CN114478949A - Preparation method of wide-distribution three-arm comb-shaped star-branched butyl rubber - Google Patents

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

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CN114478949A
CN114478949A CN202011264517.3A CN202011264517A CN114478949A CN 114478949 A CN114478949 A CN 114478949A CN 202011264517 A CN202011264517 A CN 202011264517A CN 114478949 A CN114478949 A CN 114478949A
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CN114478949B (en
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徐典宏
牛承祥
王在花
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
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft 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
    • 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
    • C08F297/046—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 polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
    • 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
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Abstract

The invention firstly adopts an anion polymerization method, uses isoprene, styrene, butadiene and Divinylbenzene (DVB) as reaction monomers, utilizes temperature-changing polymerization, is coupled by a benzene trihalide coupling agent, and then utilizes the divinylbenzene and a catalyst to polymerize a wide-distribution quaternary three-arm star nucleating agent ([ -PS- (DVB) BR- (DVB) IR-]nPh) and finally withIsobutene and isoprene are used as reaction monomers, and the reaction monomers and the wide-distribution quaternary three-arm star-shaped nucleating agent are subjected to cationic polymerization by a first-arm-last-nucleus method under a Lewis acid and protonic acid compounded catalytic system to prepare the wide-distribution three-arm comb-shaped star-branched butyl rubber. On the premise of ensuring the strength and the air tightness, the butyl rubber has the characteristics of quick stress relaxation and good viscoelasticity, and realizes the balance of the processability and the physical property of the butyl rubber, so that the performance of the butyl rubber is more comprehensively improved. The preparation method has the characteristics of short process flow, controllable molecular weight, good product processing performance, suitability for industrial production and the like.

Description

Preparation method of wide-distribution three-arm comb-shaped star-branched butyl rubber
Technical Field
The invention relates to a preparation method of a wide-distribution three-arm comb-shaped star-branched butyl rubber, in particular to a method for preparing the wide-distribution 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 star-branched butyl rubber is mainly prepared by a method of a first-nucleus-second-arm method, a first-arm-second-nucleus method and a nuclear-arm simultaneous 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 ℃. CN88108392.57 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 initiator tricumyl alcohol with a three-arm structure, 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-shaped branched butyl rubber (Catalysts for manufacturing efficiency of IIR with bi-modal molecular weight distribution: US, 5194538[ P ] of].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, etc. adopts 2-chloro-2, 4, 4-trimethyl pentane/titanium tetrachloride as initiator system, methane chloride/cyclohexane as solvent and active positive ion polymerSynthesis of a Star-branched Polymer having a core of divinylbenzene and arms of polyisobutylene at-80 ℃ ("preparation and characterization of Star-branched polyisobutylene having a core of divinylbenzene"; synthetic rubber industry, 2008, 31(5): 362-365.).
Disclosure of Invention
The invention aims to provide a preparation method of wide-distribution three-arm comb-shaped star-branched butyl rubber. The invention firstly uses alkyl lithium as an initiator, uses hydrocarbons as a solvent, and adopts a temperature-changing polymerization method to synthesize wide-distribution [ -IR-BR-PS-]n linear chain segment, then adding coupling agent trihalogenated benzene for coupling to prepare the star copolymer with ternary three-arm structure and wide distribution [ -PS-BR-IR-]n Ph, then adding solvent, Divinylbenzene (DVB) and catalyst in sequence to polymerize the quaternary three-arm star nucleating agent with wide distribution ([ -PS- (DVB) BR- (DVB) IR-]nPh), and finally, under a catalytic system compounded by Lewis acid and protonic acid, carrying out cationic polymerization by taking isobutene and isoprene as reaction monomers and a wide-distribution three-arm star-shaped nucleating agent by adopting a first-arm-second-nucleus method to prepare the wide-distribution three-arm comb-shaped star-branched butyl rubber. The wide-distribution three-arm comb-shaped star-branched butyl rubber not only has the characteristics of high stress relaxation rate and small extrusion swelling effect, but also has sufficient crude rubber strength and good air tightness, and realizes the balance of physical and mechanical properties and processability of the butyl rubber.
All the percentages in the present invention are percentages by mass.
The preparation of the wide-distribution 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) wide distribution quaternary three-arm star nucleators: based on 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 300-400% of solvent, 40-50% of 1, 3-butadiene, 0.05-0.5% of structure regulator and initiator into a polymerization kettle, reacting at variable temperature, and gradually increasing the temperature from 40 ℃ within 40-60 minTo 65 ℃, the temperature rising speed<1.2 ℃/min, a BR chain segment with wide distribution is formed, and the conversion rate of the 1, 3-butadiene monomer reaches 100 percent; then sequentially adding 30-40% of isoprene and 0.05-0.5% of structure regulator into a polymerization kettle, wherein the reaction is temperature-changing polymerization, the temperature is gradually increased from 65 ℃ to 75 ℃ within 30-50 min, and the temperature-increasing speed is<2.0 ℃/min, forming an IR chain segment with wide distribution, and enabling the conversion rate of the isoprene monomer to reach 100 percent; secondly, sequentially adding 10-20% of styrene and 0.05-0.1% of structure regulator into a polymerization kettle, heating to 75-80 ℃, and reacting for 30-50 min to form a widely distributed-IR-BR-PS-chain segment, wherein the conversion rate of a styrene monomer reaches 100%; finally heating to 80-90 ℃, adding a coupling agent for coupling reaction, wherein the reaction time is 70-90 min, after the reaction is finished, sequentially adding 100-200% of solvent, 3-7% of Divinylbenzene (DVB) and 0.001-0.1% of catalyst into a polymerization kettle, heating to 75-85 ℃, reacting for 30-50 min, and condensing and drying the glue solution after the reaction is finished by a wet method to prepare the nucleating agent ([ -PS- (DVB) BR- (DVB) IR-]nPh)。
(2) Preparation of wide-distribution 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 40-70% of the solvent and 1.0-3.0% of the nucleating agent with the three-arm star structure obtained in the step (1) for 3.0-5.0 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 3.0-5.0 hr, finally adding a terminator for discharging and coagulating, washing and drying to obtain the wide-distribution three-arm comb-like branched butyl rubber product.
The nucleating agent of the invention is a compound containing isoprene and butadieneFour-membered three-arm star polymers of styrene and divinylbenzene ([ -PS- (DVB) BR- (DVB) IR-]nPh), the structural general formula of which is shown in formula I:
Figure BDA0002773508510000051
wherein, the IR is an isoprene homopolymer block, the 1, 2-structure content of the block is 13 to 18 percent, and the 3, 4-structure content of the block is 7 to 11 percent; BR is a 1, 3-butadiene homopolymer block, the 1, 2-structure content of the BR is 15-20 percent, and the 3, 4-structure content of the BR is 5-10 percent; PS is a styrene homopolymer block; the content of polyisoprene block (IR) in the quaternary three-arm star polymer is 30-40%, the content of polybutadiene Block (BR) is 40-50%, and the content of polystyrene block (PS) is 10-20%; the number average molecular weight (Mn) of the quaternary three-arm star polymer is 30000-50000, and the molecular weight distribution (Mw/Mn) is 5.15-6.71.
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 HNO3Preferably HCI. 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 0.01: 1-0.2: 1.
The diluent is halogenated alkane, wherein halogen atoms 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 an anion polymerization method, uses isoprene, styrene, butadiene and divinyl benzene (DVB) as reaction monomers, utilizes temperature-changing polymerization, and couples the reaction monomers into a benzene trihalide coupling agent with a quaternary three-arm structure and unsaturated groupsWide distribution star copolymer of double bonds [ -PS-BR-IR-]nPh, respectively; then polymerizing the quaternary three-arm star nucleating agent ([ -PS- (DVB) BR- (DVB) IR-]nPh), and finally, under a catalysis system compounded by Lewis acid and protonic acid, carrying out cationic polymerization on isobutene and isoprene serving as reaction monomers and a wide-distribution quaternary three-arm star-shaped nucleating agent by adopting a first-arm-last-nucleus method to prepare the wide-distribution three-arm comb-shaped star-shaped branched butyl rubber.
The nucleating agent designed by the invention [ -PS- (DVB) BR- (DVB) IR-]nThe Ph contains a three-arm comb-shaped star-shaped structure, the structure can properly widen the molecular weight distribution of the whole butyl rubber macromolecule on the premise of not damaging the molecular chain regularity of a single isobutylene and isoprene copolymer, and meanwhile, the-IR-and-BR-chain segments in the nucleating agent contain a certain amount of wide vinyl distribution due to temperature-changing polymerization, so that the flexibility of the butyl rubber macromolecule chain segments can be obviously improved, the butyl rubber can obtain good viscoelastic performance, the stress relaxation rate is high, the extrusion swelling effect is small, and the processability of the butyl rubber is improved; in addition, the nucleating agent contains a large amount of benzene rings in the-PS-chain segment, so that the reduction of strength and air tightness caused by the improvement of the flexibility of the butyl rubber macromolecular chain segment is avoided, and the high strength and good air tightness of the butyl rubber are ensured. Therefore, the invention organically combines the characteristics of the three-arm comb-shaped star structure and the wide distribution and rigidity characteristics of various chain segments and has 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, and realizes the balance of the processability and the physical properties of the butyl rubber, so that the performance of the butyl rubber is more comprehensively improved.
Drawings
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。
Measurement of stress relaxation: the measurement was carried out by using a Mooney viscometer model GT-7080-S2 manufactured by Taiwan high-speed railway.
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 the extrusion swell ratio: using a capillary rheometer of the RH2000 type manufactured by Marwin, UK
At a temperature of 100 ℃, an aspect ratio of 16:1 and a shear rate of 10-1000S-1Is measured within the interval of (1).
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 ℃, and the test sample is a circular sea piece with the diameter of 8cm and the thickness of 1 mm.
Tensile strength: the method in standard GB/T528-2009 is executed.
Example 1
(1) Preparation of the wide-distribution three-arm star nucleating agent: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 3000g of cyclohexane, 400g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle, heating to 40 ℃, adding 19.1mmo1 n-butyllithium to start reaction, wherein the reaction is carried out within 40min, the temperature is gradually increased from 40 ℃ to 65 ℃, and the heating speed is 0.7 ℃/min, so as to form a BR chain segment with wide distribution; then sequentially adding 300g of isoprene and 0.6g of THF into the polymerization kettle, reacting within 30min, gradually raising the temperature from 65 ℃ to 75 ℃, and raising the temperature at the speed of 0.4 ℃/min to form an IR chain segment with wide distribution; then, sequentially adding 100g of styrene and 0.4g of THF into a polymerization kettle, heating to 75 ℃, and reacting for 30min to form a widely distributed-IR-BR-PS-chain segment; then heating to 80 ℃, adding 10.1mmo11,3, 5-benzene trichloride, reacting for 70min to form [ -PS-BR-IR-]nPh; after the reaction is finished, sequentially adding 1000g of cyclohexane and 30g of DVB into a polymerization kettle, heating to 75 ℃, adding 0.05g of BPO to start the reaction, after the reaction is carried out for 30min, carrying out wet condensation and drying on the glue solution to prepare the nucleating agent [ -PS- (DVB) BR- (DVB) IR-]nPh (Mn 31000, Mw/Mn 5.15).
(2) Preparation of wide-distribution 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 250g of methane chloride, 370g of cyclohexane, 265g of isobutene and 8g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then adding 120g of methane chloride, 2.0g of aluminum sesquiethylate chloride and 0.06g of HCl into the polymerization system after mixing at-85 ℃ and aging for 30min, stirring and reacting for 0.5hr, and then adding 120g of cyclohexane, 3.5g of [ -PS- (DVB) BR- (DVB) IR-]nPh, dissolving with stirring2.0hr until the grafting agent is completely dissolved, then aging for 30min at-85 ℃, then adding into a polymerization system, stirring for reaction for 3.0hr, adding 130mL of methanol to terminate the reaction, finally discharging for coagulation, 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 2
(1) Preparation of the wide-distribution 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 3200g of cyclohexane, 410g of 1, 3-butadiene and 1.2g of THF into the polymerization kettle, heating to 40 ℃, adding 20.5mmo1 n-butyllithium to start reaction, and gradually increasing the temperature from 40 ℃ to 65 ℃ within 45min at the heating speed of 0.6 ℃/min to form a wide-distribution BR chain segment; then, sequentially adding 320g of isoprene and 0.9g of THF into the polymerization kettle, reacting within 35min, gradually raising the temperature from 65 ℃ to 75 ℃, and raising the temperature at the speed of 0.3 ℃/min to form an IR chain segment with wide distribution; then, sequentially adding 110g of styrene and 0.6g of THF into a polymerization kettle, heating to 76 ℃, and reacting for 34min to form a widely distributed-IR-BR-PS-chain segment; then heating to 82 ℃, adding 12.5mmo11,3, 5-benzene trichloride, reacting for 73min to form [ -PS-BR-IR-]nPh; after the reaction is finished, 1100g of cyclohexane and 35g of DVB are sequentially added into a polymerization kettle, 0.19g of BPO is added when the temperature is raised to 77 ℃ to start the reaction, and after the reaction is carried out for 35min, the glue solution is condensed and dried by a wet method to prepare the nucleating agent [ -PS- (DVB) BR- (DVB) IR-]nPh (Mn of 38000, Mw/Mn of 5.48).
(2) Preparation of wide-distribution 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 280g of methane chloride, 320g of cyclohexane, 268g of isobutene and 12g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-92 ℃, then adding 130g of methane chloride, 2.9g 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 140g of cyclohexane, 4.2g of [ -PS- (DVB) BR- (DVB) IR-]nPh, stirring to dissolve for 2.5hr until the grafting agent is completeDissolving, aging at-85 deg.C for 35min, adding into polymerization system, stirring, reacting for 3.3hr, adding 150mL methanol to terminate reaction, discharging, coagulating, washing, and drying to obtain three-arm comb-like 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 the wide-distribution three-arm star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 3300g of cyclohexane, 430g of 1, 3-butadiene and 1.4g of THF into the polymerization kettle, heating to 40 ℃, adding 21.6mmo1 n-butyllithium to start reaction, wherein the reaction is carried out within 50min, the temperature is gradually increased from 40 ℃ to 65 ℃, and the heating speed is 0.5 ℃/min, so as to form a BR chain segment with wide distribution; then, 340g of isoprene and 1.1g of THF are sequentially added into a polymerization kettle, the reaction is carried out within 40min, the temperature is gradually increased from 65 ℃ to 75 ℃, and the temperature rising speed is 0.3 ℃/min, so as to form an IR chain segment with wide distribution; then, 130g of styrene and 0.9g of THF are sequentially added into a polymerization kettle, the temperature is raised to 77 ℃, and after reaction for 38min, a widely distributed-IR-BR-PS-chain segment is formed; then heating to 84 ℃, adding 14.1mmo11,3, 5-benzene trichloride, reacting for 78min to form [ -PS-BR-IR-]nPh; after the reaction is finished, 1300g of cyclohexane and 39g of DVB are sequentially added into a polymerization kettle, 0.21g of BPO is added when the temperature is raised to 78 ℃ to start the reaction, and after the reaction is carried out for 39min, the glue solution is condensed and dried by a wet method to prepare the nucleating agent [ -PS- (DVB) BR- (DVB) IR-]nPh (Mn 41000, Mw/Mn 5.93).
(2) Preparation of wide-distribution 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 330g of methane chloride, 310g of cyclohexane, 273g of isobutene and 17g of isoprene into the polymerization kettle in sequence, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then adding 140g of methane chloride, 3.7g of aluminum sesquiethylate chloride and 0.11g of HCl into the polymerization system after mixing at-87 ℃ and aging for 33min, stirring and reacting for 0.7hr, then adding 160g of cyclohexane, 5.3g of [ -PS- (DVB) BR- (DVB) IR-]nPh, stirring to dissolve for 2.8hr until the grafting agent is completely dissolved, and processing at-87 deg.CAging for 40min, adding into the polymerization system, stirring, reacting for 3.7hr, adding 180mL of methanol to terminate the reaction, discharging, coagulating, 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 the wide-distribution three-arm star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 3600g of cyclohexane, 450g of 1, 3-butadiene and 1.9g of THF into the polymerization kettle, heating to 40 ℃, adding 23.1mmo1 n-butyllithium to start reaction, wherein the reaction is carried out within 50min, the temperature is gradually increased from 40 ℃ to 65 ℃, and the heating speed is 0.5 ℃/min, so as to form a BR chain segment with wide distribution; then sequentially adding 360g of isoprene and 1.3g of THF into the polymerization kettle, reacting within 40min, gradually raising the temperature from 65 ℃ to 75 ℃, and raising the temperature at the speed of 0.3 ℃/min to form an IR chain segment with wide distribution; then, sequentially adding 150g of styrene and 1.0g of THF into a polymerization kettle, heating to 78 ℃, and reacting for 41min to form a widely distributed-IR-BR-PS-chain segment; then heating to 85 deg.C, adding 16.2mmo11,3, 5-benzene trichloride, reacting for 82min to form [ -PS-BR-IR-]nPh; after the reaction is finished, 1400g of cyclohexane and 43g of DVB are sequentially added into a polymerization kettle, 0.32g of BPO is added when the temperature is raised to 80 ℃ to start the reaction, and after the reaction is carried out for 41min, the glue solution is condensed and dried by a wet method to prepare the nucleating agent [ -PS- (DVB) BR- (DVB) IR-]nPh (Mn 43000, Mw/Mn 6.13).
(2) Preparation of wide-distribution 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 340g of methane chloride, 300g of cyclohexane, 278g of isobutene and 21g of isoprene into the polymerization kettle in sequence, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then adding 150g of methane chloride, 4.1g of aluminum sesquiethylate chloride and 0.15g of HCl into the polymerization system after mixing at-90 ℃ and aging for 35min, stirring and reacting for 0.8hr, then adding 180g of cyclohexane, 6.2g of [ -PS- (DVB) BR- (DVB) IR-]nPh, stirring to dissolve for 3.2hr until the grafting agent is completely dissolved, aging at-90 deg.C for 42min, and collecting the filtrateThen adding the mixture into a polymerization system, stirring and reacting for 4.0hr, adding 200mL 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 5
(1) Preparation of the wide-distribution three-arm star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 3800g of cyclohexane, 470g of 1, 3-butadiene and 2.6g of THF into the polymerization kettle, heating to 40 ℃, adding 25.1mmo1 n-butyllithium to start reaction, wherein the reaction is carried out within 55min, the temperature is gradually increased from 40 ℃ to 65 ℃, and the heating speed is 0.45 ℃/min, so as to form a BR chain segment with wide distribution; then, 380g of isoprene and 1.7g of THF are sequentially added into a polymerization kettle, the reaction is carried out within 40min, the temperature is gradually increased from 65 ℃ to 75 ℃, and the temperature rising speed is 0.3 ℃/min, so as to form an IR chain segment with wide distribution; then, 170g of styrene and 1.2g of THF are sequentially added into a polymerization kettle, the temperature is raised to 78 ℃, and after reaction for 45min, a widely distributed-IR-BR-PS-chain segment is formed; then heating to 87 ℃, adding 18.1mmo11,3, 5-benzene trichloride, reacting for 85min to form [ -PS-BR-IR-]nPh; after the reaction is finished, 1600g of cyclohexane and 50g of DVB are sequentially added into a polymerization kettle, 0.56g of BPO is added when the temperature is raised to 82 ℃ to start the reaction, and after the reaction is carried out for 45min, the glue solution is condensed and dried by a wet method to prepare the nucleating agent [ -PS- (DVB) BR- (DVB) IR-]nPh (Mn 45000, Mw/Mn 6.35).
(2) Preparation of wide-distribution 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 4 times, 350g of methane chloride, 290g of cyclohexane, 282g of isobutene and 27g of isoprene are sequentially added into a polymerization kettle, stirred and mixed until the temperature of a polymerization system is reduced to-96 ℃, then 160g of methane chloride, 4.9g of sesquiethylaluminum chloride and 0.21g of HCl are mixed at-90 ℃, aged for 37min, added into the polymerization system together and stirred for reaction for 0.9hr, then 190g of cyclohexane, 7.5g of [ -PS- (DVB) BR- (DVB) IR-]nPh, stirring to dissolve for 3.5hr until the grafting agent is completely dissolved, aging at-91 deg.C for 45min, and adding into polymerization systemStirring and reacting for 4.3hr, adding 220mL 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.
Example 6
(1) Preparation of the wide-distribution 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 3900g of cyclohexane, 480g of 1, 3-butadiene and 3.1g of THF into the polymerization kettle, heating to 40 ℃, adding 27.1mmo1 n-butyl lithium to start reaction, wherein the temperature is gradually increased from 40 ℃ to 65 ℃ within 60min, and the heating speed is 0.42 ℃/min to form a wide-distribution BR chain segment; then 390g of isoprene and 2.1g of THF are sequentially added into the polymerization kettle, the reaction is carried out within 50min, the temperature is gradually increased from 65 ℃ to 75 ℃, the temperature rising speed is 0.2 ℃/min, and an IR chain segment with wide distribution is formed; then, 190g of styrene and 1.8g of THF are sequentially added into a polymerization kettle, the temperature is raised to 80 ℃, and after reaction for 47min, a widely distributed-IR-BR-PS-chain segment is formed; then heating to 89 deg.C, adding 19.5mmo11,3, 5-benzene tribromide, reacting for 88min to form [ -PS-BR-IR-]nPh; after the reaction is finished, 1800g of cyclohexane and 60g of DVB are sequentially added into a polymerization kettle, 0.63g of BPO is added when the temperature is raised to 85 ℃ to start the reaction, after the reaction is carried out for 47min, the glue solution is condensed and dried by a wet method to prepare the nucleating agent [ -PS- (DVB) BR- (DVB) IR-]nPh (Mn 47000, Mw/Mn 6.52).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: firstly, introducing nitrogen gas into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, sequentially adding 360g of methane chloride, 280g of cyclohexane, 285g of isobutene and 30g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-98 ℃, then adding 170g of methane chloride, 5.3g of aluminum sesquiethylate chloride and 0.35g of HCl into the polymerization system after mixing at-93 ℃, aging for 39min, stirring and reacting for 0.9hr, then adding 200g of cyclohexane, 8.4g of [ -PS- (DVB) BR- (DVB) IR-]nPh, stirring to dissolve for 3.8hr until the grafting agent is completely dissolved, aging at-95 deg.C for 47min, adding into polymerization system, stirring to react for 4.7hr, addingAdding 260mL 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.
Example 7
(1) Preparation of the wide-distribution three-arm star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 4000g of cyclohexane, 500g of 1, 3-butadiene and 3.8g of THF into the polymerization kettle, heating to 40 ℃, adding 28.5mmo1 n-butyllithium to start reaction, wherein the reaction is carried out within 60min, the temperature is gradually increased from 40 ℃ to 65 ℃, and the heating speed is 0.42 ℃/min, so as to form a wide-distribution BR chain segment; then sequentially adding 400g of isoprene and 2.9g of THF into the polymerization kettle, reacting within 50min, gradually raising the temperature from 65 ℃ to 75 ℃, and raising the temperature at the speed of 0.2 ℃/min to form an IR chain segment with wide distribution; then, 200g of styrene and 2.1g of THF are sequentially added into a polymerization kettle, the temperature is raised to 80 ℃, and after 50min of reaction, a widely distributed-IR-BR-PS-chain segment is formed; then heating to 90 deg.C, adding 22.5mmo11,3, 5-benzene tribromide, reacting for 90min to form [ -PS-BR-IR-]nPh; after the reaction is finished, 2000g of cyclohexane and 70g of DVB are sequentially added into a polymerization kettle, 0.65g of BPO is added when the temperature is raised to 85 ℃ to start the reaction, after the reaction is carried out for 50min, the glue solution is condensed and dried by a wet method to prepare the nucleating agent [ -PS- (DVB) BR- (DVB) IR-]nPh (Mn 49000, Mw/Mn 6.71).
(2) Preparation of wide-distribution 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 360g of methane chloride, 260g of cyclohexane, 288g of isobutene and 35g 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, 6.5g of aluminum sesquiethylate chloride and 0.41g of HCl into the polymerization system after mixing at-95 ℃ and aging for 40min, stirring and reacting for 1.0hr, then adding 200g of cyclohexane, 9.0g of [ -PS- (DVB) BR- (DVB) IR-]nPh, stirring to dissolve for 4.0hr until the grafting agent is completely dissolved, aging at-95 deg.C for 50min, adding into polymerization system, stirring to react for 5.0hr, adding 300mL methanol to terminate the reactionAnd finally discharging, coagulating, 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 1
Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 1 except that: no nucleating agent [ -PS- (DVB) BR- (DVB) IR-]nPh, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 250g of methane chloride, 370g of cyclohexane, 265g of isobutene and 8g 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, 2.0g of aluminum sesquiethylate chloride and 0.06g of HCl at-85 ℃, aging for 30min, adding the mixture into the polymerization system together, stirring and reacting for 0.5hr, adding 130mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain the 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 2
(1) Preparation of the wide-distribution 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 3 times, sequentially adding 3200g of cyclohexane, 410g of 1, 3-butadiene and 1.2g of THF into the polymerization kettle, heating to 40 ℃, adding 20.5mmo1 n-butyllithium to start reaction, and gradually increasing the temperature from 40 ℃ to 65 ℃ within 45min at the heating speed of 0.6 ℃/min to form a wide-distribution BR chain segment; then, sequentially adding 320g of isoprene and 0.9g of THF into the polymerization kettle, reacting within 35min, gradually raising the temperature from 65 ℃ to 75 ℃, and raising the temperature at the speed of 0.3 ℃/min to form an IR chain segment with wide distribution; then, sequentially adding 110g of styrene and 0.6g of THF into a polymerization kettle, heating to 76 ℃, and reacting for 34min to form a widely distributed-IR-BR-PS-chain segment; after the reaction is finished, 1100g of cyclohexane and 35g of DVB are sequentially added into a polymerization kettle, 0.19g of BPO is added when the temperature is raised to 77 ℃ to start the reaction, after the reaction is carried out for 35min, the glue solution is subjected to wet condensation and drying to prepare the glue solution with the wide distribution and three-arm star-shaped structureNucleating agent [ -PS- (DVB) BR- (DVB) IR-]n(Mn 33000, Mw/Mn 3.36).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 2 except that: no nucleating agent [ -PS- (DVB) BR- (DVB) IR-]nPh, but the nucleating agent [ -PS- (DVB) BR- (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, 320g of cyclohexane, 268g of isobutene and 12g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-92 ℃, then adding 130g of methane chloride, 2.9g 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 140g of cyclohexane, 4.2g of [ -PS- (DVB) BR- (DVB) IR-]nStirring and dissolving for 2.5hr until the grafting agent is completely dissolved, then aging at-85 ℃ for 35min, then adding into a polymerization system, stirring and reacting for 3.3hr, adding 150mL 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 3
Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 3 except that: no nucleating agent [ -PS- (DVB) BR- (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, 273g of isobutene and 17g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then mixing 140g of methane chloride, 3.7g of aluminum sesquiethyl chloride and 0.11g of HCl at-87 ℃, aging for 33min, adding into the polymerization system together, stirring and reacting for 0.7hr, then stirring and dissolving 160g of cyclohexane and 5.3g of DVB for 2.8hr until a grafting agent is completely dissolved, aging at-87 ℃ for 40min, adding into the polymerization system, stirring and reacting for 3.7hr, adding 180mL of methanol to terminate the reaction, finally discharging, condensing, washing, drying and dryingObtaining 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
(1) Preparation of the wide-distribution three-arm star nucleating agent: the other conditions were the same as in example 4 except that: 1, 3-butadiene does not adopt temperature-variable polymerization and reacts at the constant temperature of 40 ℃, namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 3600g of cyclohexane, 450g of 1, 3-butadiene and 1.9g of THF into the polymerization kettle, heating to 40 ℃, adding 23.1mmo1 n-butyllithium for starting reaction, and reacting for 50min to form BR1A chain segment; then sequentially adding 360g of isoprene and 1.3g of THF into the polymerization kettle, reacting within 40min, gradually raising the temperature from 65 ℃ to 75 ℃, and raising the temperature at the speed of 0.3 ℃/min to form an IR chain segment with wide distribution; then, sequentially adding 150g of styrene and 1.0g of THF into a polymerization kettle, heating to 78 ℃, and reacting for 41min to form a widely distributed-IR-BR-PS-chain segment; then heating to 85 deg.C, adding 16.2mmo11,3, 5-trichlorobenzene, reacting for 82min to form [ -PS-BR ]1-IR-]nPh; after the reaction is finished, 1400g of cyclohexane and 43g of DVB are sequentially added into a polymerization kettle, 0.32g of BPO is added when the temperature is raised to 80 ℃ to start the reaction, and after the reaction is carried out for 41min, the glue solution is condensed and dried by a wet method to prepare the nucleating agent [ -PS- (DVB) BR ] with a wide distribution and three-arm star structure1-(DVB)IR-]nPh (Mn 40000, Mw/Mn 4.22).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 4 except that: no nucleating agent [ -PS- (DVB) BR- (DVB) IR-]nPh, but a nucleating agent [ -PS- (DVB) BR ] is added1-(DVB)IR-]nPh, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing for 4 times, adding 340g of methane chloride, 300g of cyclohexane, 278g of isobutene and 21g of isoprene into the polymerization kettle in sequence, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then adding 150g of methane chloride, 4.1g of aluminum sesquiethyl chloride and 0.15g of HCl into the polymerization system after mixing at-90 ℃ and aging for 35min, stirring and reacting for 0.8hr, and then adding180g of cyclohexane, 6.2g of [ -PS- (DVB) BR1-(DVB)IR-]nPh, stirring to dissolve for 3.2hr until the grafting agent is completely dissolved, then aging for 42min at-90 ℃, then adding into a polymerization system, stirring to react for 4.0hr, adding 200mL 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 5
(1) Preparation of the wide-distribution three-arm star nucleating agent: the other conditions were the same as in example 5 except that: isoprene is not subjected to temperature-variable polymerization and reacts at the constant temperature of 65 ℃, namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 3800g of cyclohexane, 470g of 1, 3-butadiene and 2.6g of THF into the polymerization kettle, heating to 40 ℃, adding 25.1mmo1 n-butyllithium to start reaction, wherein the reaction is carried out within 55min, the temperature is gradually increased from 40 ℃ to 65 ℃, and the heating speed is 0.45 ℃/min, so as to form a BR chain segment with wide distribution; then 380g of isoprene and 1.7g of THF are added into the polymerization kettle in turn, the temperature is raised to 65 ℃, and after 40min of reaction, IR is formed1A chain segment; then 170g of styrene and 1.2g of THF are added into the polymerization kettle in turn, the temperature is raised to 78 ℃, and after reaction for 45min, the wide-distribution-IR is formed1-a BR-PS-segment; then heating to 87 ℃, adding 18.1mmo11,3, 5-trichlorobenzene, reacting for 85min to form [ -PS-BR-IR1-]nPh; after the reaction is finished, 1600g of cyclohexane and 50g of DVB are sequentially added into a polymerization kettle, 0.56g of BPO is added when the temperature is raised to 82 ℃ to start the reaction, after the reaction is carried out for 45min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ -PS- (DVB) BR- (DVB) IR with a wide distribution and three-arm star structure is prepared1-]nPh (Mn 43000, Mw/Mn 4.87).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 5 except that: no nucleating agent [ -PS- (DVB) BR- (DVB) IR-]nPh, but a nucleating agent [ -PS- (DVB) BR- (DVB) IR1-]nPh, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for replacement for 4 times, and then conducting polymerization350g of methyl chloride, 290g of cyclohexane, 282g of isobutene and 27g of isoprene are sequentially added into a synthesis kettle, stirred and mixed until the temperature of a polymerization system is reduced to-96 ℃, then 160g of methyl chloride, 4.9g of sesquiethylaluminum chloride and 0.21g of HCl are mixed at-90 ℃, aged for 37min, added into the polymerization system together and stirred for reaction for 0.9hr, and then 190g of cyclohexane and 7.5g of [ -PS- (DVB) BR- (DVB) IR are added into the polymerization system1-]nPh, stirring to dissolve for 3.5hr until the grafting agent is completely dissolved, then aging for 45min at-91 ℃, then adding into a polymerization system, stirring to react for 4.3hr, adding 220mL 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 6
(1) Preparation of the wide-distribution three-arm star nucleating agent: the other conditions were the same as in example 6 except that: styrene was not 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 3900g of cyclohexane, 480g of 1, 3-butadiene and 3.1g of THF into the polymerization kettle, heating to 40 ℃, adding 27.1mmo1 n-butyllithium for starting reaction, wherein the temperature is gradually increased from 40 ℃ to 65 ℃ within 60min, and the heating speed is 0.42 ℃/min, so as to form a BR chain segment with wide distribution; then 390g of isoprene and 2.1g of THF are sequentially added into a polymerization kettle, the reaction is carried out within 50min, the temperature is gradually increased from 65 ℃ to 75 ℃, the temperature rising speed is 0.2 ℃/min, and a-IR-BR-chain segment with wide distribution is formed; then heating to 89 deg.C, adding 19.5mmo11,3, 5-benzene tribromide, reacting for 88min to form [ -BR-IR-]nPh; after the reaction is finished, 1800g of cyclohexane and 60g of DVB are sequentially added into a polymerization kettle, 0.63g of BPO is added when the temperature is raised to 85 ℃ to start the reaction, after the reaction is carried out for 47min, the glue solution is condensed and dried by a wet method to prepare the nucleating agent [ - (DVB) BR- (DVB) IR-]nPh (Mn 39000, Mw/Mn 5.06).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 6 except that: no nucleating agent [ -PS- (DVB) BR- (DVB) IR-]nPh, andis added with a nucleating agent [ - (DVB) BR- (DVB) IR1-]nPh, namely: firstly, introducing nitrogen gas into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, sequentially adding 360g of methane chloride, 280g of cyclohexane, 285g of isobutene and 30g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-98 ℃, then adding 170g of methane chloride, 5.3g of aluminum sesquiethylate chloride and 0.35g of HCl into the polymerization system after mixing at-93 ℃, aging for 39min, stirring and reacting for 0.9hr, then adding 200g of cyclohexane, 8.4g [ - (DVB) BR- (DVB) IR-]nPh, stirring to dissolve for 3.8hr until the grafting agent is completely dissolved, aging at-95 ℃ for 47min, adding into a polymerization system, stirring to react for 4.7hr, adding 260mL 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 7
(1) Preparation of the wide-distribution three-arm star nucleating agent: the other conditions were the same as in example 7 except that: in the temperature-changing polymerization of 1, 3-butadiene, the temperature-rising speed is 1.4 ℃/min, namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 4000g of cyclohexane, 500g of 1, 3-butadiene and 3.8g of THF into the polymerization kettle, heating to 40 ℃, adding 28.5mmo1 n-butyllithium to start reaction, wherein the reaction is carried out within 60min, the temperature is gradually increased from 40 ℃ to 65 ℃, the heating speed is 1.4 ℃/min, and the widely distributed BR is formed2A chain segment; then sequentially adding 400g of isoprene and 2.9g of THF into the polymerization kettle, reacting within 50min, gradually raising the temperature from 65 ℃ to 75 ℃, and raising the temperature at the speed of 0.2 ℃/min to form an IR chain segment with wide distribution; then, 200g of styrene and 2.1g of THF are sequentially added into a polymerization kettle, the temperature is raised to 80 ℃, and after 50min of reaction, a widely distributed-IR-BR-PS-chain segment is formed; then heating to 90 deg.C, adding 22.5mmo11,3, 5-benzene tribromide, reacting for 90min to form [ -PS-BR [ -2-IR-]nPh; after the reaction is finished, adding 2000g of cyclohexane and 70g of DVB into a polymerization kettle in sequence, heating to 85 ℃, adding 0.65g of BPO to start the reaction, after the reaction is carried out for 50min, carrying out wet coagulation and drying on glue solution to obtain the rubber with wide distribution,Nucleating agent [ -PS- (DVB) BR of three-arm star structure2-(DVB)IR-]nPh (Mn 48000, Mw/Mn 4.54).
(2) Preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 7 except that: no nucleating agent [ -PS- (DVB) BR- (DVB) IR-]nPh, but the nucleating agent [ - (DVB) BR is added2-(DVB)IR-]nPh, namely: firstly, introducing nitrogen gas into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, sequentially adding 360g of methane chloride, 260g of cyclohexane, 288g of isobutene and 35g 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, 6.5g of aluminum sesquiethylate chloride and 0.41g of HCl into the polymerization system after mixing at-95 ℃ and aging for 40min, stirring and reacting for 1.0hr, then adding 200g of cyclohexane and 9.0g of [ -PS- (DVB) BR2-(DVB)IR-]nPh, stirring to dissolve for 4.0hr until the grafting agent is completely dissolved, then aging for 50min at-95 ℃, then adding into a polymerization system, stirring to react for 5.0hr, adding 300mL 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 Wide-distribution three-arm comb-like Star-branched butyl rubber
Figure BDA0002773508510000191
As can be seen from Table 1: the wide-distribution three-arm comb-like 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 (22)

1. A preparation method of a wide-distribution three-arm comb-shaped star-branched butyl rubber comprises the process of adding an isobutene monomer and an 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 FDA0002773508500000011
based on the total mass of the three-arm star-shaped nucleating agent, wherein IR is an isoprene homopolymer block, and the content is 30-40%; BR is a 1, 3-butadiene homopolymer block with the content of 40-50 percent; PS is a styrene homopolymer block, and the content is 10-20%; the number average molecular weight of the three-arm star nucleating agent is 30000-50000, and the ratio of the weight average molecular weight to the number average molecular weight is 5.15-6.71.
2. The method of claim 1, wherein the IR block has a 1, 2-structure content of 13 wt% to 18 wt% and a 3, 4-structure content of 7 wt% to 11 wt%; the content of 1, 2-structure in BR block is 15 wt% -20 wt%, and the content of 3, 4-structure is 5 wt% -10 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 40-50% of solvent, 40-50% of 1, 3-butadiene, 0.05-0.5% of structure regulator and initiator into a polymerization kettle, wherein the reaction is temperature-changing polymerization, the temperature is gradually increased from 40 ℃ to 65 ℃, and the temperature-increasing speed is less than 1.2 ℃/min until the conversion rate of the 1, 3-butadiene monomer reaches 100%; then sequentially adding 30-40% of isoprene and 0.05-0.5% of structure regulator into a polymerization kettle, wherein the reaction is variable temperature polymerization, the temperature is gradually increased from 65 ℃ to 75 ℃, and the temperature increase speed is less than 2.0 ℃/min until the conversion rate of isoprene monomer reaches 100%; secondly, sequentially adding 10-20% of styrene and 0.05-0.1% of structure regulator into the polymerization kettle, and heating to 75-80 ℃ until the conversion rate of styrene monomer reaches 100%; finally, heating to 80-90 ℃, adding a coupling agent for reaction for 70-90 min, after the reaction is finished, sequentially adding a solvent, 3-7% of divinylbenzene and 0.001-0.1% of a catalyst into a polymerization kettle, heating to 75-85 ℃, and performing wet condensation and drying on a glue solution after the reaction is finished to prepare the wide-distribution three-arm star nucleating agent;
(2) preparation of wide-distribution three-arm comb-shaped star-branched butyl rubber: based on the total mass parts of reaction monomers, firstly, sequentially adding a mixed solvent with a diluent/solvent 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 ℃, mixing and aging 0.05-3.0% of diluent and co-initiator at-95-85 ℃ for 30-40 min, adding the components into a polymerization kettle, stirring and reacting for 0.5-1.0 hr, then mixing and dissolving 1.0-3.0% of the solvent and the three-arm star-shaped nucleating agent obtained in the step (1) for 3.0-5.0 hr, aging at-95 to-85 ℃, adding the mixture into a polymerization kettle, stirring and reacting for 3.0 to 5.0 hours, finally adding a terminator, discharging, condensing, washing and drying to obtain a wide-distribution 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 3, 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 3, 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 3, wherein the terminating agent is selected from one or more of methanol, ethanol, butanol.
22. The method of claim 3, wherein steps (1) and (2) are performed in an inert gas environment.
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