CN113831472B - Preparation method of ultra-wide molecular weight distribution and hyperbranched butyl rubber - Google Patents

Preparation method of ultra-wide molecular weight distribution and hyperbranched butyl rubber Download PDF

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CN113831472B
CN113831472B CN202010589783.7A CN202010589783A CN113831472B CN 113831472 B CN113831472 B CN 113831472B CN 202010589783 A CN202010589783 A CN 202010589783A CN 113831472 B CN113831472 B CN 113831472B
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polymerization kettle
polymerization
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isoprene
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CN113831472A (en
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徐典宏
李福崇
杨绮波
翟云芳
朱晶
李旭
窦彤彤
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/044—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
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
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Abstract

The invention relates to a preparation method of ultra-wide molecular weight distribution and hyperbranched butyl rubber, which comprises the steps of firstly synthesizing a novel coupling agent of 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane, then preparing four kinds of chain segments with different wide vinyl content distribution and wide molecular weight distribution through four-kettle reaction by taking isoprene, styrene and butadiene as reaction monomers, and preparing a ternary four-hybrid-arm star copolymer through coupling by adopting variable temperature polymerization and variable speed polymerization. The ternary tetra-heteroarm star-shaped copolymer is used as a grafting agent to prepare ultra-wide molecular weight distribution and hyperbranched butyl rubber by cationic polymerization with isobutene and isoprene under a catalytic system compounded by alkyl aluminum halide and protonic acid. The invention realizes the optimal balance between the processability and the physical and mechanical properties of the butyl rubber, and ensures that the butyl rubber has good processability while having enough green rubber strength and good air tightness.

Description

Preparation method of ultra-wide molecular weight distribution and hyperbranched butyl rubber
Technical Field
The invention relates to a preparation method of ultra-wide molecular weight distribution and hyperbranched butyl rubber, in particular to a method for preparing ultra-wide molecular weight distribution and hyperbranched butyl rubber by taking ternary four-hetero-arm star-shaped copolymer synthesized by isoprene, styrene and butadiene as a grafting agent and carrying out cationic polymerization on the ternary four-hetero-arm star-shaped copolymer, isobutylene and isoprene.
Background
Butyl Rubber (IIR) is known to be copolymerized from isobutylene and a small amount of isoprene by cationic polymerization. Butyl rubber has been industrialized by Exxon corporation in the united states in the 40 th century for over seventy years, and has been widely used in the fields of inner tubes, inner liners, curing bladder, medical plugs, etc. for manufacturing tires for vehicles because of its excellent air tightness, damping property, heat aging resistance, ozone resistance, weather resistance, etc.
However, the molecular chain of butyl rubber mainly consists of single bonds of carbon and carbon, the number of double bonds is small, substituent methyl groups are symmetrically arranged, and the defects of high crystallinity, poor flexibility of the molecular chain, low stress relaxation rate, low vulcanization speed, poor adhesion, poor compatibility with other general rubber and the like exist, so that the butyl rubber is easy to excessively flow and deform in the processing process. How to achieve a balance of physical and mechanical properties and processability of butyl rubber has become a bottleneck in the preparation of high performance butyl rubber materials.
In recent years, researchers find that star-shaped highly branched butyl rubber with a unique three-dimensional network structure, which consists of a high molecular weight grafted structure and a low molecular weight linear structure, has excellent viscoelastic performance, high green strength and fast stress relaxation rate, can keep low melt viscosity in the processing process, can obtain a high molecular weight polymer, and realizes uniform balance of physical and mechanical properties and processing properties. The star-shaped hyperbranched structure has become one of the hot spots in the future butyl rubber research field.
In the prior art, the synthesis of star-shaped hyperbranched butyl rubber is mainly prepared by adopting a method of a first nucleus and then arm method, a method of a first arm and then nucleus and a method of a simultaneous nuclear arm method. Such as: US5395885 discloses a star-shaped hyperbranched polymer which is synthesized by a method of firstly preparing arms and then preparing cores under the condition of minus 90 ℃ to minus 100 ℃ by taking polyisobutene as arms, taking Polydivinylbenzene (PDVB) as cores, taking a complex of aluminum chloride and water as an initiator and taking chloromethane as a diluentStar-shaped hyperbranched polyisobutene-polydivinylbenzene polymers. CN 107344982A discloses a process for producing butyl rubber with broad/bimodal molecular weight distribution, which comprises: mixing isobutene and isoprene in a molar ratio of 97:3 to 99:1, mixing the mixture with a diluent (methyl chloride) to obtain a monomer stream, mixing an initiator (an aluminum chloride system and a complex of HCl/aluminum alkyl chloride) and the diluent (methyl chloride) to obtain an initiator stream, mixing the monomer stream and the initiator stream, feeding the mixed mixture into a first loop reactor zone, and carrying out polymerization for 5-10min at a temperature of-98 ℃ to-96 ℃ and a pressure of 0.3 to 0.4Mpa to obtain a first part of butyl rubber slurry; the second step, the first part of butyl rubber slurry is sent into a second loop reactor zone, and the butyl rubber slurry with broad/bimodal molecular weight distribution is finally obtained after polymerization reaction for 5-10min at the temperature of-92 ℃ to-90 ℃ and the pressure of 0.1 to 0.2 Mpa; and thirdly, contacting the butyl rubber slurry with the broad/bimodal molecular weight distribution with water, removing unreacted monomers and diluents to obtain colloidal particle water, and dehydrating and drying the colloidal particle water to obtain the butyl rubber with the broad/bimodal molecular weight distribution (Mw/Mn) of at least 5.0. CN1427851a discloses a process for preparing butyl rubber with a broad molecular weight distribution. The process uses a mixed catalyst system comprising a mixture of a major amount of internalized dialkylaluminum, a minor amount of monoalkylaluminum dihalide and a minor amount of aluminoxane to provide a broad distribution butyl rubber having a molecular weight distribution of greater than 3.5 and up to 7.6. CN 101353403B discloses a preparation method of star-shaped hyperbranched polyisobutene or butyl rubber, which adopts a polystyrene/isoprene segmented copolymer with a silicon-chlorine group at the end or a polystyrene/butadiene segmented copolymer with a silicon-chlorine group at the end as a grafting agent for initiating cationic polymerization, and directly participates in the cationic polymerization in a cationic polymerization system with a chloromethane/cyclohexane v ratio of 20-80/80-20 mixed solvent under the temperature condition of 0-minus 100 ℃, and prepares the star-shaped hyperbranched polyisobutene or butyl rubber product by initiating the cationic polymerization of the silicon-chlorine group and participating in the grafting reaction through an unsaturated chain. CN01817708.5 provides a method of crosslinking by adding a multiolefin to a mixture of isoolefin monomers and diolefin monomers Agents such as divinylbenzene) and chain transfer agents (e.g., 2,4, 1-trimethyl-1-pentene), star-shaped hyperbranched polymers are prepared by multiolefin crosslinking agents. CN88108392.5 discloses a star-shaped graft butyl rubber with comb structure prepared by using a hydrochloride polystyrene-isoprene copolymer as a polyfunctional initiator or using polystyrene-butadiene or polystyrene-isoprene as a grafting agent. CN 107793535A provides a butyl rubber having a molecular weight of 90 to 260 tens of thousands, log (MW)>6 and contains structural units derived from isobutylene, structural units derived from conjugated dienes, and optionally structural units derived from aryl olefins. US3780002 proposes a complex initiator comprising a metal halide of group II or III of the periodic Table and a tetrahalide of a metal of group IV of the periodic Table, e.g. AICl 3 With TiC1 4 For combined use, or by combining A1C1 3 With SnC1 4 The composite use makes each initiator independently initiate cationic polymerization, and the butyl rubber with the molecular weight distribution index Mw/Mn above 5.0 is synthesized under the conventional Ding Mou rubber polymerization condition.
CN 101353386a discloses an initiating system for star-shaped hyperbranched polyisobutene or butyl rubber cationic polymerization, which consists of an initiating-grafting agent, a co-initiating agent and a nucleophilic reagent, and is used for initiating vinyl monomers to carry out homo-, block-and star-polymerization and graft copolymerization, and the obtained polymer shows obvious bimodal distribution. Puskas (Catalysts for manufacture of IIR with bimodal molecular weight distribution: U.S. Pat. No. 5,94538,1993-3-16.) uses trimesic acid as raw material to synthesize the initiator tricumyl alcohol with three-arm structure, and then uses the tricumyl alcohol/aluminum trichloride initiation system to initiate isobutene and isoprene copolymerization in inert organic solvent at-120 deg.C to-50 deg.C, thus synthesizing the star-shaped hyperbranched butyl rubber with bimodal molecular weight distribution. Wieland et al (Synthesis of new graft copolymers containing polyisobutylene by acombination of the, 1-diphenylethylene techniqueand cationic polymerization [ J ]. Polymer Science: polymer Chemistry,2002, 40:3725-3733.) synthesized a macroinitiator P (MMA-b-St-co-CMS) containing a ternary of 4-chloromethylstyrene, styrene and methyl methacrylate in the presence of 1, 2-stilbene (DPE) by radical polymerization, and initiated cationic polymerization of isobutylene and isoprene with the macroinitiator to successfully prepare a multi-arm star butyl rubber. Wu Yibo et al (Davang S H, et al, skid resistant coatings for aircraft carrier decks [ J ]. Coat technology, 1980, 52 (671): 65-69.) Poly (isoprene-styrene) block copolymers were prepared by living anionic polymerization as grafting agents and star-shaped hyperbranched butyl rubber exhibiting a distinct bimodal appearance was prepared by living carbon cationic polymerization in the initiation system of 2-chloro-2, 4-trimethylpentane/titanium tetrachloride/proton scavenger.
Disclosure of Invention
The invention aims to provide a preparation method of ultra-wide molecular weight distribution and hyperbranched butyl rubber. The invention adopts a four-kettle reaction, takes alkyl lithium as an initiator, takes synthesized 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane as a coupling agent, and adopts a reaction monomer consisting of isoprene, styrene and butadiene to prepare the star-shaped copolymer with a ternary four-hetero-arm structure through temperature and speed changing polymerization. Finally, under the catalysis system of Lewis acid and protonic acid, the ternary four-hetero-arm star-shaped copolymer is used as a grafting agent to carry out cationic polymerization with isobutene and isoprene to prepare the ultra-wide molecular weight distribution and hyperbranched butyl rubber. The method solves the problems of easy extrusion swelling and slow stress relaxation rate of the butyl rubber in the processing process, so that the ultra-wide molecular weight distribution and the hyperbranched butyl rubber can obtain excellent processability with fast stress relaxation rate and small extrusion swelling effect in the processing process, meanwhile, the butyl rubber is ensured to have enough green rubber strength and good air tightness, and the balance of physical and mechanical properties and processability is realized.
The "%" of the invention refers to mass percent.
The preparation of the hyperbranched star-shaped butyl rubber is carried out in a reaction kettle, and the specific preparation process comprises the following steps:
(1) Preparation of grafting agent:
a, preparation of a coupling agent: based on hundred percent of the total mass of reactants, firstly, 100 to 200 percent of deionized water, 3, 9-dioxy [5.5] spiro undecane, halogenating agent and 1 to 5 percent of catalyst are sequentially added into a polymerization kettle in inert gas atmosphere, the temperature is raised to 50 to 80 ℃, after the reaction is carried out for 1 to 3 hours, 20 to 40 percent of NaOH aqueous solution with the mass concentration of 10 to 20 percent is added for terminating the reaction, and finally 200 to 300 percent of chloromethane is added for extraction, separation, washing and drying, thus obtaining the coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane (the yield is 85 to 95 percent).
b, preparation of grafting agent: sequentially adding 100-200% of solvent, 0.1-0.3% of structure regulator and initiator into a polymerization kettle A in an inert gas atmosphere according to one hundred percent of the total mass of reaction monomers, heating to 70-80 ℃, stirring and mixing 20-30% of styrene and 10-20% of 1, 3-butadiene for 10-30 min, reacting to obtain variable-speed polymerization, adding the mixture into the polymerization kettle in a continuous injection mode, reacting within 60-80 min, and initiating the feeding speed >10.0% of mixture/min, the feeding speed reduction amplitude is determined according to the reaction time, a random and long transition section-SB/(S-B) -chain section is formed, the conversion rate of styrene and 1, 3-butadiene monomer reaches 100%, the temperature is increased to 80-90 ℃, and the coupling agent prepared in the step a is added for coupling reaction for 60-90 min; simultaneously, in a polymerization kettle B, under the atmosphere of inert gas, sequentially adding 100-200% of solvent, 10-20% of styrene, 5-10% of 1, 3-butadiene, 0.05-0.3% of structure regulator and initiator, wherein the reaction is variable-temperature polymerization, the temperature is gradually increased from 50 ℃ to 80 ℃ within 60-90 min, the temperature rise is a continuous gradual change process, so that an SBR-chain segment with wide vinyl content distribution is formed, the conversion rate of the styrene and 1, 3-butadiene monomers reaches 100%, and after the monomers are completely converted, adding materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 60-90 min; simultaneously, in a polymerization kettle C, under the atmosphere of inert gas, sequentially adding 100-200% of solvent, 5-10% of isoprene, 0.01-0.1% of structure regulator and initiator into the polymerization kettle C, heating to 50-70 ℃ and reacting for 50-70 min to form an IR chain segment; then sequentially adding 5-10% of styrene, 0.05-0.2% of structure regulator and reacting for 40-60 min to form the final product Forming an-IR-PS-chain segment, adding the materials in the polymerization kettle C into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 60-90 min; simultaneously, in a polymerization kettle D, under the atmosphere of inert gas, 100 to 200 percent of solvent, 10 to 15 percent of isoprene and 0.01 to 0.1 percent of structure regulator are sequentially added into the polymerization kettle D, the reaction is temperature-variable polymerization, and the temperature is gradually increased from 40 ℃ to 70 ℃ within 40 to 60min, so that IR with wide molecular weight distribution is formed 1 Adding the materials in the polymerization kettle D into the polymerization kettle A after the isoprene monomer is completely converted, and carrying out coupling reaction for 60-90 min; finally adding 1-4% of 1, 3-butadiene into the polymerization kettle A for end capping, reacting for 20-40 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 the glue solution to obtain the ternary four-hetero-arm star-shaped copolymer ([ -IR-PS-B ]] n [-B-SB/(S→B)-] n Y[-SBR-B-] n [-IR 1 -] n )。
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: firstly, adding 100-200% of diluent and solvent in a polymerization kettle in an inert gas atmosphere according to one hundred percent of the total mass of the reaction monomers: the V ratio is 70-30: 30-70 of a mixed solvent, 1-7% of a grafting agent, and stirring and dissolving for 20-30 min until the grafting agent is completely dissolved; then cooling to minus 75 ℃ to minus 85 ℃, adding 100 to 200 percent of diluent, 85 to 95 percent of isobutene and 1 to 5 percent of isoprene in turn, stirring and mixing until the temperature of a polymerization system is reduced to minus 100 ℃ to minus 90 ℃, then mixing and aging 30 to 50 percent of diluent and 0.05 to 3.0 percent of co-initiator for 20 to 30 minutes at minus 85 ℃ to minus 95 ℃, adding the mixture into the polymerization system together, stirring and reacting for 3.0 to 5.0 hours, discharging, condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product.
The grafting agent is a ternary four-hetero-arm star-type copolymer of isoprene, styrene and butadiene, and the structural general formula of the grafting agent is shown in formula I:
wherein Y is 3, 3-diethyl pentane; SB in SB/(S.fwdarw.B) is a random segment of styrene and butadiene; (S.fwdarw.B) is a gradual change section of styrene and butadiene; SBR is a styrene, butadiene random block copolymer with a broad vinyl content distribution; IR is a homopolymer segment of isoprene; PS is a styrene homopolymer segment; IR (IR) 1 Is an isoprene homopolymer with wide molecular weight distribution; b is a capped butadiene, n=1 to 3; the styrene content in the ternary four-arm star polymer is 45-65%, the 1, 3-butadiene content is 15-25%, and the isoprene content is 10-25%; the ternary four-hetero-arm star-shaped copolymer has a number average molecular weight (Mn) of 10000-50000 and a molecular weight distribution (Mw/Mn) of 16.2-20.1.
The halogenating agent is one of liquid chlorine and liquid bromine, preferably liquid bromine, the dosage of the halogenating agent depends on the dosage of 3, 9-dioxy [5.5] spiro-undecane, and the molar ratio of the dosage of the liquid bromine to the 3, 9-dioxy [5.5] spiro-undecane is 4.5-6.5.
The type of the polymerizer according to the present invention is not limited, but is preferably a jacketed stainless steel polymerizer.
The catalyst of the invention is HCl-CH 3 A mixed aqueous solution of OH, wherein the molar concentration of HCl is: 0.1 to 0.7mol/L.
The structure regulator is a polar organic compound which generates solvation effect in a polymerization system, and can regulate the reactivity ratio of styrene and butadiene to enable the styrene and the butadiene to be 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 initiator is a hydrocarbyl mono-lithium compound, namely RLi, wherein R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or composite group of the above groups containing 1-20 carbon atoms. The hydrocarbyl monolithium compound is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium, dodecyllithium, preferably n-butyllithium. The amount of organolithium added is determined by the molecular weight of the polymer being designed.
The amount of the coupling agent is determined according to the amount of the initiator, and the star polymer with the heteroarm structure is finally formed through gradual polymerization of excessive coupling agent, wherein the molar ratio of the amount of the coupling agent to the total organic lithium is 2.0-5.0.
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 C 1 -C 4 . The haloalkane is selected from one of chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, preferably chloromethane.
The co-initiator is formed by compounding alkyl aluminum halide and protonic acid according to different proportions. The alkyl aluminum halide is at least one selected from diethyl aluminum chloride, diisobutyl aluminum chloride, methyl aluminum dichloride, aluminum sesquioxide, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride and ethyl aluminum chloride, preferably aluminum sesquioxide. The protonic acid is selected from HCl, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 And HNO 3 Preferably HCl. Wherein the total addition amount of the co-initiator is 0.1-3.0%, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.01:1-0.1:1.
The polymerization reactions of the present invention are all carried out in an oxygen-free, water-free, preferably inert gas atmosphere. The polymerization and dissolution processes are both carried out in a hydrocarbon solvent, which is a hydrocarbon solvent, including straight chain alkanes, aromatic hydrocarbons and cycloalkanes, selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably cyclohexane.
The inert gas is nitrogen or one of all the element gases which do not contain radon in the group 0 of the periodic table.
The invention firstly aims at 3, 9-dioxy [5.5 ]]Halogenated reaction of spiro undecane to synthesize a new kind of dollThe coupling agent 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane, then the styrene-isoprene, ethylene and butadiene reaction monomers are reacted by adopting four kettles, four different chain segments with wide vinyl content distribution and wide molecular weight distribution are prepared by variable temperature polymerization and variable speed polymerization, and the ternary four-hetero-arm star-shaped copolymer [ -IR-PS-B [ -A ] is prepared by coupling] n [-B-SB/(S→B)-] n Y[-SBR-B-] n [-IR 1 -] n (see FIG. 1). The ternary tetra-heteroarm star-shaped copolymer is used as a grafting agent to prepare ultra-wide molecular weight distribution hyperbranched butyl rubber (see figure 2) through cationic polymerization with isobutene and isoprene under a catalytic system compounded by alkyl aluminum halide and protonic acid.
The invention combines the long chain segments with four different microstructures on one macromolecular chain to form a four-hetero-arm star-shaped structure through a four-kettle feeding method, temperature changing and speed changing polymerization, thus the performances of different chain segments and the four-hetero-arm star-shaped structure can be organically combined together and cooperatively act, and IR is utilized 1 The wide molecular weight distribution in the chain segment, the wide vinyl distribution of the SBR chain segment, the randomness and gradual change of the SB/(S-B) -chain segment, and the difference of reactivity ratio and steric hindrance effect of each chain segment in the heteroarm structure, the disorder of the molecular chain segment is increased in the grafting polymerization process of the butyl rubber, the regularity of the molecular chain is obviously destroyed, the molecular weight distribution is obviously widened, the butyl rubber can obtain good viscoelastic performance, the quick stress relaxation rate is provided, and the processing performance of the butyl rubber is improved; meanwhile, the segment of-PS-, -SBR-and-SB/(S- & gt B) -contains a large amount of benzene rings, so that the reduction of strength and air tightness caused by the widening 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.
The invention solves the contradictory relation problem of poor processability and excellent air tightness of butyl rubber by synthesizing the novel coupling agent 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane, synthesizing four long chain segments with wide vinyl content distribution and wide molecular weight distribution and designing a ternary four-hetero-arm star structure, and finally realizes the optimal balance between the processability and physical and mechanical properties of the butyl rubber. The preparation method provided by the invention has the characteristics of controllable process strips, stable product performance, suitability for industrial production and the like.
Drawings
FIG. 1 is [ -IR-PS-B ]] n [-B-SB/(S→B)-] n Y[-SBR-B-] n [-IR 1 -] n And synthesizing a roadmap.
FIG. 2 is 1 # Sample of butyl rubber IIR301 with 2 # Comparison of GPC spectra of the samples of example 1.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
The raw materials used in the examples are all industrial polymer grade, and are used after purification without other special requirements.
(1) The raw material sources are as follows:
styrene, butadiene, polymer grade China petrochemical Co
Isobutene, isoprene, polymeric grade Zhejiang Xinhui New Material Co., ltd
N-butyllithium with purity of 98% Nanjing Tonglian chemical Co., ltd
3, 9-Dioxo [5.5] spirocyclic undecane purity was 99% of Hubei ferry chemical Co.Ltd
Sesquiethyl aluminum chloride with purity of 98% of carbofuran technology Co., ltd
The other reagents are all commercial products.
(2) The analytical test method comprises the following steps:
determination of molecular weight and distribution thereof: measured by using a 2414 Gel Permeation Chromatograph (GPC) manufactured by Waters corporation of the United states. The polystyrene standard sample is used as a calibration curve, the mobile phase is tetrahydrofuran, the column temperature is 40 ℃, the sample concentration is 1mg/ml, the sample injection amount is 50 mu L, the elution time is 40min, and the flow rate is 1 ml.min -1 。
Determination of mooney viscosity and stress relaxation: the measurement was carried out by using a Mooney viscometer model GT-7080-S2 manufactured by Taiwan high-speed rail company. The Mooney relaxation time was 120s as determined with the large rotor under 125℃1+8 conditions with reference to GB/T1232.1-2000.
Measurement of air tightness: an automatic air tightness tester is adopted to measure the air permeability number according to ISO 2782:1995, and the test gas is N 2 The test temperature is 23 ℃, the test sample piece is an 8cm diameter circular sea piece, and the thickness is 1mm.
Tensile strength: the method in standard GB/T528-2009 is performed.
Characterization of the degree of branching: degree of branching = polymer molecular weight after branching/polymer molecular weight before branching.
Example 1
(1) Preparation of grafting agent:
a, preparation of a coupling agent: firstly, in a 4L stainless steel polymerization kettle with a jacket, argon is introduced for replacement for 3 times, 600g of deionized water and 60g of 3, 9-dioxy [5.5 ] are sequentially added into the polymerization kettle]Spirocyclic undecane, 340g liquid bromine, 20g HCl-CH 3 OH solution (molar concentration of HCl: 0.7 mol/L), heating to 80 ℃, reacting for 3.0hr, adding 300g of 15% NaOH aqueous solution to terminate the reaction, finally adding 800g of chloromethane for extraction, separation, washing and drying to obtain the coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane (yield 94%).
b, preparation of grafting agent: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 3 times, sequentially adding 1590g of cyclohexane and 1.5g THF,20.5mmo1 n-butyllithium into the polymerization kettle A, heating to 70 ℃, stirring and mixing 320g of styrene and 160g of 1, 3-butadiene for 10min, reducing the feeding speed by 10g of the mixture per minute at the initial feeding speed of 50g of the mixture per min within 60min to form a random and long gradual change section-SB/(S- & gtB) -chain segment, heating to 80 ℃, adding 230mmo of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 60min; simultaneously, in a 15L stainless steel polymerization kettle B, argon is introduced to replace the system for 3 times, 1610g of cyclohexane, 155g of styrene, 82g of 1, 3-butadiene and 0.9g of THF are sequentially added, the temperature is raised to 50 ℃, 22.1 mmol 1 of n-butyllithium is added to start the reaction, and the temperature is kept within 60 minutes Gradually increasing the temperature from 50 ℃ to 80 ℃, reacting at the temperature increasing speed of 0.5 ℃/min for 60min to form a SBR-chain segment with wide vinyl content distribution, adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 60min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 1520g cyclohexane, 80g isoprene and 0.4g THF into the polymerization kettle C, heating to 50 ℃, adding 25.1 mmol 1 n-butyllithium to start the reaction, and reacting for 50min to form the-SBR 1 Segment, then adding 85g of styrene and 1.0g of THF into a polymerization kettle B in sequence, and reacting for 40min to form the-IR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 60min; simultaneously, in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 3 times, sequentially adding 1530g of cyclohexane, 160g of isoprene, 0.6g of THF into the polymerization kettle D, heating to 40 ℃, adding 17.6mmo1 of n-butyllithium to start reaction, gradually heating from 40 ℃ to 70 ℃ within 40min, and reacting at a heating speed of 0.8 ℃/min for 40min to form wide molecular weight distribution-IR 1 Segment, adding the materials in the polymerization kettle D into the polymerization kettle A after the isoprene monomer is completely converted, and carrying out coupling reaction for 60min; finally, 23g of 1, 3-butadiene is added into a polymerization kettle A for end capping, the reaction is carried out for 20min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, and the glue solution is subjected to wet condensation and drying to prepare the ternary four-hetero-arm star-shaped copolymer [ -IR-PS-B [ -A ] ] n [-B-SB/(S→B)-] n Y[-SBR-B-] n [-IR 1 -] n Grafting agent (Mn 23550, mw/Mn 16.8).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 520g of methyl chloride, 315g of cyclohexane and [ -IR-PS-B ]] n [-B-SB/(S→B)-] n Y[-SBR-B-] n [-IR 1 -] n 15.5g of grafting agent, stirring and dissolving for 20min until the grafting agent is completely dissolved; then cooling to-75deg.C, sequentially adding 512g of chloromethane, 425g of isobutene and 9g of isoprene, stirring and mixing until the temperature of the polymerization system is reduced to-90deg.C, and then adding 155g of chloromethane and sesqui4.02g of ethylaluminum chloride and 0.103g of HCl are mixed at the temperature of minus 85 ℃ and then aged for 20min, then added into a polymerization system together for stirring reaction for 3.0hr, discharged and condensed, washed and dried to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 2
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of grafting agent: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 3 times, sequentially adding 1610g of cyclohexane and 1.7g THF,23.5mmo1 n-butyllithium into the polymerization kettle A, heating to 70 ℃, stirring and mixing 350g of styrene and 180g of 1, 3-butadiene for 15min, reducing the feeding speed by 13g of the mixture per minute at the initial feeding speed of 60g of the mixture per min within 60min to form a random and long gradual change section-SB/(S-B) -chain segment, heating to 80 ℃, adding 280mmo of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 70min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1750g of cyclohexane, 180g of styrene, 100g of 1, 3-butadiene and 1.2g of THF, heating to 50 ℃, adding 25.1 mmol of n-butyllithium to start reaction, gradually heating from 50 ℃ to 80 ℃ within 60min, heating at a speed of 0.5 ℃/min, reacting for 60min to form a SBR-chain segment with wide vinyl content distribution, adding materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 70min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 1680g cyclohexane, 95g isoprene and 0.6g THF into the polymerization kettle C, heating to 55 ℃, adding 27.3mmo1 of n-butyllithium to start reaction, and reacting for 55min to form the-SBR 1 Segment, then adding 100g of styrene and 1.3g of THF into a polymerization kettle B in sequence, and reacting for 45min to form the-IR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 70min; simultaneously, in a 15L stainless steel polymerization kettle D, argon is introduced to replace the system for 3 times, 1670g of cyclohexane, 187g of isoprene and 0.8g of THF are sequentially added into the polymerization kettle D, the temperature is raised to 40 ℃,19.5mm o1 n-butyllithium is added to start the reaction, the temperature is gradually increased from 40 ℃ to 70 ℃ within 40min, the heating speed is 0.8 ℃/min, and the reaction is carried out for 40min, so that the-IR with wide molecular weight distribution is formed 1 Segment, adding the materials in the polymerization kettle D into the polymerization kettle A after the isoprene monomer is completely converted, and carrying out coupling reaction for 70min; finally, 32g of 1, 3-butadiene is added into a polymerization kettle A for end capping, the reaction is carried out for 20min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, and the glue solution is subjected to wet condensation and drying to prepare the ternary four-hetero-arm star-shaped copolymer [ -IR-PS-B [ -A ]] n [-B-SB/(S→B)-] n Y[-SBR-B-] n [-IR 1 -] n Grafting agent (Mn 34200, mw/Mn 18.2).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 500g of chloromethane and 340g of cyclohexane are added into the polymerization kettle, [ -IR-PS-B ] ] n [-B-SB/(S→B)-] n Y[-SBR-B-] n [-IR 1 -] n 19.5g of grafting agent, stirring and dissolving for 20min until the grafting agent is completely dissolved; then cooling to-75 ℃, sequentially adding 520g of methyl chloride, 435g of isobutene and 12g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-92 ℃, then mixing 165g of methyl chloride, 4.85g of aluminum sesquichloride and 0.221g of HCl at-85 ℃, aging for 20min, adding the mixture into the polymerization system together, stirring and reacting for 3.5hr, discharging and condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 3
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of grafting agent: in a 15L stainless steel polymerizer A with a jacket, the system was replaced 3 times by introducing argon, 1920g of cyclohexane, 2.3g THF,26.5mmo1 n-butyllithium were sequentially added to the polymerizer A, the temperature was raised to 70 ℃, 390g of styrene and 200g of 1, 3-butadiene were then stirred and mixed for 20 minutes, and 60g of mixture/mi was fed at an initial feed rate within 70 minutesn, the feeding speed is reduced by 15g of mixture per minute, a random long transition section-SB/(S.fwdarw.B) -chain segment is formed, the temperature is increased to 85 ℃, 300mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane is added, and the coupling reaction is carried out for 80min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1910g of cyclohexane, 200g of styrene, 110g of 1, 3-butadiene and 1.3g of THF, heating to 50 ℃, adding 27.1 mmol of n-butyllithium to start reaction, gradually heating from 50 ℃ to 80 ℃ within 80 minutes, heating at a speed of 0.4 ℃/min, reacting for 80 minutes to form a SBR-chain segment with wide vinyl content distribution, adding materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 80 minutes; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 1850g of cyclohexane, 110g of isoprene and 0.8g of THF into the polymerization kettle C, heating to 60 ℃, adding 28.2 mmol 1 of n-butyllithium to start the reaction, and reacting for 60min to form the-SBR 1 Segment, then 110g of styrene, 1.5g of THF are sequentially added into a polymerization kettle B to react for 50min to form the-IR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 80min; simultaneously, in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 3 times, sequentially adding 1850g of cyclohexane, 205g of isoprene and 0.9g of THF into the polymerization kettle D, heating to 40 ℃, adding 20.5 mmol 1 of n-butyllithium to start reaction, gradually heating from 40 ℃ to 70 ℃ within 50min, and reacting at a heating speed of 0.6 ℃/min for 50min to form wide molecular weight distribution-IR 1 Segment, adding the materials in the polymerization kettle D into the polymerization kettle A after the isoprene monomer is completely converted, and carrying out coupling reaction for 80min; finally, 45g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction is carried out for 30min until no free monomer exists, the reaction mixture after the coupling is treated by water after the reaction is finished, the glue solution is subjected to wet condensation and drying, and the ternary four-hetero-arm star-shaped copolymer [ -IR-PS-B [ -A- ] is prepared] n [-B-SB/(S→B)-] n Y[-SBR-B-] n [-IR 1 -] n Grafting agent (Mn 39600, mw/Mn 18.9).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: first, in a 4L stainless steel reaction kettle with a jacket Introducing nitrogen for 3 times, adding 480g of chloromethane and 380g of cyclohexane into a polymerization kettle, and performing [ -IR-PS-B ]] n [-B-SB/(S→B)-] n Y[-SBR-B-] n [-IR 1 -] n 25.5g of grafting agent, stirring and dissolving for 25min until the grafting agent is completely dissolved; then cooling to-80 ℃, sequentially adding 530g of methyl chloride, 445g of isobutene and 15g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 170g of methyl chloride, 5.15g of aluminum sesquichloride and 0.289g of HCl at-90 ℃, aging for 25min, adding the mixture into the polymerization system together, stirring and reacting for 4.0hr, discharging and condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 4
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of grafting agent: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 3 times, sequentially adding 2320g of cyclohexane and 2.9g THF,29.5mmo1 n-butyllithium into the polymerization kettle A, heating to 70 ℃, stirring and mixing 410g of styrene and 230g of 1, 3-butadiene for 25min, within 70min, reducing the feeding speed by 17g of the mixture per minute at the initial feeding speed of 65g of the mixture per min to form a random and long gradual change section-SB/(S- & gt B) -chain segment, heating to 85 ℃, adding 340mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and performing coupling reaction for 80min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 2010g of cyclohexane, 230g of styrene, 130g of 1, 3-butadiene and 1.6g of THF, heating to 50 ℃, adding 29.2mm & lt 1 & gt n-butyllithium to start reaction, gradually heating from 50 ℃ to 80 ℃ within 80 minutes, heating at a speed of 0.4 ℃/min, reacting for 80 minutes to form a SBR-chain segment with wide vinyl content distribution, adding materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 80 minutes; simultaneously, in a 15L stainless steel polymerization kettle C, argon is introduced to replace the system for 3 times, 2050g of cyclohexane, 125g of isoprene and 1.1g of THF are sequentially added into the polymerization kettle C, the temperature is raised to 65 ℃, and 29.5m of THF is added The mo1 n-butyllithium starts to react for 65min to form-SBR 1 Segment, then 130g of styrene, 1.7g of THF are added into the polymerization kettle B in sequence to react for 55min to form the-IR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 80min; simultaneously, in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 3 times, sequentially adding 2150g cyclohexane, 230g isoprene and 1.2g THF into the polymerization kettle D, heating to 40 ℃, adding 22.5 mmol 1 n-butyllithium to start reaction, gradually heating from 40 ℃ to 70 ℃ within 50min, and reacting at a heating speed of 0.6 ℃/min for 50min to form wide molecular weight distribution-IR 1 Segment, adding the materials in the polymerization kettle D into the polymerization kettle A after the isoprene monomer is completely converted, and carrying out coupling reaction for 80min; finally, 50g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction is carried out for 35min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, the glue solution is subjected to wet condensation and drying, and the ternary four-hetero-arm star-shaped copolymer [ -IR-PS-B [ -A- ] is prepared] n [-B-SB/(S→B)-] n Y[-SBR-B-] n [-IR 1 -] n Grafting agent (Mn 42500, mw/Mn 19.3).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 320g of chloromethane and 450g of cyclohexane into the polymerization kettle, [ -IR-PS-B ] ] n [-B-SB/(S→B)-] n Y[-SBR-B-] n [-IR 1 -] n 28.5g of grafting agent, stirring and dissolving for 25min until the grafting agent is completely dissolved; then cooling to-80 ℃, then sequentially adding 540g of methyl chloride, 456g of isobutene and 18g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 190g of methyl chloride, 5.86g of aluminum sesquichloride and 0.312g of HCl at-95 ℃ and aging for 25min, then adding the mixture into the polymerization system together for stirring and reacting for 4.5hr, discharging and condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 5
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of grafting agent: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 3 times, sequentially adding 2520g of cyclohexane and 3.2g THF,30.5mmo1 n-butyllithium into the polymerization kettle A, heating to 70 ℃, stirring and mixing 430g of styrene and 240g of 1, 3-butadiene for 30min, within 80min, reducing the feeding speed by 19g of the mixture per minute at the initial feeding speed of 70g of mixture per min to form a random and long gradual change section-SB/(S- & gtB) -chain segment, heating to 90 ℃, adding 390mm 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and performing coupling reaction for 90min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 2300g of cyclohexane, 270g of styrene, 150g of 1, 3-butadiene and 1.9g of THF, heating to 50 ℃, adding 31.2mm & lt 1 & gt n-butyllithium to start reaction, gradually heating from 50 ℃ to 80 ℃ within 90min, heating at a speed of 0.3 ℃/min, reacting for 90min to form a SBR-chain segment with wide vinyl content distribution, adding materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 90min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 2300g of cyclohexane, 140g of isoprene and 1.5g of THF into the polymerization kettle C, heating to 70 ℃, adding 31.5 mmol of n-butyllithium to start the reaction, and reacting for 70min to form the-SBR 1 Segment, then 150g of styrene, 2.0g of THF are sequentially added into a polymerization kettle B to react for 60min to form the-IR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 90min; simultaneously, in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 3 times, sequentially adding 2350g of cyclohexane, 245g of isoprene and 1.5g of THF into the polymerization kettle D, heating to 40 ℃, adding 25.5 mmol 1 of n-butyllithium to start the reaction, gradually heating from 40 ℃ to 70 ℃ within 60min, and reacting at a heating speed of 0.5 ℃/min for 60min to form the wide molecular weight distribution-IR 1 Segment, adding the materials in the polymerization kettle D into the polymerization kettle A after the isoprene monomer is completely converted, and carrying out coupling reaction for 90min; finally, 60g of 1, 3-butadiene is added into the polymerization kettle A for end capping, and the reaction is carried out for 40min until no free monomer existsAfter the reaction is completed, the coupled reaction mixture is treated by water, and the glue solution is subjected to wet condensation and drying to obtain the ternary four-hetero-arm star-shaped copolymer [ -IR-PS-B [ -R-PS-B ]] n [-B-SB/(S→B)-] n Y[-SBR-B-] n [-IR 1 -] n Grafting agent (Mn 49200, mw/Mn 19.8).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 300g of methyl chloride and 470g of cyclohexane into the polymerization kettle, [ -IR-PS-B ] ] n [-B-SB/(S→B)-] n Y[-SBR-B-] n [-IR 1 -] n 33.5g of grafting agent, stirring and dissolving for 30min until the grafting agent is completely dissolved; then cooling to-85 ℃, then adding 550g of methyl chloride, 470g of isobutene and 25g of isoprene in sequence, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 190g of methyl chloride, 6.25g of aluminum sesquichloride and 0.462g of HCl at-95 ℃ and aging for 30min, then adding the mixture into the polymerization system together and stirring and reacting for 5.0hr, discharging and condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 1
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of grafting agent: other conditions were the same as in example 1 except that: in the polymerizer A, the mixture of styrene and 1, 3-butadiene is not continuously injected into the polymerizer, but is added at one time, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 3 times, sequentially adding 1590g of cyclohexane, 1.5g THF,20.5mmo1 n-butyllithium into the polymerization kettle A, heating to 70 ℃, then stirring and mixing 320g of styrene and 160g of 1, 3-butadiene for 10min, adding the mixture into the polymerization kettle A at one time, and reacting for 60min to form the random-SBR 1 -segment, finally heating to 80 ℃, adding 230mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 60min; simultaneously, argon is introduced into a 15L stainless steel polymerization kettle B to lead the system to beChanging for 3 times, sequentially adding 1610g cyclohexane, 155g styrene, 82g 1, 3-butadiene and 0.9g THF, heating to 50 ℃, adding 22.1 mmol 1 n-butyllithium to start reaction, gradually increasing the temperature from 50 ℃ to 80 ℃ within 60min, reacting at a heating speed of 0.5 ℃/min, forming SBR-chain segments with wide vinyl content distribution, adding materials in a polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 60min; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 1520g cyclohexane, 80g isoprene and 0.4g THF into the polymerization kettle C, heating to 50 ℃, adding 25.1 mmol 1 n-butyllithium to start the reaction, and reacting for 50min to form the-SBR 1 Segment, then adding 85g of styrene and 1.0g of THF into a polymerization kettle B in sequence, and reacting for 40min to form the-IR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 60min; simultaneously, in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 3 times, sequentially adding 1530g of cyclohexane, 160g of isoprene, 0.6g of THF into the polymerization kettle D, heating to 40 ℃, adding 17.6mmo1 of n-butyllithium to start reaction, gradually heating from 40 ℃ to 70 ℃ within 40min, and reacting at a heating speed of 0.8 ℃/min for 40min to form wide molecular weight distribution-IR 1 Segment, adding the materials in the polymerization kettle D into the polymerization kettle A after the isoprene monomer is completely converted, and carrying out coupling reaction for 60min; finally, 23g of 1, 3-butadiene is added into a polymerization kettle A for end capping, the reaction is carried out for 20min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, and the glue solution is subjected to wet condensation and drying to prepare the ternary four-hetero-arm star-shaped copolymer [ -IR-PS-B [ -A ]] n [-B-SBR 1 -] n Y[-SBR-B-] n [-IR 1 -] n Grafting agent (Mn 21300, mw/Mn 9.8).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: other conditions were the same as in example 1 except that: during the synthesis process, no [ -IR-PS-B ]]n[-B-SB/(S→B)-]n Y[-SBR-B-]n[-IR 1 -]n grafting agent, instead of [ -IR-PS-B ]] n [-B-SBR 1 -] n Y[-SBR-B-] n [-IR 1 -] n Grafting agent, namely: first, with jacketIn a 4L stainless steel reaction kettle, introducing nitrogen for 3 times, adding 520g of chloromethane and 315g of cyclohexane into the polymerization kettle, [ -IR-PS-B ]] n [-B-SBR 1 -] n Y[-SBR-B-] n [-IR 1 -] n 15.5g of grafting agent, stirring and dissolving for 20min until the grafting agent is completely dissolved; then cooling to-75 ℃, sequentially adding 512g of methyl chloride, 425g of isobutene and 9g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 155g of methyl chloride, 4.02g of aluminum sesquichloride and 0.103g of HCl at-85 ℃, aging for 20min, adding the mixture into the polymerization system together, stirring and reacting for 3.0hr, discharging and condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 2
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 2.
b, preparation of grafting agent: the difference is that: in the polymerization kettle B, the SBR-chain segment does not adopt variable temperature polymerization, and reacts at the constant temperature of 50 ℃, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 3 times, sequentially adding 1610g of cyclohexane and 1.7g THF,23.5mmo1 n-butyllithium into the polymerization kettle A, heating to 70 ℃, stirring and mixing 350g of styrene and 180g of 1, 3-butadiene for 15min, reducing the feeding speed by 13g of the mixture per minute at the initial feeding speed of 60g of the mixture per min within 60min to form a random and long gradual change section-SB/(S-B) -chain segment, heating to 80 ℃, adding 280mmo of 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 70min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace the system for 3 times, sequentially adding 1750g of cyclohexane, 180g of styrene, 100g of 1, 3-butadiene and 1.2g of THF, heating to 50 ℃, adding 25.1 mmol 1 of n-butyllithium to start the reaction, and reacting for 60min to form the-SBR 2 Segment, 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 70min; simultaneously, in a 15L stainless steel polymerization kettle C, argon is introduced to replace the system for 3 times, 1680g cyclohexane and 95g iso-hexane are sequentially added into the polymerization kettle C Pentadiene, 0.6g THF, heating to 55 ℃, adding 27.3mmo1 of n-butyllithium to start reaction, reacting for 55min, and forming-SBR 1 Segment, then adding 100g of styrene and 1.3g of THF into a polymerization kettle B in sequence, and reacting for 45min to form the-IR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 70min; simultaneously, in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 3 times, sequentially adding 1670g of cyclohexane, 187g of isoprene, 0.8g of THF into the polymerization kettle D, heating to 40 ℃, adding 19.5mm o1 of n-butyllithium to start reaction, gradually heating from 40 ℃ to 70 ℃ within 40min, and reacting for 40min at a heating speed of 0.8 ℃/min to form the wide molecular weight distribution-IR 1 Segment, adding the materials in the polymerization kettle D into the polymerization kettle A after the isoprene monomer is completely converted, and carrying out coupling reaction for 70min; finally, 32g of 1, 3-butadiene is added into a polymerization kettle A for end capping, the reaction is carried out for 20min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, and the glue solution is subjected to wet condensation and drying to prepare the ternary four-hetero-arm star-shaped copolymer [ -IR-PS-B [ -A ]] n [-B-SB/(S→B)-] n Y[-SBR 2 -B-] n [-IR 1 -] n Grafting agent (Mn 32100, mw/Mn 7.5).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: other conditions were the same as in example 2 except that: during the synthesis process, no [ -IR-PS-B ]]n[-B-SB/(S→B)-]n Y[-SBR-B-]n[-IR 1 -]n grafting agent, instead of [ -IR-PS-B ]] n [-B-SB/(S→B)-] n Y[-SBR 2 -B-] n [-IR 1 -] n Grafting agent, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 500g of chloromethane and 340g of cyclohexane are added into the polymerization kettle, [ -IR-PS-B ]] n [-B-SB/(S→B)-] n Y[-SBR 2 -B-] n [-IR 1 -] n 19.5g of grafting agent, stirring and dissolving for 20min until the grafting agent is completely dissolved; then cooling to-75deg.C, sequentially adding 520g of chloromethane, 435g of isobutene and 12g of isoprene, stirring and mixing until the temperature of the polymerization system is reduced to-92 deg.C, and then adding 165g of chloromethaneMixing 4.85g of half-ethylaluminum chloride and 0.221g of HCl at the temperature of minus 85 ℃ and aging for 20min, then adding the mixture into a polymerization system together and stirring the mixture for reaction for 3.5hr, discharging the mixture for coagulation, washing and drying the mixture to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 3
(1) Preparation of grafting agent:
a, preparation of a coupling agent: same as in example 3.
b, preparation of grafting agent: the difference is that: in a polymerization vessel D-IR 1 The chain segment is not polymerized at variable temperature, and reacts at constant temperature of 40 ℃, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 3 times, sequentially adding 1920g of cyclohexane and 2.3g THF,26.5mmo1 n-butyllithium into the polymerization kettle A, heating to 70 ℃, stirring and mixing 390g of styrene and 200g of 1, 3-butadiene for 20min, within 70min, reducing the feeding speed by 15g of the mixture per minute at the initial feeding speed of 60g of the mixture per min to form a random and long gradual change section-SB/(S-B) -chain segment, heating to 85 ℃, adding 300mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 80min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1910g of cyclohexane, 200g of styrene, 110g of 1, 3-butadiene and 1.3g of THF, heating to 50 ℃, adding 27.1 mmol of n-butyllithium to start reaction, gradually heating from 50 ℃ to 80 ℃ within 80 minutes, heating at a speed of 0.4 ℃/min, reacting for 80 minutes to form a SBR-chain segment with wide vinyl content distribution, adding materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 80 minutes; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, sequentially adding 1850g of cyclohexane, 110g of isoprene and 0.8g of THF into the polymerization kettle C, heating to 60 ℃, adding 28.2 mmol 1 of n-butyllithium to start the reaction, and reacting for 60min to form the-SBR 1 Segment, then 110g of styrene, 1.5g of THF are sequentially added into a polymerization kettle B to react for 50min to form the-IR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle C into the polymerization kettle A, and carrying out coupling reaction for 80min; at the same time in a 15L stainless steel polymerization kettle DThe system was replaced 3 times by introducing argon, 1850g cyclohexane, 205g isoprene, 0.9g THF were added sequentially to the polymerization vessel D, the temperature was raised to 40℃and 20.5 mmol 1 of n-butyllithium was added to start the reaction, and the reaction was continued for 50 minutes to form-IR 2 Segment, adding the materials in the polymerization kettle D into the polymerization kettle A after the isoprene monomer is completely converted, and carrying out coupling reaction for 80min; finally, 45g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction is carried out for 30min until no free monomer exists, the reaction mixture after the coupling is treated by water after the reaction is finished, the glue solution is subjected to wet condensation and drying, and the ternary four-hetero-arm star-shaped copolymer [ -IR-PS-B [ -A- ] is prepared] n [-B-SB/(S→B)-] n Y[-SBR-B-] n [-IR 2 -] n Grafting agent (Mn 37200, mw/Mn 8.6).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: other conditions were the same as in example 3 except that: during the synthesis process, no [ -IR-PS-B ]]n[-B-SB/(S→B)-]n Y[-SBR-B-]n[-IR 1 -]n grafting agent, instead of [ -IR-PS-B ]] n [-B-SB/(S→B)-] n Y[-SBR-B-] n [-IR 2 -] n Grafting agent, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 480g of chloromethane and 380g of cyclohexane into the polymerization kettle, [ -IR-PS-B ] ]n[-B-SB/(S→B)-]n Y[-SBR-B-]n[-IR 2 -]25.5g of grafting agent, stirring and dissolving for 25min until the grafting agent is completely dissolved; then cooling to-80 ℃, sequentially adding 530g of methyl chloride, 445g of isobutene and 15g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 170g of methyl chloride, 5.15g of aluminum sesquichloride and 0.289g of HCl at-90 ℃, aging for 25min, adding the mixture into the polymerization system together, stirring and reacting for 4.0hr, discharging and condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 4
(1) Preparation of grafting agent:
a, preparation of a coupling agent: same as in example 4.
b, preparation of grafting agent: other conditionsThe same as in example 4, except that: the single kettle polymerization is adopted, namely materials in a polymerization kettle B, a polymerization kettle C and a polymerization kettle D are sequentially added into the polymerization kettle A for reaction, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 3 times, sequentially adding 2320g of cyclohexane and 2.9g THF,29.5mmo1 n-butyllithium into the polymerization kettle A, heating to 70 ℃, stirring and mixing 410g of styrene and 230g of 1, 3-butadiene for 25min, and within 70min, reducing the feeding speed by 17g of the mixture per minute at the initial feeding speed of 65g of the mixture per min to form a random and long gradient-SB/(S-B) -chain segment; sequentially adding 2010g of cyclohexane, 230g of styrene, 130g of 1, 3-butadiene and 1.6g of THF into a polymerization kettle A again, heating to 50 ℃, adding 29.2 mmol 1 of n-butyllithium to start the reaction, gradually heating from 50 ℃ to 80 ℃ within 80min at a heating rate of 0.4 ℃/min, and reacting for 80min to form a wide vinyl content distribution-SBR-chain segment; then, 2050g of cyclohexane, 125g of isoprene, 1.1g of THF were sequentially added into the polymerization vessel A, the temperature was raised to 65 ℃,29.5 mmol 1 of n-butyllithium was added again to start the reaction, and the reaction was carried out for 65 minutes, thereby forming-SBR 1 Segment, then 130g of styrene, 1.7g of THF are added into the polymerization kettle A in sequence to react for 55min to form the-IR-SBR 1 -a segment; adding 2150g cyclohexane, 230g isoprene, 1.2g THF into the polymerization kettle A in turn, heating to 40 ℃, adding 22.5 mmol 1 n-butyllithium to start reaction, gradually heating from 40 ℃ to 70 ℃ within 50min, and reacting for 50min at a heating speed of 0.6 ℃/min to form the wide molecular weight distribution-IR 1 -a segment; then heating to 85 ℃, adding 340mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 80min; finally, 50g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction is carried out for 35min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, the glue solution is subjected to wet condensation and drying, and the ternary four-hetero-arm star-shaped copolymer [ -B-SB/(S.fwdarw.B) -SBR-IR-PS-IR is prepared 1 -] n Y grafting agent (Mn 41200, mw/Mn 11.5).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: other conditions were the same as in example 4 except that: during the synthesis process, no [ -IR-P is addedS-B-]n[-B-SB/(S→B)-]n Y[-SBR-B-]n[-IR 1 -]n grafting agent, wherein the grafting agent is a grafting agent, instead [ -B-SB/(S.fwdarw.B) -SBR-IR-PS-IR is added 1 -] n Y grafting agent, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 320g of chloromethane and 450g of cyclohexane into the polymerization kettle, and [ (B-SB/(S.fwdarw.B) -SBR-IR-PS-IR 1 -] n 28.5g of Y grafting agent, stirring and dissolving for 25min until the grafting agent is completely dissolved; then cooling to-80 ℃, then sequentially adding 540g of methyl chloride, 456g of isobutene and 18g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 190g of methyl chloride, 5.86g of aluminum sesquichloride and 0.312g of HCl at-95 ℃ and aging for 25min, then adding the mixture into the polymerization system together for stirring and reacting for 4.5hr, discharging and condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 5
(1) Preparation of grafting agent: other conditions were the same as in example 5 except that: the coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane is not added in the synthesis process, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 3 times, sequentially adding 2520g of cyclohexane, 3.2g THF,30.5mmo1 n-butyllithium into the polymerization kettle A, heating to 70 ℃, stirring and mixing 430g of styrene and 240g of 1, 3-butadiene for 30min, within 80min, at an initial feeding speed of 70g of mixture/min, reducing the feeding speed by 19g of mixture per minute to form a random and long gradient-SB/(S- & gt B) -chain segment, and finally heating to 90 ℃; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 2300g of cyclohexane, 270g of styrene, 150g of 1, 3-butadiene and 1.9g of THF, heating to 50 ℃, adding 31.2mm 1 of n-butyllithium to start reaction, gradually heating from 50 ℃ to 80 ℃ within 90min, heating at a speed of 0.3 ℃/min, reacting for 90min to form a SBR-chain segment with wide vinyl content distribution, and adding materials in the polymerization kettle B into the polymerization kettle A after complete conversion of monomers; simultaneously, in a 15L stainless steel polymerization kettle C, introducing argon to replace the system for 3 times, and sequentially adding 2300g of cyclohexane and 140g of isoglutaryl into the polymerization kettle C Alkene, 1.5g THF, heating to 70 ℃, adding 31.5 mmol 1 n-butyllithium to start reaction, reacting for 70min, and forming-SBR 1 Segment, then 150g of styrene, 2.0g of THF are sequentially added into a polymerization kettle B to react for 60min to form the-IR-SBR 1 -a segment; after the monomer is completely converted, adding the materials in the polymerization kettle C into a polymerization kettle A; simultaneously, in a 15L stainless steel polymerization kettle D, introducing argon to replace the system for 3 times, sequentially adding 2350g of cyclohexane, 245g of isoprene and 1.5g of THF into the polymerization kettle D, heating to 40 ℃, adding 25.5 mmol 1 of n-butyllithium to start the reaction, gradually heating from 40 ℃ to 70 ℃ within 60min, and reacting at a heating speed of 0.5 ℃/min for 60min to form the wide molecular weight distribution-IR 1 Segment, adding the materials in the polymerization kettle D into the polymerization kettle A after the isoprene monomer is completely converted; finally, 60g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction is carried out for 40min until no free monomer exists, the reaction mixture after the coupling is treated by water after the reaction is finished, the glue solution is subjected to wet condensation and drying, and the ternary four-hetero-arm star-shaped copolymer [ -IR-PS-B [ -A- ] is prepared] n [-B-SB/(S→B)-] n [-SBR-B-] n [-IR 1 -] n Grafting agent (Mn 46300, mw/Mn 5.7).
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: other conditions were the same as in the examples, except that: during the synthesis process, no [ -IR-PS-B ] ]n[-B-SB/(S→B)-]n Y[-SBR-B-]n[-IR 1 -]n grafting agent, instead of [ -IR-PS-B ]] n [-B-SB/(S→B)-] n [-SBR-B-] n [-IR 1 -] n Grafting agent, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 300g of methyl chloride and 470g of cyclohexane into the polymerization kettle, [ -IR-PS-B ]]n[-B-SB/(S→B)-]n[-SBR-B-]n[-IR 1 -]33.5g of n grafting agent, stirring and dissolving for 30min until the grafting agent is completely dissolved; then cooling to-85deg.C, sequentially adding 550g of chloromethane, 470g of isobutene and 25g of isoprene, stirring and mixing until the temperature of the polymerization system is reduced to-95deg.C, mixing 190g of chloromethane, 6.25g of sesquiethylaluminum chloride and 0.462g of HCl at-95deg.C, aging for 30min, adding into the polymerization system, stirring and reacting for 5.0hrAnd then discharging, condensing, washing and drying to obtain the ultra-wide molecular weight distribution hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
TABLE 1 ultra-broad molecular weight distribution, hyperbranched butyl rubber Properties
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As can be seen from table 1: the ultra-wide molecular weight distribution and ultra-wide molecular weight distribution of the ultra-wide molecular weight distribution butyl rubber disclosed by the invention has the advantages of small Mooney relaxation area, good air tightness and high tensile strength, and shows that the ultra-wide molecular weight distribution and ultra-wide molecular weight distribution butyl rubber has good processability while maintaining excellent physical and mechanical properties.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.

Claims (11)

1. The preparation method of the ultra-wide molecular weight distribution hyperbranched butyl rubber is characterized by comprising the following steps of:
(1) Preparation of grafting agent:
a, preparation of a coupling agent: firstly, adding 100% -200% of deionized water, 3, 9-dioxygen [5.5] spiro undecane, a halogenating agent and 1% -5% of a catalyst into a polymerization kettle in turn under the inert gas atmosphere, heating to 50-80 ℃, reacting for 1-3 hr, adding 20% -40% of 10% -20% NaOH aqueous solution with the mass concentration to terminate the reaction, and finally adding 200% -300% of chloromethane to extract, separate, wash and dry to obtain a coupling agent;
b, preparation of grafting agent: sequentially adding 100-200% of solvent, 0.1-0.3% of structure regulator and initiator into a polymerization kettle A in inert gas atmosphere, heating to 70-80 ℃, stirring and mixing 20-30% of styrene and 10-20% of 1, 3-butadiene for 10-30 min, reacting to obtain variable-speed polymerization, adding the variable-speed polymerization into the polymerization kettle in a continuous injection mode, reacting within 60-80 min, wherein the initial feeding speed is higher than 10.0% of the mixture/min, the feeding speed is reduced according to the reaction time, heating to 80-90 ℃, and adding the coupling agent prepared in the step a for coupling reaction for 60-90 min; simultaneously, in a polymerization kettle B, under the atmosphere of inert gas, sequentially adding 100% -200% of solvent, 10% -20% of styrene, 5% -10% of 1, 3-butadiene, 0.05% -0.3% of structure regulator and initiator, carrying out variable temperature polymerization, gradually increasing the temperature from 50 ℃ to 80 ℃ within 60-90 min, adding materials in the polymerization kettle B into the polymerization kettle A after complete conversion of monomers, and carrying out coupling reaction for 60-90 min; simultaneously, in a polymerization kettle C, under the atmosphere of inert gas, sequentially adding 100% -200% of solvent, 5% -10% of isoprene, 0.01% -0.1% of structure regulator and initiator into the polymerization kettle C, heating to 50-70 ℃ and reacting for 50-70 min; sequentially adding 5-10% of styrene and 0.05-0.2% of structure regulator into a polymerization kettle C, reacting for 40-60 min, adding materials in the polymerization kettle C into a polymerization kettle A after the monomers are completely converted, and performing coupling reaction for 60-90 min; simultaneously, in a polymerization kettle D, under the atmosphere of inert gas, sequentially adding 100% -200% of solvent, 10% -15% of isoprene, 0.01% -0.1% of structure regulator and initiator into the polymerization kettle D, reacting for variable-temperature polymerization, gradually increasing the temperature from 40 ℃ to 70 ℃ within 40-60 min, adding materials in the polymerization kettle D into the polymerization kettle A after isoprene monomers are completely converted, and performing coupling reaction for 60-90 min; finally, adding 1% -4% of 1, 3-butadiene into the polymerization kettle A for end capping, reacting until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain a grafting agent;
(2) Preparation of ultra-wide molecular weight distribution and hyperbranched butyl rubber: firstly, adding 100% -200% of diluent and solvent into a polymerization kettle in an inert gas atmosphere according to the volume ratio of 70-30: 30-70 percent of mixed solvent, 1-7 percent of grafting agent, and stirring and dissolving for 20-30 min until the grafting agent is completely dissolved; then cooling to-75 to-85 ℃, sequentially adding 100-200% of diluent, 85-95% of isobutene and 1-5% of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-100 to-90 ℃, then mixing and ageing 30-50% of diluent and 0.05-3.0% of co-initiator at-85 to-95 ℃ for 20-30 min, adding the mixture into the polymerization system together, stirring and reacting for 3.0-5.0 hr, discharging, condensing, washing and drying to obtain ultra-wide molecular weight distribution hyperbranched butyl rubber products;
wherein the initiator is selected from one of n-butyllithium, sec-butyllithium, methyl butyllithium, phenyl butyllithium, naphthalene lithium, cyclohexyl lithium and dodecyl lithium; the coupling agent is 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane, and the molar ratio of the amount of the coupling agent to the amount of the initiator is 2.0-5.0; the co-initiator is formed by compounding alkyl aluminum halide and protonic acid.
2. The method of claim 1, wherein the grafting agent is a four-arm star copolymer synthesized from isoprene, styrene and butadiene and having the structural formula shown in formula I:
wherein SB in SB/(S.fwdarw.B) is a random segment of styrene and butadiene; (S.fwdarw.B) is a gradual change section of styrene and butadiene; SBR is a styrene, butadiene random block copolymer block with a broad vinyl content distribution; IR is a homopolymer segment of isoprene; PS is a styrene homopolymer segment;IR 1 an isoprene homopolymer segment with a broad molecular weight distribution; b is a blocked butadiene segment, n=1.
3. The method of claim 2, wherein the four-arm star polymer has a styrene content of 45% to 65%, a 1, 3-butadiene content of 15% to 25%, and an isoprene content of 10% to 25%.
4. The method of claim 2, wherein the four-arm star polymer has a number average molecular weight of 10000-50000 and a ratio of weight average molecular weight to number average molecular weight of 16.2-20.1.
5. The method of claim 1, wherein the halogenating agent is one of liquid chlorine and liquid bromine.
6. The method of claim 5, wherein the halogenating agent is liquid bromine and the molar ratio of liquid bromine to 3, 9-dioxo [5.5] spiroundecane is from 4.5 to 6.5.
7. The process according to claim 1, wherein the catalyst is HCl-CH 3 And mixed aqueous solution of OH, wherein the molar concentration of HCl is 0.1-0.7 mol/L.
8. The method of claim 1, 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.
9. The method of claim 1, wherein the diluent is selected from one of methane chloride, methylene chloride, carbon tetrachloride, ethylene dichloride, tetrachloropropane, heptachloropropane, methane monofluoride, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.
10. The method of claim 1, wherein the alkyl aluminum halide is selected from at least one of diethyl aluminum monochloride, diisobutyl aluminum monochloride, dichloromethyl aluminum, sesquiethyl aluminum chloride, sesquiisobutyl aluminum chloride, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride, and ethyl aluminum chloride.
11. The method of claim 1, wherein said protonic acid is selected from the group consisting of HCl, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 And HNO 3 One of them.
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CN1432586A (en) * 2002-01-15 2003-07-30 北京燕山石油化工公司研究院 Conjugated diene copolymer rubber and its prepn process
CN109134765A (en) * 2017-06-28 2019-01-04 北京化工大学 A kind of polyisobutene and the graft copolymer of polyisoprene and preparation method thereof

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AU2002225394A1 (en) * 2002-01-10 2003-07-30 Japan Elastomer Co., Ltd. Block copolymer

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CN1432586A (en) * 2002-01-15 2003-07-30 北京燕山石油化工公司研究院 Conjugated diene copolymer rubber and its prepn process
CN109134765A (en) * 2017-06-28 2019-01-04 北京化工大学 A kind of polyisobutene and the graft copolymer of polyisoprene and preparation method thereof

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