阅读说明：本技术 一种超支化、超宽分子量分布丁基橡胶的制备方法 (Preparation method of hyperbranched and ultra-wide molecular weight distribution butyl rubber ) 是由 徐典宏 牛承祥 杨珊珊 孟令坤 翟云芳 朱晶 于 2020-06-24 设计创作，主要内容包括：本发明涉及一种超支化、超宽分子量分布丁基橡胶的制备方法,包括如下步骤：首先对3,9-二氧[5.5]螺环十一烷进行卤化反应,合成出一种新型偶联剂1,5-二卤-3,3二(2-卤乙基)戊烷,然后苯乙烯和丁二烯反应单体通过变温聚合制备出[-B-PS-SBR-]-(n)链段和[-BR-PS-B-]-(n)链段,最后经偶合反应制备出二元二杂臂星型共聚物[-B-PS-SBR-]-(n)Y[-BR-PS-B-]-(n)。将这种二元二杂臂星型共聚物[-B-PS-SBR-]-(n)Y[-BR-PS-B-]-(n)作为接枝剂在烷基卤化铝和质子酸复配的催化体系下,与异丁烯和异戊二烯通过阳离子聚合制备出超支化、超宽分子量分布的丁基橡胶。(The invention relates to a preparation method of hyperbranched and ultra-wide molecular weight distribution butyl rubber, which comprises the following steps: first, to 3, 9-dioxo [5.5]]The spiro undecane is halogenated to synthesize a novel coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane, and then the styrene and butadiene reaction monomer are polymerized at variable temperature to prepare [ -B-PS-SBR-] n Segment and [ -BR-PS-B-] n Segment, finally preparing the binary two-hetero-arm star-shaped copolymer [ -B-PS-SBR-] n Y[‑BR‑PS‑B‑] n . The binary two-hetero-arm star-shaped copolymer [ -B-PS-SBR-] n Y[‑BR‑PS‑B‑] n As a grafting agent inUnder the catalysis system compounded by alkyl aluminum halide and protonic acid, the alkyl aluminum halide, isobutene and isoprene are subjected to cationic polymerization to prepare the hyperbranched butyl rubber with ultra-wide molecular weight distribution.)

1. A preparation method of hyperbranched and ultra-wide molecular weight distribution butyl rubber is characterized by comprising the following steps:

(1) preparation of grafting agent:

a preparation of a coupling agent: according to the total mass percentage of reactants, firstly, 100-200% of deionized water, 3, 9-dioxy [5.5] spiro undecane, a halogenating agent and 1-5% of a catalyst are sequentially added into a reaction kettle under the atmosphere of inert gas, the temperature is raised to 50-80 ℃, after the reaction is carried out for 1-3 hours, 20-40% of NaOH aqueous solution with the mass concentration of 10-20% is added to terminate the reaction, and finally 200-300% of methane chloride is added to carry out extraction, separation, washing and drying to obtain a coupling agent;

b preparation of grafting agent: according to the total mass percentage of the reaction monomers, 100-200% of solvent, 10-20% of 1, 3-butadiene, 0.05-0.3% of structure regulator and initiator are sequentially added into a reaction kettle A under the atmosphere of inert gas, the reaction is temperature-changing polymerization, the temperature is increased from 40 ℃ to 70 ℃ within 50-70 min, and the temperature rise is a continuous gradual change process; then sequentially adding 20-30% of styrene and 0.05-0.1% of structure regulator into the reaction kettle A, reacting for 40-60 min, heating to 70-90 ℃, and adding a coupling agent to perform coupling reaction for 60-90 min; meanwhile, introducing inert gas into a reaction kettle B to replace the system for 3-5 times, sequentially adding 100-200% of solvent, 30-40% of styrene, 20-30% of 1, 3-butadiene, 0.05-0.2% of structure regulator and initiator, reacting at variable temperature for polymerization, increasing the temperature from 50 ℃ to 70 ℃ within 60-90 min, sequentially adding 10-20% of styrene and 0.05-0.2% of structure regulator into the reaction kettle B, and reacting for 30-50 min; after the monomers are completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 60-90 min; finally, adding 1-4% of 1, 3-butadiene into the reaction kettle A for end capping until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on glue solution to prepare a grafting agent;

(2) preparing hyperbranched and ultra-wide molecular weight distribution butyl rubber: according to the total mass percentage of reaction monomers, firstly, 100-200 percent of diluent and solvent are added into a reaction kettle in an inert gas atmosphere, and the volume ratio of the diluent to the solvent is 70-30: 30-70 percent of mixed solvent and 1-9 percent of grafting agent obtained in the step (1), and stirring and dissolving for 10-30 min until the grafting agent is completely dissolved; and (2) cooling to-75 to-85 ℃, sequentially adding 100-200% of the diluent obtained in the step (1), 87-93% 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 aging 30-50% of the diluent and 0.05-3.0% of a co-initiator for 20-30 min at-85 to-95 ℃, adding the mixture into the polymerization system together, stirring and reacting for 2.0-5.0 hr, discharging, condensing, washing and drying to obtain the hyperbranched and ultra-broad molecular weight distribution butyl rubber product.

2. The method of claim 1, wherein the grafting agent is a binary disarm star copolymer comprising styrene and butadiene, and having a general structural formula shown in formula I:

wherein Y is 3, 3-diethylpentane; BR is a1, 3-butadiene homopolymer block with wide molecular weight distribution, and the 1, 2-structure mass content of the BR is 20-40 percent; PS is a styrene homopolymer segment; SBR is a styrene and butadiene random block copolymer with wide vinyl content distribution, wherein the mass content of styrene is 50-60%, and the mass content of butadiene is 30-50%; b is terminated butadiene, and n is 1-4.

3. The method according to claim 2, wherein the binary four-arm star polymer comprises 20 to 40 mass% of 1, 3-butadiene and 60 to 80 mass% of styrene.

4. The method of claim 2, wherein the binary four-arm star polymer has a number average molecular weight of 10000 to 50000 and a ratio of weight average molecular weight to number average molecular weight of 11.5 to 15.6.

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 the amount of liquid bromine to the amount of 3, 9-dioxo [5.5] spiroundecane is 4.5 to 6.5.

7. The method of claim 1, wherein said method is performed in a batch processThe catalyst is HCl-CH₃OH, 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 process of claim 1, wherein the initiator is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, lithium naphthalide, cyclohexyllithium, or dodecyllithium.

10. The method of claim 9, wherein the initiator is n-butyl lithium.

11. The method of claim 1, wherein the coupling agent is 1, 5-dihalo-3, 3-bis (2-haloethyl) pentane and the molar ratio of the amount of coupling agent to the initiator is 2.0 to 5.0.

12. The method of claim 1, wherein the diluent is selected from one of methyl chloride, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride, or fluorobutane.

13. The method according to claim 1, wherein the co-initiator is prepared by compounding an alkyl aluminum halide and a protonic acid, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.01: 1-0.1: 1.

14. The method of claim 13, 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.

15. The method of claim 13, wherein the protic acid is selected from the group consisting of HCI, HF, HBr, H₂SO₄、H₂CO₃、H₃PO₄And HNO₃One kind of (1).

Technical Field

The invention relates to a preparation method of hyperbranched butyl rubber with ultra-wide molecular weight distribution, in particular to a method for preparing hyperbranched butyl rubber with ultra-wide molecular weight distribution by taking a binary bihetero arm star-shaped copolymer produced by styrene and butadiene as a grafting agent and carrying out cationic polymerization on isobutene and isoprene.

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 highly-branched butyl rubber which is composed of a high-molecular-weight graft structure and a low-molecular-weight linear structure and has a unique three-dimensional net structure has excellent viscoelastic property, high crude rubber strength and a fast stress relaxation rate, low melt viscosity can be kept in a processing process, a high-molecular-weight polymer can be obtained, and balance and unification of physical and mechanical properties and processing properties are realized. Therefore, the star-shaped highly-branched structure becomes one of the hot spots in the research field of future butyl rubber.

In the prior art, the synthesis of star-shaped highly branched butyl rubber is mainly prepared by a method of a first-arm-after-core method, a first-arm-after-core method and a core-arm simultaneous method. Such as: US5395885 discloses a star-shaped highly-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 ℃. CN 107344982 a discloses a method for producing a wide/bimodal molecular weight distribution butyl rubber, which comprises: mixing isobutene and isoprene at a molar ratio of 97:3 to 99:1, then mixing the mixture with a diluent (methane chloride) to obtain a monomer stream, mixing an initiator (an aluminum chloride system and an HCl/alkylaluminum chloride complex) with the diluent (methane chloride) to obtain an initiator stream, mixing the monomer stream and the initiator stream, conveying the mixture into a first loop reactor zone, and carrying out polymerization reaction 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; secondly, sending the first part of butyl rubber slurry into a second loop reactor zone, and carrying out polymerization reaction for 5-10min at the temperature of-92 ℃ to-90 ℃ and the pressure of 0.1 to 0.2Mpa to finally obtain the butyl rubber slurry with broad/bimodal molecular weight distribution; and thirdly, contacting the butyl rubber slurry with broad/bimodal molecular weight distribution with water, removing unreacted monomers and a diluent to obtain colloidal particle water, and then dehydrating and drying the colloidal particle water to obtain the butyl rubber with broad/bimodal molecular weight distribution and molecular weight distribution (Mw/Mn) of at least 5.0. CN1427851A discloses a preparation method of butyl rubber with wide molecular weight distribution. The process uses a mixed catalyst system comprising a major amount of an internalized dialkylaluminum and a minor amount of a monoalkyl dihalideA mixture of aluminum and minor amounts of aluminoxane) to give a broad distribution butyl rubber having a molecular weight distribution of greater than 3.5, up to 7.6. CN 101353403B discloses a preparation method of star-shaped highly-branched polyisobutylene or butyl rubber, wherein a polystyrene/isoprene block copolymer with a silicon-chlorine group at the tail end or a polystyrene/butadiene block copolymer with a silicon-chlorine group at the tail end is used as a grafting initiating agent for positive ion polymerization, and under the condition of 0-100 ℃, a chloromethane/cyclohexane v ratio is 20-80/80-20 in a mixed solvent positive ion polymerization system to directly participate in the positive ion polymerization, and the star-shaped highly-branched polyisobutylene or butyl rubber product is prepared by the grafting reaction of an unsaturated chain through the initiated positive ion polymerization of the silicon-chlorine group. CN01817708.5 provides a method for preparing star-shaped highly branched polymers by adding a multiolefin crosslinking agent such as divinylbenzene and a chain transfer agent such as 2,4, 1-trimethyl-1-pentene to a mixture of isoolefin monomers and diolefin monomers. CN88108392.5 discloses a star-shaped grafted butyl rubber with a comb-shaped structure, which is prepared by using a hydrochloric acid polystyrene-isoprene copolymer as a multifunctional initiator or using polystyrene-butadiene or polystyrene-isoprene as a grafting agent. 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. US3780002 teaches a composite initiator using a halide of a metal from group II or III of the periodic Table of the elements in combination with a tetrahalide of a metal from group IV of the periodic Table of the elements, e.g. AICl₃And TiC1₄Combined use, or A1C1₃And SnC1₄The composite use enables each initiator to independently initiate cationic polymerization, and butyl rubber with molecular weight distribution index Mw/Mn of above 5.0 is synthesized under the conventional butadiene rubber polymerization condition.

CN 101353386A discloses an initiation system for starlike highly branched polyisobutylene or butyl rubber cationic polymerization, which is composed of an initiation-grafting agent, a coinitiator and a nucleophilic reagent, and is used for initiating vinyl monomers to perform homopolymerization, block copolymerization, star polymerization and graft copolymerization, wherein the obtained polymer presents obvious bimodal distribution. Puskas (Catalysts for manufacturing of IIR with bi-modal molecular weight distribution: US, 5194538[ P ] 1993-3-16.) adopts trimesic acid as raw material to synthesize initiator tri-cumyl alcohol with a three-arm structure, and then adopts a tri-cumyl alcohol/aluminum trichloride initiating system to initiate isobutylene and isoprene to copolymerize in an inert organic solvent under the condition of-120 to-50 ℃ to synthesize star-shaped highly branched butyl rubber with bi-modal molecular weight distribution. Wieland et al (Synthesis of new graft copolymer polymerization by polymerization of the 1,1-diphenylethylene technology and cationic polymerization [ J ]. Polymer Science: Polymer Chemistry, 2002, 40: 3725-co-3733.) synthesized a macroinitiator P (MMA-b-St-co-CMS) containing the three members of 4-chloromethylstyrene, styrene and methyl methacrylate in the presence of 1, 2-Diphenylethylene (DPE) by a radical polymerization method, and then initiated cationic polymerization of isobutylene and isoprene to successfully prepare the multi-arm star butyl rubber. Wubo et al (Davang S H, et al. Ski resistant coatings for air craft carrier decks [ J ]. Coat Technol, 1980, 52 (671): 65-69.) prepared a poly (isoprene-styrene) block copolymer as a grafting agent by living anionic polymerization, and prepared a star-shaped highly branched butyl rubber exhibiting significant bimodal properties by living cationic polymerization in an initiation system of 2-chloro-2, 4, 4-trimethylpentane/titanium tetrachloride/proton scavenger.

Disclosure of Invention

The invention aims to provide a preparation method of hyperbranched butyl rubber with ultra-wide molecular weight distribution. The method comprises the steps of firstly, taking alkyl lithium as an initiator, taking hydrocarbon as a solvent, taking reaction monomers comprising styrene and butadiene, adopting temperature-changing polymerization, and coupling with a novel long-chain tetrahalide coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane to prepare the star copolymer with a binary double-hybrid-arm structure. Finally, under the catalysis system of compounding Lewis acid and protonic acid, the binary bihetero-arm star-shaped copolymer is used as a grafting agent to carry out cationic polymerization with isobutene and isoprene to prepare the hyperbranched butyl rubber with ultra-wide molecular weight distribution. The method solves the problems of extrusion swelling and low stress relaxation rate of the butyl rubber in the processing process, so that the hyperbranched and ultra-broad molecular weight distribution butyl rubber has the excellent processability of high stress relaxation rate and small extrusion swelling effect in the processing process under the premise of ensuring that the butyl rubber has enough crude rubber strength and good air tightness, and the balance of the physical and mechanical properties and the processability of the hyperbranched and ultra-broad molecular weight distribution butyl rubber is realized.

All the percentages in the present invention are percentages by mass.

The preparation method of the hyperbranched and ultra-wide molecular weight distribution 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: according to one hundred percent of the total mass of reactants, firstly, 100-200 percent of deionized water, 3, 9-dioxo [5.5] spiro undecane, a halogenating agent and 1-5 percent of catalyst are sequentially added into a reaction kettle under the atmosphere of inert gas, the temperature is raised to 50-80 ℃, after the reaction is carried out for 1-3 hours, 20-40 percent of NaOH aqueous solution with the mass concentration of 10-20 percent is added to stop the reaction, and finally, 200-300 percent of monochloromethane is added to carry out extraction, separation, washing and drying to prepare the coupling agent 1, 5-dihalo-3, 3-bis (2-haloethyl) pentane (the yield is 85-95 percent).

b preparation of grafting agent: taking the total mass percentage of a reaction monomer as a hundred percent, sequentially adding 100-200% of a solvent, 10-20% of 1, 3-butadiene, 0.05-0.3% of a structure regulator and an initiator into a reaction kettle A in an inert gas atmosphere, wherein the reaction is temperature-changing polymerization, the temperature is gradually increased from 40 ℃ to 70 ℃ within 50-70 min, and the temperature rise is a continuous gradual change process to form a BR chain segment with wide molecular weight distribution; then sequentially adding 20-30% of styrene and 0.05-0.1% of structure regulator into the polymerization kettle A, and reacting for 40-60 min to form a-BR-PS-chain segment, wherein the conversion rate of styrene and 1, 3-butadiene monomer reaches 100%, finally heating to 70-90 ℃, and adding a coupling agent to perform coupling reaction for 60-90 min;simultaneously, under the inert gas atmosphere, sequentially adding 100-200% of solvent, 30-40% of styrene, 20-30% of 1, 3-butadiene, 0.05-0.2% of structure regulator and initiator into a reaction kettle B, wherein the reaction is temperature-changing polymerization, the temperature is gradually increased from 50 ℃ to 70 ℃ within 60-90 min, the temperature rise is a continuous gradual change process, a-SBR-chain segment with wide vinyl content distribution is formed, then sequentially adding 10-20% of styrene and 0.05-0.2% of structure regulator into the reaction kettle B, and reacting for 30-50 min to form a-PS-SBR-chain segment; after the monomer is completely converted, adding the material in the reaction kettle B into the reaction kettle A, and carrying out coupling reaction for 60-90 min; finally, adding 1-4% of 1, 3-butadiene into the reaction 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 the star-shaped copolymer with binary two hybrid arms ([ -B-PS-SBR-]_nY[-BR-PS-B-]_n)。

(2) Preparing hyperbranched and ultra-wide molecular weight distribution butyl rubber: firstly, adding 100-200% of a diluent and a solvent in the following proportion of V: the V ratio is 70-30: 30-70 percent of mixed solvent and 1-9 percent of grafting agent, stirring and dissolving for 10-30 min until the grafting agent is completely dissolved; and then cooling to-75 to-85 ℃, sequentially adding 100 to 200 percent of diluent, 87 to 93 percent of isobutene and 1 to 5 percent of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-100 to-90 ℃, then adding 30 to 50 percent of diluent and 0.05 to 3.0 percent of co-initiator into the polymerization system for stirring and reacting for 2.0 to 5.0 hours after mixing and aging for 20 to 30 minutes at-85 to-95 ℃, discharging and coagulating, washing and drying to obtain the hyperbranched and ultra-broad molecular weight distribution butyl rubber product.

The grafting agent contains a binary two-hybrid-arm star-shaped copolymer synthesized by styrene and butadiene, and the structural general formula of the grafting agent is shown as a formula I:

wherein Y is 3, 3-diethylpentane; BR is a1, 3-butadiene homopolymer block with wide molecular weight distribution, and the 1, 2-structure content of the BR is 20-40%; PS is a styrene homopolymer segment; the SBR is a styrene and butadiene random block copolymer with wide vinyl content distribution, wherein the styrene content is 50-60%, and the butadiene content is 30-50%; b is terminated butadiene, and n is 1-4; the content of 1, 3-butadiene in the binary four-arm star polymer is 20-40%, and the content of styrene is 60-80%; the number average molecular weight (Mn) of the binary two-hetero-arm star-shaped copolymer is 10000-50000, and the molecular weight distribution (Mw/Mn) is 11.5-15.6.

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 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 initiator is an alkyl monolithium compound, namely RLi, wherein R is a saturated aliphatic alkyl, alicyclic alkyl, aromatic alkyl containing 1-20 carbon atoms or a composite group of the above groups. The alkyl monolithium compound is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium and dodecyllithium, preferably n-butyllithium. The amount of organolithium added is determined by the molecular weight of the polymer being designed.

The dosage of the coupling agent is determined according to the amount of the initiator, the star polymer with the hetero-arm structure is finally formed through gradual polymerization of excessive coupling agent, and the molar ratio of the dosage 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 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 HCI, HF, HBr, H₂SO₄、H₂CO₃、H₃PO₄And HNO₃Preferably HCI. Wherein the total addition amount of the coinitiator is 0.05-2.0%, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.01: 1-0.1: 1.

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]]The spiro undecane is halogenated to synthesize a novel coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane, and then the styrene and butadiene reaction monomers are polymerized at variable temperature to prepare two [ -B-PS-SBR-]_nSegment and [ -BR-PS-B-]_nSegment, finally preparing binary two-hetero-arm star copolymer [ -B-PS-SBR-]_nY[-BR-PS-B-]_n(see FIG. 1). The binary two-hetero-arm star-shaped copolymer [ -B-PS-SBR-]_nY[-BR-PS-B-]_nThe grafted copolymer is used as a grafting agent to prepare hyperbranched butyl rubber with ultra-wide molecular weight distribution by cationic polymerization with isobutene and isoprene in a catalyst system compounded by alkyl aluminum halide and protonic acid (see attached figure 2).

According to the invention, two-kettle feeding method and variable temperature polymerization are adopted to combine long chain segments with two different microstructures on one macromolecular chain to form a two-hetero-arm star structure, so that the properties of different chain segments and the two-hetero-arm star structure are organically combined together and act synergistically, the disorder of the molecular chain segments is increased in the graft polymerization process of butyl rubber by utilizing the wide vinyl distribution in BR and SBR chain segments and the difference of the reactivity ratio and the steric hindrance effect of each chain segment in the hetero-arm structure, the regularity of the molecular chain segments is obviously destroyed, the molecular weight distribution is obviously widened, the butyl rubber can obtain good viscoelastic property, the stress relaxation rate is fast, and the processability of the butyl rubber is improved; meanwhile, the-PS-and-SBR-chain segments contain a large number of benzene rings, so that the reduction of strength and air tightness caused by the broadening of the molecular weight distribution of the butyl rubber is avoided, and the high strength and good air tightness of the butyl rubber are ensured.

The invention synthesizes 1, 5-dihalo-3, 3-di (2-haloethyl) pentane as a novel coupling agent, and synthesizes [ -B-PS-SBR-]_nAnd [ -BR-PS-B-]_nThe long chain segment is coupled to design a binary two-hybrid-arm star-shaped structure, so that the problem of contradiction between poor processability and excellent air tightness of the butyl rubber is solved, and the processability and the physical and mechanical properties of the butyl rubber are optimally balanced. The preparation method provided by the invention has the characteristics of controllable process bars, stable product performance, suitability for industrial production and the like.

Drawings

FIG. 1 shows [ -B-PS-SBR-]_nY[-BR-PS-B-]_nAnd synthesizing a route map.

FIG. 2 is 1^#Sample of-butyl rubber IIR301 with 2^#Comparison of the GPC spectra of the samples of example 1.

Detailed Description

The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions. All the raw materials used in the examples are of industrial polymerization grade, and are used after purification without other special requirements.

(1) The raw material sources are as follows:

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

Aluminum sesquiethylate chloride, 98% pure Profenor technologies Ltd

Other reagents are all commercial products

(2) The analysis and test method comprises the following steps:

determination of the molecular weights and their distribution: the measurement was carried out by using 2414 Gel Permeation Chromatograph (GPC) manufactured by Waters corporation, USA. Taking polystyrene standard sample as calibration curve, tetrahydrofuran as mobile phase, column temperature of 40 deg.C, sample concentration of 1mg/ml, sample amount of 50 μ L, elution time of 40min, and flow rate of 1 ml/min^-1。

Determination of Mooney viscosity and stress relaxation: the measurement was carried out by using a Mooney viscometer model GT-7080-S2 manufactured by Taiwan high-speed railway. The Mooney relaxation time, determined with a large rotor at 125 ℃ C (1+8) according to the method of GB/T1232.1-2000, is 120 s.

Measurement of airtightness: the permeability was determined using an automated air tightness tester according to ISO 2782:1995 with a test gas of 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.

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, introducing argon for 3 times of replacement, and then adding 600g of deionized water and 58g of 3, 9-dioxygen [5.5] into the polymerization kettle in sequence]Spiroundecane, 320g of liquid bromine, 18g of HCl-CH₃OH solution (HCl molar concentration: 0.7mol/L), heating to 70 ℃, reacting for 3.0hr, adding 300g of NaOH aqueous solution with mass concentration of 15% to terminate the reaction, and finally adding 800g of monochloromethane to extract, separate, wash and dry to obtain the coupling agent 1, 5-dibromo-3, 3 bis (2-bromoethyl) pentane (yield 93%).

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 1650g of cyclohexane, 170g of 1, 3-butadiene and 1.0g of THF into the polymerization kettle, heating to 40 ℃, adding 30.1mmo1 n-butyllithium to start reaction, reacting for 50min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 50min, and heating at the speed of 0.6 ℃/min to form a BR chain segment with wide molecular weight distribution; then, adding 310g of styrene and 0.4g of THF into the polymerization kettle A in sequence, reacting for 40min to form a-BR-PS-chain segment, heating to 70 ℃, adding 135mmo 11, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 60 min; meanwhile, in a 15L stainless steel polymerization kettle B, introducing argon to replace the system for 3 times, sequentially adding 2100g of cyclohexane, 460g of styrene, 312g of 1, 3-butadiene and 1.5g of THF, heating to 50 ℃, adding 32.1mmo1 n-butyllithium to start reaction, reacting for 60min, gradually increasing the temperature from 50 ℃ to 70 ℃ within 60min, and heating at the speed of 0.4 ℃/min to form a-SBR-chain segment with wide vinyl content distribution; then, 160g of styrene and 1.5g of THF are sequentially added into the polymerization kettle B, and the reaction is carried out for 30min to form a-PS-SBR-chain segment; after the monomers are completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 60 min; finally, 16g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction lasts 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 coagulated and dried by a wet method to prepare the binary two-armed star copolymer [ -B-PS-SBR-]_nY[-BR-PS-B-]_nGrafting agent (Mn 10350, Mw/Mn 11.9).

(2) Preparing hyperbranched and ultra-wide molecular weight distribution butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 620g of methane chloride, 370g of cyclohexane, 12.5g of [ -B-PS-SBR- ] nY [ -BR-PS-B- ] n grafting agent into the polymerization kettle, and stirring and dissolving for 10min until the grafting agent is completely dissolved; and then cooling to-75 ℃, sequentially adding 520g of methane chloride, 430g of isobutene and 9g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 150g of methane chloride, 3.12g of aluminum sesquiethylate chloride and 0.075g of HCl at-85 ℃, aging for 20min, then adding the mixture into the polymerization system together, stirring and reacting for 2.0hr, discharging, condensing, washing and drying to obtain the hyperbranched 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 grafting agent:

a preparation of a coupling agent: the same 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 1750g of cyclohexane, 190g of 1, 3-butadiene and 1.2g of THF into the polymerization kettle, heating to 40 ℃, adding 32.1mmo1 n-butyllithium to start reaction, reacting for 50min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 50min, and heating at the speed of 0.6 ℃/min to form a BR chain segment with wide molecular weight distribution; then, 350g of styrene and 0.7g of THF are sequentially added into the polymerization kettle A to react for 45min to form a-BR-PS-chain segment, then the temperature is raised to 75 ℃, 150mmo 11, 5-dibromo-3, 3-di (2-bromoethyl) pentane is added to carry out coupling reaction for 65 min; meanwhile, in a 15L stainless steel polymerization kettle B, introducing argon to replace the system for 3 times, sequentially adding 2200g of cyclohexane, 480g of styrene, 330g of 1, 3-butadiene and 1.7g of THF, heating to 50 ℃, adding 34.1mmo1 n-butyllithium to start reaction, reacting for 70min, gradually increasing the temperature from 50 ℃ to 70 ℃ within 70min, and heating at the speed of 0.3 ℃/min to form a-SBR-chain segment with wide vinyl content distribution; then, sequentially adding 180g of styrene and 1.6g of THF into the polymerization kettle B, and reacting for 35min to form a-PS-SBR-chain segment; when the monomer is completely rotatedAdding the materials in the polymerization kettle B into the polymerization kettle A after the materials are dissolved, and carrying out coupling reaction for 70 min; finally, 20g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction lasts 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 coagulated and dried by a wet method to prepare the binary two-hybrid-arm star-shaped copolymer [ -B-PS-SBR-]_nY[-BR-PS-B-]_nGrafting agent (Mn 22650, Mw/Mn 12.5).

(2) Preparing hyperbranched and ultra-wide molecular weight distribution butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 590g of methane chloride, 400g of cyclohexane, 16.3g of (-B-PS-SBR-) ] nY (-BR-PS-B-) ] n grafting agent into the polymerization kettle, and stirring and dissolving for 15min until the grafting agent is completely dissolved; and then cooling to-80 ℃, sequentially adding 540g of methane chloride, 440g of isobutene and 11g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 160g of methane chloride, 4.05g of aluminum sesquiethylate chloride and 0.089g of HCl at-85 ℃, aging for 20min, then adding the materials into the polymerization system together, stirring and reacting for 3.0hr, discharging, condensing, washing and drying to obtain the hyperbranched 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 grafting agent:

a preparation of a coupling agent: the same 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 1820g of cyclohexane, 220g of 1, 3-butadiene and 1.5g of THF into the polymerization kettle, heating to 40 ℃, adding 35.1mmo1 n-butyllithium to start reaction, reacting for 60min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 60min, and heating at the speed of 0.4 ℃/min to form a BR chain segment with wide molecular weight distribution; then, 380g of styrene and 0.9g of THF are sequentially added into the polymerization kettle A, the reaction is carried out for 50min, a-BR-PS-chain segment is formed, then the temperature is increased to 80 ℃, 180mmo 11, 5-dibromo-3, 3 di (2-bromoethyl) pentane is added, and the coupling reaction is carried out for 70 min; meanwhile, in a 15L stainless steel polymerizer B, argon gas was introduced to replace the system for 3 times, and 2200g of cyclohexane, 500g of styrene and 350g of 1, 3-butylene were sequentially addedDiene, 1.9g THF, heating to 50 deg.C, adding 36.5mmo1 n-butyllithium to start reaction, reacting for 80min, gradually heating from 50 deg.C to 70 deg.C within 80min, and heating at 0.3 deg.C/min to form-SBR-chain segment with wide vinyl content distribution; then, 200g of styrene and 1.8g of THF are sequentially added into the polymerization kettle B, and the reaction is carried out for 40min to form a-PS-SBR-chain segment; after the monomers are completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 80 min; finally, adding 25g of 1, 3-butadiene into the polymerization kettle A for end capping, reacting for 25min 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 binary two-hybrid-arm star-shaped copolymer [ -B-PS-SBR-]_nY[-BR-PS-B-]_nGrafting agent (Mn of 30250 and Mw/Mn of 13.6).

(2) Preparing hyperbranched and ultra-wide molecular weight distribution butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 560g of methane chloride, 430g of cyclohexane, 22.5g of (-B-PS-SBR-) ] nY (-BR-PS-B-) ] n grafting agent into the polymerization kettle, and stirring for dissolving for 20min until the grafting agent is completely dissolved; and then cooling to-80 ℃, sequentially adding 550g of methane chloride, 450g of isobutene and 13g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 170g of methane chloride, 4.85g of aluminum sesquiethylate chloride and 0.102g of HCl at-85 ℃, aging for 20min, then adding the mixture into the polymerization system together, stirring and reacting for 3.5hr, discharging, condensing, washing and drying to obtain the hyperbranched 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 grafting agent:

a preparation of a coupling agent: the same 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, adding 1950g of cyclohexane, 240g of 1, 3-butadiene and 1.7g of THF into the polymerization kettle in sequence, heating to 40 ℃, adding 37.5mmo1 n-butyllithium to start reaction, reacting for 70min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 70min, and heating at the speed of 0.3 ℃/min to form BR chain segments with wide molecular weight distribution(ii) a Then, 400g of styrene and 1.2g of THF are sequentially added into the polymerization kettle A to react for 55min to form a-BR-PS-chain segment, then the temperature is raised to 85 ℃, 200mmo 11, 5-dibromo-3, 3-di (2-bromoethyl) pentane is added to carry out coupling reaction for 80 min; meanwhile, in a 15L stainless steel polymerization kettle B, introducing argon to replace the system for 3 times, sequentially adding 2300g of cyclohexane, 530g of styrene, 370g of 1, 3-butadiene and 2.1g of THF, heating to 50 ℃, adding 38.5mmo1 n-butyllithium to start reaction, reacting for 80min, gradually increasing the temperature from 50 ℃ to 70 ℃ within 80min, and heating at the speed of 0.3 ℃/min to form a-SBR-chain segment with wide vinyl content distribution; then, 230g of styrene and 1.9g of THF are sequentially added into the polymerization kettle B, and the reaction is carried out for 45min to form a-PS-SBR-chain segment; after the monomers are completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 85 min; finally, 30g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction lasts 25min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, and the glue solution is coagulated and dried by a wet method to prepare the binary two-hybrid-arm star-shaped copolymer [ -B-PS-SBR-]_nY[-BR-PS-B-]_nGrafting agent (Mn 39650, Mw/Mn 14.1).

(2) Preparing hyperbranched and ultra-wide molecular weight distribution butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 520g of methane chloride, 450g of cyclohexane, 30.1g of [ -B-PS-SBR- ] nY [ -BR-PS-B- ] n grafting agent into the polymerization kettle, and stirring and dissolving for 25min until the grafting agent is completely dissolved; and then cooling to-80 ℃, sequentially adding 560g of methane chloride, 460g of isobutene and 15g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 180g of methane chloride, 5.02g of sesquiethylaluminum chloride and 0.262g of HCl at-90 ℃, aging for 25min, then adding the materials into the polymerization system together, stirring and reacting for 4.0hr, discharging, condensing, washing and drying to obtain the hyperbranched 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 grafting agent:

a preparation of a coupling agent: the same as in example 1.

b preparation of grafting agent: in thatIntroducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 5 times, sequentially adding 2100g of cyclohexane, 270g of 1, 3-butadiene and 2.1g of THF into the polymerization kettle, heating to 40 ℃, adding 39.2mmo1 n-butyllithium to start reaction, reacting for 70min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 70min, and heating at the speed of 0.3 ℃/min to form a BR chain segment with wide molecular weight distribution; then, 430g of styrene and 1.5g of THF are sequentially added into the polymerization kettle A, the reaction is carried out for 60min, a-BR-PS-chain segment is formed, then the temperature is increased to 90 ℃, 300mmo 11, 5-dibromo-3, 3 di (2-bromoethyl) pentane is added, and the coupling reaction is carried out for 90 min; meanwhile, in a 15L stainless steel polymerization kettle B, introducing argon to replace the system for 3 times, sequentially adding 2500g of cyclohexane, 580g of styrene, 400g of 1, 3-butadiene and 2.6g of THF, heating to 50 ℃, adding 42.5mmo1 n-butyllithium to start reaction, reacting for 90min, gradually increasing the temperature from 50 ℃ to 70 ℃ within 90min, and heating at the speed of 0.25 ℃/min to form a-SBR-chain segment with wide vinyl content distribution; then, 270g of styrene and 2.2g of THF are sequentially added into the polymerization kettle B, and the reaction is carried out for 50min to form a-PS-SBR-chain segment; after the monomers are completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 90 min; finally, 40g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction lasts for 30min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, and the glue solution is coagulated and dried by a wet method to prepare the binary two-hybrid-arm star-shaped copolymer [ -B-PS-SBR-]_nY[-BR-PS-B-]_nGrafting agent (Mn 45800, Mw/Mn 15.2).

(2) Preparing hyperbranched and ultra-wide molecular weight distribution butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 450g of methane chloride, 530g of cyclohexane, 40.5g of [ -B-PS-SBR- ] nY [ -BR-PS-B- ] n grafting agent into the polymerization kettle, and stirring for dissolving for 30min until the grafting agent is completely dissolved; then cooling to-85 ℃, sequentially adding 590g of methane chloride, 480g of isobutene and 20g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 190g of methane chloride, 6.22g of sesquiethylaluminum chloride and 0.312g of HCl at-95 ℃, aging for 30min, then adding the materials into the polymerization system together, stirring and reacting for 5.0hr, discharging, condensing, washing and drying to obtain the hyperbranched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.

Comparative example 1

(1) Preparation of grafting agent:

a preparation of a coupling agent: the same as in example 1.

b preparation of grafting agent: the other conditions were the same as in example 1 except that: in a polymerizer A, 1, 3-butadiene is reacted at a constant temperature of 40 ℃ without adopting temperature-variable polymerization, namely: in a 15L stainless steel polymerization vessel A with a jacket, the system was replaced 3 times by introducing argon, 1650g of cyclohexane, 170g of 1, 3-butadiene and 1.0g of THF were sequentially added to the polymerization vessel, the temperature was raised to 40 ℃ and 30.1mmo1 n-butyllithium was added to start the reaction, and the reaction was carried out for 50min to obtain BR₁A chain segment; then, 310g of styrene and 0.4g of THF were sequentially added into the polymerization reactor A, and the reaction was carried out for 40min to form-BR₁Heating the PS-chain segment to 70 ℃, adding 135mmo 11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and carrying out coupling reaction for 60 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 2100g of cyclohexane, 460g of styrene, 312g of 1, 3-butadiene and 1.5g of THF, heating to 50 ℃, adding 32.1mmo1 n-butyllithium to start reaction, reacting for 60min, gradually increasing the temperature from 50 ℃ to 70 ℃ within 60min, and heating at the speed of 0.4 ℃/min to form a-SBR-chain segment with wide vinyl content distribution; then, 160g of styrene and 1.5g of THF are sequentially added into the polymerization kettle B, and the reaction is carried out for 30min to form a-PS-SBR-chain segment; after the monomers are completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 60 min; finally, 16g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction lasts 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 coagulated and dried by a wet method to prepare the binary two-armed star copolymer [ -B-PS-SBR-]_nY[-BR₁-PS-B-]_nGrafting agent (Mn 10120, Mw/Mn 6.3).

(2) Preparing hyperbranched and ultra-wide molecular weight distribution butyl rubber: the other conditions were the same as in example 1 except that: no [ -B-PS-SBR-]nY[-BR-PS-B-]n grafting agent, but adding [ -B-PS-SBR-]nY[-BR₁-PS-B-]n grafting agent, namely: firstly, nitrogen is introduced into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, 620g of methane chloride, 370g of cyclohexane and [ -B-PS-SBR-]nY[-BR₁-PS-B-]n grafting agent 12.5g, stirring and dissolving for 10min until the grafting agent is completely dissolved; and then cooling to-75 ℃, sequentially adding 520g of methane chloride, 430g of isobutene and 9g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 150g of methane chloride, 3.12g of aluminum sesquiethylate chloride and 0.075g of HCl at-85 ℃, aging for 20min, then adding the mixture into the polymerization system together, stirring and reacting for 2.0hr, discharging, condensing, washing and drying to obtain the hyperbranched 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 grafting agent:

a preparation of a coupling agent: the same as in example 2.

b preparation of grafting agent: the other conditions were the same as in example 2 except that: in a polymerizer B, the-SBR-chain segment is reacted at a constant temperature of 50 ℃ without adopting temperature-variable polymerization, namely: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 3 times, sequentially adding 1750g of cyclohexane, 190g of 1, 3-butadiene and 1.2g of THF into the polymerization kettle, heating to 40 ℃, adding 32.1mmo1 n-butyllithium to start reaction, reacting for 50min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 50min, and heating at the speed of 0.6 ℃/min to form a BR chain segment with wide molecular weight distribution; then, 350g of styrene and 0.7g of THF are sequentially added into the polymerization kettle A to react for 45min to form a-BR-PS-chain segment, then the temperature is raised to 75 ℃, 150mmo 11, 5-dibromo-3, 3-di (2-bromoethyl) pentane is added to carry out coupling reaction for 65 min; meanwhile, in a 15L stainless steel polymerization kettle B, argon is introduced to replace the system for 3 times, 2200g of cyclohexane, 480g of styrene, 330g of 1, 3-butadiene and 1.7g of THF are sequentially added, the temperature is raised to 50 ℃, 34.1mmo1 n-butyllithium is added to start reaction, and the reaction is carried out for 70min to form SBR₁-a segment; then, 180g of styrene and 1.6g of THF are sequentially added into the polymerization kettle B for reaction for 35min to form-PS-SBR₁-a segment; adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted,coupling reaction is carried out for 70 min; finally, adding 20g of 1, 3-butadiene into the polymerization kettle A for end capping, reacting for 20min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the binary disambiguated star-shaped copolymer [ -B-PS-SBR₁-]_nY[-BR-PS-B-]_nGrafting agent (Mn 21320, Mw/Mn 5.2).

(2) Preparing hyperbranched and ultra-wide molecular weight distribution butyl rubber: the other conditions were the same as in example 2 except that: no [ -B-PS-SBR-]nY[-BR-PS-B-]n grafting agent, but adding [ -B-PS-SBR₁-]nY[-BR-PS-B-]n grafting agent, namely: firstly, nitrogen is introduced into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, 590g of methane chloride, 400g of cyclohexane and [ -B-PS-SBR are added into a polymerization kettle₁-]nY[-BR-PS-B-]n grafting agent 16.3g, stirring and dissolving for 15min until the grafting agent is completely dissolved; and then cooling to-80 ℃, sequentially adding 540g of methane chloride, 440g of isobutene and 11g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 160g of methane chloride, 4.05g of aluminum sesquiethylate chloride and 0.089g of HCl at-85 ℃, aging for 20min, then adding the materials into the polymerization system together, stirring and reacting for 3.0hr, discharging, condensing, washing and drying to obtain the hyperbranched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.

Comparative example 3

(1) Preparation of grafting agent:

a preparation of a coupling agent: the same as in example 3.

b preparation of grafting agent: the other conditions were the same as in example 3 except that: adopting single-kettle polymerization, namely adding the materials in the polymerization kettle B into the polymerization kettle A for reaction, namely: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 3 times, sequentially adding 1820g of cyclohexane, 220g of 1, 3-butadiene and 1.5g of THF into the polymerization kettle, heating to 40 ℃, adding 35.1mmo1 n-butyllithium to start reaction, reacting for 60min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 60min, and heating at the speed of 0.4 ℃/min to form a BR chain segment with wide molecular weight distribution; then feeding the mixture to a polymerization kettle AAdding 380g of styrene and 0.9g of THF in sequence, reacting for 50min to form a-BR-PS-chain segment, then adding 2200g of cyclohexane, 500g of styrene, 350g of 1, 3-butadiene and 1.9g of THF in sequence, heating to 50 ℃, adding 36.5mmo1 n-butyllithium to start reaction, reacting for 80min, gradually increasing the temperature from 50 ℃ to 70 ℃ within 80min, and heating at a speed of 0.3 ℃/min to form a-SBR-chain segment with wide vinyl content distribution; then 200g of styrene and 1.8g of THF are added into the polymerization kettle B in sequence for reaction for 40min to form-PS₁-SBR-segment; then heating to 80 ℃, adding 180mmo 11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and carrying out coupling reaction for 70 min; finally adding 25g of 1, 3-butadiene into the polymerization kettle A for end capping, reacting for 25min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the binary four-arm star-shaped copolymer [ -B-PS [ -B-PS [ -B-B-PS [ -B-PS [ -C-PS [ -B-PS [ -C-B₁-SBR-PS-BR-]_nY grafting agent (Mn 29120, Mw/Mn 9.5).

(2) Preparing hyperbranched and ultra-wide molecular weight distribution butyl rubber: the other conditions were the same as in example 3 except that: no [ -B-PS-SBR-]nY[-BR-PS-B-]n grafting agent, but adding [ -B-PS ]₁-SBR-PS-BR-]nY grafting agent, i.e.: firstly, nitrogen gas is introduced into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, and 560g of methane chloride, 430g of cyclohexane and [ -B-PS ] are added into a polymerization kettle₁-SBR-PS-BR-]22.5g of nY grafting agent is stirred and dissolved for 20min until the grafting agent is completely dissolved; and then cooling to-80 ℃, sequentially adding 550g of methane chloride, 450g of isobutene and 13g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 170g of methane chloride, 4.85g of aluminum sesquiethylate chloride and 0.102g of HCl at-85 ℃, aging for 20min, then adding the mixture into the polymerization system together, stirring and reacting for 3.5hr, discharging, condensing, washing and drying to obtain the hyperbranched 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 grafting agent:

a preparation of a coupling agent: the same as in example 1.

b graftingPreparation of the agent: the other conditions were the same as in example 4 except that: with a one pot polymerization, there is no reaction of polymerizer B, i.e.: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 3 times, sequentially adding 1950g of cyclohexane, 240g of 1, 3-butadiene and 1.7g of THF into the polymerization kettle, heating to 40 ℃, adding 37.5mmo1 n-butyllithium to start reaction, reacting for 70min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 70min, and heating at the speed of 0.3 ℃/min to form a BR chain segment with wide molecular weight distribution; then, 400g of styrene and 1.2g of THF are sequentially added into the polymerization kettle A to react for 55min to form a-BR-PS-chain segment, then the temperature is raised to 85 ℃, 200mmo 11, 5-dibromo-3, 3-di (2-bromoethyl) pentane is added to carry out coupling reaction for 80 min; finally, 30g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction lasts 25min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, and the glue solution is coagulated and dried by a wet method to prepare the binary two-hybrid-arm star-shaped copolymer [ -B-PS-BR-]_nY grafting agent (Mn 10210, Mw/Mn 4.2).

(2) Preparing hyperbranched and ultra-wide molecular weight distribution butyl rubber: the other conditions were the same as in example 4 except that: during the synthesis process, the grafting agent of [ -B-PS-SBR- ] nY [ -BR-PS-B- ] n is not added, but the grafting agent of [ -B-PS-BR- ] nY is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 520g of methane chloride, 450g of cyclohexane and 30.1g of [ -B-PS-BR- ] nY grafting agent into the polymerization kettle, and stirring and dissolving for 25min until the grafting agent is completely dissolved; and then cooling to-80 ℃, sequentially adding 560g of methane chloride, 460g of isobutene and 15g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 180g of methane chloride, 5.02g of sesquiethylaluminum chloride and 0.262g of HCl at-90 ℃, aging for 25min, then adding the materials into the polymerization system together, stirring and reacting for 4.0hr, discharging, condensing, washing and drying to obtain the hyperbranched 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 grafting agent: the other conditions were the same as in example 5 except that: during the synthesis process, no addition ofThe coupling agent 1, 5-dibromo-3, 3 bis (2-bromoethyl) pentane, namely: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 5 times, sequentially adding 2100g of cyclohexane, 270g of 1, 3-butadiene and 2.1g of THF into the polymerization kettle, heating to 40 ℃, adding 39.2mmo1 n-butyllithium to start reaction, reacting for 70min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 70min, and heating at the speed of 0.3 ℃/min to form a BR chain segment with wide molecular weight distribution; then, 430g of styrene and 1.5g of THF are sequentially added into a polymerization kettle A, the mixture is reacted for 60min to form a-BR-PS-chain segment, meanwhile, argon is introduced into a 15L stainless steel polymerization kettle B to replace the system for 3 times, 2500g of cyclohexane, 580g of styrene, 400g of 1, 3-butadiene and 2.6g of THF are sequentially added, the temperature is raised to 50 ℃, 42.5mmo1 n-butyl lithium is added to start the reaction, the reaction is carried out for 90min, the temperature is gradually raised from 50 ℃ to 70 ℃ within 90min, and the temperature raising speed is 0.25 ℃/min, so that the-SBR-chain segment with wide vinyl content distribution is formed; then, 270g of styrene and 2.2g of THF are sequentially added into the polymerization kettle B, and the reaction is carried out for 50min to form a-PS-SBR-chain segment; after the monomers are completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 90 min; finally, 40g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction lasts for 30min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, and the glue solution is coagulated and dried by a wet method to prepare the binary single-arm copolymer [ -B-PS-SBR-]_n[-BR-PS-B-]_nGrafting agent (Mn 32800, Mw/Mn 3.6).

(2) Preparing hyperbranched and ultra-wide molecular weight distribution butyl rubber: the other conditions were the same as in example 5 except that: during the synthesis process, the grafting agent of [ -B-PS-SBR- ] nY [ -BR-PS-B- ] n is not added, but the grafting agent of [ -B-PS-SBR- ] n [ -BR-PS-B- ] n is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 450g of methane chloride, 530g of cyclohexane, 40.5g of a grafting agent of [ -B-PS-SBR- ] n [ -BR-PS-B- ] n into the polymerization kettle, and stirring for dissolving for 30min until the grafting agent is completely dissolved; then cooling to-85 ℃, sequentially adding 590g of methane chloride, 480g of isobutene and 20g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 190g of methane chloride, 6.22g of sesquiethylaluminum chloride and 0.312g of HCl at-95 ℃, aging for 30min, then adding the materials into the polymerization system together, stirring and reacting for 5.0hr, discharging, condensing, washing and drying to obtain the hyperbranched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.

TABLE 1 Properties of hyperbranched, ultra-broad molecular weight distribution butyl rubber

As can be seen from Table 1: the hyperbranched and ultra-wide molecular weight distribution butyl rubber has ultra-high branching degree and ultra-wide molecular weight distribution, so that the Mooney relaxation area is small, and the hyperbranched and ultra-wide molecular weight distribution butyl rubber has good air tightness and high tensile strength, which shows that the hyperbranched and ultra-wide molecular weight distribution butyl rubber has good processability while maintaining excellent physical and mechanical properties.

The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.