CN113831466B - Preparation method of hyperbranched ultra-wide molecular weight distribution butyl rubber - Google Patents

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

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CN113831466B
CN113831466B CN202010589659.0A CN202010589659A CN113831466B CN 113831466 B CN113831466 B CN 113831466B CN 202010589659 A CN202010589659 A CN 202010589659A CN 113831466 B CN113831466 B CN 113831466B
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polymerization
butyl rubber
molecular weight
butadiene
polymerization kettle
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CN113831466A (en
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徐典宏
杨珊珊
王在花
孟令坤
翟云芳
朱晶
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Abstract

The invention relates to a preparation method of hyperbranched ultra-wide molecular weight distribution butyl rubber, which utilizes isoprene, styrene and butadiene reaction monomers to prepare two chain segments [ -B-SB/(S- & gtB) -BR- ] and [ -IR-PS-B- ] n through temperature and speed changing polymerization, and finally prepares a ternary two-heteroarm star copolymer through coupling of a coupling agent 1, 5-dihalogen-3, 3-bis (2-haloethyl) pentane. The ternary diheteroarm star copolymer is used as a grafting agent to prepare hyperbranched ultra-wide molecular weight distribution butyl rubber with isobutene and isoprene through cationic polymerization under a catalytic system compounded by alkyl aluminum halide and protonic acid. The invention realizes the balance of the physical and mechanical properties and the processing properties of the butyl rubber, ensures that the butyl rubber has good viscoelastic property, and simultaneously has enough green rubber strength and good air tightness.

Description

Preparation method of hyperbranched ultra-wide molecular weight distribution butyl rubber
Technical Field
The invention relates to a preparation method of hyperbranched ultra-wide molecular weight distribution butyl rubber, in particular to a method for preparing hyperbranched ultra-wide molecular weight distribution butyl rubber by taking ternary two-hetero-arm star-shaped copolymer synthesized from isoprene, styrene and butadiene as a grafting agent and carrying out cationic polymerization on the ternary two-hetero-arm star-shaped copolymer, isobutylene and isoprene.
Background
Butyl Rubber (IIR) is known to be copolymerized from isobutylene and a small amount of isoprene by cationic polymerization. Butyl rubber has been industrialized by Exxon corporation in the united states in the 40 th century for over seventy years, and has been widely used in the fields of inner tubes, inner liners, curing bladder, medical plugs, etc. for manufacturing tires for vehicles because of its excellent air tightness, damping property, heat aging resistance, ozone resistance, weather resistance, etc.
However, the molecular chain of butyl rubber mainly consists of single bonds of carbon and carbon, the number of double bonds is small, substituent methyl groups are symmetrically arranged, and the defects of high crystallinity, poor flexibility of the molecular chain, low stress relaxation rate, low vulcanization speed, poor adhesion, poor compatibility with other general rubber and the like exist, so that the butyl rubber is easy to excessively flow and deform in the processing process. How to achieve a balance of physical and mechanical properties and processability of butyl rubber has become a bottleneck in the preparation of high performance butyl rubber materials.
In recent years, researchers find that star-shaped highly branched butyl rubber with a unique three-dimensional network structure, which consists of a high molecular weight grafted structure and a low molecular weight linear structure, has excellent viscoelastic performance, high green strength and fast stress relaxation rate, can keep low melt viscosity in the processing process, can obtain a high molecular weight polymer, and realizes uniform balance of physical and mechanical properties and processing properties. The star-shaped hyperbranched structure has become one of the hot spots in the future butyl rubber research field.
In the prior art, the synthesis of star-shaped hyperbranched butyl rubber is mainly prepared by adopting a method of a first nucleus and then arm method, a method of a first arm and then nucleus and a method of a simultaneous nuclear arm method. Such as: US5395885 discloses a star-shaped hyperbranched polymer, which is synthesized by a method of first-arm-then-core method under the condition of-90 ℃ to-100 ℃ by taking polyisobutylene as an arm, taking Polydivinylbenzene (PDVB) as a core, taking a complex of alkyl chloridizing aluminum and water as an initiator and taking chloromethane as a diluent. CN 107344982A discloses a process for producing butyl rubber with broad/bimodal molecular weight distribution, which comprises: in the first step, the molar ratio of isobutene to isoprene is 97:mixing 3 to 99:1 followed by mixing with a diluent (methyl chloride) to obtain a monomer stream, then mixing an initiator (aluminum chloride system and HCl/alkyl aluminum chloride complex) with the diluent (methyl chloride) to obtain an initiator stream, finally mixing the monomer stream and the initiator stream and feeding the mixed initiator stream into a first loop reactor zone, polymerizing at a temperature of-98 ℃ to-96 ℃ and a pressure of 0.3 to 0.4Mpa for 5 to 10 minutes to obtain a first portion of butyl rubber slurry; the second step, the first part of butyl rubber slurry is sent into a second loop reactor zone, and the butyl rubber slurry with broad/bimodal molecular weight distribution is finally obtained after polymerization reaction for 5-10min at the temperature of-92 ℃ to-90 ℃ and the pressure of 0.1 to 0.2 Mpa; and thirdly, contacting the butyl rubber slurry with the broad/bimodal molecular weight distribution with water, removing unreacted monomers and diluents to obtain colloidal particle water, and dehydrating and drying the colloidal particle water to obtain the butyl rubber with the broad/bimodal molecular weight distribution (Mw/Mn) of at least 5.0. CN1427851a discloses a process for preparing butyl rubber with a broad molecular weight distribution. The process uses a mixed catalyst system comprising a mixture of a major amount of internalized dialkylaluminum, a minor amount of monoalkylaluminum dihalide and a minor amount of aluminoxane to provide a broad distribution butyl rubber having a molecular weight distribution of greater than 3.5 and up to 7.6. CN101353403B discloses a preparation method of star-shaped hyperbranched polyisobutene or butyl rubber, which adopts a polystyrene/isoprene segmented copolymer with a silicon-chlorine group at the end or a polystyrene/butadiene segmented copolymer with a silicon-chlorine group at the end as a grafting agent for initiating cationic polymerization, and directly participates in the cationic polymerization in a cationic polymerization system with a chloromethane/cyclohexane v ratio of 20-80/80-20 mixed solvent under the temperature condition of 0-minus 100 ℃, and prepares the star-shaped hyperbranched polyisobutene or butyl rubber product by initiating the cationic polymerization of the silicon-chlorine group and participating in the grafting reaction through an unsaturated chain. CN01817708.5 provides a method of 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 by which star-shaped hyperbranched polymers are prepared. CN88108392.5 discloses the use of a hydrochloride polystyrene-isoprene copolymer as poly (styrene-isoprene) The functional group initiator or the polystyrene-butadiene or polystyrene-isoprene is used as a grafting agent to prepare the star-shaped grafted butyl rubber with a comb-shaped structure. CN 107793535a provides a butyl rubber having a molecular weight of 90 to 260 tens of thousands, log (MW)>6 and contains structural units derived from isobutylene, structural units derived from conjugated dienes, and optionally structural units derived from aryl olefins. US3780002 proposes a complex initiator comprising a metal halide of group II or III of the periodic Table and a tetrahalide of a metal of group IV of the periodic Table, e.g. AlCl 3 With TiC1 4 For combined use, or by combining A1C1 3 With SnC1 4 The composite use makes each initiator independently initiate cationic polymerization, and the butyl rubber with the molecular weight distribution index Mw/Mn above 5.0 is synthesized under the conventional Ding Mou rubber polymerization condition.
CN101353386a discloses an initiating system for star-shaped hyperbranched polyisobutene or butyl rubber cationic polymerization, which consists of an initiating-grafting agent, a co-initiating agent and a nucleophilic reagent, and is used for initiating vinyl monomers to carry out homo-, block-and star-polymerization and graft copolymerization, and the obtained polymer shows obvious bimodal distribution. Puskas (Catalysts for manufacture of IIR with bimodal molecular weight distribution: U.S. Pat. No. 5,94538,1993-3-16.) uses trimesic acid as raw material to synthesize the initiator tricumyl alcohol with three-arm structure, and then uses the tricumyl alcohol/aluminum trichloride initiation system to initiate isobutene and isoprene copolymerization in inert organic solvent at-120 deg.C to-50 deg.C, thus synthesizing the star-shaped hyperbranched butyl rubber with bimodal molecular weight distribution. Wieland et al (Synthesis of new graft copolymers containing polyisobutylene by acombination of the, 1-diphenylethylene techniqueand cationic polymerization [ J ]. Polymer Science: polymer Chemistry,2002, 40:3725-3733.) synthesized a macroinitiator P (MMA-b-St-co-CMS) containing a ternary of 4-chloromethylstyrene, styrene and methyl methacrylate in the presence of 1, 2-stilbene (DPE) by radical polymerization, and initiated cationic polymerization of isobutylene and isoprene with the macroinitiator to successfully prepare a multi-arm star butyl rubber. Wu Yibo et al (Davang S H, et al, skid resistant coatings for aircraft carrier decks [ J ]. Coat technology, 1980, 52 (671): 65-69.) Poly (isoprene-styrene) block copolymers were prepared by living anionic polymerization as grafting agents and star-shaped hyperbranched butyl rubber exhibiting a distinct bimodal appearance was prepared by living carbon cationic polymerization in the initiation system of 2-chloro-2, 4-trimethylpentane/titanium tetrachloride/proton scavenger.
Disclosure of Invention
The invention aims to provide a preparation method of hyperbranched ultra-wide molecular weight distribution butyl rubber. The invention firstly takes alkyl lithium as an initiator, takes hydrocarbons as a solvent, and takes a reaction monomer composed of isoprene, styrene and butadiene, and the star-shaped copolymer with a ternary diheteroarm structure is prepared by two-kettle reaction, adopting variable temperature and variable speed polymerization and then coupling with a novel long-chain tetrahalide coupling agent 1, 5-dihalogen-3, 3-bis (2-haloethyl) pentane. Finally, under the catalysis system of Lewis acid and protonic acid, the ternary diheteroarm star 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 easy extrusion swelling and slow stress relaxation rate of the butyl rubber in the processing process, so that the hyperbranched ultra-wide molecular weight distribution butyl rubber has the excellent processability with fast stress relaxation rate and small extrusion swelling effect in the processing process under the precondition of ensuring the sufficient raw rubber strength and good air tightness of the butyl rubber, and the balance of the physical and mechanical properties and the processing properties of the hyperbranched ultra-wide molecular weight distribution butyl rubber is realized.
The "%" of the invention refers to mass percent.
The preparation of the hyperbranched 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: firstly, in a polymerization kettle, introducing inert gas to replace for 2-4 times, sequentially adding 100-200% of deionized water, 3, 9-dioxy [5.5] spiro undecane, a halogenating agent and 1-5% of 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 chloromethane to extract, separate, wash and dry to obtain the coupling agent 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane (the yield is 85-95%).
b, preparation of grafting agent: based on hundred percent of the total mass of the reaction monomers, introducing inert gas into a polymerization kettle A to replace a system for 3-5 times, sequentially adding 100-200% of solvent, 10-20% of 1, 3-butadiene and 0.05-0.3% of structure regulator into the polymerization kettle, heating to 50-70 ℃ by using an initiator, and reacting for 50-70 min to form BR chain segments; then adding 100-200% solvent, 0.1-0.3% structure regulator, heating to 70-80 deg.c, mixing 30-40% styrene and 10-20% 1, 3-butadiene for 10-30 min, adding into the polymerization kettle in continuous injection mode, reacting in 60-80 min, and initial feeding speed >10.0% of the mixture/min, the magnitude of the decrease of the feeding speed is determined according to the reaction time, a random and long transition section-SB/(S.fwdarw.B) -chain segment is formed, the conversion rate of the styrene and the 1, 3-butadiene monomer reaches 100%, the temperature is finally increased to 80-90 ℃, and a coupling agent is added for coupling reaction for 60-90 min, so that [ -SB/(S.fwdarw.B) -BR [ -SB ]] n Y. Meanwhile, in a polymerization kettle B, introducing inert gas to replace a 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 for variable-temperature polymerization, gradually increasing the temperature from 40 ℃ to 70 ℃ within 50-70 min, and continuously gradually increasing the temperature to form an IR chain segment with wide vinyl distribution until the conversion rate of isoprene monomers 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 materials 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 min-3After the reaction is completed, the coupled reaction mixture is treated by water and the glue solution is subjected to wet condensation and drying to obtain the ternary two-hetero-arm star-type copolymer ([ -B-SB/(S- & gtB) -BR ] ] n Y[-IR-PS-B-] n )。
(2) Preparation of hyperbranched and ultra-wide molecular weight distribution butyl rubber: firstly, introducing inert gas into a polymerization kettle for replacement for 3-5 times, adding 100-200% of diluent and solvent into the polymerization kettle according to the ratio of V: the V ratio is 70-30: 30-70 of a mixed solvent, 1-10% of a grafting agent, and stirring and dissolving for 20-30 min until the grafting agent is completely dissolved; then cooling to minus 75 ℃ to minus 85 ℃, adding 100 to 200 percent of diluent, 85 to 95 percent of isobutene and 1 to 5 percent of isoprene in turn, stirring and mixing until the temperature of a polymerization system is reduced to minus 100 ℃ to minus 90 ℃, then mixing and aging 30 to 50 percent of diluent and 0.05 to 3.0 percent of co-initiator for 20 to 30 minutes at minus 85 ℃ to minus 95 ℃, adding the mixture into the polymerization system together, stirring and reacting for 2.0 to 5.0 hours, discharging, condensing, washing and drying to obtain the hyperbranched ultra-wide molecular weight distribution butyl rubber product.
The grafting agent is a ternary diheteroarm star copolymer synthesized by isoprene, styrene and butadiene, and the structural general formula of the grafting agent is shown in formula I:
wherein Y is 3, 3-diethyl pentane; BR is a 1, 3-butadiene homopolymer block, the 1, 2-structure content of which is 20-40%; PS is a styrene homopolymer segment; SB is a random segment of styrene and butadiene; (S.fwdarw.B) is a gradual change section of styrene and butadiene; IR is a homopolymer segment of isoprene wide vinyl distribution; b is a capped butadiene, n=1 to 4; the ternary two-hybrid arm star-shaped copolymer has the advantages that the isoprene content is 10-20%, the styrene content is 50-70% and the butadiene content is 20-30%; the ternary diheteroarm star copolymer has a number average molecular weight (Mn) of 10000-50000 and a molecular weight distribution (Mw/Mn) of 12.5-16.7.
The halogenating agent is one of liquid chlorine and liquid bromine, preferably liquid bromine, the dosage of the halogenating agent depends on the dosage of 3, 9-dioxy [5.5] spiro-undecane, and the molar ratio of the dosage of the liquid bromine to the 3, 9-dioxy [5.5] spiro-undecane is 4.5-6.5.
The polymerization kettle is not limited, but is preferably a stainless steel polymerization kettle with a jacket.
The catalyst of the invention is HCl-CH 3 A mixed aqueous solution of OH, wherein the molar concentration of HCl is: 0.1 to 0.7mol/L.
The structure regulator is a polar organic compound which generates solvation effect in a polymerization system, and can regulate the reactivity ratio of styrene and butadiene to enable the styrene and the butadiene to be randomly copolymerized. Such polar organic compound is selected from one of diethylene glycol dimethyl ether (2G), tetrahydrofuran (THF), diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME), triethylamine, preferably Tetrahydrofuran (THF).
The initiator is a hydrocarbyl mono-lithium compound, namely RLi, wherein R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or composite group of the above groups containing 1-20 carbon atoms. The hydrocarbyl monolithium compound is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium, dodecyllithium, preferably n-butyllithium. The amount of organolithium added is determined by the molecular weight of the polymer being designed.
The amount of the coupling agent is determined according to the amount of the initiator, and the star polymer with the heteroarm structure is finally formed through gradual polymerization of excessive coupling agent, wherein the molar ratio of the amount of the coupling agent to the total organic lithium is 2.0-5.0.
The diluent is halogenated alkane, wherein halogen atoms in the halogenated alkane can be chlorine, bromine or fluorine; the number of carbon atoms in the halogenated alkane being C 1 -C 4 . The haloalkane is selected from one of chloromethane, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, preferably chloromethane.
The co-initiator is formed by compounding alkyl aluminum halide and protonic acid according to different proportions. The alkyl aluminum halide is at least one selected from diethyl aluminum chloride, diisobutyl aluminum chloride, methyl aluminum dichloride, aluminum sesquioxide, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride and ethyl aluminum chloride, preferably aluminum sesquioxide. The protonic acid is selected from HCI, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 And HNO 3 Preferably HCI. Wherein the total addition amount of the co-initiator is 0.1-3.0%, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.01:1-0.1:1.
The polymerization reactions of the present invention are all carried out in an oxygen-free, water-free, preferably inert gas atmosphere. The polymerization and dissolution processes are both carried out in a hydrocarbon solvent, which is a hydrocarbon solvent, including straight chain alkanes, aromatic hydrocarbons and cycloalkanes, selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably cyclohexane.
The inert gas is nitrogen or one of all the element gases which do not contain radon in the group 0 of the periodic table.
The invention firstly aims at 3, 9-dioxy [5.5 ]]The spiro undecane is halogenated to synthesize a new coupling agent 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane, then the three reaction monomers of isoprene, styrene and butadiene are reacted by two kettles, and the temperature-changing and speed-changing polymerization is adopted, and then the coupling agent 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane is coupled to prepare the ternary di-hetero-arm star copolymer [ -B-SB/(S.fwdarw.B) -BR ]] n Y[-IR-PS-B-] n (see FIG. 1). The [ -B-SB/(S.fwdarw.B) -BR ]] n Y[-IR-PS-B-] n The hyperbranched ultra-wide molecular weight distribution butyl rubber is prepared by cationic polymerization of the grafting agent, isobutene and isoprene under the catalysis system of the combination of alkyl aluminum halide and protonic acid (see figure 2).
The invention uses two kettles feeding method, variable temperature and variable speed polymerization to make two kinds of microstructureLong chain segment [ -B-SB/(S.fwdarw.B) -BR-] n And [ -IR-PS-B ]] n The 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane coupling agent is coupled on a macromolecular chain to form a ternary two-hetero-arm star structure, so that the performances of different chain segments and the two-hetero-arm star structure are organically combined together and cooperatively act, the randomness and the gradient of an-SB/(S- & gtB) -chain segment in the IR chain segment are utilized, the reactivity ratio and the difference of the steric hindrance effect of each chain segment in the hetero-arm structure are utilized, the disorder of the molecular chain segment is increased in the grafting polymerization process of the butyl rubber, the regularity of the molecular chain is obviously damaged, the molecular weight distribution is obviously widened, the butyl rubber can obtain good viscoelastic performance, the quick stress relaxation rate is realized, and the processability of the butyl rubber is improved; meanwhile, the segment of the-PS-and-SB/(S-B) -contains a large amount of benzene rings, so that the decrease of strength and air tightness caused by the widening of the molecular weight distribution of the butyl rubber is avoided, and the high strength and good air tightness of the butyl rubber are ensured.
The invention solves the problem of contradictory relation of poor processability and excellent air tightness of butyl rubber by the synthesis of the novel coupling agent 1, 5-dihalo-3, 3-di (2-haloethyl) pentane and the design of a ternary two-hetero-arm star-shaped structure, and finally realizes the optimal balance between the processability and physical and mechanical properties of the butyl rubber. The preparation method provided by the invention has the characteristics of controllable process strips, stable product performance, suitability for industrial production and the like.
Drawings
FIG. 1 shows [ -B-SB/(S.fwdarw.B) -BR-] n Y[-IR-PS-B-] n And synthesizing a roadmap.
FIG. 2 is 1 # Sample of butyl rubber IIR301 with 2 # Comparison of GPC spectra of the samples of example 1.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions. The raw materials used in the examples are all industrial polymer grade, and are used after purification without other special requirements.
(1) The raw material sources are as follows:
styrene, butadiene, polymer grade China petrochemical Co
Isobutene, isoprene, polymeric grade Zhejiang Xinhui New Material Co., ltd
N-butyllithium with purity of 98% Nanjing Tonglian chemical Co., ltd
3, 9-Dioxo [5.5] spirocyclic undecane purity was 99% of Hubei ferry chemical Co.Ltd
Sesquiethyl aluminum chloride with purity of 98% of carbofuran technology Co., ltd
The other reagents are all commercial products.
(2) The analytical test method comprises the following steps:
determination of molecular weight and distribution thereof: measured by using a 2414 Gel Permeation Chromatograph (GPC) manufactured by Waters corporation of the United states. The polystyrene standard sample is used as a calibration curve, the mobile phase is tetrahydrofuran, the column temperature is 40 ℃, the sample concentration is 1mg/ml, the sample injection amount is 50 mu L, the elution time is 40min, and the flow rate is 1 ml.min -1 。
Determination of mooney viscosity and stress relaxation: the measurement was carried out by using a Mooney viscometer model GT-7080-S2 manufactured by Taiwan high-speed rail company. The Mooney relaxation time was 120s as determined with the large rotor under 125℃1+8 conditions with reference to GB/T1232.1-2000.
Measurement of air tightness: an automatic air tightness tester is adopted to measure the air permeability number according to ISO 2782:1995, and the test gas is N 2 The test temperature is 23 ℃, the test sample piece is an 8cm diameter circular sea piece, and the thickness is 1mm.
Tensile strength: the method in standard GB/T528-2009 is performed.
Characterization of the degree of branching: degree of branching = polymer molecular weight after branching/polymer molecular weight before branching.
Example 1
(1) Preparation of grafting agent:
a, preparation of a coupling agent: first in 4L stainless steel with jacketIn a polymerization kettle, argon is introduced for 3 times, 600g of deionized water and 60g of 3, 9-dioxy [5.5 ] are sequentially added into the polymerization kettle]Spirocyclic undecane, 340g liquid bromine, 20g HCl-CH 3 OH solution (molar concentration of HCl: 0.7 mol/L), heating to 80 ℃, reacting for 3.0hr, adding 300g of 15% NaOH aqueous solution to terminate the reaction, finally adding 800g of chloromethane for extraction, separation, washing and drying to obtain the coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane (yield 94%).
b, preparation of grafting agent: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 3 times, sequentially adding 1650g of cyclohexane, 170g of 1, 3-butadiene and 0.6g of THF into the polymerization kettle, heating to 50 ℃, adding 35.1 mmol of n-butyllithium to start reaction, and reacting for 50min to form BR chain segments; then adding 1950g cyclohexane and 1.5g THF into a polymerization kettle A in sequence, heating to 70 ℃, stirring and mixing 460g styrene and 160g 1, 3-butadiene for 10min, and reacting for 60min at an initial feeding speed of 80g mixture/min of styrene and 1, 3-butadiene, wherein the feeding speed is reduced by 10g mixture per minute, so as to form a random and long graded segment-SB/(S-B) -chain segment; finally, heating to 80 ℃, adding 155mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 60min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1550g of cyclohexane, 160g of isoprene and 0.5g of THF, heating to 40 ℃, adding 25.1 mmol of n-butyllithium to start reaction, gradually heating from 40 ℃ to 70 ℃ within 50min, and reacting at a heating speed of 0.6 ℃/min for 50min to form 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 to react for 40min, so as to form an-IR-PS-chain segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 60min; finally, adding 17g 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 condensation and drying on the glue solution to obtain the ternary two-hetero-arm star-shaped copolymer [ -B-SB/(S- & gtB) -BR [ -17 ] ] n Y[-IR-PS-B-] n Grafting agent (Mn 13650, mw/Mn 12.8).
(2) Preparation of hyperbranched and ultra-wide molecular weight distribution butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3 times for replacement, adding 600g of methyl chloride and 350g of cyclohexane into the polymerization kettle, and stirring and dissolving 9.5g of [ (-B-SB/(S- & gt B) -BR- ] nY [ -IR-PS-B- ] n grafting agent until the grafting agent is completely dissolved; then cooling to-75 ℃, sequentially adding 505g of methyl 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 methyl chloride, 3.85g of aluminum sesquichloride and 0.082g of HCl at-85 ℃ and aging for 20min, then adding the materials into the polymerization system together and stirring and reacting for 2.0hr, discharging and condensing, washing and drying to obtain the hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 2
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of grafting agent: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace 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 38.2 mmol 1 of n-butyllithium to start reaction, and reacting for 55min to form BR chain segments; then adding 2050g cyclohexane, 1.7g THF into a polymerization kettle A in sequence, heating to 75 ℃, stirring and mixing 490g styrene and 180g 1, 3-butadiene for 10min, and reacting for 70min at an initial feeding speed of 70g mixture/min of styrene and 1, 3-butadiene, wherein the feeding speed is reduced by 12g mixture per minute, so as to form a random and long gradient-SB/(S-B) -chain segment; finally, heating to 80 ℃, adding 175mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 70min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1650g of cyclohexane, 180g of isoprene and 0.7g of THF, heating to 40 ℃, adding 27.5 mmol 1 of n-butyllithium to start reaction, gradually heating from 40 ℃ to 70 ℃ within 50min, and reacting for 50min at a heating speed of 0.6 ℃/min to form 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 to react for 45min, so as to form an-IR-PS-chain segment; to be treated After the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 70min; finally, adding 20g of 1, 3-butadiene into a polymerization kettle A for end capping, reacting for 22min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain the ternary two-hetero-arm star-shaped copolymer [ -B-SB/(S- & gtB) -BR [ -17 ]] n Y[-IR-PS-B-] n Grafting agent (Mn 20230, mw/Mn 13.9).
(2) Preparation of hyperbranched and ultra-wide molecular weight distribution butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3 times for replacement, adding 580g of methyl chloride and 380g of cyclohexane into the polymerization kettle, and stirring and dissolving 16g of [ (-B-SB/(S- & gt B) -BR- ] nY [ -IR-PS-B- ] n grafting agent until the grafting agent is completely dissolved; then cooling to-78 ℃, sequentially adding 520g of methyl 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 methyl chloride, 4.12g of aluminum sesquichloride and 0.098g of HCl at-85 ℃, aging for 20min, adding the mixture into the polymerization system together, stirring and reacting for 3.0hr, discharging and condensing, washing and drying to obtain the hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 3
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of grafting agent: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 3 times, sequentially adding 1950g cyclohexane, 210g 1, 3-butadiene and 0.9g THF into the polymerization kettle, heating to 60 ℃, adding 39.5 mmol 1 of n-butyllithium to start reaction, and reacting for 60min to form BR chain segments; then adding 2150g cyclohexane, 1.9g THF into a polymerization kettle A in turn, heating to 80 ℃, stirring and mixing 510g styrene and 200g 1, 3-butadiene for 20min, and reacting for 70min at an initial charging speed of 70g mixture/min of styrene and 1, 3-butadiene, wherein the charging speed is reduced by 12g mixture per minute, so as to form a random and long graded segment-SB/(S-B) -chain segment; finally, heating to 85 ℃, adding 190mmo1, 5-diBromine-3, 3 di (2-bromoethyl) pentane, and carrying out coupling reaction for 80min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1720g of cyclohexane, 200g of isoprene and 0.9g of THF, heating to 40 ℃, adding 29.5 mmol 1 of n-butyllithium to start reaction, gradually heating from 40 ℃ to 70 ℃ within 60min, and reacting for 60min at a heating speed of 0.5 ℃/min to form an IR chain segment with wide molecular weight distribution; then sequentially adding 350g of styrene and 0.8g of THF into the polymerization kettle B, and reacting for 50min to form an-IR-PS-chain segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 80min; finally, 23g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction is carried out for 25min until no free monomer exists, the reaction mixture after the coupling is treated by water after the reaction is finished, the glue solution is subjected to wet condensation and drying, and the ternary two-hetero-arm star-shaped copolymer [ -B-SB/(S- & gtB) -BR [ -17 ] ] n Y[-IR-PS-B-] n Grafting agent (Mn 36150, mw/Mn 14.6).
(2) Preparation of hyperbranched and ultra-wide molecular weight distribution butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3 times for replacement, adding 550g of methyl chloride, 400g of cyclohexane and 22g of [ (-B-SB/(S- & gtB) -BR- ] nY [ -IR-PS-B- ] n grafting agent into the polymerization kettle, stirring and dissolving for 25min until the grafting agent is completely dissolved; then cooling to minus 78 ℃, then adding 530g of methyl chloride, 445g of isobutene and 13g of isoprene in turn, stirring and mixing until the temperature of a polymerization system is reduced to minus 93 ℃, then mixing 170g of methyl chloride, 4.85g of aluminum sesquichloride and 0.098g of HCl at minus 90 ℃ and aging for 25min, then adding the mixture into the polymerization system together and stirring and reacting for 3.5hr, discharging and condensing, washing and drying to obtain the hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 4
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of grafting agent: in a jacketed 15L stainless steel polymerizer A, the system was replaced 3 times with argon, 2010g of cyclohexane, 230g of 1, 3-butadiene, 1.1g of THF were sequentially added to the polymerizer, and the temperature was raised to 6 Adding 41.2mm 1 n-butyllithium at 5 ℃ to start reaction, and reacting for 65min to form BR chain segments; then sequentially adding 2230g of cyclohexane, 2.2g of THF (tetrahydrofuran) into a polymerization kettle A, 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 mixture/min of styrene and 1, 3-butadiene, wherein the feeding speed is reduced by 12g of mixture per minute, so as to form a random and long gradient-SB/(S-B) -chain segment; finally, heating to 85 ℃, adding 220mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 85min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1950g cyclohexane, 210g isoprene and 1.2g THF, heating to 40 ℃, adding 31.5 mmol 1 n-butyllithium to start reaction, gradually heating from 40 ℃ to 70 ℃ within 60min, and reacting at a heating speed of 0.5 ℃/min for 60min to form an IR chain segment with wide molecular weight distribution; then sequentially adding 370g of styrene and 1.0g of THF into the polymerization kettle B, and reacting for 60min to form an-IR-PS-chain segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 85min; finally, adding 25g of 1, 3-butadiene into a 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 ternary two-hetero-arm star-shaped copolymer [ -B-SB/(S- & gtB) -BR [ -17 ] ] n Y[-IR-PS-B-] n Grafting agent (Mn 41020, mw/Mn 15.3).
(2) Preparation of hyperbranched and ultra-wide molecular weight distribution butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3 times for replacement, adding 530g of methyl chloride, 430g of cyclohexane and 25g of [ (-B-SB/(S- & gtB) -BR- ] nY [ -IR-PS-B- ] n grafting agent into the polymerization kettle, stirring and dissolving for 25min until the grafting agent is completely dissolved; then cooling to-80 ℃, then adding 540g of methyl chloride, 456g of isobutene and 15g of isoprene in turn, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then mixing 180g of methyl chloride, 5.15g of aluminum sesquichloride and 0.103g of HCl at-95 ℃ and aging for 25min, then adding the mixture into the polymerization system together and stirring and reacting for 4.0hr, discharging and condensing, washing and drying to obtain the hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 5
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of grafting agent: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a 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 43.5 mmol 1 of n-butyllithium to start reaction, and reacting for 70min to form BR chain segments; then adding 2360g of cyclohexane, 2.5g of THF into a polymerization kettle A in sequence, heating to 80 ℃, stirring and mixing 530g of styrene and 210g of 1, 3-butadiene for 20min, and reacting for 80min at an initial feeding speed of 80g of mixture of styrene and 1, 3-butadiene per min at a feeding speed reducing range of 15g of mixture per min to form a random and long gradient-SB/(S-B) -chain segment; finally, heating to 90 ℃, adding 270mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 90min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 2000g cyclohexane, 230g isoprene and 1.3g THF, heating to 40 ℃, adding 33.5 mmol 1 n-butyllithium to start reaction, gradually increasing the temperature from 40 ℃ to 70 ℃ within 70min, and reacting for 70min at a heating rate 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 to react for 60min, so as to form an-IR-PS-chain segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 90min; finally, 28g of 1, 3-butadiene is added into the polymerization kettle A for end capping, the reaction is carried out for 30min until no free monomer exists, the reaction mixture after the coupling is treated by water after the reaction is finished, the glue solution is subjected to wet condensation and drying, and the ternary two-hetero-arm star-shaped copolymer [ -B-SB/(S- & gtB) -BR [ -17 ] ] n Y[-IR-PS-B-] n Grafting agent (Mn 49620, mw/Mn 16.5).
(2) Preparation of hyperbranched and ultra-wide molecular weight distribution butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 500g of methyl chloride and 470g of cyclohexane into the polymerization kettle, and stirring and dissolving 30g of [ (-B-SB/(S- & gt B) -BR- ] nY [ -IR-PS-B- ] n grafting agent until the grafting agent is completely dissolved; then cooling to-85 ℃, then adding 550g of methyl chloride, 465g of isobutene and 20g of isoprene in sequence, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 190g of methyl chloride, 5.85g of aluminum sesquichloride and 0.213g of HCl at-95 ℃ and aging for 30min, then adding the mixture into the polymerization system together and stirring and reacting for 5.0hr, discharging and condensing, washing and drying to obtain the hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 1
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 1.
b, preparation of grafting agent: other conditions were the same as in example 1 except that: in the polymerization kettle B, isoprene does not adopt variable temperature polymerization, and reacts at the constant temperature of 40 ℃, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 3 times, sequentially adding 1650g of cyclohexane, 170g of 1, 3-butadiene and 0.6g of THF into the polymerization kettle, heating to 50 ℃, adding 35.1 mmol of n-butyllithium to start reaction, and reacting for 50min to form a BR chain segment; then adding 1950g cyclohexane and 1.5g THF into a polymerization kettle A in sequence, heating to 70 ℃, stirring and mixing 460g styrene and 160g1, 3-butadiene for 10min, and reacting for 60min at an initial feeding speed of 80g mixture/min of styrene and 1, 3-butadiene, wherein the feeding speed is reduced by 10g mixture per minute, so as to form a random and long graded segment-SB/(S-B) -chain segment; finally, heating to 80 ℃, adding 155mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 60min; simultaneously, 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 25.1 mmol of n-butyllithium to start reaction, reacting for 50min, and forming IR 1 A segment; then 305g of styrene, 0.4g of THF are added into the polymerization kettle B in sequence and react for 40min to form-IR 1 -PS-segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 60min; finally, the polymer is gatheredAdding 17g of 1, 3-butadiene into a reaction kettle A for end capping, reacting for 20min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is completed, condensing the glue solution by a wet method, and drying to obtain the ternary two-hetero-arm star-shaped copolymer [ -B-SB/(S- & gtB) -BR ]] n Y[-IR 1 -PS-B-] n Grafting agent (Mn 12550, mw/Mn 6.5).
(2) Preparation of hyperbranched and ultra-wide molecular weight distribution butyl rubber: other conditions were the same as in example 1 except that: during the synthesis process, no [ -B-SB/(S.fwdarw.B) -BR-]nY[-IR-PS-B-]n grafting agent, instead [ -B-SB/(S.fwdarw.B) -BR ]]nY[-IR 1 -PS-B-]n grafting agent, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 600g of methyl chloride and 350g of cyclohexane into the polymerization kettle, and adding [ -B-SB/(S.fwdarw.B) -BR-]nY[-IR 1 -PS-B-]n grafting agent 9.5g, stirring and dissolving for 20min until the grafting agent is completely dissolved; then cooling to-75 ℃, sequentially adding 505g of methyl 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 methyl chloride, 3.85g of aluminum sesquichloride and 0.082g of HCl at-85 ℃ and aging for 20min, then adding the materials into the polymerization system together and stirring and reacting for 2.0hr, discharging and condensing, washing and drying to obtain the hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 2
(1) Preparation of grafting agent:
a, preparation of a coupling agent: as in example 2.
b, preparation of grafting agent: other conditions were the same as in example 3 except that: in the polymerization vessel A, the polymerization is not carried out at a variable speed, and the styrene and the 1, 3-butadiene are not mixed, but are added into the polymerization vessel at one time, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 3 times, sequentially adding 1850g of cyclohexane, 190g of 1, 3-butadiene and 0.8g of THF into the polymerization kettle, heating to 50 ℃, adding 38.2 mmol 1 of n-butyllithium to start reaction, and reacting for 55min to form BR chain segments; then 2050g of cyclohexane, 1.7g of THF, 490g of styrene and 180g of 1, 3-butanedium are added to the polymerization vessel A in this orderHeating alkene to 75 ℃, and reacting for 70min to form-SBR-chain segments; finally, heating to 80 ℃, adding 175mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 70min; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1650g of cyclohexane, 180g of isoprene and 0.7g of THF, heating to 40 ℃, adding 27.5 mmol 1 of n-butyllithium to start reaction, gradually heating from 40 ℃ to 70 ℃ within 50min, and reacting for 50min at a heating speed of 0.6 ℃/min to form 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 to react for 45min, so as to form an-IR-PS-chain segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 70min; finally, adding 20g of 1, 3-butadiene into a polymerization kettle A for end capping, reacting for 22min until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, condensing the glue solution by wet method, and drying to obtain the ternary two-hetero-arm star-shaped copolymer [ -B-SBR-BR ] ] n Y[-IR-PS-B-] n Grafting agent (Mn 19230, mw/Mn 5.7).
(2) Preparation of hyperbranched and ultra-wide molecular weight distribution butyl rubber: other conditions were the same as in example 2 except that: in the synthesis process, the [ -B-SB/(S.fwdarw.B) -BR- ] nY [ -IR-PS-B- ] n grafting agent is not added, but the [ -B-SBR-BR- ] nY [ -IR-PS-B- ] n grafting agent is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3 times for replacement, adding 580g of chloromethane and 380g of cyclohexane into the polymerization kettle, and stirring and dissolving 16g of [ (-B-SBR-BR- ] nY [ -IR-PS-B- ] n grafting agent until the grafting agent is completely dissolved; then cooling to-78 ℃, sequentially adding 520g of methyl 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 methyl chloride, 4.12g of aluminum sesquichloride and 0.098g of HCl at-85 ℃, aging for 20min, adding the mixture into the polymerization system together, stirring and reacting for 3.0hr, discharging and condensing, washing and drying to obtain the hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 3
(1) Preparation of grafting agent:
a, preparation of a coupling agent: same as in example 3.
b, preparation of grafting agent: other conditions were the same as in example 3 except that: the single kettle polymerization is adopted, namely the materials in the polymerization kettle B are added into the polymerization kettle A for reaction, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace the system for 3 times, sequentially adding 1950g cyclohexane, 210g 1, 3-butadiene and 0.9g THF into the polymerization kettle, heating to 60 ℃, adding 39.5 mmol 1 of n-butyllithium to start reaction, and reacting for 60min to form BR chain segments; then adding 2150g cyclohexane, 1.9g THF into a polymerization kettle A in turn, heating to 80 ℃, stirring and mixing 510g styrene and 200g1, 3-butadiene for 20min, and reacting for 70min at an initial feeding speed of 70g mixture/min of styrene and 1, 3-butadiene, wherein the feeding speed is reduced by 12g mixture per minute, so as to form a random and long graded segment-SB/(S-B) -chain segment; then 1720g cyclohexane, 200g isoprene, 0.9g THF are added into the polymerization kettle A in sequence, the temperature is raised to 40 ℃, 29.5mm 1 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, and the reaction is carried out for 60min, so that an IR chain segment with wide molecular weight distribution is formed; then sequentially adding 350g of styrene and 0.8g of THF into the polymerization kettle B, and reacting for 50min to form a-PS-chain segment; secondly, heating to 85 ℃, adding 190mmo1, 5-dibromo-3, 3-di (2-bromoethyl) pentane, and carrying out coupling reaction for 80min; finally, 23g of 1, 3-butadiene is added into a polymerization kettle A for end capping, the reaction is carried out for 25min until no free monomer exists, the reaction mixture after coupling is treated by water after the reaction is finished, the glue solution is subjected to wet condensation and drying, and the ternary single-arm star-shaped copolymer [ -B-PS-IR-SB/(S→B) -BR [ -B ] ] n Y grafting agent (Mn 33150, mw/Mn 8.6).
(2) Preparation of hyperbranched and ultra-wide molecular weight distribution butyl rubber: other conditions were the same as in example 3 except that: in the synthesis process, the [ -B-SB/(S.fwdarw.B) -BR- ] nY [ -IR-PS-B- ] n grafting agent is not added, but the [ -B-PS-IR-SB/(S.fwdarw.B) -BR- ] nY grafting agent is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3 times for replacement, adding 550g of methyl chloride, 400g of cyclohexane and 22g of [ (-B-SB/(S- & gtB) -BR- ] nY [ -IR-PS-B- ] n grafting agent into the polymerization kettle, stirring and dissolving for 25min until the grafting agent is completely dissolved; then cooling to minus 78 ℃, then adding 530g of methyl chloride, 445g of isobutene and 13g of isoprene in turn, stirring and mixing until the temperature of a polymerization system is reduced to minus 93 ℃, then mixing 170g of methyl chloride, 4.85g of aluminum sesquichloride and 0.098g of HCl at minus 90 ℃ and aging for 25min, then adding the mixture into the polymerization system together and stirring and reacting for 3.5hr, discharging and condensing, washing and drying to obtain the hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 4
(1) Preparation of grafting agent:
a, preparation of a coupling agent: same as in example 4.
b, preparation of grafting agent: other conditions were the same as in example 4 except that: the coupling agent 1, 5-dibromo-3, 3-di (2-bromoethyl) pentane is not added in the synthesis process, namely: in a 15L stainless steel polymerization kettle A with a jacket, introducing argon to replace a system for 3 times, sequentially adding 2010g of cyclohexane, 230g of 1, 3-butadiene and 1.1g of THF into the polymerization kettle, heating to 65 ℃, adding 41.2 mmol 1 of n-butyllithium to start reaction, and reacting for 65min to form BR chain segments; then sequentially adding 2230g of cyclohexane, 2.2g of THF (tetrahydrofuran) into a polymerization kettle A, 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 mixture/min of styrene and 1, 3-butadiene, wherein the feeding speed is reduced by 12g of mixture per minute, so as to form a random and long gradient-SB/(S-B) -chain segment; simultaneously, in a 15L stainless steel polymerization kettle B, introducing argon to replace a system for 3 times, sequentially adding 1950g cyclohexane, 210g isoprene and 1.2g THF, heating to 40 ℃, adding 31.5 mmol 1 n-butyllithium to start reaction, gradually heating from 40 ℃ to 70 ℃ within 60min, and reacting at a heating speed of 0.5 ℃/min for 60min to form an IR chain segment with wide molecular weight distribution; then sequentially adding 370g of styrene and 1.0g of THF into the polymerization kettle B, and reacting for 60min to form an-IR-PS-chain segment; after the monomer is completely converted, adding the materials in the polymerization kettle B into the polymerization kettle A, and carrying out coupling reaction for 85min; finally, 25g of 1, 3-butadiene is added into the polymerization kettle A for end capping, and the reaction is carried out for 25min until no play exists When the monomer exists, the reaction mixture after the coupling is treated by water after the reaction is finished, and the glue solution is subjected to wet condensation and drying to obtain the ternary long-chain copolymer [ -B-SB/(S.fwdarw.B) -BR-IR-PS-B ]] n Grafting agent (Mn 35920, mw/Mn 4.1).
(2) Preparation of hyperbranched and ultra-wide molecular weight distribution butyl rubber: other conditions were the same as in example 4 except that: in the synthesis process, the [ -B-SB/(S.fwdarw.B) -BR- ] nY [ -IR-PS-B- ] n grafting agent is not added, but the [ -B-SB/(S.fwdarw.B) -BR-IR-PS-B- ] n grafting agent is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3 times for replacement, adding 530g of methyl chloride and 430g of cyclohexane into the polymerization kettle, and stirring and dissolving 25g of [ (-B-SB/(S- & gt B) -BR-IR-PS-B- ] n grafting agent until the grafting agent is completely dissolved; then cooling to-80 ℃, then adding 540g of methyl chloride, 456g of isobutene and 15g of isoprene in turn, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then mixing 180g of methyl chloride, 5.15g of aluminum sesquichloride and 0.103g of HCl at-95 ℃ and aging for 25min, then adding the mixture into the polymerization system together and stirring and reacting for 4.0hr, discharging and condensing, washing and drying to obtain the hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 5
(1) Preparation of grafting agent:
a, preparation of a coupling agent: same as in example 5.
b, preparation of grafting agent: same as in example 5.
(2) Preparation of 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 [ -B-SB/(S.fwdarw.B) -BR- ] nY [ -IR-PS-B- ] n grafting agent added during the synthesis was 3.0g, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, introducing nitrogen for 3 times for replacement, adding 500g of methyl chloride and 470g of cyclohexane into the polymerization kettle, and stirring and dissolving 3.0g of [ (-B-SB/(S- & gt B) -BR- ] nY [ -IR-PS-B- ] n grafting agent until the grafting agent is completely dissolved; then cooling to-85 ℃, then adding 550g of methyl chloride, 465g of isobutene and 20g of isoprene in sequence, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing 190g of methyl chloride, 5.85g of aluminum sesquichloride and 0.213g of HCl at-95 ℃ and aging for 30min, then adding the mixture into the polymerization system together and stirring and reacting for 5.0hr, discharging and condensing, washing and drying to obtain the hyperbranched butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
TABLE 1 hyperbranched, ultra-wide molecular weight distribution Properties of butyl rubber
As can be seen from table 1: the hyperbranched ultra-wide molecular weight distribution butyl rubber disclosed by the invention has the advantages that the ultra-high branching degree and the ultra-wide molecular weight distribution lead to small Mooney relaxation area, and meanwhile, the ultra-branched ultra-wide molecular weight distribution butyl rubber has good air tightness and high tensile strength, so that the ultra-branched ultra-wide molecular weight distribution butyl rubber has good processability while maintaining excellent physical and mechanical properties.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.

Claims (14)

1. The preparation method of the hyperbranched ultra-wide molecular weight distribution butyl rubber is characterized by comprising the following steps of:
(1) Preparation of grafting agent:
a, preparation of a coupling agent: firstly, adding 100% -200% of deionized water, 3, 9-dioxygen [5.5] spiro undecane, a halogenating agent and 1% -5% of a catalyst into a polymerization kettle in turn under the inert gas atmosphere, heating to 50-80 ℃, reacting for 1-3 hr, adding 20% -40% of 10% -20% NaOH aqueous solution with the mass concentration to terminate the reaction, and finally adding 200% -300% of chloromethane to extract, separate, wash and dry to obtain a coupling agent;
b, preparation of grafting agent: sequentially adding 100-200% of solvent, 10-20% of 1, 3-butadiene, 0.05-0.3% of structure regulator and initiator into a polymerization kettle A in an inert gas atmosphere, heating to 50-70 ℃ and reacting for 50-70 min; then adding 100% -200% of solvent and 0.1% -0.3% of structure regulator into a polymerization kettle A in turn, heating to 70-80 ℃, stirring and mixing 30% -40% of styrene and 10% -20% of 1, 3-butadiene for 10-30 min, reacting to obtain variable-speed polymerization, adding the variable-speed polymerization into the polymerization kettle in a continuous injection mode, reacting within 60-80 min, and adding a coupling agent for coupling reaction for 60-90 min, wherein the initial feeding speed is higher than 10.0% of mixture/min, the feeding speed reduction range is determined according to the reaction time, and finally heating to 80-90 ℃; simultaneously, under the inert gas atmosphere, 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 for 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, adding the materials in the polymerization kettle B into the polymerization kettle A after the monomers are completely converted, and carrying out coupling reaction for 60-90 min; finally, adding 1% -4% of 1, 3-butadiene into the polymerization kettle A for end capping, reacting until no free monomer exists, treating the coupled reaction mixture with water after the reaction is finished, and performing wet condensation and drying on the glue solution to obtain a grafting agent;
(2) Preparation of hyperbranched and ultra-wide molecular weight distribution butyl rubber: firstly, replacing 3-5 times in inert gas atmosphere, adding 100-200% of diluent and solvent into a polymerization kettle according to the volume ratio of 70-30: 30-70 percent of mixed solvent, 1-10 percent of grafting agent, and stirring and dissolving for 20-30 min until the grafting agent is completely dissolved; then cooling to-75 to-85 ℃, sequentially adding 100-200% of diluent, 85-95% of isobutene and 1-5% of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-100 to-90 ℃, then mixing and ageing 30-50% of diluent and 0.05-3.0% of co-initiator at-85 to-95 ℃ for 20-30 min, adding the mixture into the polymerization system together, stirring and reacting for 2.0-5.0 hr, discharging, condensing, washing and drying to obtain a hyperbranched ultra-wide molecular weight distribution butyl rubber product;
wherein the initiator is selected from one of n-butyllithium, sec-butyllithium, methyl butyllithium, phenyl butyllithium, naphthalene lithium, cyclohexyl lithium or dodecyl lithium; the coupling agent is 1, 5-dihalogen-3, 3-di (2-haloethyl) pentane, and the molar ratio of the coupling agent to the initiator is 2.0-5.0; the co-initiator is formed by compounding alkyl aluminum halide and protonic acid, and the molar ratio of protonic acid to alkyl aluminum halide is 0.01:1-0.1:1.
2. The method of claim 1, wherein the grafting agent is a ternary four-arm star copolymer synthesized from isoprene, styrene and butadiene, and has a structural formula shown in formula I:
wherein BR is a 1, 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 segment of styrene and butadiene; (S.fwdarw.B) is a gradual change section of styrene and butadiene; IR is a homopolymer segment of isoprene wide vinyl distribution; b is a blocked butadiene segment, n=1.
3. The method of claim 2, wherein the ternary four-arm 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 four-arm star copolymer has a number average molecular weight of 10000-50000 and a ratio of weight average molecular weight to number average molecular weight of 12.5-16.7.
5. The process 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-CH 3 And mixed aqueous solution of OH, 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 modifier is tetrahydrofuran.
9. The method of claim 1, wherein the initiator is n-butyllithium.
10. The method of claim 1, wherein the diluent is methyl chloride, methylene chloride, carbon tetrachloride, ethylene dichloride, tetrachloropropane, heptachloropropane, methyl fluoride, difluoromethane, tetrafluoroethane, carbon hexafluoride, or fluorobutane.
11. The method of claim 1, wherein the alkyl aluminum halide is selected from at least one of diethyl aluminum monochloride, diisobutyl aluminum monochloride, dichloromethyl aluminum, sesquiethyl aluminum chloride, sesquiisobutyl aluminum chloride, n-propyl aluminum dichloride, isopropyl aluminum dichloride, dimethyl aluminum chloride, and ethyl aluminum chloride.
12. The method of claim 11, wherein the alkyl aluminum halide is aluminum sesquiethyl chloride.
13. The method of claim 1, wherein the protonic acid is HCl, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 Or HNO (HNO) 3 。
14. The method of claim 13, wherein the protic acid is HCl.
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CN102786621A (en) * 2012-07-19 2012-11-21 大连理工大学 Rare earth catalytic system based high-cis styrene/isoprene/butadiene ternary polymer and its preparation method
CN109134765A (en) * 2017-06-28 2019-01-04 北京化工大学 A kind of polyisobutene and the graft copolymer of polyisoprene and preparation method thereof

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WO2005054320A1 (en) * 2003-12-04 2005-06-16 Korea Kumho Petrochemical Co., Ltd. Hetero-branched radial polystyrene-polyisoprene block copolymer composition and preparation method thereof

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CN102786621A (en) * 2012-07-19 2012-11-21 大连理工大学 Rare earth catalytic system based high-cis styrene/isoprene/butadiene ternary polymer and its preparation method
CN109134765A (en) * 2017-06-28 2019-01-04 北京化工大学 A kind of polyisobutene and the graft copolymer of polyisoprene and preparation method thereof

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