtain a first block system.

4) Preparation of the second Block System: in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 4 times, sequentially adding 2000g of cyclohexane, 300g of 1, 3-butadiene, heating to 50 ℃,3.0g of THF, then adding 38.0 mmol 1 of n-butyllithium to react for 50min, then adding 430g of isoprene into the polymerization kettle B, heating to 60 ℃, and reacting for 70min to form a-BR-IR-chain segment; and finally, sequentially adding 520g of a first brominating agent into the polymerization kettle B, heating to 70 ℃, and reacting for 120min to obtain a second block system.

5) Preparation of the third Block System: in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 4 times, sequentially adding 2000g of cyclohexane, 320g of 1, 3-butadiene and 3.0g of THF, heating to 50 ℃, and then adding 38.0 mmol 1 of n-butyllithium to react for 50min to form a-BR-chain segment; then sequentially adding 320g of styrene, 200g of 1, 3-butadiene and 4.0g of THF into a polymerization kettle C, heating to 60 ℃, reacting for 70min to form a-BR-SBR-chain segment, finally sequentially adding 310g of a first brominating agent into the polymerization kettle C, heating to 70 ℃, and reacting for 80min to obtain a third block system.

6) Preparation of the fourth Block System: in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 4 times, sequentially adding 2000g of cyclohexane, 330g of isoprene and 3.0g of THF, heating to 50 ℃, and then adding 31.0mm 1 of n-butyllithium to react for 40min to form an-IR-segment; then 200g of styrene, 3.0g of THF are sequentially added into the polymerization kettle D, the temperature is raised to 60 ℃, and the reaction is carried out for 40min, so that an-IR-PS-chain segment is formed, and a fourth block system is obtained.

7) Mixing the first block system, the second block system and the third block system with the fourth block system, heating to 90 ℃, adding 510mmo1 of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane for coupling reaction for 160min, then treating the coupled reaction mixture with water, and carrying out wet condensation and drying on the glue solution to obtain the brominated grafting agent H of the embodiment.

1) Adding 500g of methylene dichloride, 500g of cyclohexane and 40.0g of brominated grafting agent H into a 4L stainless steel reaction kettle with a jacket, stirring and dissolving for 90min until the brominated grafting agent H is completely dissolved, then cooling to the temperature of minus 90 ℃, sequentially adding 1000g of methylene dichloride, 425g of isobutene and 35.0g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to minus 100 ℃ to obtain a first system;

3) Adding the second system into the first system, stirring and reacting for 7.0H, finally adding 45g of methanol, discharging, condensing, washing and drying to obtain the brominated butyl rubber H of the embodiment.

Comparative example 1

The preparation method of the brominated grafting agent a of this comparative example was substantially the same as that of example 1 except that the procedure for the preparation of the first brominating agent was not included, and 1-bromovinylbenzene was used instead of the first brominating agent in example 1.

The preparation method of the brominated butyl rubber a of this comparative example is substantially the same as that of example 1, except that the brominated butyl rubber a of example 1 is replaced with the brominated butyl rubber a.

Comparative example 2

The preparation of the brominated grafting agent b of this comparative example was essentially identical to that of example 2, except that the amount of p-bromomethylstyrene added during the preparation of the first block system was 100g.

The preparation method of the brominated butyl rubber B of this comparative example is substantially the same as that of example 2, except that the brominated butyl rubber B of example 2 is replaced with the brominated butyl rubber B.

Comparative example 3

The preparation of the brominated grafting agent c of this comparative example was identical to that of example 3.

The preparation of the brominated butyl rubber C of this comparative example was substantially identical to that of example 3, except that in the preparation of the first system, the brominated grafting agent C was added in an amount of 10.0g.

Comparative example 4

The preparation of the brominated grafting agent d of this comparative example was essentially identical to that of example 4, except that in the preparation of the first block system, p-bromomethylstyrene was replaced by allyl bromide.

The preparation method of the brominated butyl rubber D of this comparative example is substantially the same as that of example 4, except that the brominated butyl rubber D of example 4 is replaced with the brominated butyl rubber D.

Comparative example 5

The preparation of the brominated grafting agent e of this comparative example is substantially identical to that of example 5, except that no continuous deceleration addition is employed during the preparation of the first block system, and no-SB/(S.fwdarw.B) -segment is formed, in particular the preparation of the first block system: in a 15L stainless steel reaction kettle A with a jacket, introducing argon for replacement for 4 times, sequentially adding 1800g of cyclohexane, 5.0g of THF, 660g of styrene and 380g of 1, 3-butadiene into the polymerization kettle, heating to 58 ℃, and then adding 36.5mm 1 of n-butyllithium for reaction for 70min to form a-SBR-chain segment; then adding 380g of p-bromomethylstyrene into the polymerization kettle A, heating to 68 ℃, and reacting for 65min to obtain a first block system.

The preparation method of the brominated butyl rubber E of this comparative example is substantially the same as that of example 5, except that the brominated butyl rubber E of example 5 is replaced with brominated butyl rubber E.

Comparative example 6

The preparation of the brominated grafting agent f of this comparative example was essentially identical to example 6, except that the preparation of the coupling agent was excluded and the reaction conditions at step 7) were: mixing the first block system, the second block system and the third block system with the fourth block system, heating to 90 ℃ and mixing for 160min, and carrying out wet condensation and drying on the glue solution to prepare the brominated grafting agent f of the comparative example.

The preparation method of the brominated butyl rubber F of this comparative example is substantially the same as that of example 6, except that the brominated butyl rubber F in example 6 is replaced with the brominated butyl rubber F.

Test examples

1. The following parameters were examined in the brominated grafting agent in the above examples and comparative examples, and the specific results are shown in Table 1.

The mass percent of bromine is as follows: the detection method comprises the following steps: 10mg of the sample is weighed, and the sample is thermally degraded in a nitrogen atmosphere with the flow rate of 50mL/min by adopting a Q600 type TG/DTG thermogravimetric analyzer and the heating rate of 10 ℃/min. The first stage of thermal degradation is to remove bromine from a bromine-containing unit of a sample to form HBr, and then reversely calculate the bromine content (X) in the sample by the percentage of the removed HBr, wherein the calculation formula is as follows:

wherein Y: the percentage of the sample at 220 ℃;79.904: bromine element relative atomic mass; 1.008: hydrogen element relative to atomic mass.

Molecular weight and distribution thereof: measured by using a 2414 Gel Permeation Chromatograph (GPC) manufactured by Waters corporation of the United states.

The polystyrene standard sample is used as a calibration curve, the mobile phase is tetrahydrofuran, the column temperature is 40 ℃, the sample concentration is 1mg/ml, the sample injection amount is 50 mu L, the elution time is 40min, and the flow rate is 1 ml.min ^-1 。

TABLE 1

	Bromine mass percent%	Number average molecular weight/molecular weight distribution
			Example 1	12.2％	111000/19.05
Example 2	13.8％	113000/19.37
			Example 3	14.2％	115000/19.61
Example 4	15.3％	117000/19.85
			Example 5	16.1％	119000/20.15
Example 6	16.9％	120000/20.32
			Example 7	12.1％	107000/18.26
Example 8	16.8％	131000/20.78
			Comparative example 1	8.6％	85000/15.05
Comparative example 2	10.4％	101000/17.36
			Comparative example 3	14.2％	115000/19.61
Comparative example 4	11.8％	91000/15.78
			Comparative example 5	16.1％	117000/13.15
Comparative example 6	16.3％	102000/6.32

As can be seen from Table 1, the preparation method provided by the invention can prepare the brominated grafting agent shown in the formula 1 with the bromine content not less than 12 wt%.

2. The brominated butyl rubber in the above examples and comparative examples was sampled and tested after preparing standard samples according to the test requirements of the following relevant parameters, and the results are shown in table 2.

The mass percent of bromine is as follows: the method is the same as above.

Mooney viscosity: the measurement was carried out by using a GT-7080-S2 Mooney viscometer produced by high-speed rail company in Taiwan area. The Mooney relaxation time was 120s as determined with the large rotor under 125℃1+8 conditions with reference to GB/T1232.1-2000.

Vulcanization characteristics: according to GB/T16584-1996. Wherein T is ₁₀ To reflect the scorch safety window size, T ₉₀ The positive vulcanization time reflects the vulcanization speed.

Air tightness: an automatic air tightness tester is adopted to measure the air permeability number according to ISO 2782:1995, and the test gas is N ₂ The test temperature is 23 ℃, the test sample piece is an 8cm diameter circular sea piece, and the thickness is 1mm.

Die swell ratio: RH2000 capillary rheometer manufactured by Markov company in England was used at a temperature of 100℃and an aspect ratio of 16:1 and a shear rate of 10-1000S ^-1 Is measured in the interval of (2).

Tensile strength: refer to GB/T528-2009.

TABLE 2

As can be seen from Table 2, the brominated grafting agent of the present invention contributes to the realization of efficient modification of butyl rubber, so that the modified brominated butyl rubber has high bromine content and low Mooney viscosity, and exhibits excellent vulcanization processing characteristics, dimensional stability, mechanical properties and air tightness.

Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims

1. A brominated grafting agent, characterized in that the brominated grafting agent has a structure represented by formula 1:

2. The brominated grafting agent of claim 1, wherein the brominated grafting agent has a number average molecular weight of 110000 ～ 120000 and a molecular weight distribution of 19.05 to 20.32.

3. The brominated grafting agent of claim 1 or 2, wherein the brominated grafting agent is prepared by a process comprising:

4. A brominated grafting agent as claimed in claim 3, characterized in that,

in the preparation of the first brominating agent, the mass ratio of the brominating agent to the 2-bromovinylbenzene, the molecular weight regulator, the first initiator and the 1, 3-butadiene is 1:1: (0.002-0.005): (0.0005-0.005): (0.01-0.05); and/or the number of the groups of groups,

in the preparation of the fourth block system, the mass ratio of the brominating agent to the isoprene, the fifth structure regulator, the styrene and the sixth structure regulator is 1: (0.2-0.3): (0.001-0.003): (0.2-0.3): (0.001-0.003);

The brominating agent comprises, by mass, 30-40% of p-bromomethylstyrene in the preparation of the first block system, 40-50% of the first brominating agent in the preparation of the second block system, and 20-30% of the first brominating agent in the preparation of the third block system.

5. The brominated grafting agent of claim 3 or 4, wherein the molar ratio of the coupling agent 1, 5-dihalo-3, 3-bis (2-haloethyl) pentane to the polymerization initiator is (2-4): 1;

the polymerization initiator is composed of the second initiator, the third initiator, the fourth initiator and the fifth initiator.

6. The preparation method of the brominated grafting agent is characterized by comprising the following steps:

The brominated grafting agent has a structure shown in a formula 1,

7. A brominated butyl rubber obtained by polymerizing a brominated grafting agent as defined in any one of claims 1 to 5 or a brominated grafting agent prepared as defined in claim 6 with a system comprising isobutylene and isoprene;

8. The brominated butyl rubber of claim 7, wherein the brominated butyl rubber is prepared by a process comprising:

Mixing a second diluent and a co-initiator at the temperature of minus 95 ℃ to minus 85 ℃ and aging for 20 min to 30min, adding an aging system into the first system to react for 5 h to 7h, and stopping the reaction to obtain the brominated butyl rubber.

9. The brominated butyl rubber of claim 8 wherein the mass ratio of the brominated grafting agent to the isoprene, the isobutylene, the first diluent, the second diluent, the co-initiator is (5-8): (5-7): (85-90): (100-200): (10-20): (0.2-0.5).

10. A rubber article, wherein said rubber article is processed from the brominated butyl rubber of any one of claims 7-9.