CN113493548A - Preparation method of branched butyl rubber - Google Patents
Preparation method of branched butyl rubber Download PDFInfo
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- CN113493548A CN113493548A CN202010271959.4A CN202010271959A CN113493548A CN 113493548 A CN113493548 A CN 113493548A CN 202010271959 A CN202010271959 A CN 202010271959A CN 113493548 A CN113493548 A CN 113493548A
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Abstract
The invention aims to provide a preparation method of branched butyl rubber. The invention firstly takes alkyl lithium as an initiator, hydrocarbons as a solvent, organic matters with certain polarity as a structure regulator, reaction monomers comprise isoprene, styrene and butadiene to synthesize an [ -IR-SBR-PS-B- ] n segmented copolymer as a grafting agent, and then the grafting agent, isobutene and isoprene are adopted to prepare the branched butyl rubber with the three-dimensional comb structure of the IR, PS and SBR graft chain segments by cationic polymerization under a catalyst system compounded by alkyl aluminum halide and protonic acid. The invention keeps that the butyl rubber has high crude rubber strength and air tightness and has high stress relaxation rate, and realizes the balance of physical and mechanical properties and processability.
Description
Technical Field
The invention relates to a preparation method of branched butyl rubber, in particular to a method for preparing branched butyl rubber by grafting polyisobutylene on an isoprene/styrene/butadiene block copolymer.
Background
It is known that Butyl Rubber (IIR) is produced by the cationic polymerization of isobutylene and a small amount of isoprene. Butyl rubber has been commercialized by Exxon corporation in the 40 th century for over seventy years since now, and has excellent properties such as airtightness, damping properties, thermal aging resistance, ozone resistance, and weather resistance, and thus it is widely used in the fields of manufacturing inner tubes, airtight layers, curing bladders, medical stoppers of tires for vehicles, and the like, and is one of the most important synthetic rubber products.
However, the molecular chain of the butyl rubber is mainly composed of carbon-carbon single bonds, the number of double bonds is small, and the substituent methyl groups are symmetrically arranged, so that the defects of high crystallinity, poor flexibility of the molecular chain, low stress relaxation rate, low vulcanization speed, poor adhesiveness, poor compatibility with other general rubbers and the like exist, and the butyl rubber is easy to excessively flow and deform in the processing process. Therefore, how to balance the physical and mechanical properties and the processability of the butyl rubber becomes a bottleneck for preparing high-performance butyl rubber materials.
In recent years, researchers find that star-shaped branched butyl rubber which is composed of a high-molecular-weight graft structure and a low-molecular-weight linear structure and has a unique three-dimensional net structure has excellent viscoelastic performance, high crude rubber strength and a fast stress relaxation rate, low melt viscosity can be kept in a processing process, a high-molecular-weight polymer can be obtained, and balance and unification of physical and mechanical properties and processing properties are realized. Therefore, the star-branched structure has become one of the hot spots in the research field of future butyl rubber.
In the prior art, the star-branched butyl rubber is mainly prepared by a method of a first-nucleus-second-arm method, a first-arm-second-nucleus method and a nuclear-arm simultaneous method. Such as: US5395885 discloses a star-branched polyisobutylene-polydivinylbenzene polymer, which is synthesized by taking polyisobutylene as an arm, Polydivinylbenzene (PDVB) as a core, a complex of aluminium chloride and water as an initiator, and methyl chloride as a diluent through a first-arm-second-core method at-90 ℃ to-100 ℃. CN 107344982 a discloses a method for producing a wide/bimodal molecular weight distribution butyl rubber, which comprises: mixing isobutene and isoprene at a molar ratio of 97:3 to 99:1, then mixing the mixture with a diluent (methane chloride) to obtain a monomer stream, mixing an initiator (an aluminum chloride system and an HCl/alkylaluminum chloride complex) with the diluent (methane chloride) to obtain an initiator stream, mixing the monomer stream and the initiator stream, conveying the mixture into a first loop reactor zone, and carrying out polymerization reaction for 5-10min at a temperature of-98 ℃ to-96 ℃ and a pressure of 0.3 to 0.4MPa to obtain a first part of butyl rubber slurry; secondly, sending the first part of butyl rubber slurry into a second loop reactor zone, and carrying out polymerization reaction for 5-10min at the temperature of-92 ℃ to-90 ℃ and the pressure of 0.1 to 0.2Mpa to finally obtain the butyl rubber slurry with broad/bimodal molecular weight distribution; and thirdly, contacting the butyl rubber slurry with broad/bimodal molecular weight distribution with water, removing unreacted monomers and a diluent to obtain colloidal particle water, and then dehydrating and drying the colloidal particle water to obtain the butyl rubber with broad/bimodal molecular weight distribution and molecular weight distribution (Mw/Mn) of at least 5.0. CN1427851A discloses a preparation method of butyl rubber with wide molecular weight distribution. The process uses a mixed catalyst system comprising a mixture of a major amount of an internalized dialkylaluminum, a minor amount of a monoalkylaluminum dihalide, and a minor amount of an aluminoxane to provide a broad distribution butyl rubber having a molecular weight distribution of greater than 3.5 up to 7.6. CN 101353403B discloses a preparation method of star-shaped branched polyisobutylene or butyl rubber, which adopts polystyrene/iso-butyl rubber with a silicon-chlorine group at the terminalThe pentadiene block copolymer or the polystyrene/butadiene block copolymer with the end containing the silicon-chlorine group is used as a grafting agent for initiating the cationic polymerization, and directly participates in the cationic polymerization in a mixed solvent system with the V: V ratio of methane chloride/cyclohexane of 20-80/80-20 at the temperature of 0-100 ℃, and the star-branched polyisobutylene or butyl rubber product is prepared by the initiating cationic polymerization of the silicon-chlorine group and participating in the grafting reaction of an unsaturated chain. CN01817708.5 provides a method of making star-branched polymers 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 diolefin monomers. CN88108392.57 discloses a star-shaped grafted butyl rubber with a comb-shaped structure, which is prepared by using a hydrochloric acid polystyrene-isoprene copolymer as a multifunctional initiator or using polystyrene-butadiene or polystyrene-isoprene as a grafting agent. CN 107793535A provides a butyl rubber having a molecular weight of 90 to 260 ten thousand, Log (MW)>And contains structural units derived from isobutylene, structural units derived from a conjugated diene, and optionally structural units derived from an aryl olefin. US3780002 teaches a composite initiator using a halide of a metal from group II or III of the periodic Table of the elements in combination with a tetrahalide of a metal from group IV of the periodic Table of the elements, e.g. AICl3And TiC14Combined use, or A1C13And SnC14The composite use enables each initiator to independently initiate cationic polymerization, and butyl rubber with molecular weight distribution index Mw/Mn of above 5.0 is synthesized under the conventional butadiene rubber polymerization condition.
CN 101353386A discloses an initiation system for cationic polymerization of star-branched polyisobutylene or butyl rubber, which is composed of an initiation-grafting agent, a coinitiator and a nucleophilic reagent, and is used for initiating vinyl monomers to perform homopolymerization, block copolymerization, star polymerization and graft copolymerization, wherein the obtained polymer presents obvious bimodal distribution. Puskas (Catalysts for manufacturing of IIR with bi-modal molecular weight distribution: US, 5194538[ P ] 1993-3-16.) adopts trimesic acid as raw material to synthesize initiator tri-cumyl alcohol with a three-arm structure, and then adopts a tri-cumyl alcohol/aluminum trichloride initiating system to initiate isobutylene and isoprene to copolymerize in an inert organic solvent under the condition of-120 to-50 ℃ to synthesize star-shaped branched butyl rubber with bi-modal molecular weight distribution. Wieland et al (Synthesis of new graft copolymer polymerization by polymerization of the 1,1-diphenylethylene technology and cationic polymerization [ J ]. Polymer Science: Polymer Chemistry, 2002, 40: 3725-co-3733.) synthesized a macroinitiator P (MMA-b-St-co-CMS) containing the three members of 4-chloromethylstyrene, styrene and methyl methacrylate in the presence of 1, 2-Diphenylethylene (DPE) by a radical polymerization method, and then initiated cationic polymerization of isobutylene and isoprene to successfully prepare the multi-arm star butyl rubber. Wubo et al (Davang S H, et al. Ski resistant coatings for air craft carrier decks [ J ]. Coat Technol, 1980, 52 (671): 65-69.) prepared a poly (isoprene-styrene) block copolymer as a grafting agent by living anionic polymerization, and prepared star-branched butyl rubber exhibiting significant bimodal properties by living cationic polymerization in an initiation system of 2-chloro-2, 4, 4-trimethylpentane/titanium tetrachloride/proton scavenger.
Disclosure of Invention
The invention aims to provide a preparation method of branched butyl rubber. The invention firstly takes alkyl lithium as an initiator, hydrocarbons as a solvent, organic matters with certain polarity as a structure regulator, reaction monomers comprise isoprene, styrene and butadiene to synthesize [ -IR-SBR-PS-B- ] n block copolymer as a grafting agent, and then the grafting agent, isobutene and isoprene are adopted to prepare the branched butyl rubber by cationic polymerization under a catalyst system compounded by alkyl aluminum halide and protonic acid. The invention keeps a proper balance of high and low molecular weights, not only effectively solves the problem of slow stress relaxation rate of the butyl rubber in the processing process, but also keeps enough green strength and good air tightness of the butyl rubber and endows the butyl rubber with a balance of physical and mechanical properties and processing properties.
The percentages stated in the invention are all percentages by mass.
The preparation of the branched butyl rubber is carried out in a reaction kettle, and the specific preparation process comprises the following steps:
(1) preparation of grafting agent: according to one hundred percent of the total mass of reaction monomers, firstly introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2-4 times, sequentially adding 100-200% of solvent, 20-30% of isoprene, 0.01-0.1% of structure regulator and initiator into the polymerization kettle, wherein the reaction is temperature-changing polymerization, and the temperature is gradually increased from 45 ℃ to 60 ℃ within 50-80 min to form an IR chain segment with wide distribution, and the conversion rate of the isoprene monomer reaches 100%; then sequentially adding 200-300% of solvent, 20-30% of styrene, 30-40% of butadiene and 0.05-0.15% of structure regulator into a polymerization kettle, heating to 60-70 ℃, and reacting for 50-70 min to form an-IR-SBR-chain segment; secondly, sequentially adding 30-40% of styrene and 0.05-0.1% of structure regulator into the polymerization kettle, heating to 70-80 ℃, and reacting for 40-70 min to form an-IR-SBR-PS-chain segment, wherein the conversion rate of a styrene monomer reaches 100%; and finally, adding 3-7% of butadiene into a polymerization kettle for end capping, reacting for 10-30 min until no free monomer exists, and performing wet coagulation and drying on the glue solution to obtain the grafting agent with the [ -IR-SBR-PS-B- ] n block structure.
(2) Preparation of branched butyl rubber: according to one hundred percent of the total mass of reaction monomers, firstly introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3-5 times, and adding 200-300 percent of diluent/solvent V: the V ratio is 60-40/40-60, the mixed solvent and the grafting agent are 2-7%, and the mixed solvent and the grafting agent are stirred and dissolved for 10-30 min until the grafting agent is completely dissolved; and then cooling to-65 to-85 ℃, sequentially adding 200 to 300 percent of diluent, 89 to 95 percent of isobutene and 2 to 4 percent of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-100 to-90 ℃, then adding 20 to 30 percent of diluent and 0.08 to 2.0 percent of co-initiator into the polymerization system for stirring and reacting for 1.0 to 3.0 hours after mixing and aging for 10 to 20 minutes at-95 to-85 ℃, discharging and coagulating, washing and drying to obtain the branched butyl rubber product.
The grafting agent is an isoprene, styrene and butadiene block copolymer, and the structure of the grafting agent is represented as the following [ -IR-SBR-PS-B- ] n, wherein: IR is an isoprene homopolymer block; SBR is a random copolymer block of styrene and butadiene; PS is a styrene homopolymer block; b is terminated butadiene, and n is 2-3; the [ -IR-SBR-PS-B- ] n block copolymer has a number average molecular weight (Mn) of 20000 to 50000 and a molecular weight distribution (Mw/Mn) of 2.57 to 4.12.
The structure regulator of the invention is a polar organic compound which generates solvation effect in a polymerization system and can regulate the reactivity ratio of styrene and butadiene so as to ensure that the styrene and the butadiene are randomly copolymerized. Such polar organic compound is selected from one of diethylene glycol dimethyl ether (2G), Tetrahydrofuran (THF), diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME), triethylamine, preferably Tetrahydrofuran (THF).
The initiator is an alkyl monolithium compound, namely RLi, wherein R is a saturated aliphatic alkyl, alicyclic alkyl, aromatic alkyl containing 1-20 carbon atoms or a composite group of the above groups. The alkyl monolithium compound is selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium and dodecyllithium, preferably n-butyllithium. The amount of organolithium added is determined by the molecular weight of the polymer being designed.
The 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 alkyl halide is selected from one of methyl chloride, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, preferably methyl chloride.
The co-initiator is prepared by compounding alkyl aluminum halide and protonic acid according to different proportions. The alkyl aluminum halide is selected from diethyl aluminum monochloride, diisobutyl aluminum monochloride, methyl aluminum dichloroide, ethyl aluminum sesquichloride, isobutyl aluminum sesquichloride, and diAt least one of chloro-n-propylaluminum, dichloroisopropylaluminum, dimethylaluminum chloride and ethylaluminum chloride, preferably ethylaluminum sesquichloride. The protonic acid is selected from HCI, HF, HBr, H2SO4、H2CO3、H3PO4And HNO3Preferably HCI. Wherein the total addition amount of the coinitiator is 0.08-2.0%, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.01: 1-0.1: 1.
The polymerization reaction of the present invention is carried out in an oxygen-free, water-free, preferably inert gas atmosphere. The polymerization and dissolution are carried out in a hydrocarbon solvent, which is a hydrocarbon solvent including straight-chain alkanes, aromatic hydrocarbons and cycloalkanes, and is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably cyclohexane.
The invention firstly adopts alkyl lithium as an initiator, hydrocarbons as a solvent, organic matters with certain polarity as a structure regulator, reaction monomers comprise isoprene, styrene and butadiene, the initiator is added once, the reaction monomers are added into a polymerization system in a determined sequence for three times, and variable temperature polymerization is adopted in-IR-synthesis to synthesize a [ -IR-SBR-PS-B- ] n block copolymer with wide distribution, and then the block copolymer is used as a grafting agent to prepare branched butyl rubber with a comb-shaped structure by cationic polymerization with isobutene and isoprene under a catalytic system compounded by alkyl aluminum halide and protonic acid (see attached figures 1 and 2). Because the branched butyl rubber has a unique three-dimensional comb structure and wide molecular weight distribution, excellent viscoelastic property and excellent processing property are obtained, but as the molecular weight distribution becomes wider, the regularity of a molecular chain becomes worse, the crystallinity becomes lower, and the strength and the air tightness of raw rubber are reduced, at the moment, an [ -IR-SBR-PS-B- ] n block copolymer contains-IR-, -PS-and-SBR-chain segments with three different microstructures, the-IR-adopts temperature-changing polymerization to cause wider vinyl distribution, and in addition, the-SBR-chain segment has a certain vinyl distribution width, the flexibility of the chain segment can be obviously improved, and a fast stress relaxation rate can be obtained; meanwhile, the-PS-and-SBR-chain segments contain a large number of benzene rings, and the benzene rings have high rigidity and large steric hindrance, so that high strength and air tightness can be obtained; the [ -IR-SBR-PS-B- ] n block copolymer designed by the invention organically combines and cooperatively plays the performances of the three chain segments, solves the problem of contradiction relation between poor processability and good physical performance of butyl rubber, and realizes the balance of processability, strength and air tightness of the butyl rubber. In addition, the coinitiator consisting of the alkyl aluminum halide and the protonic acid adopted by the invention can initiate a chain segment of a higher molecular weight component without generating gel, so that the performance of the butyl rubber is more comprehensively improved.
Therefore, the branched butyl rubber with the three-dimensional comb-shaped structure has the advantages of high stress relaxation rate, excellent viscoelasticity, high green rubber strength and air tightness, and the balance of physical and mechanical properties and processability. The preparation method of the star-branched butyl rubber provided by the invention has the characteristics of short process flow, controllable molecular weight, good product processability, suitability for industrial production and the like.
Drawings
FIG. 1 is a schematic representation of the molecular structure of the branched butyl rubber of the present invention.
FIG. 2 is a comparison of GPC spectra of # 1-butyl rubber IIR301 samples versus # 2-example 1 samples.
Detailed Description
The following examples of the present invention are described in detail, and the present invention is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and procedures are given, but the scope of the present invention is not limited to the following examples, and the following examples are experimental methods without specific conditions noted, and generally follow conventional conditions.
The following examples and comparative examples are given to illustrate the effects of the present invention, but the scope of the present invention is not limited to these examples and comparative examples. All the raw materials used in the examples are of industrial polymerization grade, and are used after purification without other special requirements.
The raw material sources are as follows:
other reagents are all commercial products
The analysis and test method comprises the following steps:
determination of the molecular weights and their distribution: the measurement was carried out by using 2414 Gel Permeation Chromatograph (GPC) manufactured by Waters corporation, USA. Taking a polystyrene standard sample as a calibration curve, taking tetrahydrofuran as a mobile phase, controlling the column temperature to be 40 ℃, the sample concentration to be 1mg/ml, the sample injection amount to be 50 mu L, the elution time to be 40min and the flow rate to be 1 ml.min < -1 >.
Determination of Mooney viscosity and stress relaxation: adopting the model GT-7080-S2 Menni of high-speed rail company in Taiwan
And (5) measuring by a viscometer. The Mooney relaxation time, determined with a large rotor at 125 ℃ C (1+8) according to the method of GB/T1232.1-2000, is 120 s.
Measurement of airtightness: the air permeability was determined using an automated air tightness tester according to ISO 2782:1995,
the test gas is N2, the test temperature is 23 ℃, and the test sample is a circular sea piece with the diameter of 8cm and the thickness is 1 mm.
Tensile strength: the method in standard GB/T528-2009 is executed.
Example 1
(1) Preparation of grafting agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 3120g of cyclohexane, 410g of isoprene and 11.2g of THF into the polymerization kettle, heating to 45 ℃, adding 10.2mmo1 n-butyllithium to start reaction, and gradually increasing the reaction temperature from 45 ℃ to 60 ℃ within 50min to form an IR chain segment with wide distribution; then, 4220g of cyclohexane, 450g of styrene, 605g of butadiene and 15.2g of THF are sequentially added into a polymerization kettle, the temperature is raised to 60 ℃, and the reaction is carried out for 50min to form an-IR-SBR-chain segment; then, 615g of styrene and 10.5g of THF are sequentially added into the polymerization kettle, the temperature is raised to 70 ℃, and the reaction is carried out for 40min to form an-IR-SBR-PS-chain segment; finally, 61g of butadiene is added into a polymerization kettle, after end-capping reaction is carried out for 10min, glue solution is led out, and the grafting agent (Mn is 21150, Mw/Mn is 2.62) with the [ -IR-SBR-PS-B- ] n block structure copolymer is prepared through wet coagulation and drying.
(2) Preparation of branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 590g of methane chloride, 410g of cyclohexane and 10.1g of [ -IR-SBR-PS-B- ] n grafting agent into a polymerization kettle, and stirring and dissolving for 10min until the grafting agent is completely dissolved; then, when the temperature is reduced to-65 ℃, 1050g of methane chloride, 445g of isobutene and 10.5g of isoprene are sequentially added, stirred and mixed until the temperature of a polymerization system is reduced to-90 ℃, then 105g of methane chloride, 1.37g of sesquiethylaluminum chloride and 0.025g of HCl are mixed and aged for 10min at-85 ℃, added into the polymerization system together and stirred for reaction for 1.0hr, and then the branched butyl rubber product is obtained after discharging, coagulation, washing and drying. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 2
(1) Preparation of grafting agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3270g of cyclohexane, 452g of isoprene and 12.6g of THF into the polymerization kettle, heating to 45 ℃, adding 13.2mmo1 n-butyllithium to start reaction, and gradually increasing the reaction temperature from 45 ℃ to 60 ℃ within 60min to form an IR chain segment with wide distribution; then, 4520g of cyclohexane, 471g of styrene, 634g of butadiene and 18.1g of THF are sequentially added into the polymerization kettle, the temperature is raised to 62 ℃, and the reaction is carried out for 55min to form an-IR-SBR-chain segment; then, 632g of styrene and 12.2g of THF are sequentially added into the polymerization kettle, the temperature is raised to 71 ℃, and the reaction is carried out for 45min to form an-IR-SBR-PS-chain segment; and finally, adding 68g of butadiene into the polymerization kettle, carrying out end-capping reaction for 15min, then leading out glue solution, and carrying out wet coagulation and drying to obtain the grafting agent (Mn is 28620, Mw/Mn is 2.81) with the [ -IR-SBR-PS-B- ] n block copolymer.
(2) Preparation of branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 670g of methane chloride, 530g of cyclohexane and 13.8g of [ -IR-SBR-PS-B- ] n grafting agent into a polymerization kettle, and stirring and dissolving for 15min until the grafting agent is completely dissolved; and then cooling to-70 ℃, sequentially adding 1180g of methane chloride, 451g of isobutene and 11.6g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing and aging 113g of methane chloride, 1.48g of aluminum sesquiethyl chloride and 0.042g of HCl for 12min at-87 ℃, adding the mixture into the polymerization system together, stirring and reacting for 1.3hr, discharging, condensing, washing and drying to obtain the branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 3
(1) Preparation of grafting agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3520g of cyclohexane, 486g of isoprene and 13.7g of THF into the polymerization kettle, heating to 45 ℃, adding 14.1mmo1 n-butyllithium to start reaction, and gradually increasing the reaction temperature from 45 ℃ to 60 ℃ within 65min to form an IR chain segment with wide distribution; then, 4910g of cyclohexane, 513g of styrene, 671g of butadiene and 20.2g of THF are sequentially added into the polymerization kettle, the temperature is raised to 65 ℃, and the reaction is carried out for 58min to form an-IR-SBR-chain segment; then, 691g of styrene and 13.1g of THF are sequentially added into the polymerization kettle, the temperature is raised to 73 ℃, and the reaction is carried out for 50min, so as to form an-IR-SBR-PS-chain segment; and finally, adding 75g of butadiene into the polymerization kettle, carrying out end-capping reaction for 17min, then leading out glue solution, and carrying out wet coagulation and drying to obtain the grafting agent (Mn is 34170, Mw/Mn is 3.14) with the [ -IR-SBR-PS-B- ] n block copolymer.
(2) Preparation of branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 710g of methane chloride, 680g of cyclohexane and 17.6g of [ -IR-SBR-PS-B- ] n grafting agent into a polymerization kettle, and stirring and dissolving for 18min until the grafting agent is completely dissolved; then cooling to-75 ℃, sequentially adding 1230g of methane chloride, 458g of isobutene and 13.5g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-92 ℃, then adding 128g of methane chloride, 3.27g of sesquiethylaluminum chloride and 0.062g of HCl into the polymerization system together for stirring and reacting for 1.8 hours after mixing and aging at-90 ℃, discharging and condensing, washing and drying to obtain the branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 4
(1) Preparation of grafting agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3760g of cyclohexane, 513g of isoprene and 15.1g of THF into the polymerization kettle, heating to 45 ℃, adding 15.8mmo1 n-butyllithium to start reaction, and gradually increasing the reaction temperature from 45 ℃ to 60 ℃ within 65min to form an IR chain segment with wide distribution; then, 5300g of cyclohexane, 535g of styrene, 714g of butadiene and 23.6g of THF are sequentially added into the polymerization kettle, the temperature is raised to 67 ℃, and the reaction is carried out for 60min to form an-IR-SBR-chain segment; then, 705g of styrene and 15.2g of THF are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, and the reaction is carried out for 55min to form an-IR-SBR-PS-chain segment; and finally, adding 83g of butadiene into the polymerization kettle, carrying out end-capping reaction for 19min, then leading out glue solution, and carrying out wet coagulation and drying to obtain the grafting agent (Mn is 37670, Mw/Mn is 3.78) with the [ -IR-SBR-PS-B- ] n block copolymer.
(2) Preparation of branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 680g of methane chloride, 710g of cyclohexane and 21.4g of [ -IR-SBR-PS-B- ] n grafting agent into the polymerization kettle, and stirring and dissolving for 25min until the grafting agent is completely dissolved; then cooling to-81 ℃, adding 1360g of methane chloride, 461g of isobutene and 15.2g of isoprene in sequence, stirring and mixing until the temperature of the polymerization system is reduced to-93 ℃, then adding 132g of methane chloride, 4.16g of sesquiethylaluminum chloride and 0.087g of HCl into the polymerization system for stirring and reacting for 2.1 hours after mixing and aging for 17 minutes under the condition of-92 ℃, discharging, condensing, washing and drying to obtain the branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 5
(1) Preparation of grafting agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3850g of cyclohexane, 557g of isoprene and 17.3g of THF into the polymerization kettle, heating to 45 ℃, adding 17.1mmo1 n-butyllithium to start reaction, and gradually increasing the reaction temperature from 45 ℃ to 60 ℃ within 70min to form an IR chain segment with wide distribution; then 5500g of cyclohexane, 561g of styrene, 746g of butadiene and 27.1g of THF are sequentially added into the polymerization kettle, the temperature is raised to 68 ℃, and the reaction is carried out for 63min to form an-IR-SBR-chain segment; secondly, 749g of styrene and 16.3g of THF are sequentially added into the polymerization kettle, the temperature is raised to 77 ℃, and the reaction is carried out for 57min to form an-IR-SBR-PS-chain segment; and finally, adding 91g of butadiene into the polymerization kettle, carrying out end-capping reaction for 21min, then leading out glue solution, and carrying out wet coagulation and drying to obtain the grafting agent (Mn is 39130, Mw/Mn is 3.95) with the [ -IR-SBR-PS-B- ] n block copolymer.
(2) Preparation of branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 620g of methane chloride, 740g of cyclohexane and 23.6g of [ -IR-SBR-PS-B- ] n grafting agent into the polymerization kettle, and stirring and dissolving for 27min until the grafting agent is completely dissolved; then cooling to-82 ℃, sequentially adding 1410g of methane chloride, 468g of isobutene and 17.1g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then mixing and aging 143g of methane chloride, 5.36g of sesquiethylaluminum chloride and 0.092g of HCl at-93 ℃ for 18min, adding the mixture into the polymerization system, stirring and reacting for 2.5hr, discharging, condensing, washing and drying to obtain the branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 6
(1) Preparation of grafting agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3910g of cyclohexane, 571g of isoprene and 18.3g of THF into the polymerization kettle, heating to 45 ℃, adding 17.6mmo1 n-butyllithium to start reaction, and gradually increasing the reaction temperature from 45 ℃ to 60 ℃ within 75min to form an IR chain segment with wide distribution; then, 5700g of cyclohexane, 573g of styrene, 763g of butadiene and 27.9g of THF are sequentially added into a polymerization kettle, the temperature is raised to 69 ℃, and the reaction is carried out for 65min to form an-IR-SBR-chain segment; then, 773g of styrene and 18.5g of THF are sequentially added into the polymerization kettle, the temperature is raised to 79 ℃, and the reaction is carried out for 59min, so as to form an-IR-SBR-PS-chain segment; and finally, adding 102g of butadiene into the polymerization kettle, carrying out end-capping reaction for 25min, then leading out glue solution, and carrying out wet coagulation and drying to obtain the grafting agent (Mn is 40270, Mw/Mn is 4.01) with the [ -IR-SBR-PS-B- ] n block copolymer.
(2) Preparation of branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 610g of methane chloride, 790g of cyclohexane and 27.1g of [ -IR-SBR-PS-B- ] n grafting agent into the polymerization kettle, and stirring and dissolving for 28min until the grafting agent is completely dissolved; then cooling to-83 ℃, sequentially adding 1470g of methane chloride, 471g of isobutene and 18.5g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-94 ℃, then adding 147g of methane chloride, 6.16g of aluminum sesquiethylate chloride and 0.102g of HCl into the polymerization system for stirring and reacting for 2.7 hours after mixing and aging for 19 minutes under the condition of-94 ℃, discharging and condensing, washing and drying to obtain the branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 7
(1) Preparation of grafting agent: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3980g of cyclohexane, 585g of isoprene and 19.1g of THF into the polymerization kettle, heating to 45 ℃, adding 18.6mmo1 n-butyllithium to start reaction, and gradually increasing the reaction temperature from 45 ℃ to 60 ℃ within 80min to form an IR chain segment with wide distribution; then, 5900g of cyclohexane, 593g of styrene, 781g of butadiene and 29.6g of THF are sequentially added into a polymerization kettle, the temperature is raised to 70 ℃, and the reaction is carried out for 70min to form an-IR-SBR-chain segment; secondly, 783g of styrene and 19.5g of THF are sequentially added into the polymerization kettle, the temperature is raised to 80 ℃, and the reaction is carried out for 70min to form an-IR-SBR-PS-chain segment; and finally, adding 121g of butadiene into the polymerization kettle, carrying out end-capping reaction for 30min, then leading out glue solution, and carrying out wet coagulation and drying to obtain the grafting agent (Mn is 43250 and Mw/Mn is 4.09) with the [ -IR-SBR-PS-B- ] n block copolymer.
(2) Preparation of branched butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 580g of methane chloride, 870g of cyclohexane and 32.1g of [ -IR-SBR-PS-B- ] n grafting agent into a polymerization kettle, and stirring and dissolving for 30min until the grafting agent is completely dissolved; then cooling to-85 ℃, sequentially adding 1490g of methane chloride, 475g of isobutene and 19.7g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing and aging 151g of methane chloride, 7.32g of sesquiethylaluminum chloride and 0.312g of HCl for 20min at-95 ℃, adding the mixture into the polymerization system together, stirring and reacting for 3.0hr, discharging, condensing, washing and drying to obtain the branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 1
(1) Preparation of grafting agent: the other conditions were the same as in example 1 except that: no monomeric isoprene was added, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 3120g of cyclohexane and 11.2g of THF, heating to 45 ℃, adding 10.2mmo1 n-butyllithium, then sequentially adding 4220g of cyclohexane, 450g of styrene, 605g of butadiene and 15.2g of THF, heating to 60 ℃, and starting to react for 50min to form a-SBR-chain segment; then, 615g of styrene and 10.5g of THF are sequentially added into the polymerization kettle, the temperature is raised to 70 ℃, and the reaction is carried out for 40min to form a-SBR-PS-chain segment; finally, 61g of butadiene is added into a polymerization kettle, after end-capping reaction is carried out for 10min, glue solution is led out, and the grafting agent (Mn is 17150, Mw/Mn is 1.14) with the [ SBR-PS-B- ] n segmented copolymer is prepared through wet coagulation and drying.
(2) Preparation of branched butyl rubber: the other conditions were the same as in example 1 except that: during the synthesis process, the [ IR-SBR-PS-B- ] n grafting agent is not added, but the [ SBR-PS-B- ] n grafting agent is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 590g of methane chloride and 10.1g of cyclohexane 410g of [ -SBR-PS-B- ] n grafting agent into the polymerization kettle, and stirring and dissolving for 10min until the grafting agent is completely dissolved; then, when the temperature is reduced to-65 ℃, 1050g of methane chloride, 445g of isobutene and 10.5g of isoprene are sequentially added, stirred and mixed until the temperature of a polymerization system is reduced to-90 ℃, then 105g of methane chloride, 1.37g of sesquiethylaluminum chloride and 0.025g of HCl are mixed and aged for 10min at-85 ℃, added into the polymerization system together and stirred for reaction for 1.0hr, and then the branched butyl rubber product is obtained after discharging, coagulation, washing and drying. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 2
(1) Preparation of grafting agent: the other conditions were the same as in example 2 except that: the IR zone is not polymerized by temperature-variable polymerization, but only at 45 ℃, namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3270g of cyclohexane, 452g of isoprene and 12.6g of THF into the polymerization kettle, heating to 45 ℃, adding 13.2mmo1 n-butyllithium to start reaction for 60min, and forming an IR1 chain segment with narrow distribution; then, 4520g of cyclohexane, 471g of styrene, 634g of butadiene and 18.1g of THF are sequentially added into the polymerization kettle, the temperature is raised to 62 ℃, and the reaction is carried out for 55min to form an-IR-SBR-chain segment; then, 632g of styrene and 12.2g of THF are sequentially added into the polymerization kettle, the temperature is raised to 71 ℃, and the reaction is carried out for 45min to form an-IR-SBR-PS-chain segment; and finally, adding 68g of butadiene into the polymerization kettle, carrying out end-capping reaction for 15min, then leading out glue solution, and carrying out wet condensation and drying to obtain the grafting agent (Mn is 27820, Mw/Mn is 1.52) with the [ -IR1-SBR-PS-B- ] n block copolymer.
(2) Preparation of branched butyl rubber: the other conditions were the same as in example 2 except that: during the synthesis process, the grafting agent of [ -IR-SBR-PS-B- ] n is not added, but [ -IR1-SBR-PS-B- ] n is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 670g of methane chloride, 530g of cyclohexane and 13.8g of [ -IR1-SBR-PS-B- ] n grafting agent into a polymerization kettle, and stirring and dissolving for 15min until the grafting agent is completely dissolved; and then cooling to-70 ℃, sequentially adding 1180g of methane chloride, 451g of isobutene and 11.6g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then mixing and aging 113g of methane chloride, 1.48g of aluminum sesquiethyl chloride and 0.042g of HCl for 12min at-87 ℃, adding the mixture into the polymerization system together, stirring and reacting for 1.3hr, discharging, condensing, washing and drying to obtain the branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 3
Preparation of grafting agent: the other conditions were the same as in example 3 except that: monomer phenethyl ether
Alkene is not added for the second time, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3520g of cyclohexane, 486g of isoprene and 13.7g of THF into the polymerization kettle, heating to 45 ℃, adding 14.1mmo1 n-butyllithium to start reaction, and gradually increasing the reaction temperature from 45 ℃ to 60 ℃ within 65min to form an IR chain segment with wide distribution; then, 4910g of cyclohexane, 513g of styrene, 671g of butadiene and 20.2g of THF are sequentially added into the polymerization kettle, the temperature is raised to 65 ℃, and the reaction is carried out for 58min to form an-IR-SBR-chain segment; and finally, adding 75g of butadiene into the polymerization kettle, carrying out end-capping reaction for 17min, then leading out glue solution, and carrying out wet condensation and drying to obtain the grafting agent (Mn is 31450, Mw/Mn is 2.85) with the [ -IR-SBR-B- ] n segmented copolymer.
(2) Preparation of branched butyl rubber: the other conditions were the same as in example 3 except that: during the synthesis process, the grafting agent of [ -IR-SBR-PS-B- ] n is not added, but the grafting agent of [ -IR-SBR-B- ] n is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 710g of methane chloride, 680g of cyclohexane and 17.6g of [ -IR-SBR-B- ] n grafting agent into the polymerization kettle, and stirring and dissolving for 18min until the grafting agent is completely dissolved; then cooling to-75 ℃, sequentially adding 1230g of methane chloride, 458g of isobutene and 13.5g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-92 ℃, then adding 128g of methane chloride, 3.27g of sesquiethylaluminum chloride and 0.062g of HCl into the polymerization system together for stirring and reacting for 1.8 hours after mixing and aging at-90 ℃, discharging and condensing, washing and drying to obtain the branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 4
(1) Preparation of grafting agent: the other conditions were the same as in example 4 except that: monomeric styrene was not added for the first time, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3760g of cyclohexane, 513g of isoprene and 15.1g of THF into the polymerization kettle, heating to 45 ℃, adding 15.8mmo1 n-butyllithium to start reaction, and gradually increasing the reaction temperature from 45 ℃ to 60 ℃ within 65min to form an IR chain segment with wide distribution; then, 5300g of cyclohexane, 714g of butadiene and 23.6g of THF are sequentially added into a polymerization kettle, the temperature is raised to 67 ℃, and the reaction is carried out for 60min to form an-IR-BR-chain segment; then, 705g of styrene and 15.2g of THF are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, and the reaction is carried out for 55min to form an-IR-BR-PS-chain segment; and finally, adding 83g of butadiene into the polymerization kettle, carrying out end-capping reaction for 19min, then leading out glue solution, and carrying out wet coagulation and drying to obtain the grafting agent (Mn is 35670, Mw/Mn is 3.41) with the copolymer of the [ -IR-BR-PS-B- ] n block structure.
(2) Preparation of branched butyl rubber: the other conditions were the same as in example 4 except that: during the synthesis process, the grafting agent of [ -IR-SBR-PS-B- ] n is not added, but the grafting agent of [ -IR-BR-PS-B- ] n is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 680g of methane chloride, 710g of cyclohexane and 21.4g of [ -IR-BR-PS-B- ] n grafting agent into the polymerization kettle, stirring and dissolving for 25min until the grafting agent is completely dissolved; then cooling to-81 ℃, adding 1360g of methane chloride, 461g of isobutene and 15.2g of isoprene in sequence, stirring and mixing until the temperature of the polymerization system is reduced to-93 ℃, then adding 132g of methane chloride, 4.16g of sesquiethylaluminum chloride and 0.087g of HCl into the polymerization system for stirring and reacting for 2.1 hours after mixing and aging for 17 minutes under the condition of-92 ℃, discharging, condensing, washing and drying to obtain the branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 5
(1) Preparation of grafting agent: the other conditions were the same as in example 5 except that: without the addition of the monomer butadiene, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3850g of cyclohexane, 557g of isoprene and 17.3g of THF into the polymerization kettle, heating to 45 ℃, adding 17.1mmo1 n-butyllithium to start reaction, and gradually increasing the reaction temperature from 45 ℃ to 60 ℃ within 70min to form an IR chain segment with wide distribution; then 5500g of cyclohexane, 561g of styrene and 27.1g of THF are sequentially added into the polymerization kettle, the temperature is raised to 68 ℃, and the reaction is carried out for 63min to form an-IR-PS 1-chain segment; secondly, 749g of styrene and 16.3g of THF are sequentially added into the polymerization kettle, the temperature is raised to 77 ℃, and the reaction is carried out for 57min to form an-IR-PS 1-PS-chain segment; and finally, adding 91g of butadiene into the polymerization kettle, carrying out end-capping reaction for 21min, then leading out glue solution, and carrying out wet coagulation and drying to obtain the grafting agent (Mn is 35870, Mw/Mn is 3.35) with the [ -IR-PS1-PS-B- ] n block copolymer.
(2) Preparation of branched butyl rubber: the other conditions were the same as in example 5 except that: during the synthesis process, the grafting agent of [ -IR-SBR-PS-B- ] n is not added, but the grafting agent of [ -IR-PS1-PS-B- ] n is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 620g of methane chloride, 740g of cyclohexane and 23.6g of [ -IR-PS1-PS-B- ] n grafting agent into a polymerization kettle, and stirring and dissolving for 27min until the grafting agent is completely dissolved; then cooling to-82 ℃, sequentially adding 1410g of methane chloride, 468g of isobutene and 17.1g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then mixing and aging 143g of methane chloride, 5.36g of sesquiethylaluminum chloride and 0.092g of HCl at-93 ℃ for 18min, adding the mixture into the polymerization system, stirring and reacting for 2.5hr, discharging, condensing, washing and drying to obtain the branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 6
(1) Preparation of grafting agent: the same as in example 6.
(2) Preparation of branched butyl rubber: the other conditions were the same as in example 6, except that the amount of the [ IR-SBR-PS-B- ] n grafting agent added during the synthesis was 3.2g, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 610g of methane chloride, 790g of cyclohexane and 3.2g of [ -IR-SBR-PS-B- ] n grafting agent into the polymerization kettle, and stirring and dissolving for 28min until the grafting agent is completely dissolved; then cooling to-83 ℃, sequentially adding 1470g of methane chloride, 471g of isobutene and 18.5g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-94 ℃, then adding 147g of methane chloride, 6.16g of aluminum sesquiethylate chloride and 0.102g of HCl into the polymerization system for stirring and reacting for 2.7 hours after mixing and aging for 19 minutes under the condition of-94 ℃, discharging and condensing, washing and drying to obtain the branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 7
(1) Preparation of grafting agent: the other conditions were the same as in example 7 except that: the amount of non-human monomeric isoprene added was not 585g, but 128g, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3980g of cyclohexane, 128g of isoprene and 19.1g of THF into the polymerization kettle, heating to 45 ℃, adding 18.6mmo1 n-butyllithium to start reaction, and gradually increasing the reaction temperature from 45 ℃ to 60 ℃ within 80min to form a widely distributed IR1 chain segment; then, 5900g of cyclohexane, 593g of styrene, 781g of butadiene and 29.6g of THF are sequentially added into a polymerization kettle, the temperature is raised to 70 ℃, and the reaction is carried out for 70min to form-IR 1-SBR-chain segment; secondly, 783g of styrene and 19.5g of THF are sequentially added into the polymerization kettle, the temperature is raised to 80 ℃, and the reaction is carried out for 70min to form an-IR 1-SBR-PS-chain segment; and finally, adding 121g of butadiene into the polymerization kettle, carrying out end-capping reaction for 30min, then leading out glue solution, and carrying out wet condensation and drying to obtain the grafting agent (Mn is 40320, and Mw/Mn is 3.85) with the [ -IR1-SBR-PS-B- ] n block copolymer.
(2) Preparation of branched butyl rubber: the other conditions were the same as in example 7, except that the grafting agent of [ -IR-SBR-PS-B- ] n was not added during the synthesis, but the grafting agent of [ -IR1-SBR-PS-B- ] n was added, that is: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 580g of methane chloride, 870g of cyclohexane and 32.1g of [ -IR1-SBR-PS-B- ] n grafting agent into a polymerization kettle, and stirring and dissolving for 30min until the grafting agent is completely dissolved; then cooling to-85 ℃, sequentially adding 1490g of methane chloride, 475g of isobutene and 19.7g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then mixing and aging 151g of methane chloride, 7.32g of sesquiethylaluminum chloride and 0.312g of HCl for 20min at-95 ℃, adding the mixture into the polymerization system together, stirring and reacting for 3.0hr, discharging, condensing, washing and drying to obtain the branched butyl rubber product. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
TABLE 1 Properties of branched butyl rubber
As can be seen from Table 1: the branched butyl rubber has high tensile strength, good air tightness, low Mooney relaxation area and good processability (the smaller the area under a stress relaxation curve is, the lower the mixing processing energy consumption is).
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (17)
1. The preparation method of the branched butyl rubber is characterized by comprising the following steps:
(1) preparation of grafting agent: according to the total mass parts of reaction monomers, firstly introducing argon into a reaction kettle with a jacket for replacement for 2-4 times, sequentially adding 100-200% of solvent, 20-30% of isoprene, 0.01-0.1% of structure regulator and initiator into a polymerization kettle, reacting to change temperature and polymerizing, and gradually heating to 50-60 ℃ within 50-80 min; then sequentially adding 200-300% of solvent, 20-30% of styrene, 30-40% of butadiene and 0.05-0.15% of structure regulator into a polymerization kettle, heating to 60-70 ℃, and reacting for 50-70 min; secondly, sequentially adding 30-40% of styrene and 0.05-0.1% of structure regulator into the polymerization kettle, heating to 70-80 ℃, and reacting for 40-70 min, wherein the conversion rate of styrene monomer reaches 100%; finally, adding 3-7% of butadiene into the polymerization kettle for end capping, reacting for 10-30 min until no free monomer exists, and performing wet condensation and drying on the glue solution to prepare a grafting agent;
(2) preparation of branched butyl rubber: according to the total mass parts of reaction monomers, firstly introducing nitrogen into a reaction kettle with a jacket for replacing for 3-5 times, adding 200-300% of a diluent/solvent mixed solvent with the volume ratio of 60-40/40-60 into a polymerization kettle, and stirring and dissolving for 10-30 min, wherein the grafting agent accounts for 2% -7%; then cooling to-65-85 ℃, then sequentially adding 200-300% of diluent, 89-95% of isobutene and 2-4% of isoprene, and stirring and mixing until the temperature of a polymerization system is reduced to-100-90 ℃; and mixing and aging 20-30% of diluent and 0.08-2.0% of co-initiator for 10-20 min at the temperature of-95 to-85 ℃, adding the mixture into a polymerization system, stirring and reacting for 1.0-3.0 hr, discharging, condensing, washing and drying to obtain the branched butyl rubber product.
2. The method of claim 1, wherein the grafting agent is an isoprene, styrene and butadiene block copolymer having the structure [ -IR-SBR-PS-B- ] n, wherein IR is an isoprene homopolymer block, SBR is a styrene and butadiene random copolymer block, PS is a styrene homopolymer block, B is a terminated butadiene, and n is 2 to 3.
3. The method according to claim 2, wherein the [ -IR-SBR-PS-B- ] n block copolymer has a number average molecular weight of 20000 to 50000 and a ratio of weight average molecular weight to number average molecular weight of 2.57 to 4.12.
4. The method of claim 1, wherein the structure-controlling agent is a polar organic compound capable of controlling reactivity ratios of styrene and butadiene in the polymerization system to produce random copolymerization of the styrene and butadiene.
5. The method according to claim 4, 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 5, wherein the structure modifier is tetrahydrofuran.
7. The method of claim 1, wherein the initiator is a hydrocarbon based monolithium compound, wherein the hydrocarbon group is a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a complex thereof.
8. The method of claim 7, wherein the initiator is selected from the group consisting of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, lithium naphthalide, cyclohexyllithium, and dodecyllithium.
9. The method of claim 8 wherein said initiator is n-butyllithium.
10. The method of claim 1 wherein the diluent is a halogenated alkane, wherein the halogen atom in the halogenated alkane is selected from the group consisting of chlorine, bromine, and fluorine; the number of carbon atoms in the halogenated alkane is 1 to 4.
11. The method of claim 10, wherein the diluent is selected from the group consisting of methyl chloride, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, fluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.
12. The method of claim 11, wherein the diluent is methyl chloride.
13. The method according to claim 1, wherein the coinitiator is prepared by compounding an alkyl aluminum halide and a protonic acid in different proportions, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.01: 1-0.1: 1.
14. The method of claim 13 wherein the alkyl aluminum halide is selected from the group consisting of diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloroide, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, n-propylaluminum dichloride, diisopropylaluminum dichloride, dimethylaluminum chloride and ethylaluminum chloride.
15. The method of claim 14 wherein the alkyl aluminum halide is aluminum sesquiethyl chloride.
16. The method of claim 13, wherein the protic acid is selected from the group consisting of HCI, HF, HBr, H2SO4、H2CO3、H3PO4And HNO3One kind of (1).
17. The method of claim 16, wherein the protic acid is HCI.
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| WO2024067013A1 (en) * | 2022-09-26 | 2024-04-04 | 中国石油天然气股份有限公司 | Multi-component copolymer, preparation method therefor, and use thereof, and halogenated branched butyl rubber, preparation method therefor, and use thereof |
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| WO2024066787A1 (en) * | 2022-09-27 | 2024-04-04 | 中国石油天然气股份有限公司 | Halogenated grafting agent and halogenated branched butyl rubber, preparation method therefor, and use thereof |
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