CN114478955A - Preparation method of wide-distribution four-arm comb-shaped star-branched butyl rubber - Google Patents

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

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CN114478955A
CN114478955A CN202011264674.4A CN202011264674A CN114478955A CN 114478955 A CN114478955 A CN 114478955A CN 202011264674 A CN202011264674 A CN 202011264674A CN 114478955 A CN114478955 A CN 114478955A
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butyl rubber
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CN114478955B (en
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徐典宏
翟月勤
张华强
孟令坤
燕鹏华
翟云芳
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Petrochina Co Ltd
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
    • 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
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Abstract

The invention synthesizes coupling agent 1, 5-dibromo-3, 3 di (2-bromoethyl) pentane, then couples with reaction monomer by isoprene, 1, 3-butadiene, styrene and Divinylbenzene (DVB) to prepare the wide distribution quaternary quadriarm pectinate star-structured nucleating agent ([ - (DVB) SBR- (DVB) BR- (DVB) IR-]nY), 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 adopting a first-arm-second-core method with the wide-distribution four-arm comb-shaped star-branched butyl rubber. The nucleating agent prepared by temperature-variable polymerization can increase the regularity of a butyl rubber molecular chain without damaging the regularity of the butyl rubber molecular chainThe flexibility of the molecular chain segment of the butyl rubber solves the problems of extrusion swelling and low stress relaxation rate of the butyl rubber during processing, so that the butyl rubber has the characteristics of high stress relaxation rate and small extrusion swelling effect on the premise of keeping sufficient crude rubber strength and good air tightness.

Description

Preparation method of wide-distribution four-arm comb-shaped star-branched butyl rubber
Technical Field
The invention relates to a preparation method of a wide-distribution four-arm comb-shaped star-branched butyl rubber, in particular to a method for preparing the wide-distribution four-arm comb-shaped star-branched butyl rubber by using an isoprene/butadiene/styrene/Divinylbenzene (DVB) quaternary four-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 with a unique four-dimensional net structure, which is composed of a high-molecular-weight graft structure and a low-molecular-weight linear structure, has excellent viscoelastic performance, high crude rubber strength and a fast stress relaxation rate, can keep low melt viscosity in the processing process, can obtain a high-molecular-weight polymer, and realizes the balance and unification of physical and mechanical properties and processing properties. 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-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 of the tetra-cumyl alcohol with a four-arm structure, and then adopt a tetra-cumyl alcohol/aluminum tetrachloride initiation systemIsobutylene and isoprene are initiated to copolymerize in an inert organic solvent under the condition of-120 to-50 ℃, and star-shaped branched butyl rubber (Catalysts for manufacturing of IIR with biomodal molecular weight distribution: US, 5194538[ P ] with bimodal molecular weight distribution is synthesized].1993-3-16.). Wieland et al successfully prepared multi-arm star butyl rubber (synthetic of new copolymers stabilizing a polymeric isobutylene by polymerization of the 1,1-diphenylethylene technology and cationic polymerization [ J ] by synthesizing a macroinitiator P (MMA-b-St-co-CMS) containing the quaternary form of 4-chloromethylstyrene, styrene and methyl methacrylate in the presence of 1, 2-Diphenylethylene (DPE) and then using the macroinitiator to initiate cationic polymerization of isobutylene and isoprene]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). Hadjrichists adopts high vacuum technique to obtain styrene polybutadiene macromonomer by reacting active polybutadiene lithium with 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. well-Defined Comb, Star-Comb, and Comb-on-Comb polymers by Anionic Polymerization and the macromolecular Polymerization [ J ] of]Macromolecules,2005,38(12): 4996-. Gong Hui et al synthesized a star-branched polymer with divinylbenzene as a core and polyisobutylene as an arm at-80 ℃ by using 2-chloro-2, 4, 4-tetramethylpentane/titanium tetrachloride as an initiator system and monochloromethane/cyclohexane as a solvent and adopting active positive ion polymerization ("preparation and characterization of star-branched polyisobutylene with divinylbenzene as a core", synthetic rubber industry, 2008, 31(5): 362-365).
Disclosure of Invention
The invention aims to provide a preparation method of wide-distribution four-arm comb-shaped star-branched butyl rubber. Firstly, alkyl lithium is taken as an initiator to be added at one time, a reaction monomer is composed of isoprene, 1, 3-butadiene and styrene, and a long-chain segment [ -BR-IR-SBR-]nThen coupled with a novel tetrahalide coupling agent 1, 5-dihalo-3, 3 di (2-haloethyl) pentane to prepare the star copolymer [ -SBR-BR-IR-]nY, then polymerizing with Divinylbenzene (DVB) to obtain the wide-distribution four-arm star-shaped nucleating agent ([ - (DVB) SBR- (DVB) B R- (DVB) IR-]nY), 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 adopting a first-arm-second-core method with the wide-distribution four-arm comb-shaped star-branched butyl rubber. The method solves the problems of extrusion swelling and low stress relaxation rate of the butyl rubber in the processing process, so that the wide-distribution four-arm comb-shaped star-shaped branched butyl rubber has the characteristics of high stress relaxation rate and small extrusion swelling effect, has sufficient green rubber strength and good air tightness, and realizes the balance of the physical and mechanical properties and the processing performance of the butyl rubber.
All the percentages in the present invention are percentages by mass.
The preparation of the wide-distribution four-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 the wide-distribution four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: based on one hundred percent of the total mass of the reactants, 4L of the first jacket was charged
Introducing argon into a stainless steel polymerization kettle for 2-4 times of replacement, sequentially adding 100-200% of deionized water, 3, 9-dioxo [5.5] spiro undecane, a halogenating agent and 1-5% of a catalyst into the polymerization kettle, heating to 50-80 ℃, reacting for 1-3 hours, adding 20-40% of NaOH aqueous solution with the mass concentration of 10-20% to terminate the reaction, and finally adding 200-300% of monochloromethane to extract, separate, wash and dry to obtain the coupling agent 1, 5-dihalo-3, 3-bis (2-haloethyl) pentane (the yield is 85-95%).
b preparation of the wide-distribution four-arm comb-shaped star nucleating agent: according to the total mass parts of reaction monomers, firstly introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2-4 times, sequentially adding 200-400% of solvent, 30-40% of 1, 3-butadiene, 0.05-0.1% of structure regulator and 1% of initiator into the polymerization kettle, wherein the reaction is temperature-changing polymerization, the temperature is gradually increased from 40 ℃ to 60 ℃ within 40-60 min, and the temperature-increasing speed is increased<1.3 ℃/min, forming a BR chain segment with wide distribution, and enabling the conversion rate of 1, 3-butadiene monomer to reach 100%; then sequentially adding 20-30% of isoprene and 0.05-0.1% of structure regulator into a polymerization kettle, wherein the reaction is variable temperature polymerization, the temperature is gradually increased from 60 ℃ to 75 ℃ within 30-60 min, and the temperature rising speed is increased<1.0 ℃/min, forming an IR chain segment with wide distribution, and enabling the conversion rate of the isoprene monomer to reach 100 percent; then sequentially adding 20-30% of styrene, 10-20% of 1, 3-butadiene and 0.05-0.5% of structure regulator into a polymerization kettle, heating to 75-80 ℃, and reacting for 40-50 min to form a wide-distribution linear chain segment [ -SBR-BR-IR-]n(ii) a Finally heating to 80-90 ℃, adding a coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane for coupling reaction, wherein the reaction time is 80-100 min, after the reaction is finished, sequentially adding 100-200% of solvent, 5-10% of Divinylbenzene (DVB) and 20.001-0.2% of initiator into a polymerization kettle, heating to 75-85 ℃, reacting for 40-60 min, and condensing and drying the glue solution after the reaction is finished by a wet method to obtain the nucleating agent (namely- (DVB) SBR- (DVB) BR- (DVB) IR-]n Y)。
(2) Preparation of wide-distribution four-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 with a V ratio of 60-40/40-60, isobutene of 93-97% and isoprene of 3-7%, 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 0.05-3.0% 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 3.0-5.0% 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 5.0-7.0 hr, finally adding a terminator, discharging, coagulating, washing and drying to obtain the wide-distribution four-arm comb-branched butyl rubber product.
The nucleating agent is a quaternary four-arm comb-shaped star polymer (SBR- (DVB) BR- (DVB) IR-) containing isoprene, 1, 3-butadiene, styrene and divinyl benzene (DVB) and having wide vinyl distribution]nY) with a general structural formula shown in formula I:
Figure BDA0002773984480000051
wherein Y is 3, 3-diethylpentane; DVB is divinylbenzene; IR is an isoprene homopolymer block, and the 1, 2-structure content of the block is 14-19 percent; BR is a 1, 3-butadiene homopolymer block, and the 1, 2-structure content of the BR is 15-20%; SBR is a styrene and butadiene random block copolymer, wherein the content of styrene is 20-30 percent, and the content of 1, 3-butadiene is 10-20 percent; the quaternary four-arm comb star polymer has the number average molecular weight (Mn) of 60000-80000 and the molecular weight distribution (Mw/Mn) of 7.35-8.68.
The halogenating agent is one of liquid chlorine and liquid bromine, preferably liquid bromine, the dosage of the halogenating agent is determined according to the dosage of the 3, 9-dioxo [5.5] spiroundecane, and the molar ratio of the dosage of the liquid bromine to the 3, 9-dioxo [5.5] spiroundecane is 4.5-6.5.
The catalyst of the invention is HCl-CH3A mixed aqueous solution of OH, wherein the molar concentration of HCl is: 0.1 to 0.7 mol/L.
The dosage of the coupling agent is determined according to the amount of the initiator, and the molar ratio of the dosage of the coupling agent to the organic lithium is 1.0-5.0.
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 one of 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, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, preferably methyl chloride.
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 HCl. Wherein the total addition of the coinitiator is0.1 to 2.0% by mole of protonic acid to alkylaluminum halide, 0.05:1 to 0.5: 1.
The diluent is selected from one of methane chloride, methylene dichloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, and the methane chloride is preferred.
The solvent is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene or ethylbenzene, and cyclohexane is preferred.
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 treats 3, 9-dioxo [5.5]]Performing halogenation reaction on the spiro undecane to synthesize a novel coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane; then alkyl lithium is taken as an initiator to be added at one time, a reaction monomer consists of isoprene, 1, 3-butadiene and styrene, and a long chain segment [ -SBR-BR-IR-]n(ii) a Then coupled with a novel coupling agent 1, 5-dibromo-3, 3 bis (2-bromoethyl) to prepare the ternary four-arm star polymer [ -SBR-BR-IR-]nY, then synthesizing the wide-distribution quaternary four-arm comb-shaped star nucleating agent ([ - (DVB) SBR- (DVB) BR- (DVB) IR-) with Divinylbenzene (DVB) under the action of an initiator 2]nY); finally, under the catalysis system of compounding alkyl aluminum halide and protonic acid, isobutene and isoprene utilize nucleating agent ([ - (DVB) SBR- (DVB) BR- (DVB) IR-]nY) preparing the four-arm comb-shaped star-branched butyl rubber with wide molecular weight distribution by a first-arm and second-core method through cationic polymerization.
Wide-distribution four-element four-arm combStar nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nThe Y contains a four-arm comb-shaped star structure, the structure can 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 viscoelasticity, the stress relaxation rate is high, the extrusion swelling effect is small, and the processability of the butyl rubber is improved; in addition, a certain amount of benzene rings are contained in the-SBR-chain segment in the nucleating agent, 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 four-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. The preparation method provided by the invention has the characteristics of controllable process conditions, stable product performance, suitability for industrial production and the like.
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
N-butyl lithium, 98% purity Nanjing Tongtiang chemical Co., Ltd
3, 9-dioxo [5.5] spiroundecane of 99% purity from Hubei Ferry chemical Co., Ltd
Dibenzoyl peroxide (BPO), Lanzhou auxiliary works
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 four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: firstly, 4L stainless steel with a jacketArgon is introduced into a steel polymerization kettle for 3 times of replacement, 500g of deionized water and 48g of 3, 9-dioxy [5.5] are sequentially added into the polymerization kettle]Spiroundecane, 250g of liquid bromine, 7g of HCl-CH3OH solution (HCl molar concentration: 0.3mol/L), heating to 52 ℃, reacting for 1.8hr, adding 200g NaOH aqueous solution with mass concentration of 15% to terminate the reaction, and finally adding 600g methane chloride to extract, separate, wash and dry to obtain the coupling agent 1, 5-dibromo-3, 3 bis (2-bromoethyl) pentane (yield 87%).
b preparation of the wide-distribution four-arm comb-shaped star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2000g of cyclohexane, 300g of 1, 3-butadiene and 0.8g of THF into the polymerization kettle, heating to 40 ℃, adding 27.1mmo1 n-butyllithium to start reaction, wherein the temperature is gradually increased from 40 ℃ to 60 ℃ within 40min, and the heating speed is 0.5 ℃/min, so as to form a wide-distribution BR chain segment; then sequentially adding 200g of isoprene and 0.7g of THF into a polymerization kettle, reacting within 30min, gradually raising the temperature from 60 ℃ to 75 ℃, and raising the temperature at the speed of 0.5 ℃/min to form an IR chain segment with wide distribution; then 200g of styrene, 100g of 1, 3-butadiene and 1.5g of THF are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, and the reaction is carried out for 40min to form a linear chain segment [ -SBR-BR-IR-]n(ii) a Then the temperature is raised to 80 ℃, 22.5 mmols 11, 5-dibromo-3, 3-di (2-bromoethyl) pentane is added for reaction for 80min, and the [ -SBR-BR-IR-]nY; after the reaction is finished, 1000g of cyclohexane, 50g of DVB and 0.12g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, after the reaction is carried out for 40min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nY (Mn 61000, Mw/Mn 7.38).
(2) Preparation of wide-distribution four-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, 340g of cyclohexane, 280g of isobutene and 9g 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, 2.1g of aluminum sesquiethylate chloride and 0.08g of HCl at-85 ℃, aging for 30min, adding the mixture into the polymerization system, stirring and reactingAfter 0.5hr, 150g of cyclohexane, 9.0g [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nAnd Y, stirring and dissolving for 4.0hr until the nucleating agent is completely dissolved, aging at-85 ℃ for 40min, adding the materials into a polymerization system, stirring and reacting for 5.0hr, adding 200mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the wide-distribution four-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 four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: the same as in example 1.
b, preparation of a wide-distribution four-arm comb-shaped star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2500g of cyclohexane, 320g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle, heating to 40 ℃, adding 29.2mmo1 n-butyllithium to start reaction, wherein the reaction is carried out within 40min, the temperature is gradually increased from 40 ℃ to 60 ℃, and the heating speed is 0.5 ℃/min, so as to form a wide-distribution BR chain segment; then, 220g of isoprene and 1.1g of THF are sequentially added into a polymerization kettle, the reaction is carried out within 30min, the temperature is gradually increased from 60 ℃ to 75 ℃, and the temperature rising speed is 0.5 ℃/min, so as to form an IR chain segment with wide distribution; then, 220g of styrene, 120g of 1, 3-butadiene and 1.9g of THF are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, and the reaction is carried out for 42min to form a wide-distribution linear chain segment [ -SBR-BR-IR-]n(ii) a Then heating to 80 ℃, adding 25.7 mmols of 11, 5-dibromo-3, 3-di (2-bromoethyl) pentane, reacting for 85min to form [ -SBR-BR-IR-]nY; after the reaction is finished, 1200g of cyclohexane, 55g of DVB and 0.18g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, after the reaction is carried out for 45min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nY (Mn of 65000, Mw/Mn of 7.71).
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: firstly, nitrogen gas is introduced into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, 330g of methane chloride, 320g of cyclohexane, 282g of isobutene and 12g of isoprene are sequentially added into a polymerization kettle,stirring and mixing until the temperature of the polymerization system is reduced to-90 ℃, then mixing 130g of methane chloride, 2.5g of aluminum sesquiethylate and 0.09g of HCl at-85 ℃, aging for 32min, adding into the polymerization system together, stirring and reacting for 0.6hr, then adding 160g of cyclohexane, 10.0g of [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nAnd Y, stirring and dissolving for 4.5 hours until the nucleating agent is completely dissolved, aging for 45min at-85 ℃, adding the materials into a polymerization system, stirring and reacting for 5.5 hours, adding 200mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the wide-distribution four-arm comb-shaped star-branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 3
(1) Preparation of the wide-distribution four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: the same as in example 1.
b preparation of the wide-distribution four-arm comb-shaped star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3000g of cyclohexane, 350g of 1, 3-butadiene and 1.3g of THF into the polymerization kettle, heating to 40 ℃, adding 32.2mmo1 n-butyllithium to start reaction, wherein the reaction is carried out within 50min, the temperature is gradually increased from 40 ℃ to 60 ℃, and the heating speed is 0.4 ℃/min, so as to form a BR chain segment with wide distribution; then, sequentially adding 240g of isoprene and 1.5g of THF into the polymerization kettle, reacting within 40min, gradually raising the temperature from 60 ℃ to 75 ℃, and raising the temperature at the speed of 0.4 ℃/min to form an IR chain segment with wide distribution; then 240g of styrene, 140g of 1, 3-butadiene and 2.3g of THF are sequentially added into a polymerization kettle, the temperature is raised to 77 ℃, and the reaction is carried out for 45min to form a wide-distribution linear chain segment [ -SBR-BR-IR-]n(ii) a Then the temperature is raised to 85 ℃, 27.2mmo 11, 5-dibromo-3, 3-di (2-bromoethyl) pentane is added for reaction for 90min, and [ -SBR-BR-IR-]nY; after the reaction is finished, 1400g of cyclohexane, 60g of DVB and 0.24g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 80 ℃, after 50min of reaction, the glue solution is coagulated and dried by a wet method to prepare the nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nY (Mn 72000, Mw/Mn 7.92).
(2) Wide distribution four-arm comb-shaped starPreparation of 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, 284g of isobutene and 14g 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, 3.2g of aluminum sesquiethylate chloride and 0.13g of HCl into the polymerization system after mixing at-90 ℃ and aging for 34min, stirring and reacting for 0.7hr, then adding 170g of cyclohexane and 11.0g of [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nAnd Y, stirring and dissolving for 5.0hr until the nucleating agent is completely dissolved, aging at-90 ℃ for 50min, adding the materials into a polymerization system, stirring and reacting for 6.0hr, adding 230mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the wide-distribution four-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 four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: the same as in example 1.
b preparation of the wide-distribution four-arm comb-shaped star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3300g of cyclohexane, 370g of 1, 3-butadiene and 1.5g of THF into the polymerization kettle, heating to 40 ℃, adding 33.2mmo1 n-butyllithium to start reaction, wherein the reaction is carried out within 50min, the temperature is gradually increased from 40 ℃ to 60 ℃, and the heating speed is 0.4 ℃/min, so as to form a BR chain segment with wide distribution; then, 260g of isoprene and 1.9g of THF are sequentially added into a polymerization kettle, the reaction is carried out within 40min, the temperature is gradually increased from 60 ℃ to 75 ℃, and the temperature rising speed is 0.4 ℃/min, so as to form an IR chain segment with wide distribution; then 260g of styrene, 150g of 1, 3-butadiene and 2.5g of THF are sequentially added into a polymerization kettle, the temperature is raised to 77 ℃, and the reaction is carried out for 47min to form a wide-distribution linear chain segment [ -SBR-BR-IR-]n(ii) a Then heating to 85 ℃, adding 29.5mmo 11, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and reacting for 93min to form [ -SBR-BR-IR-]nY; after the reaction is finished, 1600g of cyclohexane, 70g of DVB and 0.31g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 80 ℃, after 53min of reaction, the glue solution is subjected to wet coagulation and dryingThe nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR-) with a wide distribution four-arm comb-shaped star structure is prepared]nY (Mn 74000, Mw/Mn 8.19).
(2) Preparation of wide-distribution four-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, 286g of isobutene and 16g 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, 3.7g of aluminum sesquiethylate chloride and 0.26g of HCl at-90 ℃, aging for 36min, adding into the polymerization system together, stirring and reacting for 0.8hr, then adding 180g of cyclohexane, 12.0g of [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nAnd Y, stirring and dissolving for 6.0hr until the nucleating agent is completely dissolved, aging at-90 ℃ for 53min, adding the materials into a polymerization system, stirring and reacting for 6.2hr, adding 260mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the wide-distribution four-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 four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: firstly, in a 4L stainless steel polymerization kettle with a jacket, introducing argon for 4 times of replacement, and then adding 600g of deionized water and 65g of 3, 9-dioxygen [5.5] into the polymerization kettle in sequence]Spirocycloundecane, 290g of liquid chlorine, 15g of HCl-CH3OH solution (HCl molar concentration: 0.7mol/L), heating to 85 deg.C, reacting for 4.0hr, adding 300g NaOH aqueous solution with mass concentration of 20% to terminate the reaction, and finally adding 900g methane chloride to extract, separate, wash and dry to obtain the coupling agent 1, 5-dichloro-3, 3 bis (2-chloroethyl) pentane (yield 93%).
b preparation of the wide-distribution four-arm comb-shaped star nucleating agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3700g of cyclohexane, 390g of 1, 3-butadiene and 2.1g of THF into the polymerization kettle, heating to 40 ℃, adding 35.6mmo1 n-butyllithium for starting reaction, wherein the reaction is carried out within 60min, the temperature is gradually increased from 40 ℃ to 60 ℃, the heating speed is 0.6 ℃/min, and wide-distribution B is formedAn R chain segment; then sequentially adding 280g of isoprene and 2.3g of THF into a polymerization kettle, reacting within 60min, gradually increasing the temperature from 60 ℃ to 75 ℃, and increasing the temperature at a speed of 0.3 ℃/min to form an IR chain segment with wide distribution; then adding 280g of styrene, 180g of 1, 3-butadiene and 3.2g of THF into a polymerization kettle in sequence, heating to 80 ℃, and reacting for 49min to form a wide-distribution linear chain segment [ -SBR-BR-IR-]n(ii) a Then heating to 85 deg.C, adding 30.2mmo 11, 5-dichloro-3, 3 bis (2-chloroethyl) pentane, reacting for 96min to form [ -SBR-BR-IR-]nY; after the reaction is finished, 1800g of cyclohexane, 80g of DVB and 0.37g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 83 ℃, after the reaction is carried out for 55min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nY (Mn 77000, Mw/Mn 8.31).
(2) Preparation of wide-distribution four-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 360g of methane chloride, 280g of cyclohexane, 289g of isobutene and 18g of isoprene into the polymerization kettle, stirring and mixing until the temperature of a polymerization system is reduced to-100 ℃, then adding 180g of methane chloride, 4.9g of aluminum sesquiethylate chloride and 0.35g of HCl into the polymerization system after mixing at-95 ℃, aging for 37min, stirring and reacting for 0.9hr, then adding 190g of cyclohexane, 14.0g of [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nAnd Y, stirring and dissolving for 5.5 hours until the grafting agent is completely dissolved, aging at-95 ℃ for 57min, adding the materials into a polymerization system, stirring and reacting for 6.5 hours, adding 300mL of methanol to terminate the reaction, discharging, condensing, washing and drying to obtain the wide-distribution four-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 four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: the same as in example 5.
b preparation of the wide-distribution four-arm comb-shaped star nucleating agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 4 times, and sequentially adding 4000g of argon into the polymerization kettleCyclohexane, 400g of 1, 3-butadiene and 2.9g of THF, heating to 40 ℃, adding 37.5mmo1 n-butyllithium to start reaction, reacting within 60min, gradually heating from 40 ℃ to 60 ℃, and heating at the speed of 0.6 ℃/min to form a BR chain segment with wide distribution; then sequentially adding 300g of isoprene and 3.3g of THF into the polymerization kettle, reacting within 60min, gradually raising the temperature from 60 ℃ to 75 ℃, and raising the temperature at the speed of 0.3 ℃/min to form an IR chain segment with wide distribution; then 300g of styrene, 200g of 1, 3-butadiene and 4.3g of THF are sequentially added into a polymerization kettle, the temperature is raised to 80 ℃, and the reaction is carried out for 50min to form a linear chain segment [ -SBR-BR-IR-]n(ii) a Then heating to 90 deg.C, adding 32.5mmo 11, 5-dichloro-3, 3-di (2-chloroethyl) pentane, reacting for 100min to form [ -SBR-BR-IR-]nY; after the reaction is finished, 2000g of cyclohexane, 90g of DVB and 0.45g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 85 ℃, after the reaction is carried out for 60min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nY (Mn of 79000, Mw/Mn of 8.62).
(2) Preparation of the wide-distribution four-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, adding 340g of methane chloride, 270g of cyclohexane, 291g of isobutene and 20g of isoprene into the polymerization kettle in sequence, stirring and mixing until the temperature of a polymerization system is reduced to-100 ℃, then adding 180g of methane chloride, 5.2g of aluminum sesquiethylate chloride and 0.42g 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 15.0g of [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nAnd Y, stirring and dissolving for 6.0hr until the grafting agent is completely dissolved, aging at-95 ℃ for 60min, adding the materials into a polymerization system, stirring and reacting for 7.0hr, adding 350mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the wide-distribution four-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 four-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 1 except that:no nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nY, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 320g of methane chloride, 340g of cyclohexane, 280g of isobutene and 9g 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, 2.1g of aluminum sesquiethyl 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 200mL of methanol to terminate the reaction, finally discharging, condensing, washing and drying to obtain the wide-distribution four-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 2
(1) Preparation of the wide-distribution four-arm comb-shaped star nucleating agent: the other conditions were the same as in example 2 except that: in the synthesis process, 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane is not added, but a conventional coupling agent of silicon tetrachloride (SiCl) is added4) Namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2500g of cyclohexane, 320g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle, heating to 40 ℃, adding 29.2mmo1 n-butyllithium to start reaction, wherein the reaction is carried out within 40min, the temperature is gradually increased from 40 ℃ to 60 ℃, and the heating speed is 0.5 ℃/min, so as to form a wide-distribution BR chain segment; then, 220g of isoprene and 1.1g of THF are sequentially added into a polymerization kettle, the reaction is carried out within 30min, the temperature is gradually increased from 60 ℃ to 75 ℃, and the temperature rising speed is 0.5 ℃/min, so as to form an IR chain segment with wide distribution; then, 220g of styrene, 120g of 1, 3-butadiene and 1.9g of THF are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, and the reaction is carried out for 42min to form a wide-distribution linear chain segment [ -SBR-BR-IR-]n(ii) a Subsequently, the temperature was increased to 80 ℃ and 25.7mmo1 SiCl was added4Reacting for 85min to form [ -SBR-BR-IR-]nSi; after the reaction is finished, 1200g of cyclohexane, 55g of DVB and 0.18g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, after the reaction is carried out for 45min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nSi (Mn 61000, Mw/Mn 5.87).
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 2 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nY, but adding a nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nSi, namely: firstly, nitrogen gas is introduced into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, 330g of methane chloride, 320g of cyclohexane, 282g of isobutene and 12g of isoprene are sequentially added into a polymerization kettle, stirred and mixed until the temperature of a polymerization system is reduced to minus 90 ℃, then 130g of methane chloride, 2.5g of aluminum sesquiethylate and 0.09g of HCl are mixed at the temperature of minus 85 ℃, aged for 32min, added into the polymerization system together and stirred for reaction for 0.6hr, then 160g of cyclohexane, 10.0g of [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nAnd Si, stirring and dissolving for 4.5 hours until the nucleating agent is completely dissolved, then aging for 45min at-85 ℃, adding the materials into a polymerization system together, stirring and reacting for 5.5 hours, adding 200mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the wide-distribution four-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
(1) Preparation of the wide-distribution four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: the same as in example 3.
b preparation of the wide-distribution four-arm comb-shaped star nucleating agent: the other conditions were the same as in example 3 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 3 times, sequentially adding 3000g of cyclohexane, 350g of 1, 3-butadiene and 1.3g of THF into the polymerization kettle, heating to 40 ℃, adding 32.2mmo1 n-butyllithium to start reaction, and reacting for 50min to form BR1A chain segment; then, sequentially adding 240g of isoprene and 1.5g of THF into the polymerization kettle, reacting within 40min, gradually raising the temperature from 60 ℃ to 75 ℃, and raising the temperature at the speed of 0.4 ℃/min to form an IR chain segment with wide distribution; then 240g of styrene, 140g of 1, 3-butadiene and 2.3g of THF are sequentially added into the polymerization kettle, the temperature is raised to 77 ℃, and the reaction is carried out for 45min to form the polymer with wide distributionLinear segment [ -SBR-BR ]1-IR-]n(ii) a Then heating to 85 deg.C, adding 27.2mmo 11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, reacting for 90min to form [ -SBR-BR1-IR-]nY; after the reaction is finished, 1400g of cyclohexane, 60g of DVB and 0.24g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 80 ℃, after the reaction is carried out for 50min, the glue solution is coagulated and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) BR with the wide-distribution four-arm comb-shaped star structure is prepared1-(DVB)IR-]nY (Mn of 70000, Mw/Mn of 6.52).
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 3 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nY, but adding a nucleating agent [ - (DVB) SBR- (DVB) BR1-(DVB)IR-]nY, namely: 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, 284g of isobutene and 14g 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, 3.2g of aluminum sesquiethylate chloride and 0.13g of HCl into the polymerization system after mixing at-90 ℃, aging for 34min, stirring and reacting for 0.7hr, then adding 170g of cyclohexane, 11.0g of [ - (DVB) SBR- (DVB) BR1-(DVB)IR-]nAnd Y, stirring and dissolving for 5.0hr until the nucleating agent is completely dissolved, aging at-90 ℃ for 50min, adding the materials into a polymerization system, stirring and reacting for 6.0hr, adding 230mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the wide-distribution four-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 four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: the same as in example 4.
b preparation of the wide-distribution four-arm comb-shaped star nucleating agent: the other conditions were the same as in example 4 except that: in the temperature-changing polymerization of 1, 3-butadiene, the temperature-rising speed is 1.6 ℃/min, namely: firstly, the reaction is carried out on 15L stainless steel with a jacketIntroducing argon into a polymerization kettle for 3 times of replacement, sequentially adding 3300g of cyclohexane, 370g of 1, 3-butadiene and 1.5g of THF into the polymerization kettle, heating to 40 ℃, adding 33.2mmo1 n-butyllithium to start reaction, wherein the reaction is carried out within 50min, the temperature is gradually increased from 40 ℃ to 60 ℃, and the heating rate is 1.6 ℃/min, so that widely distributed BR is formed2A chain segment; then, 260g of isoprene and 1.9g of THF are sequentially added into a polymerization kettle, the reaction is carried out within 40min, the temperature is gradually increased from 60 ℃ to 75 ℃, and the temperature rising speed is 0.4 ℃/min, so as to form an IR chain segment with wide distribution; then 260g of styrene, 150g of 1, 3-butadiene and 2.5g of THF are sequentially added into a polymerization kettle, the temperature is raised to 77 ℃, and the reaction is carried out for 47min to form a wide-distribution linear chain segment [ -SBR-BR ]2-IR-]n(ii) a Then heating to 85 deg.C, adding 29.5mmo 11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, reacting for 93min to form [ -SBR-BR2-IR-]nY; after the reaction is finished, 1600g of cyclohexane, 70g of DVB and 0.31g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 80 ℃, after 53min of reaction, the glue solution is coagulated and dried by a wet method to prepare the nucleating agent [ - (DVB) SBR- (DVB) BR with a wide-distribution four-arm comb-like star structure2-(DVB)IR-]nY (Mn 71000, Mw/Mn 6.23).
(2) Preparation of the wide-distribution four-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 4 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nY, but adding a nucleating agent [ - (DVB) SBR- (DVB) BR2-(DVB)IR-]nY, namely: firstly, nitrogen gas is introduced into a 4L stainless steel reaction kettle with a jacket for replacing 4 times, 350g of methane chloride, 300g of cyclohexane, 286g of isobutene and 16g of isoprene are sequentially added into the polymerization kettle, stirred and mixed until the temperature of a polymerization system is reduced to-95 ℃, then 160g of methane chloride, 3.7g of sesquiethylaluminum chloride and 0.26g of HCl are mixed at-90 ℃, aged for 36min, added into the polymerization system together and stirred for reaction for 0.8hr, then 180g of cyclohexane, 12.0g of [ - (DVB) SBR- (DVB) BR2-(DVB)IR-]nY, stirring and dissolving for 6.0hr until the nucleating agent is completely dissolved, aging at-90 deg.C for 53min, adding into the polymerization system, stirring and reacting for 6.2hr, adding 260mL methanol to terminate the reaction, and dischargingCoagulating, washing and drying to obtain the wide-distribution four-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 four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: the same as in example 5.
b, preparation of a four-arm comb-shaped 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 70 ℃, namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3700g of cyclohexane, 390g of 1, 3-butadiene and 2.1g of THF into the polymerization kettle, heating to 40 ℃, adding 35.6mmo1 n-butyllithium to start reaction, wherein the reaction is carried out within 60min, the temperature is gradually increased from 40 ℃ to 60 ℃, and the heating speed is 0.6 ℃/min, so as to form a BR chain segment with wide distribution; then adding 280g of isoprene and 2.3g of THF into the polymerization kettle in sequence, heating to 70 ℃ and reacting for 60min to form IR1A chain segment; then adding 280g of styrene, 180g of 1, 3-butadiene and 3.2g of THF into a polymerization kettle in sequence, heating to 80 ℃, and reacting for 49min to form a wide-distribution linear chain segment [ -SBR-BR-IR1-]n(ii) a Then heating to 85 deg.C, adding 30.2mmo 11, 5-dichloro-3, 3 di (2-chloroethyl) pentane, reacting for 96min to form [ -SBR-BR-IR1-]nY; after the reaction is finished, 1800g of cyclohexane, 80g of DVB and 0.37g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 83 ℃, after 55min of reaction, the glue solution is coagulated and dried by a wet method, and the nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR with a wide-distribution four-arm comb-shaped star structure is prepared1-]nY (Mn of 73000, Mw/Mn of 6.71).
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 5 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nY, but adding a nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR1-]nY, namely: firstly, nitrogen is introduced into a 4L stainless steel reaction kettle with a jacket for replacement for 4 times, and 360g of methane chloride and cyclohexane are sequentially added into a polymerization kettle280g of methane, 289g of isobutene and 18g of isoprene are stirred and mixed until the temperature of a polymerization system is reduced to-100 ℃, then 180g of methane chloride, 4.9g of sesquiethylaluminum chloride and 0.35g of HCl are mixed at-95 ℃, then aged for 37min, added into the polymerization system together and stirred for reaction for 0.9hr, and then 190g of cyclohexane and 14.0g of [ - (DVB) SBR- (DVB) BR- (DVB) IR1-]nAnd Y, stirring and dissolving for 5.5 hours until the grafting agent is completely dissolved, aging at-95 ℃ for 57min, adding the materials into a polymerization system, stirring and reacting for 6.5 hours, adding 300mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the wide-distribution four-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 four-arm comb-shaped star nucleating agent:
a preparation of a coupling agent: the same as in example 6.
b preparation of the wide-distribution four-arm comb-shaped star nucleating agent: the other conditions were the same as in example 6 except that: styrene and 1, 3-butadiene are not added in the synthesis process, and a-SBR-chain segment is not formed, namely: firstly, introducing argon to a 15L stainless steel reaction kettle with a jacket for replacing for 4 times, sequentially adding 4000g of cyclohexane, 400g of 1, 3-butadiene and 2.9g of THF into the polymerization kettle, heating to 40 ℃, adding 37.5mmo1 n-butyl lithium to start reaction, wherein the temperature is gradually increased from 40 ℃ to 60 ℃ within 60min, and the heating speed is 0.6 ℃/min to form a BR chain segment with wide distribution; then 300g of isoprene and 3.3g of THF are sequentially added into the polymerization kettle, the reaction is carried out within 60min, the temperature is gradually increased from 60 ℃ to 75 ℃, the temperature rising speed is 0.3 ℃/min, and the widely distributed [ -BR-IR-]nA chain segment; then heating to 90 deg.C, adding 32.5mmo 11, 5-dichloro-3, 3-di (2-chloroethyl) pentane, reacting for 100min to form [ -BR-IR-]nY; after the reaction is finished, 2000g of cyclohexane, 90g of DVB and 0.45g of BPO are sequentially added into a polymerization kettle, the temperature is raised to 85 ℃, after the reaction is carried out for 60min, the glue solution is condensed and dried by a wet method, and the nucleating agent [ - (DVB) BR- (DVB) IR-]nY (Mn of 57000, Mw/Mn of 5.62).
(2) Preparation of wide-distribution four-arm comb-shaped star-branched butyl rubber: the other conditions were the same as in example 6 except that: no nucleating agent [ - (DVB) SBR- (DVB) BR- (DVB) IR-]nY, but adding a nucleating agent [ - (DVB) BR- (DVB) IR-]nY, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, adding 340g of methane chloride, 270g of cyclohexane, 291g of isobutene and 20g of isoprene into the polymerization kettle in sequence, stirring and mixing until the temperature of a polymerization system is reduced to-100 ℃, then adding 180g of methane chloride, 5.2g of sesquiethylaluminum chloride and 0.42g of HCl into the polymerization system after aging for 40min after mixing at-95 ℃, stirring and reacting for 1.0hr, then adding 200g of cyclohexane, 15.0g of [ - (DVB) BR- (DVB) IR-]nAnd Y, stirring and dissolving for 6.0hr until the grafting agent is completely dissolved, aging at-95 ℃ for 60min, adding the materials into a polymerization system, stirring and reacting for 7.0hr, adding 350mL of methanol to terminate the reaction, and finally discharging, condensing, washing and drying to obtain the wide-distribution four-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 four-arm comb-like Star-branched butyl rubber
Figure BDA0002773984480000191
Figure BDA0002773984480000201
As can be seen from Table 1: the wide-distribution four-arm comb-shaped star-branched butyl rubber has high tensile strength, good air tightness, lower Mooney relaxation area and good processability (the smaller the area under a stress relaxation curve is, the lower the mixing processing energy consumption is).
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (19)

1. A preparation method of wide-distribution four-arm comb-shaped star-branched butyl rubber comprises the following steps:
(1) styrene, 1, 3-butadiene, isoprene and divinylbenzene are taken as reaction monomers, 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane is taken as a coupling agent, and the four-arm pectinate star-shaped nucleating agent is prepared by utilizing a method of combining temperature-changing and speed-changing polymerization, anionic polymerization and free radical polymerization;
(2) isobutene and isoprene are taken as reaction monomers to carry out cationic polymerization with a four-arm comb-shaped star nucleating agent at the temperature of-95 to-85 ℃ to prepare the four-arm comb-shaped star-branched butyl rubber;
the structural general formula of the four-arm comb-shaped star nucleating agent is shown as the formula I:
Figure FDA0002773984470000011
wherein IR is an isoprene homopolymer block, and the 1, 2-structure content of the block is 14-19 percent; BR is a 1, 3-butadiene homopolymer block, and the 1, 2-structure content of the BR is 15-20%; the SBR is a styrene and 1, 3-butadiene random block copolymer, wherein the content of the styrene is 20-30 percent, and the content of the 1, 3-butadiene is 10-20 percent; the number average molecular weight of the four-arm comb-shaped star nucleating agent is 60000-80000, and the ratio of the weight average molecular weight to the number average molecular weight is 7.35-8.68.
2. The method of claim 1, wherein the specific manufacturing process comprises the steps of:
(1) preparation of four-arm comb-shaped star nucleating agent: based on the total mass of reaction monomers, firstly, sequentially adding a solvent, 30-40% of 1, 3-butadiene, 0.05-0.1% of a structure regulator and an initiator 1 into a polymerization kettle, wherein the reaction is temperature-changing polymerization, the temperature is gradually increased from 40 ℃ to 60 ℃, and the temperature-increasing speed is less than 1.3 ℃/min until the conversion rate of the 1, 3-butadiene monomer reaches 100%; then sequentially adding 20-30% of isoprene and 0.05-0.1% of structure regulator into the polymerization kettle, gradually raising the temperature from 60 ℃ to 75 ℃, and raising the temperature at a speed of less than 1.0 ℃/min until the conversion rate of isoprene monomer reaches 100%; then sequentially adding 20-30% of styrene, 10-20% of 1, 3-butadiene and 0.05-0.5% of structure regulator into a polymerization kettle, heating to 75-80 ℃, and reacting for 40-50 min; finally, heating to 80-90 ℃, adding a 1, 5-dihalo-3, 3-di (2-haloethyl) pentane coupling agent for coupling reaction, after the reaction is finished, sequentially adding a solvent, 5-10% of divinylbenzene and 20.001-0.2% of an initiator into a polymerization kettle, heating to 75-85 ℃, condensing and drying a glue solution after the reaction is finished by a wet method, and preparing the four-arm comb-shaped star-shaped nucleating agent;
(2) preparation of four-arm comb-shaped star-branched butyl rubber: based on the total mass of reaction monomers, firstly, sequentially adding a mixed solvent consisting of a diluent and a solvent into a polymerization kettle, wherein the volume ratio of the diluent to the solvent is 60-40/40-60, the isobutylene is 93-97%, and the isoprene is 3-7%, stirring and mixing until the temperature of a polymerization system is reduced to-100-90 ℃, mixing and aging a diluent and 0.05-3.0% of a coinitiator for 30-40 min at the temperature of-95-85 ℃, adding the components into a polymerization system, stirring and reacting for 0.5-1.0 hr, then mixing and dissolving 3.0-5.0% of four-arm comb-shaped star-shaped nucleating agent and solvent for 4.0-6.0 hr, aging at-95 to-85 ℃ for 40 to 60min, adding the mixture into a polymerization kettle, stirring and reacting for 5.0 to 7.0hr, adding a terminator, discharging, condensing, washing and drying to obtain a four-arm comb-shaped star-branched butyl rubber product;
the polymerization reaction is carried out in an oxygen-free and water-free environment.
3. The method of claim 2, wherein the initiator 1 is selected from the group consisting of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, lithium naphthalide, cyclohexyllithium, and dodecyllithium.
4. The method of claim 3 wherein said initiator is n-butyllithium.
5. The method of claim 2 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.
6. The method of claim 5, wherein said initiator 2 is dibenzoyl peroxide.
7. The method of claim 2, 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.
8. The method of claim 7, wherein said structure modifier is tetrahydrofuran.
9. The method according to claim 2, 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.
10. The method of claim 9 wherein the alkyl aluminum halide is selected from at least one of diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloroide, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, n-propylaluminum dichloride, diisopropylaluminum dichloride, dimethylaluminum chloride and ethylaluminum chloride.
11. The method of claim 10 wherein the alkyl aluminum halide is aluminum sesquiethyl chloride.
12. The method of claim 9, wherein the protic acid is selected from the group consisting of HCl, HF, HBr, H2SO4、H2CO3、H3PO4Or HNO3One kind of (1).
13. The method of claim 12, wherein the protic acid is HCl.
14. The method of claim 2, 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.
15. The method of claim 14, wherein the diluent is methyl chloride.
16. The method of claim 2, wherein the solvent is selected from the group consisting of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene, and ethylbenzene.
17. The method of claim 16, wherein the solvent is cyclohexane.
18. The method of claim 2, wherein the terminating agent is selected from one or more of methanol, ethanol, butanol.
19. The method of claim 2, wherein steps (1) and (2) are performed in an inert gas environment.
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