阅读说明：本技术 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 杨珊珊 王在花 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,利用异戊二烯、苯乙烯和丁二烯反应单体通过变温和变速聚合制备出两种链段[-B-SB/(S→B)-BR-]和[-IR-PS-B-]n,最后经偶联剂1,5-二卤-3,3二(2-卤乙基)戊烷偶合制备出三元二杂臂星型共聚物。将上述三元二杂臂星型共聚物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。本发明实现了丁基橡胶物理机械性能和加工性能的平衡,保证了丁基橡胶在具有良好的粘弹性能同时,又能具有足够的生胶强度和良好的气密性。(The invention relates to a preparation method of hyperbranched and ultra-wide molecular weight distribution butyl rubber, which is characterized in that isoprene, styrene and butadiene reaction monomers are utilized to prepare two chain segments of [ -B-SB/(S → B) -BR- ] and [ -IR-PS-B- ] n through temperature-variable and speed-variable polymerization, and finally, the ternary disarm star-shaped copolymer is prepared through coupling of 1, 5-dihalo-3, 3 bis (2-haloethyl) pentane through a coupling agent. The ternary star-shaped copolymer with two hetero arms is used as a grafting agent to be polymerized with isobutene and isoprene under a catalytic system compounded by alkyl aluminum halide and protonic acid to prepare the hyperbranched butyl rubber with ultra-wide molecular weight distribution. The invention realizes the balance of the physical and mechanical properties and the processability of the butyl rubber, ensures that the butyl rubber has good viscoelasticity, sufficient crude rubber strength and good air tightness.)

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 polymerization kettle in an inert gas atmosphere, the temperature is raised to 50-80 ℃, after 1-3 hours of reaction, 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 extract, separate, wash and dry to prepare 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 polymerization kettle A under the atmosphere of inert gas, the temperature is raised to 50-70 ℃, and the reaction lasts for 50-70 min; then, sequentially adding 100-200% of solvent and 0.1-0.3% of structure regulator into a polymerization kettle A, heating to 70-80 ℃, stirring and mixing 30-40% of styrene and 10-20% of 1, 3-butadiene for 10-30 min, wherein the reaction is variable-speed polymerization, adding the mixture into the polymerization kettle in a continuous injection manner, reacting within 60-80 min, and adding the mixture at an initial feeding speed of more than 10.0% per min, and finally heating to 80-90 ℃, and adding a coupling agent for coupling reaction for 60-90 min; simultaneously, under the atmosphere of inert gas, sequentially adding 100-200% of solvent, 10-20% of isoprene, 0.01-0.1% of structure regulator and initiator into a polymerization kettle B, reacting to obtain variable temperature polymerization, and gradually increasing the temperature from 40 ℃ to 70 ℃ within 50-70 min; sequentially adding 20-30% of styrene and 0.05-0.1% of structure regulator, reacting until the monomers are completely converted, adding the material in the polymerization kettle B into the polymerization kettle A, 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 coagulating and drying the glue solution by a wet method 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 replacing for 3-5 times in an inert gas atmosphere, adding 100-200% of diluent and solvent into a polymerization kettle in a volume ratio of 70-30: 30-70 percent of mixed solvent and 1-10 percent of grafting agent, stirring and dissolving for 20-30 min until the grafting agent is completely dissolved; and 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 adding 30-50% of diluent and 0.05-3.0% of co-initiator into the polymerization system for stirring and reacting for 2.0-5.0 hr after mixing and aging for 20-30 min at-85 to-95 ℃, discharging and coagulating, 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 three-membered two-hetero-arm star copolymer synthesized from isoprene, 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, and the 1, 2-structure content of the BR is 20-40 percent; PS is a styrene homopolymer segment; SB is a random section of styrene and butadiene; (S → B) is a transition of styrene and butadiene; IR is a homopolymer segment with a broad vinyl distribution of isoprene; b is terminated butadiene, and n is 1-4.

3. The method of claim 2, wherein the ternary diheteroarm star copolymer has an isoprene content of 10% to 20%, a styrene content of 50% to 70%, and a butadiene content of 20% to 30%.

4. The method of claim 2, wherein the ternary diheteroarmed star copolymer has a number average molecular weight of 10000 to 50000 and a ratio of weight average molecular weight to number average molecular weight of 12.5 to 16.7.

5. The method of claim 1, wherein the halogenating agent is liquid bromine in a molar ratio of 4.5 to 6.5 relative to the amount of 3, 9-dioxo [5.5] spiroundecane.

6. The process of claim 1, wherein the catalyst is HCl-CH₃OH, wherein the molar concentration of HCl is 0.1-0.7 mol/L.

7. The method of claim 1, wherein the structure modifier is diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, or triethylamine.

8. The method of claim 7, wherein the structure modulator is tetrahydrofuran.

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 methyl chloride, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride, or fluorobutane.

13. The method of 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 to 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 14, wherein the alkyl aluminum halide is aluminum sesquiethyl chloride.

16. The method of claim 13, wherein the protic acid is HCI, HF, HBr, H₂SO₄、H₂CO₃、H₃PO₄Or HNO₃。

17. The method of claim 16, wherein the protic acid is HCI.

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 the hyperbranched butyl rubber with the ultra-wide molecular weight distribution by taking a ternary disarm star-shaped copolymer synthesized from isoprene, styrene and butadiene as a grafting agent and carrying out cationic polymerization with 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 mixture of a major amount of an internally dialkylaluminum dihalide, a minor amount of a monoalkylaluminum dihalide and a minor amount of aluminoxaneAnd the wide-distribution butyl rubber with the molecular weight distribution of more than 3.5 and up to 7.6 is obtained. CN101353403B 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. AlCl₃And 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.

CN101353386A 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 using alkyl lithium as an initiator, using hydrocarbons as a solvent, using reaction monomers comprising isoprene, styrene and butadiene for reaction in two kettles, adopting temperature-variable and speed-variable polymerization, and then coupling with a novel long-chain tetrahalide coupling agent 1, 5-dihalo-3, 3-bis (2-haloethyl) pentane to prepare the star copolymer with a ternary two-hybrid-arm structure. Finally, under the catalysis system of compounding Lewis acid and protonic acid, the ternary star-shaped copolymer with two hetero arms as a grafting agent is subjected to 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 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 introducing inert gas into a polymerization kettle for replacement for 2-4 times, sequentially adding 100-200% of deionized water, 3, 9-dioxo [5.5] spiro undecane, a halogenating agent and 1-5% of a catalyst into the polymerization kettle, heating to 50-80 ℃, reacting for 1-3 hours, adding 20-40% of NaOH aqueous solution with the mass concentration of 10-20% to terminate the reaction, and finally adding 200-300% of monochloromethane for extraction, separation, washing and drying to obtain the coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane (the yield is 85-95%).

b preparation of grafting agent: introducing inert gas into a polymerization kettle A for 3-5 times in percentage of the total mass of reaction monomers, sequentially adding 100-200% of solvent, 10-20% of 1, 3-butadiene, 0.05-0.3% of structure regulator and initiator into the polymerization kettle, heating to 50-70 ℃, and reacting for 50-70 min to form a BR chain segment; then, sequentially adding 100-200% of solvent and 0.1-0.3% of structure regulator into the polymerization kettle A, heating to 70-80 ℃, stirring and mixing 30-40% of styrene and 10-20% of 1, 3-butadiene for 10-30 min, wherein the reaction is variable-speed polymerization, adding the mixture into the polymerization kettle in a continuous injection manner, reacting within 60-80 min, and carrying out initial feeding at an initial feeding speed>10.0 percent of mixture/min, the reduction range of the feeding speed is determined according to the reaction time to form a random and long gradual section-SB/(S → B) -chain segment, the conversion rate of the styrene and the 1, 3-butadiene monomer reaches 100 percent, finally the temperature is increased to 80-90 ℃, and a coupling agent is added to carry out the coupling reaction for 60-90 min to form [ -SB/(S → B) -BR-]_nAnd Y. Meanwhile, introducing inert gas into a polymerization kettle B to replace the system for 3-5 times, sequentially adding 100-200% of solvent, 10-20% of isoprene, 0.01-0.1% of structure regulator and initiator, reacting to obtain variable temperature polymerization, gradually increasing the temperature from 40 ℃ to 70 ℃ within 50-70 min, wherein the temperature rise is a continuous gradual change process to form an IR chain segment with wide vinyl distribution, and when the conversion rate of the isoprene monomer reaches 100%; then sequentially adding 20-30% of styrene and 0.05-0.1% of structure regulator, reacting for 40-60 min to form an-IR-PS-chain segment, adding the material in the polymerization kettle B into the polymerization kettle A after the 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 for 20-30 min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the star-shaped copolymer with ternary two hybrid arms ([ -B-SB/(S → B) -BR-]_nY[-IR-PS-B-]_n)。

(2) Preparing hyperbranched and ultra-wide molecular weight distribution butyl rubber: according to one hundred percent of the total mass of reaction monomers, firstly introducing inert gas into a polymerization kettle for replacing for 3-5 times, adding 100-200 percent of diluent and solvent into the polymerization kettle, and mixing the mixture by weight percent: the V ratio is 70-30: 30-70 percent of mixed solvent and 1-10 percent of grafting agent, stirring and dissolving for 20-30 min until the grafting agent is completely dissolved; and then cooling to-75 to-85 ℃, sequentially adding 100 to 200 percent of diluent, 85 to 95 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 is a ternary star-shaped two-hybrid-arm copolymer synthesized from isoprene, 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, and the 1, 2-structure content of the BR is 20-40%; PS is a styrene homopolymer segment; SB is a random section of styrene and butadiene; (S → B) is a transition of styrene and butadiene; IR is a homopolymer segment with a broad vinyl distribution of isoprene; b is terminated butadiene, and n is 1-4; the content of isoprene in the ternary two-hybrid-arm star-shaped copolymer is 10-20%, the content of styrene is 50-70%, and the content of butadiene is 20-30%; the number average molecular weight (Mn) of the ternary disambiguated star-shaped copolymer is 10000-50000, and the molecular weight distribution (Mw/Mn) is 12.5-16.7.

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 polymerizer of the invention is not limited, but is preferably a stainless steel polymerizer with a jacket.

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 0.1-3.0%, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.01: 1-0.1: 1.

The polymerization 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 inert gas is nitrogen or one of all element gases in group 0 of the periodic table of elements, which do not contain radon.

The invention firstly treats 3, 9-dioxo [5.5]]Performing halogenation reaction on spiro undecane to synthesize a novel coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane, then reacting three reaction monomers isoprene, styrene and butadiene in two kettles, polymerizing by adopting temperature-changing and speed-changing processes, and then coupling the three reaction monomers isoprene, styrene and butadiene by using the coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane to prepare the ternary two-armed star copolymer [ -B-SB/(S → B) -BR-]_nY[-IR-PS-B-]_n(see FIG. 1). The [ -B-SB/(S → B) -BR-]_nY[-IR-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).

The invention uses two-kettle feeding method, temperature-variable and speed-variable polymerization to make two long-chain segments [ -B-SB/(S → B) -BR-]_nAnd [ -IR-PS-B-]_n1, 5-dihalo-3, 3-bis (2-haloethyl) pentane coupling agent is coupled on a macromolecular chain to form a ternary disambiguated star structure, so that the performances of different chain segments and the disambiguated star structure are organically combined together and act synergistically, the regularity of the molecular chain is obviously destroyed by utilizing the wide molecular weight distribution in an IR chain segment, the randomness and the gradual change of a SB/(S → B) -chain segment and the difference of reactivity ratios and steric hindrance effects of all the chain segments in the disambiguated structure in the grafting polymerization process of the butyl rubber, and the molecular weight distribution is obviously widened to ensure that the butyl rubber can obtain good viscoelastic performance, has a fast stress relaxation rate and improves the processability of the butyl rubber; meanwhile, the-PS-and-SB/(S → B) -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 solves the contradiction between poor processability and excellent air tightness of butyl rubber by synthesizing a novel coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane and designing a ternary disambiguated star structure, and finally realizes the optimal balance between the processability and the physical and mechanical properties of the butyl rubber. 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 is [ -B-SB/(S → B) -BR-]_nY[-IR-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 were all commercially available.

(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 a polystyrene standard sample as a calibration curve, taking tetrahydrofuran as a mobile phase, controlling the column temperature to be 40 ℃, controlling the sample concentration to be 1mg/ml, and controlling the sample injection amount to be50 μ L, elution time 40min, flow rate 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 gas for 3 times of replacement, and sequentially adding 600g of deionized water and 60g of 3, 9-dioxygen [5.5]]Spiroundecane, 340g of liquid bromine, 20g of HCl-CH₃OH solution (HCl molar concentration: 0.7mol/L), heating to 80 ℃, 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 94%).

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 0.6g of THF into the polymerization kettle, heating to 50 ℃, adding 35.1mmo1 n-butyllithium to start reaction, and reacting for 50min to form a BR chain segment; then adding 1950g of cyclohexane and 1.5g of THF into the polymerization kettle A in sequence, heating to 70 ℃, then stirring and mixing 460g of styrene and 160g of 1, 3-butadiene for 10min, and reacting for 60min at an initial feeding speed of 80g of mixture/min of styrene and 1, 3-butadiene and a feeding speed reduction range of 10g of mixture/min per minute to form a random and long gradual change section-SB/(S → B) -chain section; finally heating to 80 DEG CAdding 155mmo 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 1550g of cyclohexane, 160g of isoprene and 0.5g of THF, heating to 40 ℃, adding 25.1mmo1 of n-butyllithium to start reaction, gradually increasing the temperature from 40 ℃ to 70 ℃ within 50min, heating at the speed of 0.6 ℃/min, and reacting for 50min to form an IR chain segment with wide molecular weight distribution; then, 305g of styrene and 0.4g of THF are sequentially added into the polymerization kettle B, and the reaction is carried out for 40min to form an-IR-PS-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, 17g 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 ternary star-shaped diaspore-armed copolymer [ -B-SB/(S → B) -BR-]_nY[-IR-PS-B-]_nGrafting agent (Mn 13650, Mw/Mn 12.8).

(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 600g of methane chloride, 350g of cyclohexane, 9.5g of grafting agent of [ -B-SB/(S → B) -BR- ] nY [ -IR-PS-B- ] n into the polymerization kettle, stirring and dissolving for 20min until the grafting agent is completely dissolved; and then cooling to-75 ℃, sequentially adding 505g of methane chloride, 427g of isobutene and 8g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 150g of methane chloride, 3.85g of sesquiethylaluminum chloride and 0.082g 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: in a 15L stainless steel jacketed polymerization vessel A, the system was replaced 3 times by introducing argon gas, and 1850g of cyclohexane and 190g of 1, 3-butadiene were sequentially added to the polymerization vesselHeating 0.8g of THF to 50 ℃, adding 38.2mmo1 n-butyllithium to start reaction, and reacting for 55min to form a BR chain segment; then, 2050g of cyclohexane and 1.7g of THF are sequentially added into a polymerization kettle A, the temperature is raised to 75 ℃, then 490g of styrene and 180g of 1, 3-butadiene are stirred and mixed for 10min, within 70min, the initial feeding speed is 70g of the mixture of styrene and 1, 3-butadiene/min, the feeding speed is reduced by 12g of the mixture per minute, and the reaction is carried out for 70min, so that a random and long gradual change section-SB/(S → B) -chain segment is formed; finally, heating to 80 ℃, adding 175mmo 11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and carrying out coupling reaction for 70 min; meanwhile, in a 15L stainless steel polymerization kettle B, introducing argon to replace the system for 3 times, sequentially adding 1650g of cyclohexane, 180g of isoprene and 0.7g of THF, heating to 40 ℃, adding 27.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 40 ℃ to 70 ℃ within 50min, heating at a speed of 0.6 ℃/min, and reacting for 50min to form an IR chain segment with wide molecular weight distribution; then, 330g of styrene and 0.6g of THF are sequentially added into the polymerization kettle B, and the reaction is carried out for 45min to form an-IR-PS-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 70 min; finally, 20g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction lasts for 22min 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 star-shaped ternary disarm copolymer [ -B-SB/(S → B) -BR-]_nY[-IR-PS-B-]_nGrafting agent (Mn 20230, Mw/Mn 13.9).

(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 580g of methane chloride and 380g of cyclohexane into a polymerization kettle, stirring and dissolving 16g of a grafting agent [ -B-SB/(S → B) -BR- ] nY [ -IR-PS-B- ] n for 22min until the grafting agent is completely dissolved; and then cooling to-78 ℃, sequentially adding 520g of methane chloride, 435g of isobutene and 10g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 160g of methane chloride, 4.12g of sesquiethylaluminum chloride and 0.098g of HCl at-85 ℃, aging for 20min, then adding the mixture 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 1950g of cyclohexane, 210g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle, heating to 60 ℃, adding 39.5mmo1 n-butyllithium to start reaction, and reacting for 60min to form a BR chain segment; adding 2150g of cyclohexane and 1.9g of THF into the polymerization kettle A in sequence, heating to 80 ℃, stirring and mixing 510g of styrene and 200g of 1, 3-butadiene for 20min, and reacting for 70min at an initial feeding speed of 70g of the mixture of styrene and 1, 3-butadiene/min and a feeding speed reduction range of 12g of the mixture per minute to form a random and long gradual change section-SB/(S → B) -chain segment; finally, heating to 85 ℃, adding 190mmo 11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and carrying 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 1720g of cyclohexane, 200g of isoprene and 0.9g of THF, heating to 40 ℃, adding 29.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 40 ℃ to 70 ℃ within 60min, heating at a speed of 0.5 ℃/min, and reacting for 60min to form an IR chain segment with wide molecular weight distribution; then, 350g of styrene and 0.8g of THF are sequentially added into the polymerization kettle B, and the reaction is carried out for 50min to form an-IR-PS-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, 23g 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 ternary star-shaped diaspore-armed copolymer [ -B-SB/(S → B) -BR-]_nY[-IR-PS-B-]_nGrafting agent (Mn 36150, Mw/Mn 14.6).

(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 550g of methane chloride, 400g of cyclohexane, 22g of grafting agent of [ -B-SB/(S → B) -BR- ] nY [ -IR-PS-B- ] n into the polymerization kettle, and stirring and dissolving for 25min until the grafting agent is completely dissolved; and then cooling to-78 ℃, sequentially adding 530g of methane chloride, 445g of isobutene and 13g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then mixing 170g of methane chloride, 4.85g of sesquiethylaluminum chloride and 0.098g of HCl at-90 ℃, aging for 25min, 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, sequentially adding 2010g of cyclohexane, 230g of 1, 3-butadiene and 1.1g of THF into the polymerization kettle, heating to 65 ℃, adding 41.2mmo1 n-butyllithium to start reaction, and reacting for 65min to form a BR chain segment; then 2230g of cyclohexane and 2.2g of THF are sequentially added into the polymerization kettle A, the temperature is raised to 80 ℃, then 510g of styrene and 200g of 1, 3-butadiene are stirred and mixed for 20min, within 70min, the initial feeding speed is 70g of the mixture of styrene and 1, 3-butadiene/min, the feeding speed is reduced by 12g of the mixture per minute, and the reaction is carried out for 70min, so as to form a random and long gradual change section-SB/(S → B) -chain section; finally, heating to 85 ℃, adding 220mmo 11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and carrying out coupling reaction for 85 min; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 1950g of cyclohexane, 210g of isoprene and 1.2g of THF, heating to 40 ℃, adding 31.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 40 ℃ to 70 ℃ within 60min, heating at the speed of 0.5 ℃/min, and reacting for 60min to form an IR chain segment with wide molecular weight distribution; then 370g of styrene and 1.0g of THF are sequentially added into the polymerization kettle B, and the reaction is carried out for 60min to form an-IR-PS-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, 25g of 1, 3-butadiene is added into the polymerization kettle A for end capping, and thenReacting 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 ternary disarm star copolymer [ -B-SB/(S → B) -BR-]_nY[-IR-PS-B-]_nGrafting agent (Mn 41020, Mw/Mn 15.3).

(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 530g of methane chloride, 430g of cyclohexane, 25g of [ -B-SB/(S → B) -BR- ] nY [ -IR-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 540g of methane chloride, 456g of isobutene and 15g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then mixing 180g of methane chloride, 5.15g of sesquiethylaluminum chloride and 0.103g of HCl at-95 ℃, 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: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 5 times, sequentially adding 2230g of cyclohexane, 250g of 1, 3-butadiene and 1.3g of THF into the polymerization kettle, heating to 70 ℃, adding 43.5mmo1 n-butyllithium to start reaction, and reacting for 70min to form a BR chain segment; then 2360g of cyclohexane and 2.5g of THF are sequentially added into the polymerization kettle A, the temperature is raised to 80 ℃, 530g of styrene and 210g of 1, 3-butadiene are stirred and mixed for 20min, within 80min, the initial feeding speed is 80g of the mixture of styrene and 1, 3-butadiene/min, the feeding speed is reduced by 15g of the mixture per minute, and the reaction is carried out for 80min, so as to form a random and long gradual change section-SB/(S → B) -chain segment; finally, heating to 90 ℃, adding 270mmo 11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and carrying out coupling reaction for 90 min; meanwhile, in a 15L stainless steel polymerizer B, argon gas was introduced to replace the system for 3 times, and 2000g of cyclohexane was sequentially addedHeating 230g of isoprene and 1.3g of THF to 40 ℃, adding 33.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 40 ℃ to 70 ℃ within 70min, and reacting for 70min at the heating speed of 0.5 ℃/min to form an IR chain segment with wide molecular weight distribution; then 390g of styrene and 1.2g of THF are sequentially added into the polymerization kettle B for reaction for 60min to form an-IR-PS-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, adding 28g of 1, 3-butadiene into the polymerization kettle A for end capping, reacting for 30min 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 ternary disarm star copolymer [ -B-SB/(S → B) -BR-]_nY[-IR-PS-B-]_nGrafting agent (Mn 49620, Mw/Mn 16.5).

(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 500g of methane chloride, 470g of cyclohexane, 30g of [ -B-SB/(S → B) -BR- ] nY [ -IR-PS-B- ] n grafting agent into the polymerization kettle, and stirring and dissolving for 30min until the grafting agent is completely dissolved; and then cooling to-85 ℃, sequentially adding 550g of methane chloride, 465g 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, 5.85g of sesquiethylaluminum chloride and 0.213g of HCl at-95 ℃, aging for 30min, then adding the mixture 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: isoprene in the polymerizer B reacts at a constant temperature of 40 ℃ without adopting temperature-variable polymerization, namely: in a 15L stainless steel polymerizer A equipped with a jacket, the system was replaced 3 times by introducing argon, 1650g of cyclohexane, 170g of 1, 3-butadiene and 0.6g of THF were sequentially added to the polymerizer, the temperature was raised to 50 ℃,adding 35.1mmo1 n-butyllithium to start reaction for 50min to form a BR chain segment; then 1950g of cyclohexane and 1.5g of THF are sequentially added into the polymerization kettle A, the temperature is raised to 70 ℃, 460g of styrene and 160g of 1, 3-butadiene are stirred and mixed for 10min, within 60min, the initial feeding speed is 80g of mixture/min of styrene and 1, 3-butadiene, the feeding speed is reduced by 10g of mixture per minute, and the mixture is reacted for 60min to form a random and long gradual change section-SB/(S → B) -chain section; finally, heating to 80 ℃, adding 155mmo 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, argon is introduced to replace the system for 3 times, 1550g of cyclohexane, 160g of isoprene and 0.5g of THF are sequentially added, the temperature is raised to 40 ℃, 25.1mmo1 n-butyllithium is added to start reaction, and the reaction is carried out for 50min to form IR₁A chain segment; then 305g of styrene and 0.4g of THF were added in this order to polymerizer B, and reacted for 40min to form-IR₁-a PS-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, 17g 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 ternary star-shaped diaspore-armed copolymer [ -B-SB/(S → B) -BR-]_nY[-IR₁-PS-B-]_nGrafting agent (Mn 12550, Mw/Mn 6.5).

(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-SB/(S → B) -BR-]nY[-IR-PS-B-]n grafting agent, but adding [ -B-SB/(S → B) -BR-]nY[-IR₁-PS-B-]n grafting agent, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced for 3 times for replacement, 600g of methane chloride and 350g of cyclohexane are added into the polymerization kettle, [ -B-SB/(S → B) -BR-]nY[-IR₁-PS-B-]n grafting agent 9.5g, stirring and dissolving for 20min until the grafting agent is completely dissolved; then when the temperature is reduced to-75 ℃, 505g of methane chloride, 427g of isobutene and 8g of isoprene are added in sequence, the mixture is stirred and mixed until the temperature of a polymerization system is reduced to-90 ℃, and then 150g of methane chloride, 3.85g of aluminum sesquiethylate chloride and 0.082g of HCl are mixed at-85 DEG CAnd then mixing, aging for 20min, adding the mixture into a polymerization system, stirring and reacting for 2.0hr, discharging, coagulating, 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 3 except that: instead of using a variable speed polymerization in polymerizer A, styrene and 1, 3-butadiene are not mixed but added to the polymerizer at one time, i.e.: introducing argon into a 15L stainless steel polymerization kettle A with a jacket to replace the system for 3 times, sequentially adding 1850g of cyclohexane, 190g of 1, 3-butadiene and 0.8g of THF into the polymerization kettle, heating to 50 ℃, adding 38.2mmo1 n-butyllithium to start reaction, and reacting for 55min to form a BR chain segment; then, 2050g of cyclohexane, 1.7g of THF, 490g of styrene and 180g of 1, 3-butadiene are sequentially added into the polymerization kettle A, the temperature is raised to 75 ℃, and the reaction is carried out for 70min to form an SBR-chain segment; finally, heating to 80 ℃, adding 175mmo 11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and carrying out coupling reaction for 70 min; meanwhile, in a 15L stainless steel polymerization kettle B, introducing argon to replace the system for 3 times, sequentially adding 1650g of cyclohexane, 180g of isoprene and 0.7g of THF, heating to 40 ℃, adding 27.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 40 ℃ to 70 ℃ within 50min, heating at a speed of 0.6 ℃/min, and reacting for 50min to form an IR chain segment with wide molecular weight distribution; then, 330g of styrene and 0.6g of THF are sequentially added into the polymerization kettle B, and the reaction is carried out for 45min to form an-IR-PS-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 70 min; finally, 20g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction lasts for 22min 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 ternary two-hybrid-arm star-shaped copolymer [ -B-SBR-BR-]_nY[-IR-PS-B-]_nGrafting agent (Mn 19230, Mw/Mn 5.7).

(2) Preparing hyperbranched and ultra-wide molecular weight distribution butyl rubber: the other conditions were the same as in example 2 except that: during the synthesis process, the grafting agent of [ -B-SB/(S → B) -BR- ] nY [ -IR-PS-B- ] n is not added, but the grafting agent of [ -B-SBR-BR- ] nY [ -IR-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 580g of methane chloride, 380g of cyclohexane, 16g of [ -B-SBR-BR- ] nY [ -IR-PS-B- ] n grafting agent into the polymerization kettle, and stirring and dissolving for 22min until the grafting agent is completely dissolved; and then cooling to-78 ℃, sequentially adding 520g of methane chloride, 435g of isobutene and 10g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing 160g of methane chloride, 4.12g of sesquiethylaluminum chloride and 0.098g of HCl at-85 ℃, aging for 20min, then adding the mixture 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 1950g of cyclohexane, 210g of 1, 3-butadiene and 0.9g of THF into the polymerization kettle, heating to 60 ℃, adding 39.5mmo1 n-butyllithium to start reaction, and reacting for 60min to form a BR chain segment; adding 2150g of cyclohexane and 1.9g of THF into the polymerization kettle A in sequence, heating to 80 ℃, stirring and mixing 510g of styrene and 200g of 1, 3-butadiene for 20min, and reacting for 70min at an initial feeding speed of 70g of the mixture of styrene and 1, 3-butadiene/min and a feeding speed reduction range of 12g of the mixture per minute to form a random and long gradual change section-SB/(S → B) -chain segment; then, 1720g of cyclohexane, 200g of isoprene and 0.9g of THF are sequentially added into the polymerization kettle A, the temperature is raised to 40 ℃, 29.5mmo1 n-butyllithium is added to start the reaction, the temperature is gradually raised from 40 ℃ to 70 ℃ within 60min, the temperature raising speed is 0.5 ℃/min, the reaction is carried out for 60min, and the broad molecular weight distribution is formedAn IR segment of (a); then, 350g of styrene and 0.8g of THF are sequentially added into the polymerization kettle B, and the reaction is carried out for 50min to form a-PS-chain segment; secondly, heating to 85 ℃, adding 190mmo 11, 5-dibromo-3, 3 di (2-bromoethyl) pentane, and carrying out coupling reaction for 80 min; finally, 23g 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 ternary single-arm star copolymer [ -B-PS-IR-SB/(S → B) -BR-]_nY grafting agent (Mn 33150, Mw/Mn 8.6).

(2) Preparing hyperbranched and ultra-wide molecular weight distribution butyl rubber: the other conditions were the same as in example 3 except that: during the synthesis process, no grafting agent of [ -B-SB/(S → B) -BR- ] nY [ -IR-PS-B- ] n is added, but the grafting agent of [ -B-PS-IR-SB/(S → B) -BR- ] nY is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 550g of methane chloride, 400g of cyclohexane, 22g of grafting agent of [ -B-SB/(S → B) -BR- ] nY [ -IR-PS-B- ] n into the polymerization kettle, and stirring and dissolving for 25min until the grafting agent is completely dissolved; and then cooling to-78 ℃, sequentially adding 530g of methane chloride, 445g of isobutene and 13g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then mixing 170g of methane chloride, 4.85g of sesquiethylaluminum chloride and 0.098g of HCl at-90 ℃, aging for 25min, 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 4.

b preparation of grafting agent: the other conditions were the same as in example 4 except that: in the synthesis process, a coupling agent 1, 5-dibromo-3, 3 di (2-bromoethyl) pentane is not added, namely: in a 15L stainless steel polymerizer A equipped with a jacket, the system was replaced 3 times by introducing argon gas, 2010g of cyclohexane, 230g of 1, 3-butadiene and 1.1g of THF were sequentially added to the polymerizer, the temperature was raised to 65 ℃ and 41.2mmo1 n-butyllithium was added to start the reaction,reacting for 65min to form a BR chain segment; then 2230g of cyclohexane and 2.2g of THF are sequentially added into the polymerization kettle A, the temperature is raised to 80 ℃, then 510g of styrene and 200g of 1, 3-butadiene are stirred and mixed for 20min, within 70min, the initial feeding speed is 70g of the mixture of styrene and 1, 3-butadiene/min, the feeding speed is reduced by 12g of the mixture per minute, and the reaction is carried out for 70min, so as to form a random and long gradual change section-SB/(S → B) -chain section; simultaneously, introducing argon into a 15L stainless steel polymerization kettle B to replace the system for 3 times, sequentially adding 1950g of cyclohexane, 210g of isoprene and 1.2g of THF, heating to 40 ℃, adding 31.5mmo1 n-butyllithium to start reaction, gradually increasing the temperature from 40 ℃ to 70 ℃ within 60min, heating at the speed of 0.5 ℃/min, and reacting for 60min to form an IR chain segment with wide molecular weight distribution; then 370g of styrene and 1.0g of THF are sequentially added into the polymerization kettle B, and the reaction is carried out for 60min to form an-IR-PS-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, 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 ternary long-chain copolymer [ -B-SB/(S → B) -BR-IR-PS-B-]_nGrafting agent (Mn 35920, Mw/Mn 4.1).

(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, no grafting agent of [ -B-SB/(S → B) -BR- ] nY [ -IR-PS-B- ] n is added, but the grafting agent of [ -B-SB/(S → B) -BR-IR-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 530g of methane chloride, 430g of cyclohexane and 25g of [ -B-SB/(S → B) -BR-IR-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 540g of methane chloride, 456g of isobutene and 15g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then mixing 180g of methane chloride, 5.15g of sesquiethylaluminum chloride and 0.103g of HCl at-95 ℃, 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:

a preparation of a coupling agent: the same as in example 5.

b preparation of grafting agent: the same as in example 5.

(2) Preparing hyperbranched and ultra-wide molecular weight distribution butyl rubber: the other conditions were the same as in example 5 except that the amount of the grafting agent of [ -B-SB/(S → B) -BR- ] nY [ -IR-PS-B- ] n added during the synthesis was 3.0g, that is: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 500g of methane chloride, 470g of cyclohexane, 3.0g of a grafting agent of [ -B-SB/(S → B) -BR- ] nY [ -IR-PS-B- ] n into the polymerization kettle, and stirring and dissolving for 30min until the grafting agent is completely dissolved; and then cooling to-85 ℃, sequentially adding 550g of methane chloride, 465g 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, 5.85g of sesquiethylaluminum chloride and 0.213g of HCl at-95 ℃, aging for 30min, then adding the mixture 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.