CN114478956A - Preparation method of high-width-distribution three-hybrid-arm comb-shaped star-branched butyl rubber - Google Patents

Preparation method of high-width-distribution three-hybrid-arm comb-shaped star-branched butyl rubber Download PDF

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CN114478956A
CN114478956A CN202011264675.9A CN202011264675A CN114478956A CN 114478956 A CN114478956 A CN 114478956A CN 202011264675 A CN202011264675 A CN 202011264675A CN 114478956 A CN114478956 A CN 114478956A
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CN114478956B (en
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徐典宏
赵燕
赵志超
孟令坤
燕鹏华
翟云芳
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Petrochina Co Ltd
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Abstract

The invention takes isoprene, 1, 3-butadiene, styrene and divinyl benzene (DVB) as reaction monomers, takes lithium alkyl and organic peroxide as initiators, and prepares the quaternary triallel star nucleating agent ([ (DVB) SBR-]nPh[‑(DVB)BR‑PS]n[‑(DVB)IR‑PS]n) Finally, the quaternary three-hetero-arm star-shaped nucleating agent, isobutene and isoprene are subjected to cationic polymerization by adopting a first-arm-second-core method under a catalyst system compounded by alkyl aluminum halide and protonic acid to prepare the high-wide-distribution three-hetero-arm comb-shaped star-branched butyl rubber. The invention adopts the design of a four-element three-hybrid-arm star structureThe problem of contradiction between the processability and the physical and mechanical properties of the butyl rubber is solved, and the optimal balance between the processability and the physical and mechanical properties of the butyl rubber is realized.

Description

Preparation method of high-width-distribution three-hybrid-arm comb-shaped star-branched butyl rubber
Technical Field
The invention relates to a preparation method of high-width distribution three-hybrid-arm comb-shaped star-branched butyl rubber, in particular to a method for preparing high-width distribution three-hybrid-arm comb-shaped star-branched butyl rubber by using an isoprene/butadiene/styrene/Divinylbenzene (DVB) quaternary three-hybrid-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 industrialized by Exxon corporation in the 40 th century, more than seventy years ago, and has excellent air tightness, damping property, heat aging resistance, ozone resistance, weather resistance and the like, so that butyl rubber is widely applied to the fields of manufacturing inner tubes, air barriers, curing capsules, medical stoppers and the like of vehicle tires, and becomes one of the most important synthetic rubber varieties.
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 highly-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 property, 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-shaped highly-branched structure becomes one of the hot spots in the research field of future butyl rubber.
In the prior art, star-branched butyl is concernedThe rubber is mainly prepared by a method of a first nucleus and a second arm method, a first arm and 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 ℃. CN88108392.5 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-tetramethyl-1-pentene, to a mixture of isoolefin monomers and diolefin monomers. CN 107793535A 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 pyromellitic acid as a raw material to synthesize an initiator, namely the tetra-cumyl alcohol with a four-arm structure, and then adopt a tetra-cumyl alcohol/aluminum tetrachloride initiation system to initiate the copolymerization of isobutene and isoprene in an inert organic solvent at the temperature of-120 to-50 ℃ to synthesize the catalyst with double peaksStar-branched butyl rubber with molecular weight distribution (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 quaternary element 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 four-arm copolymer (Iatrou H, Hadjichristis N.Synthesisof a model 3-miktoarm star polymer [ J ] by strictly controlling the order of addition of the monomers and overranging stepwise coupling of the coupling agent]Macromolecules,1992,25: 4649). Hadjchrismists 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 then copolymerizes with butadiene in the presence of random regulator to obtain active Comb polybutadiene, and finally reacts with methyl silicon tetrachloride or silicon tetrachloride to obtain 3-arm or 4-arm Star-shaped Comb polybutadiene (KOUTALAS G, IATROU H, LOHSE D J, et al. well-Defined Comb, Star-Comb, and dComb-on-Comb polydienes by Anionic Polymerization and the macromolecular branching [ J ] of]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-tetramethylpentane/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 high-width distribution three-hybrid-arm comb-shaped branched butyl rubber. The invention takes alkyl lithium and organic peroxide as initiators, isoprene, 1, 3-butadiene, styrene and Divinylbenzene (DVB) as reaction monomers, is coupled by a coupling agent of trihalogenated benzene, adopts a temperature-variable polymerization method to prepare a quaternary three-hybrid-arm star-shaped nucleating agent, and finally adopts a first-arm and second-core method to carry out cationic polymerization on the quaternary three-hybrid-arm star-shaped nucleating agent, isobutene and isoprene to prepare the high-width distribution three-hybrid-arm comb-shaped branched butyl rubber under a catalytic system compounded by Lewis acid and protonic acid. The method solves the problems of extrusion swelling and low stress relaxation rate of the butyl rubber in the processing process, so that the high-width distribution three-hybrid-arm comb-shaped star-shaped branched butyl rubber not only has enough crude rubber strength and good air tightness, but also has the characteristics of high stress relaxation rate and small extrusion swelling effect, and the balance of the physical and mechanical properties and the processing performance of the butyl rubber is realized.
All the percentages in the present invention are percentages by mass.
The preparation of the high-width distribution three-hybrid-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 a quaternary three-hybrid-arm star nucleating agent: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 2-3 times, sequentially adding 100-200% of solvent, 20-30% of 1, 3-butadiene and 0.01-0.5% of structure regulator into the polymerization kettle A, heating to 40 ℃, adding an initiator 1, reacting to obtain temperature-changing polymerization, gradually increasing the temperature from 40 ℃ to 60 ℃ within 40-60 min, and increasing the temperature at a speed of temperature increase<1.3 ℃/min to form a wide-distribution BR chain segment, when the conversion rate of the 1, 3-butadiene monomer reaches 100 percent, then 10 to 20 percent of styrene and 0.05 to 0.5 percent of structure regulator are sequentially added into a polymerization kettle A for reaction for 30 to 50min to form the wide-distribution [ PS-BR-]nA chain segment, after the monomer is completely converted, heating to 70-90 ℃, and adding a coupling agent to perform coupling reaction for 50-70 min; meanwhile, in a 15L stainless steel polymerization kettle B, introducing argon to replace the system for 2-3 times, and sequentially adding 100-200% of solvent and 10-E of isoprene20 percent of structure regulator 0.05 to 0.5 percent, heating to 50 ℃, adding initiator 1, reacting for variable temperature polymerization, gradually heating from 50 ℃ to 70 ℃ within 30 to 50min, and heating at a speed of<1.2 ℃/min to form IR chain segments with wide distribution, when the conversion rate of isoprene monomer reaches 100 percent, then adding 5 to 10 percent of styrene and 0.05 to 0.1 percent of structure regulator into a polymerization kettle B in sequence, reacting for 30 to 40min to form PS-IR-doped with wide distribution]nA chain segment; after the monomers are completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 50-70 min; meanwhile, introducing argon into a 15L stainless steel polymerization kettle C to replace the system for 2-3 times, sequentially adding 100-200% of solvent, 25-30% of styrene, 20-30% of 1, 3-butadiene and 0.05-0.5% of structure regulator, heating to 60 ℃, adding an initiator 1, reacting for variable temperature polymerization, gradually heating from 60 ℃ to 80 ℃ within 40-60 min, and heating at a speed of<1.3 ℃/min, form [ -SBR ] with wide vinyl distribution]nA chain segment, namely adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 60-80 min; after the reaction is finished, sequentially adding 5-10% of Divinylbenzene (DVB) into a polymerization kettle A, heating to 85-95 ℃, adding an initiator 2, reacting for 50-70 min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on a glue solution to obtain the quaternary three-hybrid-arm star-shaped nucleating agent ([ - (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]n)。
(2) Preparing the high-width distribution three-hybrid-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 D with a jacket for replacing for 3-5 times, and sequentially adding 200-300% of diluent/solvent V into a polymerization kettle: mixing a solvent with a V ratio of 60-40/40-60, isobutene of 92-96% and isoprene of 3-5%, stirring and mixing until the temperature of a polymerization system is reduced to-100 to-90 ℃, then mixing and aging 40-60% of a diluent and 0.05-2.0% of a co-initiator for 30-40 min at-95 to-85 ℃, adding the mixture into the polymerization system, stirring and reacting for 0.5-1.0 hr, then mixing and dissolving 50-70% of the solvent and 2.0-6.0% of the nucleating agent obtained in the step (1) for 4.0-6.0 hr, aging for 40-60 min at-95 to-85 ℃, adding the mixture into the polymerization system, stirring and reacting for 6.0-7.0 hr, finally adding a terminator, discharging, coagulating, washing and drying to obtain the high-wide-distribution three-hybrid arm comb-shaped branched butyl rubber product.
The nucleating agent is a quaternary three-hybrid-arm comb star-shaped copolymer (SBR [ - (DVB) containing isoprene, 1, 3-butadiene, styrene and divinyl benzene (DVB) with wide vinyl distribution]n Ph[-(DVB)BR-PS]n[-(DVB)IR-PS]n) The structural general formula is shown as formula I:
Figure BDA0002773509260000051
wherein Ph is a benzene ring; DVB is divinylbenzene; BR is a butadiene wide distribution homopolymer section, and the 1, 2-structure content of the BR is 10-20 percent; IR is an isoprene wide distribution homopolymer segment, and the 1, 2-structure content of the segment is 10-15%; PS is a styrene homopolymer segment; SBR is a random section of broad vinyl distribution of styrene and butadiene; the content of styrene in the quaternary three-hybrid-arm comb-shaped star copolymer is 30-40%, the content of butadiene is 40-60%, and the content of isoprene is 10-20%; the quaternary three-hybrid-arm comb-shaped star-shaped copolymer has the number average molecular weight (Mn) of 70000-90000 and the molecular weight distribution (Mw/Mn) of 11.21-13.61.
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 1 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 amount of organolithium added is determined by the molecular weight of the polymer being designed.
The initiator 2 is an organic peroxide selected from dicumyl peroxide, cumene 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 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, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, preferably methyl chloride.
The solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene or ethylbenzene, and cyclohexane is preferred.
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 0.1-2.0%, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.05: 1-0.5: 1.
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 uses isoprene, 1, 3-butadiene, styrene and divinyl benzene (DVB) as reaction monomers, lithium alkyl and organic peroxide as initiators, and adopts temperature-changing polymerization through three-kettle reaction, and then prepares the quaternary three-hetero-arm star-shaped nucleating agent ([ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]n) Finally, the quaternary three-hetero-arm star-shaped nucleating agent, isobutene and isoprene are subjected to cationic polymerization by adopting a first-arm-second-core method under a catalyst system compounded by alkyl aluminum halide and protonic acid to prepare the high-wide-distribution three-hetero-arm comb-shaped star-branched butyl rubber.
The invention designs a quaternary three-hybrid-arm star nucleating agent ([ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]n) The nucleating agent contains a three-hybrid-arm structure, and due to the fact that structural units on each arm are different and the lengths of chain segments are different, the disorder of the whole butyl rubber macromolecular chain segment can be obviously increased; meanwhile, the-BR-, -IR-and-SBR-chain segments in the nucleating agent are all subjected to temperature-changing polymerization and contain a large amount of widely distributed vinyl; due to the two reasons, the disorder of molecular chain segments is increased in the polymerization process of the butyl rubber, the regularity of molecular chains is obviously destroyed, the molecular weight distribution is obviously widened, the butyl rubber can obtain good viscoelastic property, the stress relaxation rate is high, the extrusion swelling effect is low, and the processability of the butyl rubber is improved; all in oneAnd a large amount of benzene rings are contained in the-PS-and-SBR-chain segments, so that the reduction of strength and air tightness caused by the broadening of the molecular weight distribution of the butyl rubber is avoided, and the high strength and good air tightness of the butyl rubber are ensured.
Therefore, the preparation method provided by the invention organically combines the characteristics of the three-hybrid-arm comb-shaped star structure and the characteristics of wide distribution and rigidity of various chain segments through the design of the four-element three-hybrid-arm star structure and synergistically plays a role in solving the problem of contradiction relation between the processability and the physical and mechanical properties of the butyl rubber, and finally realizes the optimal balance between the processability and the physical and mechanical properties of the butyl rubber.
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 company
Isobutene, isoprene, Polymer grade Zhejiang Credit New materials Co Ltd
N-butyl lithium, 98% purity Nanjing Tongtiang chemical Co., Ltd
Chemical Co., Ltd of Yangzhou Haichen with a purity of 99% for 1,3, 5-trichlorobenzene
Dibenzoyl peroxide (BPO), Lanzhou auxiliary plant
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 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.
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).
Tensile strength: the method in standard GB/T528-2009 is executed.
Example 1
(1) Preparation of a quaternary three-hybrid-arm star nucleating agent: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 2 times, sequentially adding 1000g of cyclohexane, 200g of 1, 3-butadiene and 0.6g of THF into the polymerization kettle A, heating to 40 ℃, adding 30.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 40 ℃ to 60 ℃ within 40min at the heating rate of 0.5 ℃/min to form a wide-distribution BR chain segment, then sequentially adding 100g of styrene and 0.8g of THF into the polymerization kettle A, and reacting for 30min to form a wide-distribution PS-BR-shell-type copolymer]nCutting the chain, heating to 70 ℃, adding 230mmo11,3, 5-trichlorobenzene, and performing coupling reaction for 50 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 2 times, sequentially adding 1000g of cyclohexane, 100g of isoprene and 0.5g of THF, heating to 50 ℃, adding 10.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 30min, and heating at the speed of 0.7 ℃/min to formA wide distribution IR chain segment, then 50g of styrene and 0.5g of THF are added into a polymerization kettle B in sequence for reaction for 30min to form a wide distribution [ PS-IR-]nA chain segment, namely adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 50 min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1000g of cyclohexane, 250g of styrene, 200g of 1, 3-butadiene and 0.7g of THF, heating to 60 ℃, adding 15.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 60 ℃ to 80 ℃ within 40min, and heating at the speed of 0.5 ℃/min to form a widely distributed chain segment [ -SBR-]nAfter the monomers are completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 60 min; after the coupling reaction is finished, sequentially adding 50g of DVB into a polymerization kettle A, heating to 85 ℃, adding 0.13g of BPO, reacting for 50min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary three-hybrid-arm star nucleating agent [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]n(Mn 71000 and Mw/Mn 11.23).
(2) Preparing the high-width distribution three-hybrid-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 320g of methane chloride, 350g of cyclohexane, 276g of isobutene and 12g 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, 2.7g of aluminum sesquiethylate chloride and 0.08g of HCl at-85 ℃, aging for 30min, adding into the polymerization system together, stirring and reacting for 0.5hr, then adding 150g of cyclohexane and 10.0g of [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]nStirring and dissolving for 4.0hr until the mixture is completely dissolved, then aging for 40min at-85 ℃, adding the mixture into a polymerization system, stirring and reacting for 6.0hr, adding 260mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the high-wide distribution three-hybrid-arm comb-shaped star-branched butyl rubber. Sampling and analyzing: standard specimens were prepared and the test properties are shown in Table 1.
Example 2
(1) Preparation of a quaternary three-hybrid-arm star nucleating agent: in a 15L jacketed kettleIntroducing argon into a stainless steel polymerization kettle A to replace the system for 2 times, sequentially adding 1300g of cyclohexane, 220g of 1, 3-butadiene and 0.7g of THF into the polymerization kettle A, heating to 40 ℃, adding 32.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 40 ℃ to 60 ℃ within 40min at the heating speed of 0.5 ℃/min to form a widely distributed BR chain segment, sequentially adding 120g of styrene and 0.9g of THF into the polymerization kettle A, and reacting for 35min to form widely distributed PS-BR]nCutting segments, heating to 75 ℃, adding 250mmo11,3, 5-trichlorobenzene, and performing coupling reaction for 55 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 2 times, sequentially adding 1200g of cyclohexane, 120g of isoprene and 0.6g of THF, heating to 50 ℃, adding 10.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 30min at the heating speed of 0.7 ℃/min to form an IR chain segment with wide distribution, then sequentially adding 60g of styrene and 0.6g of THF into the polymerization kettle B to react for 33min to form PS-IR-doped silicon with wide distribution]nA chain segment, namely adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 55 min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1200g of cyclohexane, 260g of styrene, 230g of 1, 3-butadiene and 0.9g of THF, heating to 60 ℃, adding 15.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 60 ℃ to 80 ℃ within 40min, and heating at the speed of 0.5 ℃/min to form a widely distributed chain segment [ -SBR-]nAfter the monomers are completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 65 min; after the coupling reaction is finished, sequentially adding 60g of DVB into a polymerization kettle A, heating to 87 ℃, adding 0.21g of BPO, reacting for 55min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary three-hybrid-arm star nucleating agent [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]n(Mn of 76000 and Mw/Mn of 11.95).
(2) Preparing the high-width distribution three-hybrid-arm comb-shaped star-branched butyl rubber: firstly, nitrogen is introduced into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, 330g of methane chloride, 330g of cyclohexane, 280g of isobutene and 15g of isoprene are sequentially added into a polymerization kettle, stirred and mixed until the temperature of a polymerization system is reducedWhen the temperature is reduced to-90 ℃, 140g of methane chloride, 2.9g of aluminum sesquiethylate chloride and 0.09g of HCl are mixed at-85 ℃, then are aged for 35min, are added into a polymerization system together and are stirred for reaction for 0.6hr, and then 160g of cyclohexane and 15.0g of [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]nStirring and dissolving for 4.5 hours until the three-hybrid-arm comb-shaped star-branched butyl rubber is completely dissolved, aging for 45 minutes at the temperature of-87 ℃, adding the mixture into a polymerization system, stirring and reacting for 6.2 hours, adding 280mL of methanol to terminate the reaction, and finally discharging, coagulating, washing and drying to obtain the three-hybrid-arm comb-shaped star-branched butyl rubber with high and wide distribution. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 3
(1) Preparation of a quaternary three-hybrid-arm star nucleating agent: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 2 times, sequentially adding 1600g of cyclohexane, 240g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle A, heating to 40 ℃, adding 35.1mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 40 ℃ to 60 ℃ within 50min at the heating rate of 0.4 ℃/min to form a wide-distribution BR chain segment, then sequentially adding 150g of styrene and 1.1g of THF into the polymerization kettle A, and reacting for 40min to form a wide-distribution PS-BR-shell-type copolymer]nChain cutting, heating to 80 ℃, adding 260mmo11,3, 5-trichlorobenzene, and performing coupling reaction for 60 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 2 times, sequentially adding 1400g of cyclohexane, 140g of isoprene and 0.8g of THF, heating to 50 ℃, adding 12.1mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 40min at the heating speed of 0.6 ℃/min to form an IR chain segment with wide distribution, then sequentially adding 70g of styrene and 0.8g of THF into the polymerization kettle B to react for 36min to form PS-IR-doped silicon with wide distribution]nA chain segment, namely adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 60 min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1400g of cyclohexane, 270g of styrene, 260g of 1, 3-butadiene and 1.6g of THF, heating to 60 ℃, adding 17.2mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 60 ℃ to 80 ℃ within 50min, and heating at the speed of 0.4 ℃/min to form a widely distributed chain segment [ -SBR-]nAfter the monomers are completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 70 min; after the coupling reaction is finished, sequentially adding 70g of DVB into a polymerization kettle A, heating to 90 ℃, adding 0.34g of BPO, reacting for 60min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary three-hybrid-arm star nucleating agent [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]n(Mn 82000, Mw/Mn 12.55).
(2) Preparing the high-width distribution three-hybrid-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, 310g of cyclohexane, 283g of isobutene and 19g 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, 3.3g of aluminum sesquiethylate chloride and 0.13g of HCl into the polymerization system after mixing at-90 ℃ and aging for 35min, stirring and reacting for 0.7hr, then adding 180g of cyclohexane and 20.0g of [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]nStirring and dissolving for 5.0hr until the mixture is completely dissolved, then aging for 50min at-90 ℃, adding the mixture into a polymerization system, stirring and reacting for 6.4hr, adding 300mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the high-wide distribution three-hybrid-arm comb-shaped star-branched butyl rubber. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 4
(1) Preparation of a quaternary three-hybrid-arm star nucleating agent: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 3 times, sequentially adding 1800g of cyclohexane, 270g of 1, 3-butadiene and 1.2g of THF into the polymerization kettle A, heating to 40 ℃, adding 38.5mmo1 n-butyl lithium to start reaction, gradually increasing the temperature from 40 ℃ to 60 ℃ within 50min at the heating speed of 0.4 ℃/min to form a wide-distribution BR chain segment, then sequentially adding 180g of styrene and 1.5g of THF into the polymerization kettle A, and reacting for 45min to form a wide-distribution [ PS-BR-]nCutting segments, heating to 85 ℃, adding 290mmo11,3, 5-trichlorobenzene, and performing coupling reaction for 65 min; meanwhile, in a 15L stainless steel polymerization kettle B, argon is introduced into the kettleThe system is replaced for 3 times, 1600g of cyclohexane, 180g of isoprene and 1.2g of THF are sequentially added, 14.5mmo1 n-butyllithium is added when the temperature is raised to 50 ℃ to start the reaction, the temperature is gradually raised to 70 ℃ from 50 ℃ within 40min, the temperature raising speed is 0.6 ℃/min to form an IR chain segment with wide distribution, then 80g of styrene and 0.9g of THF are sequentially added into a polymerization kettle B to react for 38min to form PS-IR-doped material with wide distribution]nA chain segment, namely adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 65 min; meanwhile, in a 15L stainless steel polymerization kettle C, argon is introduced to replace the system for 3 times, 1700g of cyclohexane, 280g of styrene, 270g of 1, 3-butadiene and 2.2g of THF are sequentially added, 19.1mmo1 n-butyllithium is added to start the reaction when the temperature is raised to 60 ℃, the temperature is gradually raised to 80 ℃ from 60 ℃ within 50min, the temperature raising speed is 0.4 ℃/min, and a widely distributed chain segment [ -SBR-]nAfter the monomers are completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 75 min; after the coupling reaction is finished, sequentially adding 80g of DVB into a polymerization kettle A, heating to 92 ℃, adding 0.45g of BPO, reacting for 65min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary three-hybrid-arm star nucleating agent [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]n(Mn of 86000 and Mw/Mn of 12.92).
(2) Preparing the high-width distribution three-hybrid-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 350g of methane chloride, 300g of cyclohexane, 285g of isobutene and 21g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 160g of methane chloride, 3.9g of aluminum sesquiethylate chloride and 0.26g of HCl at-93 ℃, aging for 37min, adding into the polymerization system together, stirring and reacting for 0.8hr, then adding 190g of cyclohexane, 25.0g of [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]nStirring and dissolving for 5.5hr until completely dissolving, aging at-90 deg.C for 55min, adding into polymerization system, stirring and reacting for 6.8hr, adding 330mL methanol to terminate reaction, discharging, coagulating, washing, and drying to obtain high-wide distribution three-hybrid-arm comb-shaped star-branched butyl rubberAnd (6) gluing. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 5
(1) Preparation of a quaternary three-hybrid-arm star nucleating agent: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 3 times, sequentially adding 2000g of cyclohexane, 300g of 1, 3-butadiene and 1.9g of THF into the polymerization kettle A, heating to 40 ℃, adding 40.1mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 40 ℃ to 60 ℃ within 60min at the heating speed of 0.6 ℃/min to form a wide-distribution BR chain segment, then sequentially adding 200g of styrene and 1.6g of THF into the polymerization kettle A, and reacting for 50min to form a wide-distribution PS-BR-shell-type copolymer]nChain cutting, heating to 90 ℃, adding 310mmo11,3, 5-tribromobenzene, and coupling reacting for 70 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 1800g of cyclohexane, 200g of isoprene and 1.5g of THF, heating to 50 ℃, adding 15.2mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 50min at the heating speed of 0.4 ℃/min to form an IR chain segment with wide distribution, then sequentially adding 100g of styrene and 1.0g of THF into the polymerization kettle B to react for 40min to form PS-IR-doped silicon with wide distribution]nA chain segment, namely adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 70 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle C to replace the system for 3 times, sequentially adding 1900g of cyclohexane, 300g of styrene, 290g of 1, 3-butadiene and 2.6g of THF, heating to 60 ℃, adding 21.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 60 ℃ to 80 ℃ within 60min at the heating speed of 0.5 ℃/min to form a widely distributed chain segment [ -SBR-]nAfter the monomers are completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 80 min; after the coupling reaction is finished, sequentially adding 100g of DVB into a polymerization kettle A, heating to 95 ℃, adding 0.55g of BPO, reacting for 70min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary three-hybrid-arm star nucleating agent [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]n(Mn 89000, Mw/Mn 13.52).
(2) High-width distribution three-hybrid-arm comb-shaped star-branched butyl rubberThe preparation of (1): firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing 4 times, sequentially adding 350g of methane chloride, 280g of cyclohexane, 288g of isobutene and 24g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then adding 180g of methane chloride, 4.6g of aluminum sesquiethylate chloride and 0.33g 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 30.0g of [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]nStirring and dissolving for 6.0hr until the mixture is completely dissolved, then aging for 60min at-90 ℃, adding the mixture into a polymerization system, stirring and reacting for 7.0hr, adding 400mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the high-wide distribution three-hybrid-arm comb-shaped star-branched butyl rubber. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 1
Preparing the high-width distribution three-hybrid-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 1 except that: no nucleating agent [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]nNamely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 320g of methane chloride, 350g of cyclohexane, 276g of isobutene and 12g 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, 2.7g of aluminum sesquiethylate chloride and 0.08g of HCl at-85 ℃, aging for 30min, adding the mixture into the polymerization system together, stirring and reacting for 0.5hr, adding 260mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain the high-width distribution three-hybrid arm comb-shaped branched butyl rubber. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 2
(1) Preparation of a quaternary three-hybrid-arm star nucleating agent: the other conditions were the same as in example 2 except that: 1, 3-butadiene in the polymerizer A does not adopt variable temperature polymerization, and reacts at the constant temperature of 40 ℃, namely: in a 15L stainless steel polymerizer A with a jacket, argon gas was introduced to replace the system for 2 times,1300g of cyclohexane, 220g of 1, 3-butadiene and 0.7g of THF are sequentially added into a polymerization kettle A, the temperature is increased to 40 ℃, 32.5mmo1 n-butyllithium is added to start reaction, and the reaction is carried out for 40min to form BR1Chain segment, then adding 120g of styrene and 0.9g of THF into a polymerization kettle A in sequence, and reacting for 35min to form the widely distributed [ PS-BR ]1-]nCutting segments, heating to 75 ℃, adding 250mmo11,3, 5-trichlorobenzene, and performing coupling reaction for 55 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 2 times, sequentially adding 1200g of cyclohexane, 120g of isoprene and 0.6g of THF, heating to 50 ℃, adding 10.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 30min at the heating speed of 0.7 ℃/min to form an IR chain segment with wide distribution, then sequentially adding 60g of styrene and 0.6g of THF into the polymerization kettle B to react for 33min to form PS-IR-doped silicon with wide distribution]nA chain segment, namely adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 55 min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1200g of cyclohexane, 260g of styrene, 230g of 1, 3-butadiene and 0.9g of THF, heating to 60 ℃, adding 15.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 60 ℃ to 80 ℃ within 40min, and heating at the speed of 0.5 ℃/min to form a widely distributed chain segment [ -SBR-]nAfter the monomers are completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 65 min; after the coupling reaction is finished, sequentially adding 60g of DVB into a polymerization kettle A, heating to 87 ℃, adding 0.21g of BPO, reacting for 55min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary three-hybrid-arm star nucleating agent [ (DVB) SBR-]nPh[-(DVB)BR1-PS]n[-(DVB)IR-PS]n(Mn 72000 and Mw/Mn 9.15).
(2) Preparing the high-width distribution three-hybrid-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 2 except that: no nucleating agent [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]Instead, a nucleating agent [ (DVB) SBR-]nPh[-(DVB)BR1-PS]n[-(DVB)IR-PS]nNamely: first with a jacketIntroducing nitrogen into a 4L stainless steel reaction kettle for replacement for 3 times, sequentially adding 330g of methane chloride, 330g of cyclohexane, 280g of isobutene and 15g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 140g of methane chloride, 2.9g of aluminum sesquiethyl chloride and 0.09g of HCl at-85 ℃, aging for 35min, adding into the polymerization system together, stirring and reacting for 0.6hr, and then adding 160g of cyclohexane and 15.0g of [ (DVB) SBR-]nPh[-(DVB)BR1-PS]n[-(DVB)IR-PS]nStirring and dissolving for 4.5hr until the mixture is completely dissolved, then aging for 45min at-87 ℃, adding the mixture into a polymerization system, stirring and reacting for 6.2hr, adding 280mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the high-wide distribution three-hybrid-arm comb-shaped star-branched butyl rubber. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 3
(1) Preparation of a quaternary three-hybrid-arm star nucleating agent: the other conditions were the same as in example 3 except that: in the temperature-changing polymerization of isoprene in the polymerization kettle B, the temperature rising speed is 1.5 ℃/min, namely: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 2 times, sequentially adding 1600g of cyclohexane, 240g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle A, heating to 40 ℃, adding 35.1mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 40 ℃ to 60 ℃ within 50min at the heating speed of 0.4 ℃/min to form a wide-distribution BR chain segment, then sequentially adding 150g of styrene and 1.1g of THF into the polymerization kettle A, and reacting for 40min to form a wide-distribution PS-BR-shell-type copolymer]nCutting segments, heating to 80 ℃, adding 260mmo11,3, 5-trichlorobenzene, and performing coupling reaction for 60 min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace the system for 2 times, sequentially adding 1400g of cyclohexane, 140g of isoprene and 0.8g of THF, heating to 50 ℃, adding 12.1mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 40min, and heating at the speed of 1.5 ℃/min to form IR with wide distribution1Chain segment, then adding 70g of styrene and 0.8g of THF into a polymerization kettle B in sequence, and reacting for 36min to form the [ PS-IR ] with wide distribution1-]nChain segment, after the monomer is completely converted, the material in the polymerization kettle B isAdding the materials into a polymerization kettle A, and carrying out coupling reaction for 60 min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 2 times, sequentially adding 1400g of cyclohexane, 270g of styrene, 260g of 1, 3-butadiene and 1.6g of THF, heating to 60 ℃, adding 17.2mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 60 ℃ to 80 ℃ within 50min, and heating at the speed of 0.4 ℃/min to form a widely distributed chain segment [ -SBR-]nAfter the monomers are completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 70 min; after the coupling reaction is finished, sequentially adding 70g of DVB into a polymerization kettle A, heating to 90 ℃, adding 0.34g of BPO, reacting for 60min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary three-hybrid-arm star nucleating agent [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR1-PS]n(Mn of 81000 and Mw/Mn of 9.75).
(2) Preparing the high-width distribution three-hybrid-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 3 except that: no nucleating agent [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]Instead, a nucleating agent [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR1-PS]nNamely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing 4 times, adding 340g of methane chloride, 310g of cyclohexane, 283g of isobutene and 19g 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, 3.3g of aluminum sesquiethylate chloride and 0.13g of HCl into the polymerization system after mixing at-90 ℃ and aging for 35min, stirring and reacting for 0.7hr, then adding 180g of cyclohexane and 20.0g of [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR1-PS]nStirring and dissolving for 5.0hr until the mixture is completely dissolved, then aging for 50min at-90 ℃, adding the mixture into a polymerization system, stirring and reacting for 6.4hr, adding 300mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the high-wide distribution three-hybrid-arm comb-shaped star-branched butyl rubber. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 4
(1) Preparation of a quaternary three-hybrid-arm star nucleating agent: the other conditions were the same as in example 4 except that: only two kettles A and B are adopted for polymerization, the polymerization kettle C does not participate in the reaction, and a-SBR-chain segment is not formed, namely: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 3 times, sequentially adding 1800g of cyclohexane, 270g of 1, 3-butadiene and 1.2g of THF into the polymerization kettle A, heating to 40 ℃, adding 38.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 40 ℃ to 60 ℃ within 50min at the heating rate of 0.4 ℃/min to form a wide-distribution BR chain segment, sequentially adding 180g of styrene and 1.5g of THF into the polymerization kettle A, and reacting for 45min to form a wide-distribution PS-BR-chain material]nCutting segments, heating to 85 ℃, adding 290mmo11,3, 5-trichlorobenzene, and performing coupling reaction for 65 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 1600g of cyclohexane, 180g of isoprene and 1.2g of THF, heating to 50 ℃, adding 14.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 40min at the heating speed of 0.6 ℃/min to form an IR chain segment with wide distribution, then sequentially adding 80g of styrene and 0.9g of THF into the polymerization kettle B to react for 38min to form PS-IR-doped silicon with wide distribution]nA chain segment, namely adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 65 min; after the coupling reaction is finished, sequentially adding 80g of DVB into a polymerization kettle A, heating to 92 ℃, adding 0.45g of BPO, reacting for 65min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary three-hybrid-arm star-shaped nucleating agent [ - (DVB) BR-PS]nPh[-(DVB)IR-PS]n(Mn 72000 and Mw/Mn 6.92).
(2) Preparing the high-width distribution three-hybrid-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 4 except that: no nucleating agent [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]Instead, a nucleating agent [ - (DVB) BR-PS ] is added]nPh[-(DVB)IR-PS]nNamely: firstly, nitrogen is introduced into a 4L stainless steel reaction kettle with a jacket for replacement for 4 times, 350g of methane chloride, 300g of cyclohexane and 285g of isobutene are sequentially added into a polymerization kettle,21g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then adding 160g of methane chloride, 3.9g of aluminum sesquiethyl chloride and 0.26g of HCl into the polymerization system after mixing at-93 ℃, aging for 37min, stirring and reacting for 0.8hr, then adding 190g of cyclohexane, 25.0g [ - (DVB) BR-PS]n Ph[-(DVB)IR-PS]nStirring and dissolving for 5.5hr until the solution is completely dissolved, then aging for 55min at-90 ℃, adding the solution into a polymerization system, stirring and reacting for 6.8hr, adding 330mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the high-wide distribution two-hybrid-arm comb-shaped star-branched butyl rubber. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 5
(1) Preparation of a quaternary three-hybrid-arm star nucleating agent: the other conditions were the same as in example 5 except that: during the synthesis process, 1,3, 5-tribromobenzene is not added, but methyl silicon trichloride (CH) is added3SiCl3) Namely: the other conditions were the same as in example 5 except that: adopting single kettle A polymerization, namely adding the monomer materials into a polymerization kettle A in turn for reaction in a polymerization kettle B and a polymerization kettle C twice, namely: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 3 times, sequentially adding 2000g of cyclohexane, 300g of 1, 3-butadiene and 1.9g of THF into the polymerization kettle A, heating to 40 ℃, adding 40.1mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 40 ℃ to 60 ℃ within 60min at the heating speed of 0.6 ℃/min to form a wide-distribution BR chain segment, then sequentially adding 200g of styrene and 1.6g of THF into the polymerization kettle A, and reacting for 50min to form a wide-distribution PS-BR-shell-type copolymer]nSegment, then heating to 90 deg.C, adding 310mmo1 CH3SiCl3Coupling reaction is carried out for 70 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 1800g of cyclohexane, 200g of isoprene and 1.5g of THF, heating to 50 ℃, adding 15.2mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 70 ℃ within 50min at the heating speed of 0.4 ℃/min to form an IR chain segment with wide distribution, then sequentially adding 100g of styrene and 1.0g of THF into the polymerization kettle B to react for 40min to form PS-IR-doped silicon with wide distribution]nChain segment, to be monoAfter the body is completely converted, adding the material in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 70 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle C to replace the system for 3 times, sequentially adding 1900g of cyclohexane, 300g of styrene, 290g of 1, 3-butadiene and 2.6g of THF, heating to 60 ℃, adding 21.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 60 ℃ to 80 ℃ within 60min at the heating speed of 0.5 ℃/min to form a widely distributed chain segment [ -SBR-]nAfter the monomers are completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 80 min; after the coupling reaction is finished, sequentially adding 100g of DVB into a polymerization kettle A, heating to 95 ℃, adding 0.55g of BPO, reacting for 70min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the quaternary three-hybrid-arm star nucleating agent [ (DVB) SBR-]nCH3Si[-(DVB)BR-PS]n[-(DVB)IR-PS]n(Mn 83000, Mw/Mn 8.92).
(2) Preparing high-width distribution three-hybrid-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 5 except that: no nucleating agent [ (DVB) SBR-]nPh[-(DVB)BR-PS]n[-(DVB)IR-PS]Instead, a nucleating agent [ (DVB) SBR-]nCH3Si[-(DVB)BR-PS]n[-(DVB)IR-PS]nNamely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacing for 4 times, sequentially adding 350g of methane chloride, 280g of cyclohexane, 288g of isobutene and 24g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then adding 180g of methane chloride, 4.6g of sesquiethylaluminum chloride and 0.33g 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, 30.0g of [ (DVB) SBR-]nCH3Si[-(DVB)BR-PS]n[-(DVB)IR-PS]nStirring and dissolving for 6.0hr until the mixture is completely dissolved, then aging for 60min at-90 ℃, adding the mixture into a polymerization system, stirring and reacting for 7.0hr, adding 400mL of methanol to terminate the reaction, finally discharging and condensing, washing and drying to obtain the high-wide distribution three-hybrid-arm comb-shaped star-branched butyl rubber. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
TABLE 1 Properties of three-hybrid-arm comb-like branched butyl rubber with high and wide distribution
Figure BDA0002773509260000191
As can be seen from Table 1: the high-width distribution three-hybrid-arm comb-shaped star-branched butyl rubber has high tensile strength, good air tightness, lower Mooney relaxation area and low extrusion swell ratio, and shows 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 three-hybrid-arm comb-shaped star-branched butyl rubber with high and wide distribution comprises the following steps:
(1) preparing a quaternary triheteroarm star-shaped nucleating agent by taking styrene, 1, 3-butadiene, isoprene and divinylbenzene as reaction monomers and 1,3, 5-trichlorobenzene or 1,3, 5-tribromobenzene as a coupling agent under the condition of participating in the reaction by utilizing a method of combining temperature-changing polymerization, anionic polymerization and free radical polymerization;
(2) isobutene and isoprene are taken as reaction monomers, and cationic polymerization is carried out under the condition of-95 to-85 ℃ in the presence of a quaternary three-hybrid-arm star nucleating agent to prepare the high-wide-distribution three-hybrid-arm comb-shaped star-branched butyl rubber;
the structural general formula of the quaternary three-hybrid-arm star nucleating agent is shown as the formula I:
Figure FDA0002773509250000011
wherein BR is a butadiene wide distribution homopolymer section, and the 1, 2-structure content of BR is 10-20%; IR is an isoprene wide distribution homopolymer segment, and the 1, 2-structure content of the segment is 10-15%; PS is a styrene homopolymer segment; SBR is a random section of broad vinyl distribution of styrene and butadiene; the quaternary triatomic star-shaped nucleating agent has the number average molecular weight of 70000-90000 and the ratio of the weight average molecular weight to the number average molecular weight of 11.21-13.61.
2. The method as claimed in claim 1, wherein the quaternary three-hetero-arm comb-like star-shaped nucleating agent has a styrene content of 30% to 40%, a butadiene content of 40% to 60%, and an isoprene content of 10% to 20%.
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 a quaternary three-hybrid-arm star nucleating agent: adding 20-30% of solvent, 1, 3-butadiene and 0.01-0.5% of structure regulator into a polymerization kettle A in sequence according to the total mass parts of reaction monomers, heating to 40 ℃, adding an initiator 1, wherein the reaction is temperature-changing polymerization, gradually raising the temperature from 40 ℃ to 60 ℃ within 40-60 min at the temperature-raising speed of less than 1.3 ℃/min, adding 10-20% of styrene and 0.05-0.5% of structure regulator into the polymerization kettle A in sequence when the conversion rate of the 1, 3-butadiene monomer reaches 100%, heating to 70-90 ℃ after the monomer is completely converted, and adding a coupling agent to perform coupling reaction for 50-70 min; simultaneously, sequentially adding a solvent, 10-20% of isoprene and 0.05-0.5% of structure regulator into a polymerization kettle B, heating to 50 ℃, adding an initiator 1, reacting to obtain temperature-variable polymerization, gradually increasing the temperature from 50 ℃ to 70 ℃, wherein the heating speed is less than 1.2 ℃/min, sequentially adding 5-10% of styrene and 0.05-0.1% of structure regulator into the polymerization kettle B when the conversion rate of an isoprene monomer reaches 100%, adding the materials in the polymerization kettle B into a polymerization kettle A after the monomer is completely converted, and carrying out coupling reaction for 50-70 min; simultaneously, sequentially adding a solvent, 25-30% of styrene, 20-30% of 1, 3-butadiene and 0.05-0.5% of a structure regulator into a polymerization kettle C, heating to 60 ℃, adding an initiator 1, reacting at a variable temperature, gradually heating from 60 ℃ to 80 ℃, wherein the heating speed is less than 1.3 ℃/min, adding the materials in the polymerization kettle C into a polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 60-80 min; after the reaction is finished, sequentially adding 5-10% of divinylbenzene into a polymerization kettle A, heating to 85-95 ℃, adding an initiator 2, reacting for 50-70 min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on a glue solution to prepare a quaternary three-hybrid-arm star-shaped nucleating agent;
(2) preparing the high-width distribution three-hybrid-arm comb-shaped star-branched butyl rubber: based on the total mass parts of reaction monomers, firstly, 200-300% of diluent/solvent mixed solvent with the volume ratio of 60-40/40-60, 92-96% of isobutene and 3-5% of isoprene are sequentially added into a reaction kettle, stirred and mixed until the temperature of a polymerization system is reduced to-100-90 ℃, mixing and aging 0.05-2.0% of diluent and co-initiator at-95-85 ℃ for 30-40 min, adding the components into a reaction kettle together, stirring and reacting for 0.5-1.0 hr, then mixing and dissolving a solvent and 2.0-6.0% of a quaternary three-hybrid-arm star-shaped nucleating agent for 4.0-6.0 hr, aging at-95 to-85 ℃ for 40 to 60min, adding the mixture into a reaction kettle, stirring and reacting for 6.0 to 7.0hr, finally adding a terminator, discharging, condensing, washing and drying to obtain a high-wide distribution three-hybrid-arm comb-shaped 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 1 is selected from the group consisting of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, lithium naphthalide, cyclohexyllithium, and dodecyllithium.
7. The process of claim 6 wherein said initiator 1 is n-butyllithium.
8. The method of claim 3 wherein said initiator 2 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 said initiator 2 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 0.5: 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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