CN113493552B - Preparation method of wide-distribution butyl rubber - Google Patents
Preparation method of wide-distribution butyl rubber Download PDFInfo
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- CN113493552B CN113493552B CN202010273001.9A CN202010273001A CN113493552B CN 113493552 B CN113493552 B CN 113493552B CN 202010273001 A CN202010273001 A CN 202010273001A CN 113493552 B CN113493552 B CN 113493552B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
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- 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
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- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
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Abstract
The invention firstly adopts alkyl lithium as an initiator and hydrocarbon as a solvent, a reaction monomer is composed of isoprene, styrene and butadiene, the initiator is added twice, temperature-changing and speed-changing polymerization is adopted, and then trihalosilane coupling agent coupling is adopted to prepare the copolymer with a three-arm structure [ -IR-PS-SB/(S- & gtB) -B [ -A ]] n And Y, finally, taking the star-shaped copolymer with the three-arm structure as an adhesive to prepare the branched butyl rubber with the high-width molecular weight distribution. The invention adopts the modes of variable-temperature polymerization and variable-speed polymerization to realize a chain segment with a certain length, high randomness and gradual change, can obviously improve the flexibility of the chain segment, and obtain a quick stress relaxation rate, so that the molecular weight distribution of the butyl rubber is obviously widened, the good viscoelastic performance of the butyl rubber is ensured, and meanwhile, the sufficient green rubber strength and the good air tightness are also maintained. The preparation method has the characteristics of short process flow, controllable molecular weight, good product processing performance, suitability for industrial production and the like.
Description
Technical Field
The invention relates to a preparation method of wide-distribution butyl rubber, in particular to a method for preparing wide-distribution butyl rubber by grafting polyisobutene with an isoprene/styrene/butadiene segmented copolymer.
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 have found that star-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 properties, 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-branched structure has therefore become one of the hot spots in the future butyl rubber research field.
In the prior art, the synthesis of star-branched butyl rubber is mainly prepared by adopting a method of a first-nucleus and then-arm method, a first-arm and then-nucleus method and a nucleus-arm simultaneous method. Such as: US5395885 discloses a star-branched 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, polydivinylbenzene (PDVB) as a core, a complex of alkyl aluminum chloride and water as an initiator and chloromethane as a diluent. CN 107344982A discloses a raw mealA process for producing a broad/bimodal molecular weight distribution butyl rubber, the process comprising: mixing isobutene and isoprene in a molar ratio of 97:3 to 99:1, mixing the mixture with a diluent (methyl chloride) to obtain a monomer stream, mixing an initiator (an aluminum chloride system and a complex of HCl/aluminum alkyl chloride) and the diluent (methyl chloride) to obtain an initiator stream, mixing the monomer stream and the initiator stream, feeding the mixed mixture into a first loop reactor zone, and carrying out polymerization for 5-10min at a temperature of-98 ℃ to-96 ℃ and a pressure of 0.3 to 0.4Mpa to obtain a first part of butyl rubber slurry; the second step, the first part of butyl rubber slurry is sent into a second loop reactor zone, and the butyl rubber slurry with broad/bimodal molecular weight distribution is finally obtained after polymerization reaction for 5-10min at the temperature of-92 ℃ to-90 ℃ and the pressure of 0.1 to 0.2 Mpa; and thirdly, contacting the butyl rubber slurry with the broad/bimodal molecular weight distribution with water, removing unreacted monomers and diluents to obtain colloidal particle water, and dehydrating and drying the colloidal particle water to obtain the butyl rubber with the broad/bimodal molecular weight distribution (Mw/Mn) of at least 5.0. CN1427851a discloses a process for preparing butyl rubber with a broad molecular weight distribution. The process uses a mixed catalyst system comprising a mixture of a major amount of internalized dialkylaluminum, a minor amount of monoalkylaluminum dihalide and a minor amount of aluminoxane to provide a broad distribution butyl rubber having a molecular weight distribution of greater than 3.5 and up to 7.6. CN 101353403B discloses a method for preparing star-branched polyisobutylene or butyl rubber, which uses a polystyrene/isoprene block copolymer with a silicon-chlorine group at the end or a polystyrene/butadiene block copolymer with a silicon-chlorine group at the end as a grafting agent for initiating cationic polymerization, and takes part in the cationic polymerization directly in a cationic polymerization system of a mixed solvent with a chloromethane/cyclohexane v ratio of 20-80/80-20 at the temperature of 0-100 ℃ to initiate cationic polymerization by the silicon-chlorine group, and takes part in grafting reaction by an unsaturated chain to prepare the star-branched polyisobutylene or butyl rubber product. CN01817708.5 provides a process for preparing a multiolefin cross-linking agent by adding a multiolefin cross-linking agent such as divinylbenzene and a chain transfer agent such as 2,4, 1-trimethyl-1-pentene to a mixture of isoolefin monomers and diolefins Star-branched polymers are prepared. CN88108392.57 discloses a star-shaped graft butyl rubber with comb structure prepared by using a hydrochloride polystyrene-isoprene copolymer as a polyfunctional initiator or using polystyrene-butadiene or polystyrene-isoprene as a grafting agent. CN 107793535A provides a butyl rubber having a molecular weight of 90 to 260 tens of thousands, log (MW)>6 and contains structural units derived from isobutylene, structural units derived from conjugated dienes, and optionally structural units derived from aryl olefins. US3780002 proposes a complex initiator comprising a metal halide of group II or III of the periodic Table and a tetrahalide of a metal of group IV of the periodic Table, e.g. AICl 3 With TiC1 4 For combined use, or by combining A1C1 3 With SnC1 4 The composite use makes each initiator independently initiate cationic polymerization, and the butyl rubber with the molecular weight distribution index Mw/Mn above 5.0 is synthesized under the conventional Ding Mou rubber polymerization condition.
CN 101353386a discloses an initiating system for star-branched polyisobutylene or butyl rubber cationic polymerization, which consists of an initiating-grafting agent, a co-initiating agent and a nucleophilic agent, 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 star-branched 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-branched 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 wide-distribution butyl rubber. The invention firstly takes alkyl lithium as an initiator, hydrocarbon as a solvent, and a reaction monomer is composed of isoprene, styrene and butadiene, so as to synthesize a wide vinyl distribution and random transition long chain segment [ -IR-PS-SB/(S- & gt B- & gt n, then a trihalosilane coupling agent is used for preparing a star copolymer [ -IR-PS-SB/(S- & gt B) -B- & gt n Y with a three-arm structure, and the star copolymer [ -IR-PS-SB/(S- & gt B) -B- & gt n Y is used as a grafting agent and is compounded with isobutene and isoprene in a catalytic system of Lewis acid and protonic acid, and the wide distribution butyl rubber is prepared by adopting cationic polymerization. The wide-distribution butyl rubber not only well solves the problems of low stress relaxation rate and extrusion swelling of the butyl rubber in the processing process, but also maintains sufficient raw rubber strength and good air tightness of the butyl rubber, and realizes the balance of physical and mechanical properties and processing properties of the butyl rubber.
The percentages refer to mass percentages.
The preparation of the branched star-shaped butyl rubber is carried out in a reaction kettle, and the specific preparation process comprises the following steps:
(1) Preparation of grafting agent: firstly, introducing argon gas into a 15L stainless steel polymerization kettle with a jacket for replacement for 2-4 times according to one hundred percent of the total mass of reaction monomers, sequentially adding 100-200% of solvent, 10-25% of isoprene and 0.05-0.3% of structure regulator into the polymerization kettle, and reacting for temperature-changing polymerization by using an initiator, wherein the temperature gradually rises from 40 ℃ to 60 ℃ within 50-70 min to form a wide-distribution IR chain segment, and the isoprene monomer conversion rate reaches 100%; then sequentially adding 20-30% of styrene and 0.05-0.1% of structure regulator into a polymerization kettle, heating to 60-70 ℃ and reacting for 30-50 min to form an-IR-PS-chain segment, wherein the conversion rate of the styrene monomer reaches 100%; sequentially adding 100-200% of solvent, 0.05-0.2% of structure regulator and initiator into a polymerization kettle, heating to 70-80 ℃, stirring and mixing 30-45% of styrene and 10-20% of 1, 3-butadiene for 10-20 min, reacting to obtain variable-speed polymerization, adding the variable-speed polymerization into the polymerization kettle in a continuous injection mode, reacting within 50-80 min, and forming a random and long gradient section-SB/(S- & gt B) -chain segment with the initial feeding speed of more than 10.0% of mixture/min, wherein the feeding speed reduction range is determined according to the reaction time; then adding 1-5% of 1, 3-butadiene into a polymerization kettle for end capping, and reacting for 10-30 min until no free monomer exists, so as to form an-IR-PS-SB/(S-B) -B-chain segment; finally, heating to 80-90 ℃, adding a coupling agent for coupling reaction for 50-70 min, treating the coupled reaction mixture with water after the reaction is completed, and carrying out wet condensation and drying on the glue solution to obtain the grafting agent with the three-arm structure.
(2) Preparation of widely distributed butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3-5 times to replace the reaction monomer by one hundred percent of the total mass, and adding 200-300% of diluent/solvent V into the polymerization kettle: v ratio is 60-40/40-60 mixed solvent, grafting agent is 3-9%, stirring and dissolving for 10-30 min until grafting agent is completely dissolved; 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 mixing and ageing 10 to 30 percent of diluent and 0.05 to 2.5 percent of co-initiator at-95 to-85 ℃ for 20 to 30 minutes, adding the mixture into the polymerization system together, stirring and reacting for 1.0 to 3.0 hours, discharging, condensing, washing and drying to obtain the wide-distribution butyl rubber product.
The grafting agent is an isoprene, styrene and butadiene segmented copolymer ([ -IR-PS-SB/(S- & gtB) -B- & gt nY) and has a structural general formula shown in formula I:
wherein Y is silicon and Bu is tert-butyl; IR is a homopolymer segment with isoprene having wide vinyl distribution, and the 1, 2-structure content is 20-25%; 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; b is a capped butadiene, n=1 to 4; the three-arm star polymer comprises 10-15% of isoprene, 50-75% of styrene and 15-20% of butadiene; the three-arm star polymer has a number average molecular weight (Mn) of 80000 to 130000 and a molecular weight distribution (Mw/Mn) of 7.23 to 11.15.
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 coupling agent used in the invention is one of tertiary butyl trichlorosilane and tertiary butyl tribromosilane, preferably tertiary butyl trichlorosilane. The amount of the coupling agent is determined by the amount of the initiator, and the molar ratio of the coupling agent to the organic lithium is 0.5-3.0.
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 is C1-C4. 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 0.08-2.0%, 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 invention firstly adopts alkyl lithium as an initiator, hydrocarbon as a solvent and organic matters with certain polarity as a structure regulator, a reaction monomer consists of isoprene, styrene and butadiene, and the copolymer with a three-arm structure [ -IR-PS-SB/(S.fwdarw.B) -B ]] n And finally, preparing the butyl rubber with wide molecular weight distribution by cationic polymerization of the star-shaped copolymer with the three-arm structure, isobutene and isoprene under a catalytic system of alkyl aluminum halide and protonic acid (shown in figure 1). The invention adopts variable temperature polymerization, which leads to the widening of vinyl distribution of IR chain segmentThe flexibility of the chain segment is obviously improved, and the rapid stress relaxation rate can be obtained; the variable speed polymerization is adopted, so that the polymerization reaction speed is changed continuously, and the chain segment-SB/(S-B) -, which has a certain length, high randomness and gradual change, is obtained. Such segments can significantly disrupt the regularity of the molecular chain, so that the molecular weight distribution is significantly broadened.
In addition, the invention combines the chain segments with three different microstructures on one macromolecular chain to form a three-arm star-shaped structure, thus the performances of the different chain segments and the characteristics of the three-arm structure are organically combined together and cooperatively act, the molecular weight distribution of the butyl rubber can be obviously widened by utilizing the vinyl wide distribution in the IR chain segment, -SB/(S- & gtB) -random gradual change in the chain segment and the three-arm structure, the butyl rubber can be ensured to obtain good viscoelastic performance, the quick stress relaxation rate is ensured, and the processing performance 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.
Therefore, the invention develops the butyl rubber with wide molecular weight distribution, namely the butyl rubber has fast stress relaxation rate and excellent viscoelastic performance, and also has high green rubber strength and air tightness, so that the problem of contradiction between poor processability and good physical and mechanical properties of the butyl rubber is solved, the performance of the butyl rubber is more comprehensively improved, and the balance between the physical and mechanical properties and the processing properties is realized. The preparation method of the wide-distribution butyl rubber provided by the invention has the characteristics of short process flow, good product processing performance, suitability for industrial production and the like.
Drawings
FIG. 1 is a comparison of GPC spectra of a sample of 1# -butyl rubber IIR301 and a sample of 2# -example 1.
Detailed Description
The following examples and comparative examples are given to illustrate the inventive effects of the present invention, but the scope of the present invention is not limited to these examples and comparative examples. The raw materials used in the examples are all industrial polymer grade, and are used after purification without other special requirements.
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
Tert-butyltrichlorosilane purity 99% Shanghai Ji Laide New Material Co., ltd
Sesquiethyl aluminum chloride with purity of 98% of carbofuran technology Co., ltd
Other reagents are commercial industrial products
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: GT-7080-S2 Mooney manufactured by Taiwan high-speed rail company
And (5) measuring by a viscometer. 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,
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.
Example 1
(1) Preparation of grafting agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 2 times, sequentially adding 1650g of cyclohexane, 165g of isoprene and 2.3g of THF into the polymerization kettle, heating to 40 ℃, adding 21.2 mmol 1 of n-butyllithium for starting reaction, and gradually heating the reaction temperature from 40 ℃ to 60 ℃ within 50min to form a wide-distribution IR chain segment; then sequentially adding 305g of styrene and 1.1g of THF into a polymerization kettle, heating to 60 ℃, reacting for 30min to form an-IR-PS-chain segment, sequentially adding 1590g of cyclohexane and 1.5g THF,17.6mmo1 n-butyllithium into the polymerization kettle, heating to 70 ℃, stirring and mixing 450g of styrene and 160g of 1, 3-butadiene for 10min, and reducing the feeding speed by 2g of mixture per min at an initial feeding speed of 65g of mixture per min within 50min to form a random and long gradual change section-SB/(S-B) -chain segment; then adding 21g of butadiene into a polymerization kettle, and performing end-capping reaction for 10min to form an-IR-PS-SB/(S-B) -B-chain segment; finally, heating to 80 ℃, adding 21.5mm 1 tertiary butyl trichlorosilane, reacting for 50min, treating the coupled reaction mixture with water after the reaction is finished, and carrying out wet condensation and drying on the glue solution to obtain the grafting agent with the [ -IR-PS-SB/(S- & gt B) -B- ] nY three-arm structure (Mn is 81350, mw/Mn is 7.59).
(2) Preparation of widely distributed butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 590g of chloromethane, 425g of cyclohexane, [ -IR-PS-SB/(S- & gtB) -B- ] nY grafting agent and 15.5g of cyclohexane are added into the polymerization kettle, stirred and dissolved for 10min, then, when the temperature is reduced to minus 75 ℃, 516g of chloromethane, 425g of isobutene and 12g of isoprene are sequentially added, stirred and mixed until the temperature of a polymerization system is reduced to minus 90 ℃, then 110g of chloromethane, 2.12g of sesquiethyl aluminum chloride and 0.083g of HCl are mixed and aged for 20min, and then, after the mixture is added into the polymerization system together and stirred and reacted for 1.0hr, the mixture is discharged, condensed, washed and dried to obtain a wide-distribution 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: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 3 times, sequentially adding 1720g of cyclohexane, 186g of isoprene, 2.9g of THF into the polymerization kettle, heating to 40 ℃, adding 23.2 mmol 1 of n-butyllithium for starting reaction, and gradually heating the reaction temperature from 40 ℃ to 60 ℃ within 55min to form a wide-distribution IR chain segment; then sequentially adding 325g of styrene and 1.5g of THF into a polymerization kettle, heating to 65 ℃ for reaction for 35min to form an-IR-PS-chain segment, sequentially adding 1690g of cyclohexane and 1.9g THF,19.2mmo1 n-butyllithium into the polymerization kettle, heating to 72 ℃, stirring and mixing 510g of styrene and 180g of 1, 3-butadiene for 15min, and reducing the mixture by 3g per minute at an initial feeding speed of 70 g/min within 60min to form a random and long gradual change section-SB/(S- & gtB) -chain segment; then adding 25g of butadiene into a polymerization kettle, and carrying out end-capping reaction for 15min to form an-IR-PS-SB/(S-B) -B-chain segment; finally, heating to 82 ℃, adding 26.1mm 1 t-butyltrichlorosilane, reacting for 55min, treating the coupled reaction mixture with water after the reaction is finished, and carrying out wet condensation and drying on the glue solution to obtain the grafting agent with the [ -IR-PS-SB/(S.fwdarw.B) -B- ] nY three-arm structure (Mn is 87350, mw/Mn is 8.69).
(2) Preparation of widely distributed butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3 times, adding 625g of chloromethane, 575g of cyclohexane, [ -IR-PS-SB/(S- & gtB) -B- ] nY grafting agent, stirring and dissolving for 15min, then cooling to the temperature of minus 78 ℃, sequentially adding 626g of chloromethane, 432g of isobutene and 15g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to minus 92 ℃, then mixing 120g of chloromethane, 3.52g of sesquiethyl aluminum chloride and 0.095g of HCl at the temperature of minus 87 ℃ and aging for 22min, then adding the materials into the polymerization system together for stirring and reacting for 1.5hr, discharging and condensing, washing and drying to obtain the wide-distribution 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: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 3 times, sequentially adding 1890g cyclohexane, 226g isoprene and 3.2g THF into the polymerization kettle, heating to 40 ℃, adding 26.9mmo1 n-butyllithium for starting reaction, and gradually heating the reaction temperature from 40 ℃ to 60 ℃ within 60 minutes to form a wide-distribution IR chain segment; then 363g of styrene and 1.9g of THF are sequentially added into a polymerization kettle, the temperature is raised to 70 ℃ and the reaction is carried out for 40min to form an-IR-PS-chain segment, then 1750g of cyclohexane and 2.3g THF,20.2mmo1 n-butyllithium are sequentially added into the polymerization kettle, the temperature is raised to 74 ℃, 550g of styrene and 210g of 1, 3-butadiene are stirred and mixed for 15min, the initial feeding speed is 70g of mixture/min within 65min, the feeding speed reducing amplitude is 3g of mixture per minute, and a random and long gradual change section-SB/(S-B) -chain segment is formed; then adding 32g of butadiene into a polymerization kettle, and carrying out end-capping reaction for 20min to form an-IR-PS-SB/(S-B) -B-chain segment; finally, heating to 85 ℃, adding 36.8mmo1 tertiary butyl trichlorosilane, reacting for 60min, treating the coupled reaction mixture with water after the reaction is finished, and carrying out wet condensation and drying on the glue solution to obtain the grafting agent with the [ -IR-PS-SB/(S- & gt B) -B- ] nY three-arm structure (Mn is 103350, mw/Mn is 9.83).
(2) Preparation of widely distributed butyl rubber: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 615g of chloromethane, 689g of cyclohexane, [ -IR-PS-SB/(S- & gtB) -B- ] nY grafting agent and 30.1g of cyclohexane are added into the polymerization kettle, stirred and dissolved for 20min, then, when the temperature is reduced to minus 79 ℃, 642g of chloromethane, 642g of isobutene and 19g of isoprene are sequentially added, stirred and mixed until the temperature of a polymerization system is reduced to minus 94 ℃, then 130g of chloromethane, 4.16g of sesquiethyl aluminum chloride and 0.135g of HCl are mixed and aged for 25min, and then, after the materials are added into the polymerization system together and stirred and reacted for 2.0hr, the materials are discharged, condensed, washed and dried to obtain a wide-distribution 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: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 3 times, sequentially adding 2140g of cyclohexane, 256g of isoprene and 3.9g of THF into the polymerization kettle, heating to 40 ℃, adding 28.2 mmol 1 of n-butyllithium for starting reaction, and gradually heating the reaction temperature from 40 ℃ to 60 ℃ within 65min to form a wide-distribution IR chain segment; then adding 385g of styrene and 2.3g of THF into a polymerization kettle in sequence, heating to 70 ℃, reacting for 45min to form an-IR-PS-chain segment, adding 1820g of cyclohexane and 2.8g THF,22.6mmo1 n-butyllithium into the polymerization kettle in sequence, heating to 75 ℃, stirring and mixing 580g of styrene and 230g of 1, 3-butadiene for 17min, and reducing the mixture by 4g per minute at an initial feeding speed of 75 g/min within 70min to form a random and long gradual change section-SB/(S-B) -chain segment; then adding 39g of butadiene into a polymerization kettle, and carrying out end-capping reaction for 23min to form an-IR-PS-SB/(S-B) -B-chain segment; finally, heating to 87 ℃, adding 42.8mmo1 tertiary butyl trichlorosilane, reacting for 63min, treating the coupled reaction mixture with water after the reaction is completed, and carrying out wet condensation and drying on the glue solution to obtain the grafting agent with the [ -IR-PS-SB/(S- & gt B) -B- ] nY three-arm structure (Mn is 117250, and Mw/Mn is 10.56).
(2) Preparation of widely distributed butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3 times, adding 627g of chloromethane, 729g of cyclohexane, 35.7g of [ (-IR-PS-SB/(S- & gtB) -B- ] nY grafting agent, stirring and dissolving for 23min, then cooling to the temperature of-80 ℃, sequentially adding 686g of chloromethane, 452g of isobutene and 21g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to the temperature of-95 ℃, then mixing 130g of chloromethane, 5.13g of sesquiethyl aluminum chloride and 0.178g of HCl at the temperature of-90 ℃, aging for 27min, adding the materials into the polymerization system together, stirring and reacting for 2.3hr, discharging, condensing, washing and drying to obtain the wide-distribution 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: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 3 times, sequentially adding 2360g of cyclohexane, 289g of isoprene and 4.6g of THF into the polymerization kettle, heating to 40 ℃, adding 30.2mm & lt 1 & gt of n-butyllithium for starting reaction, and gradually heating the reaction temperature from 40 ℃ to 60 ℃ within 67min to form a wide-distribution IR chain segment; then adding 392g of styrene and 3.6g of THF into a polymerization kettle in sequence, heating to 70 ℃, reacting for 47min to form an-IR-PS-chain segment, adding 1930g of cyclohexane and 3.1g THF,25.6mmo1 n-butyllithium into the polymerization kettle in sequence, heating to 77 ℃, stirring and mixing 620g of styrene and 250g of 1, 3-butadiene for 20min, and reducing the mixture at an initial feeding speed of 75 g/min within 77min by 4 g/min to form a random and long gradual change section-SB/(S-B) -chain segment; then 41g of butadiene is added into a polymerization kettle to carry out end-capping reaction for 25min, and then an-IR-PS-SB/(S-B) -B-chain segment is formed; finally, heating to 89 ℃, adding 58.1mm 1 tertiary butyl trichlorosilane, reacting for 65min, treating the coupled reaction mixture with water after the reaction is finished, and carrying out wet condensation and drying on the glue solution to obtain the grafting agent with the [ -IR-PS-SB/(S- & gt B) -B- ] nY three-arm structure (Mn is 124550, mw/Mn is 10.79).
(2) Preparation of widely distributed butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3 times, adding 642g of chloromethane, 756g of cyclohexane, [ -IR-PS-SB/(S- & gtB) -B- ] nY grafting agent, stirring and dissolving for 25min, then cooling to the temperature of-80 ℃, sequentially adding 693g of chloromethane, 469g of isobutene and 23g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to the temperature of-95 ℃, then mixing 150g of chloromethane, 6.75g of sesquiethyl aluminum chloride and 0.218g of HCl at the temperature of-90 ℃ and aging for 29min, then adding the materials into the polymerization system together for stirring and reacting for 2.7hr, discharging and condensing, washing and drying to obtain the wide-distribution butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Example 6
(1) Preparation of grafting agent: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 4 times, sequentially adding 2560g of cyclohexane, 310g of isoprene and 5.6g of THF into the polymerization kettle, heating to 40 ℃, adding 35.2 mmol 1 of n-butyllithium for starting reaction, and gradually heating the reaction temperature from 40 ℃ to 60 ℃ within 70min to form a wide-distribution IR chain segment; then sequentially adding 416g of styrene and 4.6g of THF into a polymerization kettle, heating to 70 ℃, reacting for 50min to form an-IR-PS-chain segment, sequentially adding 2140g of cyclohexane and 3.9g THF,27.6mmo1 n-butyllithium into the polymerization kettle, heating to 80 ℃, stirring and mixing 650g of styrene and 270g of 1, 3-butadiene for 20min, and reducing the mixture by 5g per minute at an initial feeding speed of 80 g/min within 80min to form a random and long gradual change section-SB/(S-B) -chain segment; then adding 50g of butadiene into a polymerization kettle, and performing end-capping reaction for 30min to form an-IR-PS-SB/(S-B) -B-chain segment; finally, heating to 90 ℃, adding 72.1mm 1 tertiary butyl trichlorosilane bromine, reacting for 70min, treating the coupled reaction mixture with water after the reaction is completed, and carrying out wet condensation and drying on the glue solution to obtain the grafting agent with the [ -IR-PS-SB/(S- & gt B) -B- ] nY three-arm structure (Mn is 129550, and Mw/Mn is 11.09).
(2) Preparation of widely distributed butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, adding 662g of chloromethane, 816g of cyclohexane, [ -IR-PS-SB/(S- & gtB) -B- ] nY grafting agent 44.5g into the polymerization kettle, stirring and dissolving for 30min, then cooling to the temperature of-85 ℃, sequentially adding 703g of chloromethane, 475g of isobutene and 25g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to the temperature of-97 ℃, then mixing 170g of chloromethane, 7.32g of sesquiethyl aluminum chloride and 0.368g of HCl at the temperature of-95 ℃ and aging for 30min, then adding the materials into the polymerization system together for stirring and reacting for 3.0hr, discharging, condensing, washing and drying to obtain the wide-distribution 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: other conditions were the same as in example 1 except that: the isoprene monomer does not adopt variable temperature polymerization, and reacts at the constant temperature of 40 ℃, namely: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 2 times, sequentially adding 1650g of cyclohexane, 165g of isoprene and 2.3g of THF into the polymerization kettle, heating to 40 ℃, adding 21.2 mmol 1 of n-butyllithium for reaction, and reacting for 50min to form an IR1 chain segment; then sequentially adding 305g of styrene and 1.1g of THF into a polymerization kettle, heating to 60 ℃, reacting for 30min to form an-IR 1-PS-chain segment, sequentially adding 1590g of cyclohexane and 1.5g THF,17.6mmo1 n-butyllithium into the polymerization kettle, heating to 70 ℃, stirring and mixing 450g of styrene and 160g of 1, 3-butadiene for 10min, and reducing the feeding speed by 2g of mixture per min at an initial feeding speed of 65g of mixture per min within 50min to form a random and long gradual change section-SB/(S-B) -chain segment; then adding 21g of butadiene into a polymerization kettle, and performing end-capping reaction for 10min to form an-IR 1-PS-SB/(S-B) -B-chain segment; finally, heating to 80 ℃, adding 21.5mm 1 tertiary butyl trichlorosilane, reacting for 50min, treating the coupled reaction mixture with water after the reaction is finished, and carrying out wet condensation and drying on the glue solution to obtain the grafting agent with the [ -IR 1-PS-SB/(S.fwdarw.B) -B- ] nY three-arm structure (Mn is 80350, mw/Mn is 4.59).
(2) Preparation of widely distributed butyl rubber: other conditions were the same as in example 1 except that: in the synthesis process, the [ -IR-PS-SB/(S.fwdarw.B) -B- ] nY grafting agent is not added, but the [ -IR 1-PS-SB/(S.fwdarw.B) -B- ] nY grafting agent is added, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 590g of chloromethane, 425g of cyclohexane, [ -IR 1-PS-SB/(S- & gtB) -B- ] nY grafting agent and 15.5g of cyclohexane are added into the polymerization kettle, stirred and dissolved for 10min, then 516g of chloromethane, 425g of isobutene and 12g of isoprene are sequentially added when the temperature is reduced to minus 75 ℃, stirred and mixed until the temperature of a polymerization system is reduced to minus 90 ℃, then 110g of chloromethane, 2.12g of sesquiethyl aluminum chloride and 0.083g of HCL are mixed and aged for 20min, then the materials are added into the polymerization system together to be stirred and reacted for 1.0hr, and then discharged, coagulated, washed and dried to obtain a wide-distribution 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: other conditions were the same as in example 2 except that: the mixture of styrene and 1, 3-butadiene was fed into the polymerization vessel at a constant rate of 70g of mixture/min at the initial feed rate, namely: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 3 times, sequentially adding 1720g of cyclohexane, 186g of isoprene, 2.9g of THF into the polymerization kettle, heating to 40 ℃, adding 23.2 mmol 1 of n-butyllithium for starting reaction, and gradually heating the reaction temperature from 40 ℃ to 60 ℃ within 55min to form a wide-distribution IR chain segment; then sequentially adding 325g of styrene and 1.5g of THF into a polymerization kettle, heating to 65 ℃, reacting for 35min to form an-IR-PS-chain segment, sequentially adding 1690g of cyclohexane and 1.9g THF,19.2mmo1 n-butyllithium into the polymerization kettle, heating to 72 ℃, stirring and mixing 510g of styrene and 180g of 1, 3-butadiene for 15min, and adding the mixture into the polymerization kettle at a uniform speed of 70g of mixture/min within 60min to form a random and gradual transition-SB 1/(S- & gt B) 1-chain segment; then adding 25g of butadiene into a polymerization kettle, and carrying out end-capping reaction for 15min to form an-IR-PS-SB 1/(S-B) 1-B-chain segment; finally, heating to 82 ℃, adding 26.1mm 1 t-butyltrichlorosilane, reacting for 55min, treating the coupled reaction mixture with water after the reaction is finished, and carrying out wet condensation and drying on the glue solution to obtain the grafting agent with the [ -IR-PS-SB 1/(S.fwdarw.B) 1-B- ] nY three-arm structure (Mn is 79350, mw/Mn is 5.25).
(2) Preparation of widely distributed butyl rubber: other conditions were the same as in example 2 except that: in the synthesis process, the [ -IR-PS-SB/(S.fwdarw.B) -B- ] nY grafting agent is not added, but the [ -IR-PS-SB 1/(S.fwdarw.B) 1-B- ] nY grafting agent is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3 times, adding 625g of chloromethane, 575g of cyclohexane, [ -IR-PS-SB 1/(S- & gtB) 1-B- ] nY grafting agent, stirring and dissolving for 15min, then cooling to the temperature of minus 78 ℃, sequentially adding 626g of chloromethane, 432g of isobutene and 15g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to minus 92 ℃, then mixing 120g of chloromethane, 3.52g of sesquiethyl aluminum chloride and 0.095g of HCl at the temperature of minus 87 ℃ and aging for 22min, then adding the materials into the polymerization system together for stirring and reacting for 1.5hr, discharging and condensing, washing, and drying to obtain the wide-distribution 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: other conditions were the same as in example 3 except that: isoprene is polymerized at a single temperature, and the reaction temperature is not gradually increased from 40 ℃ to 60 ℃ in 60min, but gradually increased from 40 ℃ to 50 ℃ in 60min, namely: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 3 times, sequentially adding 1890g cyclohexane, 226g isoprene and 3.2g THF into the polymerization kettle, heating to 40 ℃, adding 26.9mmo1 n-butyllithium for starting reaction, and gradually heating the reaction temperature from 40 ℃ to 50 ℃ within 60 minutes to form a wide-distribution IR2 chain segment; then 363g of styrene and 1.9g of THF are sequentially added into a polymerization kettle, the temperature is raised to 70 ℃ and the reaction is carried out for 40min to form an-IR 2-PS-chain segment, then 1750g of cyclohexane and 2.3g THF,20.2mmo1 n-butyllithium are sequentially added into the polymerization kettle, the temperature is raised to 74 ℃, 550g of styrene and 210g of 1, 3-butadiene are stirred and mixed for 15min, the initial feeding speed is 70g of mixture/min within 65min, the feeding speed is reduced by 3g of mixture per minute, and a random and long gradual change section-SB/(S- & gtB) -chain segment is formed; then adding 32g of butadiene into a polymerization kettle, and carrying out end-capping reaction for 20min to form an-IR 2-PS-SB/(S-B) -B-chain segment; finally, heating to 85 ℃, adding 36.8mmo1 tertiary butyl trichlorosilane, reacting for 60min, treating the coupled reaction mixture with water after the reaction is finished, and carrying out wet condensation and drying on the glue solution to obtain the grafting agent with the [ -IR 2-PS-SB/(S- & gt B) -B- ] nY three-arm structure (Mn is 92350, mw/Mn is 6.13).
(2) Preparation of widely distributed butyl rubber: other conditions were the same as in example 3 except that: in the synthesis process, the [ -IR-PS-SB/(S.fwdarw.B) -B- ] nY grafting agent is not added, but the [ -IR 2-PS-SB/(S.fwdarw.B) -B- ] nY grafting agent is added, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced to replace for 3 times, 615g of chloromethane, 689g of cyclohexane, [ -IR 2-PS-SB/(S- & gtB) -B- ] nY grafting agent, 30.1g of chloromethane, 642g of isobutene and 19g of isoprene are added sequentially when the temperature is reduced to-79 ℃, and then 130g of chloromethane, 4.16g of sesquiethyl aluminum chloride and 0.135g of HCL are mixed and aged for 25 minutes when the temperature is reduced to-94 ℃ by stirring until the temperature of the polymerization system is reduced to-87 ℃, then the materials are added into the polymerization system together to be stirred and reacted for 2.0 hours, and then the materials are discharged, condensed, washed and dried to obtain a wide-distribution 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: other conditions were the same as in example 4 except that: the styrene and 1, 3-butadiene mixture was not continuously injected into the polymerizer, but was added in one portion, namely: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 3 times, sequentially adding 2140g of cyclohexane, 256g of isoprene and 3.9g of THF into the polymerization kettle, heating to 40 ℃, adding 28.2 mmol 1 of n-butyllithium for starting reaction, and gradually heating the reaction temperature from 40 ℃ to 60 ℃ within 65min to form a wide-distribution IR chain segment; then adding 385g of styrene and 2.3g of THF into a polymerization kettle in sequence, heating to 70 ℃, reacting for 45min to form an-IR-PS-chain segment, adding 1820g of cyclohexane and 2.8g THF,22.6mmo1 n-butyllithium into the polymerization kettle in sequence, heating to 75 ℃, stirring and mixing 580g of styrene and 230g of 1, 3-butadiene for 17min, and adding the mixture into the polymerization kettle together to react for 70min to form an-SBR-chain segment; then adding 39g of butadiene into a polymerization kettle, and carrying out end-capping reaction for 23min to form an-IR-PS-SBR-B-chain segment; finally, heating to 87 ℃, adding 42.8mmo1 tertiary butyl trichlorosilane, reacting for 63min, treating the coupled reaction mixture with water after the reaction is completed, and carrying out wet condensation and drying on the glue solution to obtain the grafting agent with the [ -IR-PS-SBR-B- ] nY three-arm structure (Mn is 87250, mw/Mn is 3.18).
(2) Preparation of widely distributed butyl rubber: other conditions were the same as in example 4 except that: in the synthesis process, the [ -IR-PS-SB/(S.fwdarw.B) -B- ] nY grafting agent is not added, but the [ -IR-PS-SBR-B- ] nY grafting agent is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3 times, adding 627g of methyl chloride, 729g of cyclohexane, 35.7g of [ (-IR-PS-SBR-B- ] nY grafting agent, stirring and dissolving for 23min, then cooling to the temperature of-80 ℃, sequentially adding 686g of methyl chloride, 452g of isobutene and 21g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to the temperature of-95 ℃, then mixing 130g of methyl chloride, 5.13g of sesquiethyl aluminum chloride and 0.178g of HCl at the temperature of-90 ℃, aging for 27min, adding into the polymerization system together, stirring and reacting for 2.3hr, discharging, condensing, washing and drying to obtain the wide-distribution butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 5
(1) Preparation of grafting agent: other conditions were the same as in example 5 except that: during the synthesis process, the coupling agent tertiary butyl trichlorosilane is not added, namely: firstly, in a 15L stainless steel reaction kettle with a jacket, introducing argon for replacement for 3 times, sequentially adding 2360g of cyclohexane, 289g of isoprene and 4.6g of THF into the polymerization kettle, heating to 40 ℃, adding 30.2mm & lt 1 & gt of n-butyllithium for starting reaction, and gradually heating the reaction temperature from 40 ℃ to 60 ℃ within 67min to form a wide-distribution IR chain segment; then adding 392g of styrene and 3.6g of THF into a polymerization kettle in sequence, heating to 70 ℃, reacting for 47min to form an-IR-PS-chain segment, adding 1930g of cyclohexane and 3.1g THF,25.6mmo1 n-butyllithium into the polymerization kettle in sequence, heating to 77 ℃, stirring and mixing 620g of styrene and 250g of 1, 3-butadiene for 20min, and reducing the mixture at an initial feeding speed of 75 g/min within 77min by 4 g/min to form a random and long gradual change section-SB/(S-B) -chain segment; then 41g of butadiene is added into a polymerization kettle to carry out end-capping reaction for 25min, and the glue solution is subjected to wet condensation and drying to prepare the grafting agent of [ -IR-PS-SB/(S.fwdarw.B) -B- ] n (Mn is 44230, mw/Mn is 2.13).
(2) Preparation of widely distributed butyl rubber: other conditions were the same as in example 5 except that: in the synthesis process, the [ -IR-PS-SB/(S.fwdarw.B) -B- ] nY grafting agent is not added, but the [ -IR-PS-SB/(S.fwdarw.B) -B- ] n grafting agent is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for 3 times, adding 642g of chloromethane, 756g of cyclohexane, [ -IR-PS-SB/(S- & gtB) -B- ] n grafting agent into the polymerization kettle, stirring and dissolving for 25min, then cooling to the temperature of-80 ℃, sequentially adding 693g of chloromethane, 469g of isobutene and 23g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to the temperature of-95 ℃, then mixing 150g of chloromethane, 6.75g of sesquiethyl aluminum chloride and 0.218g of HCl at the temperature of-90 ℃ and aging for 29min, then adding the materials into the polymerization system together for stirring and reacting for 2.7hr, discharging, condensing, washing and drying to obtain the wide-distribution butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
Comparative example 6
(1) Preparation of grafting agent: same as in example 6.
(2) Preparation of widely distributed butyl rubber: the other conditions were the same as in example 6, except that the amount of the [ -IR-PS-SB/(S.fwdarw.B) -B- ] nY grafting agent added during the synthesis was 7.6g, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 5 times, adding 662g of chloromethane, 816g of cyclohexane, [ -IR-PS-SB/(S- & gtB) -B- ] nY grafting agent, stirring and dissolving for 30min, then cooling to the temperature of-85 ℃, sequentially adding 703g of chloromethane, 475g of isobutene and 25g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to the temperature of-97 ℃, then mixing 170g of chloromethane, 7.32g of sesquiethyl aluminum chloride and 0.368g of HCl at the temperature of-95 ℃ and aging for 30min, then adding the materials into the polymerization system together for stirring and reacting for 3.0hr, discharging, condensing, washing and drying to obtain the wide-distribution butyl rubber product. Sampling and analyzing: standard samples were prepared and the test performance is shown in table 1.
TABLE 1 Properties of widely distributed butyl rubber
As can be seen from table 1: the wide-distribution butyl rubber provided by the invention has wide molecular weight distribution and low Mooney relaxation area, shows good processability (the smaller the area under a stress relaxation curve is, the lower the energy consumption of mixing processing is), and simultaneously has good air tightness and high tensile strength.
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 as defined in the appended claims.
Claims (12)
1. The preparation method of the wide-distribution butyl rubber is characterized by comprising the following steps of:
(1) Preparation of grafting agent: firstly, introducing argon into a polymerization kettle with a jacket for replacement for 2-4 times, sequentially adding 100-200% of solvent, 10-25% of isoprene, 0.05-0.3% of structure regulator and initiator into the polymerization kettle, reacting for variable-temperature polymerization, and gradually increasing the temperature from 40 ℃ to 60 ℃ within 50-70 min; then sequentially adding 20-30% of styrene and 0.05-0.1% of structure regulator into a polymerization kettle, heating to 60-70 ℃ and reacting for 30-50 min, wherein the conversion rate of styrene monomer reaches 100%; sequentially adding 100-200% of solvent, 0.05-0.2% of structure regulator and initiator into a polymerization kettle, heating to 70-80 ℃, stirring and mixing 30-45% of styrene and 10-20% of 1, 3-butadiene for 10-20 min, reacting to obtain variable-speed polymerization, adding the variable-speed polymerization into the polymerization kettle in a continuous injection mode, reacting within 50-80 min, and determining the initial feeding speed of the mixture/min of more than 10.0%, wherein the feeding speed reduction range is determined according to the reaction time; then adding 1% -5% of 1, 3-butadiene into the polymerization kettle for end capping, and reacting for 10-30 min until no free monomer exists; finally, heating to 80-90 ℃, adding a coupling agent for coupling reaction for 50-70 min, treating the coupled reaction mixture with water after the reaction is completed, and carrying out wet condensation and drying on the glue solution to obtain a grafting agent;
(2) Preparation of widely distributed butyl rubber: firstly, introducing nitrogen into a reaction kettle with a jacket for replacement for 3-5 times, adding 200-300% of mixed solvent of diluent/solvent with the volume ratio of 60-40/40-60 into the polymerization kettle, and stirring and dissolving 3-9% of grafting agent for 10-30 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 10-30% of diluent and 0.05-2.5% of co-initiator at-95 to-85 ℃ for 20-30 min, adding the mixture into the polymerization system together, stirring and reacting for 1.0-3.0 hr, discharging, condensing, washing and drying to obtain a wide-distribution butyl rubber product;
wherein the initiator is selected from one of n-butyllithium, sec-butyllithium, methyl butyllithium, phenyl butyllithium, naphthalene lithium, cyclohexyl lithium and dodecyl lithium; the coupling agent is selected from one of tert-butyl trichlorosilane and tert-butyl tribromosilane; the co-initiator is formed by compounding alkyl aluminum halide and protonic acid according to different proportions, 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 an isoprene, styrene and butadiene block copolymer having the general structural formula shown in formula I:
wherein Bu is tert-butyl; IR is a homopolymer segment with isoprene wide vinyl distribution, and the 1, 2-structure content is 20% -25%; 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; b is a capped butadiene, n=1 to 4.
3. The method of claim 2, wherein the three-arm star polymer has an isoprene content of 10% to 15%, a styrene content of 50% to 75%, and a butadiene content of 15% to 20%.
4. The method of claim 2 wherein the three-arm star polymer has a number average molecular weight of 80000 to 130000 and a weight average molecular weight to number average molecular weight ratio of 7.23 to 11.15.
5. The method of claim 1, wherein the structure modifier is selected from the group consisting of diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, and triethylamine.
6. The method of claim 1, wherein the structure modifier is tetrahydrofuran.
7. The method of claim 1, wherein the initiator is n-butyllithium.
8. The method of claim 1, wherein the coupling agent is t-butyltrichlorosilane.
9. 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.
10. The method of claim 9, wherein the alkyl aluminum halide is aluminum sesquichloride.
11. The method of claim 1, wherein said protonic acid is selected from the group consisting of HCl, HF, HBr, H 2 SO 4 、H 2 CO 3 、H 3 PO 4 And HNO 3 One of them.
12. The method of claim 11, wherein the protic acid is HCl.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1264714A (en) * | 1999-02-24 | 2000-08-30 | 北京燕山石油化工公司研究院 | Process for preparing atactic copolymer of conjugated diene and monovinyl arylhydrocarbon |
| WO2016108713A1 (en) * | 2014-12-30 | 2016-07-07 | Публичное акционерное общество "СИБУР Холдинг" | Method for producing butadiene-styrene block copolymers |
| CN106957400A (en) * | 2017-03-23 | 2017-07-18 | 北京石油化工学院 | A kind of soft segment is isobutene, and hard section is the preparation method of the special elastomer of Styrene and its derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1264714A (en) * | 1999-02-24 | 2000-08-30 | 北京燕山石油化工公司研究院 | Process for preparing atactic copolymer of conjugated diene and monovinyl arylhydrocarbon |
| WO2016108713A1 (en) * | 2014-12-30 | 2016-07-07 | Публичное акционерное общество "СИБУР Холдинг" | Method for producing butadiene-styrene block copolymers |
| CN106957400A (en) * | 2017-03-23 | 2017-07-18 | 北京石油化工学院 | A kind of soft segment is isobutene, and hard section is the preparation method of the special elastomer of Styrene and its derivatives |
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