CN114478953A - Preparation method of three-arm comb-shaped star-branched butyl rubber - Google Patents

Preparation method of three-arm comb-shaped star-branched butyl rubber Download PDF

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CN114478953A
CN114478953A CN202011264546.XA CN202011264546A CN114478953A CN 114478953 A CN114478953 A CN 114478953A CN 202011264546 A CN202011264546 A CN 202011264546A CN 114478953 A CN114478953 A CN 114478953A
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butyl rubber
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CN114478953B (en
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徐典宏
牛承祥
赵燕
魏绪玲
孟令坤
朱晶
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Petrochina Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
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Abstract

The invention provides a preparation method of three-arm comb-shaped star-branched butyl rubber. The invention takes isoprene, styrene and butadiene as reaction monomers, and couples star copolymer [ -SBR-IR-]nPh, followed by [ SBR-IR-]nPh and divinyl benzene (DVB) to prepare three-arm comb-shaped star nucleating agent [ - (DVB) SBR- (DVB) IR-]nPh, finally, carrying out cationic polymerization on the three-arm star-shaped nucleating agent, isobutene and isoprene by adopting a first-arm last-core method under a Lewis acid and protonic acid compounded catalytic system to prepare the three-arm comb-shaped star-shaped branched butyl rubber. The invention effectively solves the problem ofThe strength and the air tightness are reduced due to the broadening of the molecular weight distribution of the base rubber, the balance between the processability and the physical properties of the butyl rubber is realized, and the performance of the butyl rubber is comprehensively improved.

Description

Preparation method of three-arm comb-shaped star-branched butyl rubber
Technical Field
The invention relates to a preparation method of three-arm comb-shaped star-branched butyl rubber, in particular to a method for preparing the three-arm comb-shaped star-branched butyl rubber by using an isoprene/butadiene/styrene/Divinylbenzene (DVB) quaternary three-arm nucleating agent.
Background
It is known that Butyl Rubber (IIR) is produced by the cationic polymerization of isobutylene and a small amount of isoprene. Butyl rubber has been commercialized by Exxon corporation in the 40 th century for over seventy years since now, and has excellent properties such as airtightness, damping properties, thermal aging resistance, ozone resistance, and weather resistance, and thus it is widely used in the fields of manufacturing inner tubes, airtight layers, curing bladders, medical stoppers of tires for vehicles, and the like, and is one of the most important synthetic rubber products.
However, the molecular chain of the butyl rubber is mainly composed of carbon-carbon single bonds, the number of double bonds is small, and the substituent methyl groups are symmetrically arranged, so that the defects of high crystallinity, poor flexibility of the molecular chain, low stress relaxation rate, low vulcanization speed, poor adhesiveness, poor compatibility with other general rubbers and the like exist, and the butyl rubber is easy to excessively flow and deform in the processing process. Therefore, how to balance the physical and mechanical properties and the processability of the butyl rubber becomes a bottleneck for preparing high-performance butyl rubber materials.
In recent years, researchers find that star-shaped branched butyl rubber which is composed of a high-molecular-weight graft structure and a low-molecular-weight linear structure and has a unique three-dimensional net structure has excellent viscoelastic performance, high crude rubber strength and a fast stress relaxation rate, low melt viscosity can be kept in a processing process, a high-molecular-weight polymer can be obtained, and balance and unification of physical and mechanical properties and processing properties are realized. Therefore, the star-branched structure has become one of the hot spots in the research field of future butyl rubber.
In the prior art, the synthesis of star-branched butyl rubber mainly adopts a first nucleusThe posterior arm method, the first arm and the nucleus method and the simultaneous nucleus and arm method. Such as: US5395885 discloses a star-branched polyisobutylene-polydivinylbenzene polymer, which is synthesized by taking polyisobutylene as an arm, Polydivinylbenzene (PDVB) as a core, a complex of aluminium chloride and water as an initiator, and methyl chloride as a diluent through a first-arm-second-core method at-90 to-100 ℃. CN88108392.5 discloses a star-shaped grafted butyl rubber with a comb-shaped structure, which is prepared by using a hydrochloric acid polystyrene-isoprene copolymer as a multifunctional initiator or using polystyrene-butadiene or polystyrene-isoprene as a grafting agent. CN101353403B discloses a preparation method of star-branched polyisobutylene or butyl rubber, which adopts a polystyrene/isoprene block copolymer with a silicon-chlorine group at the terminal or a polystyrene/butadiene block copolymer with a silicon-chlorine group at the terminal as a grafting initiating agent for positive ion polymerization, directly participates in the positive ion polymerization in a positive ion polymerization system of a mixed solvent with a ratio of methane chloride to cyclohexane v: v of 20-80/80-20 at the temperature of 0-100 ℃, and prepares a star-branched polyisobutylene or butyl rubber product by the participation of an unsaturated chain in a grafting reaction through the initiated positive ion polymerization of the silicon-chlorine group. CN01817708.5 provides a method of making star-branched polymers by adding a multiolefin cross-linking agent, such as divinylbenzene, and a chain transfer agent, such as 2,4, 1-trimethyl-1-pentene, to a mixture of isoolefin monomers and diolefin monomers. CN107793535A provides a butyl rubber having a molecular weight of 90 to 260 ten thousand, Log (MW)>And contains structural units derived from isobutylene, structural units derived from a conjugated diene, and optionally structural units derived from an aryl olefin. CN200710129810.7 provides a method of synthesizing linear butyl rubber by a first arm and then core method, and then coupling the linear butyl rubber by divinylbenzene to obtain star-shaped branched butyl rubber. Puskas and the like adopt trimesic acid as raw materials to synthesize an initiator tricumyl alcohol with a three-arm structure, and then adopt a tricumyl alcohol/aluminum trichloride initiation system to initiate isobutylene and isoprene copolymerization in an inert organic solvent under the condition of-120 to-50 ℃ to synthesize star-branched butadiene with bimodal molecular weight distributionBase rubber (Catalysts for manufacturing of IIR with biomodal molecular weight distribution: US, 5194538[ P].1993-3-16.). Wieland et al successfully prepared a multi-arm star butyl rubber (J-styrene polymerization) by synthesizing a macroinitiator P (MMA-b-St-co-CMS) containing a ternary system of 4-chloromethylstyrene, styrene and methyl methacrylate in the presence of 1, 2-Diphenylethylene (DPE) and then initiating cationic polymerization of isobutylene and isoprene using the macroinitiator]Polymer Science: polymer Chemistry, 2002, 40: 3725-3733.). Hadjichhritidis et al uses CH3SiCl3Synthesis of PI-PS-PBd three-arm copolymer (Iatrou H, Hadjichristis N.Synthesis of a model 3-miktoarm star polymer [ J ] by strictly controlling the order of addition of the monomers and overranging fractional three-step coupling of coupling agents]Macromolecules,1992,25: 4649). Hadjchrismatisds adopts high vacuum technology to obtain styrene polybutadiene macromonomer through the reaction of active polybutadiene lithium and silicon chloride group of p-chlorodimethylsilylstyrene, the macromonomer is copolymerized with butadiene in the presence of random regulator to obtain active Comb polybutadiene, and finally reacted with methyl silicon trichloride or silicon tetrachloride to obtain 3-arm or 4-arm Star-shaped Comb polybutadiene (KOUTALAS G, IATROU H, LOHSE D J, et. well-Defined Comb, Star-Comb, and Comb-on-Comb polydienes by Anionic Polymerization and the macromolecular branching [ J]Macromolecules,2005,38(12): 4996-. Gong Hui Qin et al synthesized a star-branched polymer (preparation and characterization of star-branched polyisobutylene with divinylbenzene as core; 2008, 31(5):362 and 365.) with divinylbenzene as core and polyisobutylene as arm at-80 deg.C by using 2-chloro-2, 4, 4-trimethylpentane/titanium tetrachloride as initiator system and monochloromethane/cyclohexane as solvent and using active cationic polymerization.
Disclosure of Invention
The invention aims to provide a preparation method of three-arm comb-shaped star-branched butyl rubber. The method comprises the steps of firstly taking alkyl lithium as an initiator, taking hydrocarbons as a solvent, adding a reaction monomer consisting of isoprene, styrene and butadiene into a polymerization system twice in a fixed sequence to synthesize a [ -IR-SBR- ] n linear chain segment, then adding a coupling agent trihalogenated benzene for coupling to prepare a star copolymer [ -SBR-IR- ] nPh with a ternary three-arm structure and an unsaturated double bond structure, then sequentially adding the solvent, Divinylbenzene (DVB) and the initiator to polymerize a three-arm star nucleating agent, and finally carrying out cationic polymerization on isobutene and isoprene serving as the reaction monomer and the three-arm star nucleating agent by adopting a first-arm last-core method under a catalytic system compounded by Lewis acid and protonic acid to prepare the three-arm comb star branched butyl rubber. The three-arm comb-shaped star-branched butyl rubber not only effectively solves the problem that the stress relaxation rate of the butyl rubber is low in the processing process, but also keeps the sufficient crude rubber strength and good air tightness of the butyl rubber, and realizes the balance of the physical and mechanical properties and the processing property of the butyl rubber.
All the percentages in the present invention are percentages by mass.
The preparation of the three-arm comb-shaped star-branched butyl rubber is carried out in a reaction kettle, and the specific preparation process comprises the following steps:
(1) preparation of three-arm star nucleating agent: according to the total mass parts of reaction monomers, firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2-4 times, sequentially adding 100-200% of solvent, 20-40% of isoprene, 0.05-0.5% of structure regulator and initiator into the polymerization kettle, heating to 40-55 ℃, reacting for 30-60 min, and enabling the conversion rate of the isoprene monomer to reach 100%; then sequentially adding 100-200% of solvent and 0.05-0.5% of structure regulator into a polymerization kettle, heating to 60-75 ℃, stirring and mixing 45-60% of styrene and 20-35% of 1, 3-butadiene for 10-20 min, adding into the polymerization kettle together, and reacting for 50-70 min to form an-IR-SBR-chain segment; heating to 80-90 ℃, adding a coupling agent for coupling reaction for 60-80 min, and after the reaction is finished, sequentially adding 100-200% of solvent, 2-6% of Divinylbenzene (DVB) and 0.001% of catalyst into a polymerization kettle0.1 percent, heating to 70 to 80 ℃, reacting for 40 to 60min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to prepare the nucleating agent (DVB) SBR (DVB) IR-]n Ph)。
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: according to the total mass parts of reaction monomers, firstly introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3-5 times, and sequentially adding 200-300% of diluent/solvent V into the polymerization kettle: mixing a solvent mixture with a V ratio of 60-40/40-60, 94-98% of isobutene and 2-6% of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-100 to-90 ℃, then adding 40-60% of a diluent and 0.05-3.0% of a co-initiator into the polymerization system for mixing and aging for 30-40 min under the condition of-95 to-85 ℃, stirring and reacting for 0.5-1.0 hr, then mixing and dissolving 30-60% of the solvent and 0.5-1.5% of a nucleating agent with a three-arm star structure obtained in the step (1) for 2.0-3.0 hr, aging for 30-50 min under the condition of-95 to-85 ℃, adding the solvent and the nucleating agent into the polymerization system for stirring and reacting for 2.0-5.0 hr, finally adding a terminator for discharging and coagulating, washing and drying to obtain the three-arm comb-like star-branched butyl rubber product.
The nucleating agent is a quaternary three-arm star-shaped polymer containing isoprene, butadiene, styrene and divinylbenzene, and has a structural general formula shown in formula I:
Figure BDA0002773984250000041
wherein, the IR is an isoprene homopolymer block, the 1, 2-structure content of the block is 12 to 17 percent, and the 3, 4-structure content of the block is 5 to 10 percent; the SBR is a styrene and 1, 3-butadiene random block copolymer, wherein the content of the styrene is 40-60 percent, and the content of the 1, 3-butadiene is 20-34 percent; the content of polyisoprene blocks in the quaternary three-arm star polymer is 20-40%, and the content of polybutadiene and styrene blocks in the quaternary three-arm star polymer is 60-74%; the number average molecular weight (Mn) of the quaternary three-arm star polymer is 20000-50000, and the molecular weight distribution (Mw/Mn) is 2.85-4.71.
The coupling agent is one of 1,3, 5-trichlorobenzene and 1,3, 5-tribromobenzene, and preferably 1,3, 5-trichlorobenzene. The amount of the coupling agent is determined according to the amount of the initiator, and the molar ratio of the amount of the coupling agent to the organic lithium is 1.0-3.0.
The initiator is an alkyl monolithium compound, namely RLi, wherein R is a saturated aliphatic alkyl, alicyclic alkyl, aromatic alkyl containing 1-20 carbon atoms or a composite group of the above groups. The alkyl monolithium compound is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium and dodecyllithium, preferably n-butyllithium.
The catalyst of the invention is an organic peroxide selected from one of dicumyl peroxide, cumyl hydroperoxide, dibenzoyl peroxide and di-tert-butyl peroxide, preferably dibenzoyl peroxide (BPO).
The structure regulator of the invention is a polar organic compound which generates solvation effect in a polymerization system and can regulate the reactivity ratio of styrene and butadiene so as to ensure that the styrene and the butadiene are randomly copolymerized. Such polar organic compound is selected from one of diethylene glycol dimethyl ether (2G), Tetrahydrofuran (THF), diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME), triethylamine, preferably Tetrahydrofuran (THF).
The co-initiator is prepared by compounding alkyl aluminum halide and protonic acid according to different proportions. The alkyl aluminum halide is at least one selected from the group consisting of diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloroide, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, n-propylaluminum dichloride, isopropylaluminum dichloroide, dimethylaluminum chloride and ethylaluminum chloride, preferably ethylaluminum sesquichloride. The protonic acid is selected from HCl, HF, HBr, H2SO4、H2CO3、H3PO4And HNO3Of (1), preferably HCl. Wherein the total addition amount of the coinitiator is 0.03-2.5%, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.05: 1-0.2: 1.
The diluent of the present invention isHalogenated alkanes, wherein the halogen atom in the halogenated alkane can be chlorine, bromine, or fluorine; the number of carbon atoms in the halogenated alkane being C1～C4. The alkyl halide is selected from one of methyl chloride, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, preferably methyl chloride.
The terminator provided by the invention can be selected from one or more of methanol, ethanol and butanol.
The polymerization reaction of the present invention is carried out in an oxygen-free, water-free, preferably inert gas atmosphere. The polymerization and dissolution are carried out in a hydrocarbon solvent, which is a hydrocarbon solvent including straight-chain alkanes, aromatic hydrocarbons and cycloalkanes, and is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably cyclohexane.
The invention firstly adopts lithium alkyl as an initiator, hydrocarbons as a solvent, organic matters with certain polarity as a structure regulator, reaction monomers comprise isoprene, styrene, butadiene and divinylbenzene, the initiator is added once, the reaction monomers are added into a polymerization system in a fixed sequence twice, and then the copolymer [ -SBR-IR-]nPh, then adding divinylbenzene and the catalyst again to prepare the nucleating agent with the reactive three-arm star structure [ - (DVB) SBR- (DVB) IR-]nPh. Finally, under a catalytic system compounded by alkyl aluminum halide and protonic acid, isobutene and isoprene are subjected to cationic polymerization to obtain a butyl rubber chain segment, and then a nucleating agent with a three-arm star-shaped structure is added to prepare the three-arm comb-shaped star-branched butyl rubber. The butyl rubber prepared by the three-arm star nucleating agent designed by the invention contains a three-arm comb star structure, and the structure can effectively widen the molecular weight distribution of the whole butyl rubber macromolecule properly without destroying the molecular chain regularity of a single isobutylene and isoprene copolymer, improve the flexibility of a chain segment, and obtain a faster stress relaxation speedRate; in addition, the-IR-and-SBR-chain segments in the nucleating agent contain a certain amount of vinyl and benzene rings, the flexibility of the chain segments can be improved by the vinyl, and the benzene rings can obtain high strength and barrier property. Therefore, the invention organically combines the characteristics of the three-arm comb-shaped star structure and the performances of various chain segments and takes a synergistic effect, the synergistic effect solves the problems of slow stress relaxation and poor viscoelasticity of the butyl rubber in the processing process and the problems of strength and air tightness reduction caused by broadening of the molecular weight distribution of the butyl rubber, realizes the balance of the processability and the physical performance of the butyl rubber, and leads the performance of the butyl rubber to be more comprehensively improved. The preparation method of the three-arm comb-shaped star-branched butyl rubber provided by the invention has the characteristics of short process flow, controllable molecular weight, good product processing performance, suitability for industrial production and the like.
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FIG. 1 is 1#Comparative example 1 sample and 2#Comparison of the GPC spectra of the samples of example 1.
Detailed Description
The following examples and comparative examples are given to illustrate the effects of the present invention, but the scope of the present invention is not limited to these examples and comparative examples. All the raw materials used in the examples are of industrial polymerization grade, and are used after purification without other special requirements.
Firstly, raw material sources:
styrene, butadiene, Polymer grade, Petroleum Lanzhou petrochemical Co Ltd
Isobutene, isoprene, Polymer grade Zhejiang Credit New materials Co Ltd
Divinylbenzene (DVB), analytically pure Aladdin GmbH
N-butyl lithium, 98% purity Nanjing Tongtiang chemical Co., Ltd
Dibenzoyl peroxide (BPO), Lanzhou auxiliary plant
Chemical Co., Ltd of Yangzhou Haichen with a purity of 99% for 1,3, 5-trichlorobenzene
Chemical Co., Ltd of Yangzhou Haichen with a purity of 99% for 1,3, 5-tribromobenzene
Aluminum sesquiethylate chloride, 98% pure Profenor technologies Ltd
Other reagents are all commercial products
The method comprises the following steps:
determination of the molecular weights and their distribution: the measurement was carried out by using 2414 Gel Permeation Chromatograph (GPC) manufactured by Waters corporation, USA. Taking polystyrene standard sample as calibration curve, tetrahydrofuran as mobile phase, column temperature of 40 deg.C, sample concentration of 1mg/ml, sample amount of 50 μ L, elution time of 40min, and flow rate of 1 ml/min-1。
Determination of Mooney viscosity and stress relaxation: adopts the model GT-7080-S2 Menni produced by Taiwan high-speed railway company
And (5) measuring by a viscometer. The Mooney relaxation time, determined with a large rotor at 125 ℃ C (1+8) according to the method of GB/T1232.1-2000, is 120 s.
Measurement of airtightness: the air permeability was determined using an automated air tightness tester according to ISO 2782:1995,
test gas is N2The test temperature is 23 ℃, the test sample is a circular sea sheet with the diameter of 8cm and the thickness is 1 mm.
Tensile strength: the method in standard GB/T528-2009 is executed.
Example 1
(1) Preparation of three-arm star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 1010g of cyclohexane, 200g of isoprene, 0.5g of THF and 14.3mmo1 n-butyllithium into the polymerization kettle, heating to 40 ℃, and reacting for 30min to form an IR chain segment; then 1120g of cyclohexane and 1.6g of THF are sequentially added into a polymerization kettle, the temperature is raised to 60 ℃, 450g of styrene and 200g of 1, 3-butadiene are stirred and mixed for 10min, and then are added into the polymerization kettle together for reaction for 50min to form an-IR-SBR-chain segment; then heating to 80 ℃, adding 8.5mmo11,3, 5-benzene trichloride, reacting for 60min to form [ -SBR-IR-]nPh; after the reaction is finished, 1010g of cyclohexane, 20g of DVB and 0.03g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 70 ℃, after the reaction is carried out for 40min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) IR-]nPh (Mn 22050, Mw/Mn 2.85).
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 240g of methane chloride, 360g of cyclohexane, 264g of isobutene and 6g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 120g of methane chloride, 1.7g of aluminum sesquiethylate chloride and 0.05g of HCl at-85 ℃, aging for 30min, adding the mixture into the polymerization system together, stirring and reacting for 0.5hr, and then adding 90g of cyclohexane, 1.5g of [ - (DVB) SBR- (DVB) IR-]nPh, stirring and dissolving for 2.0hr until the grafting agent is completely dissolved, then aging for 30min at-85 ℃, adding the materials into a polymerization system, stirring and reacting for 2.0hr, adding 100mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard specimens were prepared and the test properties are shown in Table 1.
Example 2
(1) Preparation of three-arm star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 1140g of cyclohexane, 230g of isoprene, 1.2g of THF and 15.2mmo1 n-butyllithium into the polymerization kettle, heating to 42 ℃, and reacting for 35min to form an IR chain segment; then, 1250g of cyclohexane and 1.9g of THF are sequentially added into a polymerization kettle, the temperature is raised to 63 ℃, 480g of styrene and 220g of 1, 3-butadiene are stirred and mixed for 12min, then the mixture is added into the polymerization kettle together, and the reaction is carried out for 54min, so as to form an-IR-SBR-chain segment; then heating to 82 ℃, adding 10.1mmo11,3, 5-benzene trichloride, reacting for 65min to form [ -SBR-IR-]nPh; after the reaction is finished, 1050g of cyclohexane, 27g of DVB and 0.09g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 72 ℃, after the reaction is carried out for 43min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) IR-]nPh (Mn 23050, Mw/Mn 2.92).
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: firstly, nitrogen gas is introduced into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, and 280g of methane chloride, 340g of cyclohexane, 270g of isobutene and 10g of isoprene are sequentially added into a polymerization kettleStirring and mixing diene until the temperature of a polymerization system is reduced to-90 ℃, then mixing 130g of methane chloride, 2.3g of aluminum sesquiethyl chloride and 0.09g of HCl at-85 ℃, aging for 32min, adding the mixture into the polymerization system, stirring and reacting for 0.6hr, then adding 100g of cyclohexane, 2.2g of [ - (DVB) SBR- (DVB) IR-]nPh, stirring and dissolving for 2.2hr until the grafting agent is completely dissolved, then aging for 35min at-87 ℃, adding the materials into a polymerization system together, stirring and reacting for 2.5hr, adding 120mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 3
(1) Preparation of three-arm star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 1220g of cyclohexane, 270g of isoprene, 1.7g of THF and 17.9mmo1 n-butyllithium into the polymerization kettle, heating to 45 ℃, and reacting for 40min to form an IR chain segment; then 1310g of cyclohexane and 2.1g of THF are sequentially added into the polymerization kettle, the temperature is raised to 65 ℃, 500g of styrene and 260g of 1, 3-butadiene are stirred and mixed for 13min, then the mixture is added into the polymerization kettle, and the reaction lasts 57min, so that a-IR-SBR-chain segment is formed; then heating to 83 ℃, adding 12.1mmo11,3, 5-benzene trichloride, reacting for 68min to form [ -SBR-IR-]nPh; after the reaction is finished, 1150g of cyclohexane, 32g of DVB and 0.11g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, after the reaction is carried out for 49min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) IR-]nPh (Mn 26050, Mw/Mn 3.26).
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 300g of methane chloride, 330g of cyclohexane, 275g of isobutene and 15g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-92 ℃, then mixing 140g of methane chloride, 2.8g of aluminum sesquiethylate chloride and 0.12g of HCl at-87 ℃, aging for 35min, adding into the polymerization system together, stirring and reacting for 0.7hr, and then adding 110g of cyclohexane, 2.7g of [ - (DVB) SBR- (DVB) IR-]nPh, stirring to dissolve for 2.4hr until the grafting agent is completely dissolved, then aging at-89 ℃ for 38min, adding into the polymerization system together, stirring to react for 3.0hr, adding 130mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 4
(1) Preparation of three-arm star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 1350g of cyclohexane, 300g of isoprene, 2.1g of THF and 18.7mmo1 n-butyllithium into the polymerization kettle, heating to 47 ℃, and reacting for 45min to form an IR chain segment; then adding 1390g of cyclohexane and 2.7g of THF into the polymerization kettle in sequence, heating to 69 ℃, stirring and mixing 530g of styrene and 290g of 1, 3-butadiene for 15min, adding into the polymerization kettle together, and reacting for 61min to form an-IR-SBR-chain segment; then heating to 85 deg.C, adding 14.2mmo11,3, 5-benzene trichloride, reacting for 72min to form [ -SBR-IR-]nPh; after the reaction is finished, 1260g of cyclohexane, 40g of DVB and 0.23g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 76 ℃, after the reaction is carried out for 51min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) IR-]nPh (Mn 29100, Mw/Mn 3.86).
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing 4 times, sequentially adding 330g of methane chloride, 310g of cyclohexane, 280g of isobutene and 20g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then mixing 150g of methane chloride, 3.1g of aluminum sesquiethylate chloride and 0.23g of HCl at-88 ℃, aging for 37min, adding into the polymerization system together, stirring and reacting for 0.8hr, and then adding 130g of cyclohexane, 3.0g of [ - (DVB) SBR- (DVB) IR-]nPh, stirring and dissolving for 2.6hr until the grafting agent is completely dissolved, then aging at-90 ℃ for 40min, adding into the polymerization system together, stirring and reacting for 4.0hr, adding 140mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: system for makingThe test performance of the standard sample is shown in Table 1.
Example 5
(1) Preparation of three-arm star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacing 4 times, sequentially adding 1410g of cyclohexane, 330g of isoprene, 2.5g of THF and 19.6mmo1 n-butyllithium into the polymerization kettle, heating to 50 ℃, and reacting for 50min to form an IR chain segment; then, 1420g of cyclohexane and 3.1g of THF are sequentially added into a polymerization kettle, the temperature is raised to 71 ℃, 550g of styrene and 310g of 1, 3-butadiene are stirred and mixed for 17min, then the mixture is added into the polymerization kettle, and the reaction is carried out for 67min, so as to form an-IR-SBR-chain segment; then the temperature is raised to 87 ℃, 16.5mmo11,3, 5-benzene trichloride is added to react for 75min to form [ -SBR-IR-]nPh; after the reaction is finished, 1310g of cyclohexane, 45g of DVB and 0.42g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 77 ℃, after 54min of reaction, the glue solution is coagulated and dried by a wet method to prepare the nucleating agent [ - (DVB) SBR- (DVB) IR-]nPh (Mn 34000, Mw/Mn 4.06).
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing 4 times, adding 310g of methane chloride, 330g of cyclohexane, 286g of isobutene and 25g of isoprene into the polymerization kettle in sequence, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then adding 160g of methane chloride, 3.8g of aluminum sesquiethylate chloride and 0.29g of HCl into the polymerization system after mixing at-88 ℃ and aging for 38min, stirring and reacting for 0.8hr, and then adding 140g of cyclohexane, 3.5g of [ - (DVB) SBR- (DVB) IR-]nPh, stirring to dissolve for 2.8hr until the grafting agent is completely dissolved, aging at-92 ℃ for 43min, adding into the polymerization system, stirring to react for 4.2hr, adding 150mL of methanol to terminate the reaction, discharging, condensing, washing, and drying to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard specimens were prepared and the test properties are shown in Table 1.
Example 6
(1) Preparation of three-arm star nucleating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 4 times, and adding 1520g of cyclohexane and 370g of isoprene into the polymerization kettle in sequenceDiene, 3.4g THF, 21.5mmo1 n-butyllithium, heating to 52 ℃, reacting for 55min to form IR chain segment; then, 1510g of cyclohexane and 3.9g of THF are sequentially added into the polymerization kettle, the temperature is raised to 73 ℃, 570g of styrene and 330g of 1, 3-butadiene are stirred and mixed for 19min, then the mixture is added into the polymerization kettle, and the reaction is carried out for 68min, so as to form an-IR-SBR-chain segment; then heating to 88 ℃, adding 17.9mmo11,3, 5-benzene trichloride, reacting for 78min to form [ -SBR-IR-]nPh; after the reaction is finished, 1430g of cyclohexane, 51g of DVB and 0.51g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 79 ℃, after the reaction is carried out for 58min, the glue solution is coagulated and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) IR-]nPh (Mn 39000, Mw/Mn 4.35).
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing 4 times, adding 300g of methane chloride, 350g of cyclohexane, 290g of isobutene and 30g of isoprene into the polymerization kettle in sequence, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then adding 170g of methane chloride, 4.2g of aluminum sesquiethylate chloride and 0.35g of HCl into the polymerization system after mixing at-89 ℃, aging for 40min, stirring and reacting for 0.9hr, and then adding 145g of cyclohexane, 4.1g of [ - (DVB) SBR- (DVB) IR-]nPh, stirring and dissolving for 2.9hr until the grafting agent is completely dissolved, then aging for 47min at-95 ℃, adding the materials into a polymerization system together, stirring and reacting for 4.6hr, adding 160mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 7
(1) Preparation of three-arm star nucleating agent: firstly, introducing argon to a 15L stainless steel reaction kettle with a jacket for replacing for 4 times, sequentially adding 1650g of cyclohexane, 400g of isoprene, 3.9g of THF and 23.5mmo1 n-butyl lithium into the polymerization kettle, heating to 55 ℃, and reacting for 60min to form an IR chain segment; then 1610g of cyclohexane and 4.3g of THF are added into the polymerization kettle in sequence, the temperature is raised to 75 ℃, 600g of styrene and 350g of 1, 3-butadiene are stirred and mixed for 20min and then are added into the polymerization kettle together for reaction for 70min to form-IR-SBR-segments; then heating to 90 ℃, adding 20.5mmo11,3, 5-tribromobenzene, reacting for 80min to form [ -SBR-IR-]nPh; after the reaction is finished, 1500g of cyclohexane, 60g of DVB and 0.65g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 80 ℃, after the reaction is carried out for 60min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) IR-]nPh (Mn 45000, Mw/Mn 4.71).
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, sequentially adding 280g of methane chloride, 370g of cyclohexane, 296g of isobutene and 36g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-100 ℃, then adding 180g of methane chloride, 4.8g of sesquiethylaluminum chloride and 0.41g of HCl into the polymerization system after mixing at-90 ℃ and aging for 40min, stirring and reacting for 1.0hr, then adding 150g of cyclohexane, 4.5g of [ - (DVB) SBR- (DVB) IR-]nPh, stirring to dissolve for 3.0hr until the grafting agent is completely dissolved, then aging for 50min at-95 ℃, adding the materials into a polymerization system together, stirring to react for 5.0hr, adding 170mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard specimens were prepared and the test properties are shown in Table 1.
Comparative example 1
Preparation of three-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 1 except that: no nucleating agent [ - (DVB) SBR- (DVB) IR-]nPh, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 240g of methane chloride, 360g of cyclohexane, 264g of isobutene and 6g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 120g of methane chloride, 1.7g of aluminum sesquiethylate chloride and 0.05g of HCl at-85 ℃, aging for 30min, adding the mixture into the polymerization system together, stirring and reacting for 0.5hr, adding 100mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain a branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 2
(1) Preparation of three-arm star nucleating agent: the other conditions were the same as in example 2 except that: no coupling agent 1,3, 5-trichlorobenzene was added, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 1140g of cyclohexane, 230g of isoprene, 1.2g of THF and 15.2mmo1 n-butyllithium into the polymerization kettle, heating to 42 ℃, and reacting for 35min to form an IR chain segment; then, 1250g of cyclohexane and 1.9g of THF are sequentially added into a polymerization kettle, the temperature is raised to 63 ℃, 480g of styrene and 220g of 1, 3-butadiene are stirred and mixed for 12min, then the mixture is added into the polymerization kettle together, and the reaction is carried out for 54min, so as to form an-IR-SBR-chain segment; then 1050g cyclohexane, 27g DVB, 0.09g BPO are added into a polymerization kettle in turn, the temperature is raised to 72 ℃, after 43min of reaction, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) IR-]n(Mn 18000 and Mw/Mn 1.92).
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 2 except that: no nucleating agent [ - (DVB) SBR- (DVB) IR-]nPh, but the nucleating agent [ - (DVB) SBR- (DVB) IR-]nNamely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 280g of methane chloride, 340g of cyclohexane, 270g of isobutene and 10g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then adding 130g of methane chloride, 2.3g of aluminum sesquiethylate chloride and 0.09g of HCl into the polymerization system after mixing at-85 ℃ and aging for 32min, stirring and reacting for 0.6hr, and then adding 100g of cyclohexane, 2.2g of [ - (DVB) SBR- (DVB) IR-]nStirring and dissolving for 2.2hr until the grafting agent is completely dissolved, then aging at-87 ℃ for 35min, adding into the polymerization system, stirring and reacting for 2.5hr, adding 120mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain the linear branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 3
(1) Preparation of three-arm star nucleating agent: other conditions were the same as in example 3The difference lies in that: during the synthesis process, 1,3, 5-trichlorobenzene is not added, but methyl silicon trichloride (CH) is added3SiCl3) Namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 1220g of cyclohexane, 270g of isoprene, 1.7g of THF and 17.9mmo1 n-butyllithium into the polymerization kettle, heating to 45 ℃, and reacting for 40min to form an IR chain segment; then 1310g of cyclohexane and 2.1g of THF are sequentially added into the polymerization kettle, the temperature is raised to 65 ℃, 500g of styrene and 260g of 1, 3-butadiene are stirred and mixed for 13min, then the mixture is added into the polymerization kettle, and the reaction lasts 57min, so that a-IR-SBR-chain segment is formed; subsequently, the temperature was raised to 83 ℃ and 12.1mmo1 CH was added3SiCl3Reacting for 68min to form [ -SBR-IR-]nSi CH3(ii) a After the reaction is finished, 1150g of cyclohexane, 32g of DVB and 0.11g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, after the reaction is carried out for 49min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) IR-]n Si CH3(Mn 24000 and Mw/Mn 2.81).
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 3 except that: no nucleating agent [ - (DVB) SBR- (DVB) IR-]nPh, but the nucleating agent [ - (DVB) SBR- (DVB) IR-]n Si CH3Namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 300g of methane chloride, 330g of cyclohexane, 275g of isobutene and 15g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-92 ℃, then mixing 140g of methane chloride, 2.8g of aluminum sesquiethylate chloride and 0.12g of HCl at-87 ℃, aging for 35min, adding into the polymerization system together, stirring and reacting for 0.7hr, and then adding 110g of cyclohexane, 2.7g of [ - (DVB) SBR- (DVB) IR-]n Si CH3Stirring and dissolving for 2.4hr until the grafting agent is completely dissolved, then aging at-89 ℃ for 38min, adding the materials into a polymerization system, stirring and reacting for 3.0hr, adding 130mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 4
Preparation of star-branched butyl rubber: the other conditions were the same as in example 4 except that: no nucleating agent [ - (DVB) SBR- (DVB) IR-]nPh, but the nucleating agent DVB was added, i.e.: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing 4 times, sequentially adding 330g of methane chloride, 310g of cyclohexane, 280g of isobutene and 20g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then mixing 150g of methane chloride, 3.1g of aluminum sesquiethylate chloride and 0.23g of HCl at-88 ℃, aging for 37min, adding into the polymerization system together, stirring and reacting for 0.8hr, then stirring and dissolving 130g of cyclohexane and 3.0g of DVB for 2.6hr until a grafting agent is completely dissolved, aging for 40min at-90 ℃, adding into the polymerization system together, stirring and reacting for 4.0hr, adding 140mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain a three-arm comb-shaped branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 5
(1) Preparation of three-arm star nucleating agent: the other conditions were the same as in example 5 except that: no isoprene was added during the synthesis, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 1410g of cyclohexane, 2.5g of THF and 19.6mmo1 n-butyllithium into the polymerization kettle, heating to 50 ℃, then sequentially adding 1420g of cyclohexane and 3.1g of THF into the polymerization kettle, heating to 71 ℃, stirring and mixing 550g of styrene and 310g of 1, 3-butadiene for 17min, then adding the mixture into the polymerization kettle together, and reacting for 67min to form an SBR-chain segment; then heating to 87 ℃, adding 16.5mmo11,3, 5-benzene trichloride, reacting for 75min to form [ -SBR-]nPh; after the reaction is finished, 1310g of cyclohexane, 45g of DVB and 0.42g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 77 ℃, after 54min of reaction, the glue solution is coagulated and dried by a wet method to prepare the nucleating agent [ - (DVB) SBR-]nPh (Mn 22000, Mw/Mn 3.36).
(2) Preparation of three-arm comb-shaped star-branched butyl rubber:the other conditions were the same as in example 5 except that: no nucleating agent [ - (DVB) SBR- (DVB) IR-]nPh, but the nucleating agent [ - (DVB) SBR-]nPh, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing 4 times, adding 310g of methane chloride, 330g of cyclohexane, 286g of isobutene and 25g of isoprene into the polymerization kettle in sequence, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then mixing 160g of methane chloride, 3.8g of aluminum sesquiethylate chloride and 0.29g of HCl at-88 ℃, aging for 38min, adding into the polymerization system together, stirring and reacting for 0.8hr, then adding 140g of cyclohexane, 3.5g of [ - (DVB) SBR-]nPh, stirring to dissolve for 2.8hr until the grafting agent is completely dissolved, aging at-92 ℃ for 43min, adding into the polymerization system, stirring to react for 4.2hr, adding 150mL of methanol to terminate the reaction, discharging, condensing, washing, and drying to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 6
(1) Preparation of three-arm star nucleating agent: the other conditions were the same as in example 6 except that: styrene and 1, 3-butadiene were not added during the synthesis, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacing 4 times, sequentially adding 1520g of cyclohexane, 370g of isoprene, 3.4g of THF and 21.5mmo1 n-butyllithium into the polymerization kettle, heating to 52 ℃, and reacting for 55min to form an IR chain segment; then heating to 88 ℃, adding 17.9mmo11,3, 5-benzene trichloride, reacting for 78min to form [ -IR-]nPh; after the reaction is finished, 1430g of cyclohexane, 51g of DVB and 0.51g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 79 ℃, after the reaction is carried out for 58min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) IR-]nPh (Mn 23000, Mw/Mn 3.32).
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 6 except that: no nucleating agent [ - (DVB) SBR- (DVB) IR-]nPh, but the addition of a nucleating agent [ - (DVB) IR-]nPh, namely: firstly, 4L stainless steel with a jacket is usedIntroducing nitrogen into the reactor for 4 times of replacement, adding 300g of methane chloride, 350g of cyclohexane, 290g of isobutene and 30g of isoprene into the polymerization reactor in sequence, stirring and mixing until the temperature of the polymerization system is reduced to-95 ℃, then adding 170g of methane chloride, 4.2g of aluminum sesquiethylate chloride and 0.35g of HCl into the polymerization system after aging for 40min after mixing at-89 ℃, stirring and reacting for 0.9hr, and then adding 145g of cyclohexane, 4.1g of [ - (DVB) IR-]nPh, stirring and dissolving for 2.9hr until the grafting agent is completely dissolved, then aging for 47min at-95 ℃, adding the materials into a polymerization system together, stirring and reacting for 4.6hr, adding 160mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 7
(1) Preparation of three-arm star nucleating agent: the same as in example 7.
(2) Preparation of three-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 7, except that [ - (DVB) SBR- (DVB) IR-]nThe amount of Ph added was 0.5g, i.e.: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, sequentially adding 280g of methane chloride, 370g of cyclohexane, 296g of isobutene and 36g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-100 ℃, then adding 180g of methane chloride, 4.8g of sesquiethylaluminum chloride and 0.41g of HCl into the polymerization system after mixing at-90 ℃ and aging for 40min, stirring and reacting for 1.0hr, then adding 150g of cyclohexane, 0.5g of [ - (DVB) SBR- (DVB) IR-]nPh, stirring to dissolve for 3.0hr until the grafting agent is completely dissolved, then aging for 50min at-95 ℃, adding the materials into a polymerization system together, stirring to react for 5.0hr, adding 170mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain the three-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
TABLE 1 Properties of three-arm comb-like Star-branched butyl rubber
Figure BDA0002773984250000171
As can be seen from Table 1: the three-arm comb-shaped star-branched butyl rubber has high tensile strength, good air tightness, lower Mooney relaxation area and good processability (the smaller the area under a stress relaxation curve is, the lower the mixing processing energy consumption is).
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (21)

1. A preparation method of three-arm comb-shaped star-branched butyl rubber comprises the process of adding isobutene monomer and isoprene monomer for copolymerization through a cationic polymerization mechanism, and is characterized in that a three-arm star-shaped nucleating agent with a structural general formula shown as a formula I is also added in the process;
Figure FDA0002773984240000011
the three-arm star nucleating agent is a quaternary three-arm star polymer, and the mass part of the quaternary three-arm star polymer is counted, wherein IR is an isoprene homopolymer block, and the content is 20-40%; SBR is styrene, 1, 3-butadiene random block copolymer, the content is 60% -74%; the number average molecular weight of the quaternary three-arm star polymer is 20000-50000, and the ratio of the weight average molecular weight to the number average molecular weight is 2.85-4.71.
2. The method of claim 1, wherein the IR block has a 1, 2-structure content of 12 wt% to 17 wt% and a 3, 4-structure content of 5 wt% to 10 wt%; the styrene content in the SBR block is 40-60 wt%, and the 1, 3-butadiene content is 20-34 wt%.
3. The method according to any one of claims 1 or 2, characterized in that the specific preparation steps are as follows:
(1) preparation of three-arm star nucleating agent: based on the total mass parts of reaction monomers, sequentially adding a solvent, 20-40% of isoprene, 0.05-0.5% of a structure regulator and an initiator into a polymerization kettle, heating to 40-55 ℃, and reacting until the conversion rate of the isoprene monomer reaches 100%; then sequentially adding 100-200% of solvent and 0.05-0.5% of structure regulator into a polymerization kettle, heating to 60-75 ℃, stirring and mixing 45-60% of styrene and 20-35% of 1, 3-butadiene for 10-20 min, adding into the polymerization kettle together, and reacting for 50-70 min to form an-IR-SBR-chain segment; heating to 80-90 ℃, adding a coupling agent for coupling reaction, wherein the reaction time is 60-80 min, sequentially adding 100-200% of solvent, 2-6% of divinylbenzene and 0.001-0.1% of catalyst into a polymerization kettle after the reaction is finished, heating to 70-80 ℃, reacting for 40-60 min, treating the coupled reaction mixture with water after the reaction is finished, and coagulating and drying a glue solution by a wet method to prepare the three-arm star-shaped nucleating agent;
(2) preparation of three-arm comb-shaped star-branched butyl rubber: based on the total mass parts of reaction monomers, firstly, sequentially adding a diluent/solvent mixed solvent with the volume ratio of 60-40/40-60, 94-98% of isobutene and 2-6% of isoprene into a polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-100 to-90 ℃, then 0.05 to 3.0 percent of diluent and coinitiator are mixed and aged at the temperature of between 95 ℃ below zero and 85 ℃ below zero, then the mixture is added into a polymerization system together to be stirred and react for 0.5 to 1.0 hour, then 30 to 60 percent of solvent and 0.5 to 1.5 percent of the three-arm star-shaped nucleating agent obtained in the step (1) are mixed and dissolved for 2.0 to 3.0 hours, aging at-95 to-85 ℃, adding the mixture into a polymerization system, stirring and reacting for 2.0 to 5.0 hours, finally adding a terminator, discharging, condensing, washing and drying to obtain a three-arm comb-shaped star-branched butyl rubber product;
the above polymerization reactions are all carried out in an oxygen-free, anhydrous environment.
4. The method of claim 3, wherein the coupling agent is one of 1,3, 5-trichlorobenzene and 1,3, 5-tribromobenzene, and the molar ratio of the coupling agent to the initiator is 1.0-3.0.
5. The method of claim 4, wherein the coupling agent is 1,3, 5-trichlorobenzene.
6. The method of claim 3, wherein the initiator is selected from the group consisting of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, lithium naphthalide, cyclohexyllithium, and dodecyllithium.
7. The method of claim 6 wherein said initiator is n-butyllithium.
8. The method of claim 3 wherein the catalyst is an organic peroxide selected from the group consisting of dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide and di-t-butyl peroxide.
9. The method of claim 8, wherein the catalyst is dibenzoyl peroxide.
10. The method according to claim 3, wherein the structure modifier is selected from the group consisting of diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, and triethylamine.
11. The method of claim 10, wherein the structure modifier is tetrahydrofuran.
12. The method according to claim 3, wherein the co-initiator is a combination of an alkyl aluminum halide and a protonic acid, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.05:1 to 0.2: 1.
13. The method of claim 12 wherein the alkyl aluminum halide is selected from the group consisting of diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloroide, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, n-propylaluminum dichloride, diisopropylaluminum dichloride, dimethylaluminum chloride and ethylaluminum chloride.
14. The method of claim 13 wherein the alkyl aluminum halide is aluminum sesquiethyl chloride.
15. The method of claim 12, wherein the protic acid is selected from the group consisting of HCl, HF, HBr, H2SO4、H2CO3、H3PO4Or HNO3One kind of (1).
16. The method of claim 15, wherein the protic acid is HCl.
17. The method of claim 13, wherein the diluent is selected from the group consisting of methyl chloride, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, fluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.
18. The method of claim 17, wherein the diluent is methyl chloride.
19. The method of claim 13, wherein the solvent is selected from the group consisting of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.
20. The method of claim 19, wherein the solvent is cyclohexane.
21. The method of claim 13, wherein the terminating agent is selected from one or more of methanol, ethanol, butanol.
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