CN113831470A - Preparation method of butyl rubber with medium Mooney viscosity and low saturation - Google Patents

Preparation method of butyl rubber with medium Mooney viscosity and low saturation Download PDF

Info

Publication number
CN113831470A
CN113831470A CN202010589742.8A CN202010589742A CN113831470A CN 113831470 A CN113831470 A CN 113831470A CN 202010589742 A CN202010589742 A CN 202010589742A CN 113831470 A CN113831470 A CN 113831470A
Authority
CN
China
Prior art keywords
butyl rubber
reaction
isoprene
polymerization
nph
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010589742.8A
Other languages
Chinese (zh)
Other versions
CN113831470B (en
Inventor
徐典宏
牛承祥
杨珊珊
赵燕
王在花
李福崇
景丽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Petrochina Co Ltd
Original Assignee
Petrochina Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Petrochina Co Ltd filed Critical Petrochina Co Ltd
Priority to CN202010589742.8A priority Critical patent/CN113831470B/en
Publication of CN113831470A publication Critical patent/CN113831470A/en
Application granted granted Critical
Publication of CN113831470B publication Critical patent/CN113831470B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention relates to a preparation method of butyl rubber with medium Mooney viscosity and low saturation. The invention firstly takes styrene and isoprene as reaction monomers, takes alkyl lithium as an initiator and takes trihalogenated benzene as a coupling agent to couple and prepare the binary three-arm star-shaped copolymer [ -IR-PS-B- ] nPh. Under the complex catalyst system of Lewis acid and protonic acid, the butyl rubber with medium Mooney viscosity and low saturation is prepared by cationic polymerization of [ -IR-PS-B- ] nPh as grafting agent, isobutene and isoprene. According to the invention, the degree of vulcanization is increased and the processing and mixing performance is improved by improving the unsaturation degree and reducing the Mooney viscosity of the butyl rubber, so that the problem of extrusion swelling of the butyl rubber in the processing process is effectively solved, the sufficient green strength of the butyl rubber is maintained, and the balance between the physical and mechanical properties and the processing performance of the butyl rubber is endowed.

Description

Preparation method of butyl rubber with medium Mooney viscosity and low saturation
Technical Field
The invention relates to a preparation method of butyl rubber with medium Mooney viscosity and low saturation, in particular to a method for preparing butyl rubber with medium Mooney viscosity and low saturation by taking a binary three-arm star-shaped copolymer synthesized by isoprene and styrene as a grafting agent and carrying out cationic polymerization with isobutene and isoprene.
Background
It is known that Butyl Rubber (IIR) is produced by the cationic polymerization of isobutylene and a small amount of isoprene. Butyl rubber has been commercialized by Exxon corporation in the 40 th century for over seventy years since now, and has excellent properties such as airtightness, damping properties, thermal aging resistance, ozone resistance, and weather resistance, and thus it is widely used in the fields of manufacturing inner tubes, airtight layers, curing bladders, medical stoppers of tires for vehicles, and the like, and is one of the most important synthetic rubber products.
However, the molecular chain of the butyl rubber is mainly composed of carbon-carbon single bonds, the number of double bonds is small, and the substituent methyl groups are symmetrically arranged, so that the defects of high crystallinity, poor flexibility of the molecular chain, low stress relaxation rate, low vulcanization speed, poor adhesiveness, poor compatibility with other general rubbers and the like exist, and the butyl rubber is easy to excessively flow and deform in the processing process. Therefore, how to balance the physical and mechanical properties and the processability of the butyl rubber becomes a bottleneck for preparing high-performance butyl rubber materials.
In recent years, researchers find that a small amount of double bonds are introduced into a saturated molecular main chain of butyl rubber, so that the vulcanization speed can be increased, the vulcanization degree can be increased, the vulcanization performance of the butyl rubber can be improved, and the swelling phenomenon after an extrusion molding die is reduced; meanwhile, the size stability, the stress at definite elongation and the tensile strength of the rubber compound can be increased, and the compatibility of the butyl rubber and other unsaturated rubbers can be improved. In addition, with the addition of the three-dimensional star-shaped structure grafting agent, the disorder of molecular chain segments of the butyl rubber is increased in the graft polymerization process, the regularity of molecular chains is deteriorated, and the molecular weight distribution is obviously widened, so that the butyl rubber can obtain low Mooney viscosity and good viscoelastic property, the energy consumption in the processing and mixing process can be effectively reduced, and the filler is dispersed more uniformly. Therefore, the development of the butyl rubber with the Mooney viscosity and the low saturation can solve the contradiction between the strength of the butyl rubber and the extrusion swelling in the processing process, and realize the key point of the balance between the physical and mechanical properties and the processing performance of the butyl rubber.
In the prior art, researches on improving the processability of butyl rubber and improving the crude rubber strength are mainly solved by preparing broad molecular weight distribution, bimodal distribution and star-shaped high-branched butyl rubber by a core-arm-first method, an arm-first-core-second method and a core-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; in a second step, a first portion of the butyl rubber slurry is fed to a second loop reactor zone at a temperature of-92 ℃ toAt the temperature of minus 90 ℃, the pressure is 0.1 to 0.2Mpa, and butyl rubber slurry with broad/bimodal molecular weight distribution is finally obtained after polymerization reaction is carried out for 5 to 10 min; 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. CN101353403B discloses a preparation method of star-branched polyisobutylene or butyl rubber, which adopts a polystyrene/isoprene block copolymer with a silicon-chlorine group at the terminal or a polystyrene/butadiene block copolymer with a silicon-chlorine group at the terminal as a grafting initiating agent for positive ion polymerization, directly participates in the positive ion polymerization in a positive ion polymerization system of a mixed solvent with a ratio of methane chloride to cyclohexane v: v of 20-80/80-20 at the temperature of 0-100 ℃, and prepares a star-branched polyisobutylene or butyl rubber product by the participation of an unsaturated chain in a grafting reaction through the initiated positive ion polymerization of the silicon-chlorine group. 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. CN88108392.5 discloses a star-shaped grafted butyl rubber with a comb-shaped structure, which is prepared by using a hydrochloric acid polystyrene-isoprene copolymer as a multifunctional initiator or using polystyrene-butadiene or polystyrene-isoprene as a grafting agent. CN 107793535A provides a butyl rubber having a molecular weight of 90 to 260 ten thousand, Log (MW)>And contains structural units derived from isobutylene, structural units derived from a conjugated diene, and optionally structural units derived from an aryl olefin. US3780002 teaches a process for preparing a metal halide of group II or III of the periodic Table of the elements with a metal of group IV of the periodic Table of the elementsThe tetrahalide constituting a complex initiator, 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 biomodal molecular weight distribution: US, 5194538[ P]1993-3-16.) adopting trimesic acid as raw material to synthesize an initiator, namely tricumyl alcohol, with a three-arm structure, and then adopting a tricumyl alcohol/aluminum trichloride initiation system to initiate the copolymerization of isobutene and isoprene in an inert organic solvent at the temperature of-120 to-50 ℃ to synthesize the star-shaped low-saturation butyl rubber with bimodal molecular weight distribution. Wieland et al (Synthesis of new graft copolymerization polymerization by polymerization of the 1,1-diphenylethylene technology and cationic polymerization [ J]Polymer Science: polymer Chemistry, 2002, 40: 3725-3733.) A multi-arm star-shaped butyl rubber is successfully prepared by synthesizing a macroinitiator P (MMA-b-St-co-CMS) containing the ternary 4-chloromethylstyrene, styrene and methyl methacrylate in the presence of 1, 2-Diphenylethylene (DPE) by a free radical polymerization method, and then initiating cationic polymerization of isobutylene and isoprene by using the macroinitiator. Wubo et al (Davang S H, et al. Skid resistant coatings for air carrier decks [ J ]]Coat Technol, 1980, 52 (671): 65-69.) A poly (isoprene-styrene) block copolymer as a grafting agent is prepared by living anionic polymerization, and starlike low-saturation butyl rubber with obvious double peaks is prepared by active carbon cationic polymerization in an initiating system of 2-chloro-2, 4, 4-trimethylpentane/titanium tetrachloride/proton scavenger.
Disclosure of Invention
The invention aims to provide a preparation method of butyl rubber with medium Mooney viscosity and low saturation. The invention firstly takes styrene and isoprene as reaction monomers, takes alkyl lithium as an initiator and takes trihalogenated benzene as a coupling agent to couple and prepare the binary three-arm star-shaped copolymer [ -IR-PS-B- ] nPh. Under the complex catalyst system of Lewis acid and protonic acid, the butyl rubber with medium Mooney viscosity and low saturation is prepared by cationic polymerization of [ -IR-PS-B- ] nPh as grafting agent, isobutene and isoprene. According to the invention, the degree of vulcanization is increased and the processing and mixing performance is improved by improving the unsaturation degree and reducing the Mooney viscosity of the butyl rubber, so that the problem of extrusion swelling of the butyl rubber in the processing process is effectively solved, the sufficient green strength of the butyl rubber is maintained, and the balance between the physical and mechanical properties and the processing performance of the butyl rubber is endowed.
All the percentages in the present invention are percentages by mass.
The preparation of the low-saturation butyl rubber is carried out in a reaction kettle, and the specific preparation process comprises the following steps:
(1) preparation of grafting agent: firstly, sequentially adding 200-300% of solvent, 60-80% of isoprene and 0.05-0.2% of structure regulator into a polymerization kettle in an inert gas atmosphere, heating to 50-70 ℃, adding an initiator to start reaction, wherein the reaction is variable temperature polymerization, gradually heating from 40 ℃ to 70 ℃ within 50-80 min, and heating to a continuous gradual change process for reacting for 50-80 min to form an IR chain segment with wide molecular weight distribution, wherein the conversion rate of the isoprene monomer reaches 100%; then, sequentially adding 100-200% of solvent, 20-40% of styrene and 0.01-0.1% of structure regulator into a polymerization kettle, heating to 70-80 ℃, and reacting for 60-80 min to form an-IR-PS-chain segment, wherein the conversion rate of a styrene monomer reaches 100%; then adding 2-5% of butadiene into the polymerization kettle for end capping, and reacting for 10-30 min until no free monomer exists; and finally, heating to 80-90 ℃, adding a coupling agent for coupling reaction for 70-90 min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the binary three-arm star-structured copolymer grafting agent [ -IR-PS-B- ] nPh.
(2) Preparation of medium Mooney viscosity, low saturation butyl rubber: according to one hundred percent of the total mass of reaction monomers, firstly, 200 to 300 percent of diluent and solvent are added into a polymerization kettle under the atmosphere of inert gas, wherein the mass ratio of the diluent to the solvent is V: the V ratio is 60-40: 40-60 percent of mixed solvent and nPh 1-7 percent of grafting agent [ -IR-PS-B- ] are stirred and dissolved for 30-50 min until the grafting agent is completely dissolved; and then cooling to-65 to-85 ℃, sequentially adding 100 to 200 percent of diluent, 85 to 95 percent of isobutene and 2 to 5 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 0.05 to 3.0 percent of co-initiator into the polymerization system for stirring and reacting for 2.0 to 5.0 hours after mixing and aging for 20 to 30 minutes at-95 to-85 ℃, discharging and coagulating, washing and drying to obtain the butyl rubber product with medium Mooney viscosity and low saturation.
The grafting agent is a binary three-arm star-shaped copolymer [ -IR-PS-B- ] nPh synthesized from isoprene and styrene, and the structural general formula is shown as formula I:
Figure BDA0002555919030000061
wherein Ph is a benzene ring; IR is an isoprene homopolymer block with wide molecular weight distribution; PS is a styrene homopolymer block; b is terminated butadiene, and n is 1-3; the content of isoprene in the binary three-arm star polymer is 60-80%, and the content of styrene in isoprene is 20-40%; the number average molecular weight (Mn) of the binary three-arm star polymer is 10000-50000, and the molecular weight distribution (Mw/Mn) is 5.23-7.06.
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 coupling agent used in the invention is one of 1,3, 5-trichlorobenzene and 1,3, 5-tribromobenzene, and preferably 1,3, 5-trichlorobenzene. The amount of the coupling agent is determined according to the amount of the initiator, and the molar ratio of the amount of the coupling agent to the organic lithium is 1.0-3.0.
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 being C1～C4. The alkyl halide is selected from one of methyl chloride, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride and fluorobutane, preferably methyl chloride.
The co-initiator is prepared by compounding alkyl aluminum halide and protonic acid according to different proportions. The alkyl aluminum halide is at least one selected from the group consisting of diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloroide, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, n-propylaluminum dichloride, isopropylaluminum dichloroide, dimethylaluminum chloride and ethylaluminum chloride, preferably ethylaluminum sesquichloride. The protonic acid is selected from HCl, HF, HBr, H2SO4、H2CO3、H3PO4And HNO3Of (1), preferably HCl. 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 type of polymerizer used in the present invention is not limited, but a stainless steel polymerizer with a jacket is preferred.
The polymerization reaction of the present invention is carried out in an oxygen-free, water-free, preferably inert gas atmosphere. The polymerization and dissolution are carried out in a hydrocarbon solvent, which is a hydrocarbon solvent including straight-chain alkanes, aromatic hydrocarbons and cycloalkanes, and is selected from one of pentane, hexane, octane, heptane, cyclohexane, benzene, toluene, xylene and ethylbenzene, preferably cyclohexane.
The inert gas is nitrogen or one of all element gases in group 0 of the periodic table of elements, which do not contain radon.
The invention firstly adopts lithium alkyl as an initiator, hydrocarbons as a solvent, organic matters with certain polarity as a structure regulator, reaction monomers comprise isoprene and styrene, the initiator is added into a polymerization system at one time, and then the coupling agent trihalogenated benzene is used for coupling to prepare the copolymer with the high unsaturation degree and the binary three-arm star structure. The [ -IR-PS-B- ] nPh copolymer is used as grafting agent, and isobutylene and isoprene are polymerized by cation in the presence of catalyst system compounded by alkyl aluminum halide and protonic acid to prepare butyl rubber with medium Mooney viscosity and low saturation. The copolymer grafting agent [ -IR-SBR-PS-B- ] nPh with the binary three-arm star structure contains the three-arm star structure, can effectively destroy the regularity of molecular chains in isobutylene and isoprene copolymerization, obviously broaden the molecular weight distribution, effectively reduce the Mooney viscosity of butyl rubber, improve the processing and mixing performance, reduce the energy consumption in the processing and mixing process and obtain excellent processing performance; meanwhile, the IR-chain segment has a certain wide vinyl distribution, so that the flexibility of the chain segment can be improved, the fast stress relaxation rate can be obtained, a small amount of double bonds can be introduced into the saturated molecular main chain of the butyl rubber, the required vulcanization capacity can be provided, the vulcanization degree can be increased, the problem of extrusion swelling of the butyl rubber in the processing process can be solved, and the high product size stability can be obtained; in addition, the PS-chain segment contains a certain amount of benzene rings, and the benzene rings have high rigidity and steric hindrance, so that high strength and air tightness can be obtained, and the influence of strength and air tightness reduction caused by broadening of molecular weight distribution of butyl rubber is compensated.
Therefore, the copolymer of the binary three-arm star structure [ -IR-PS-B- ] nPh organically combines the characteristics of the three-arm star structure and the performances of various chain segments and acts synergistically, not only can the molecular weight distribution of the butyl rubber be widened through the structural change of the grafting agent so as to reduce the Mooney viscosity to obtain better processability, but also the content of-IR-and-PS-in the grafting agent can be adjusted to ensure that the butyl rubber obtains good vulcanization performance, thereby solving the problem of contradiction between poor processability and good physical performance of the butyl rubber, realizing the balance between processability, strength and air tightness of the butyl rubber and more comprehensively improving the performances of the butyl rubber. 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.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
All the raw materials used in the examples are of industrial polymerization grade, and are used after purification without other special requirements.
(1) The raw material sources are as follows:
styrene, butadiene, Polymer grade, Petroleum Lanzhou petrochemical Co Ltd
Isobutene, isoprene, Polymer grade Zhejiang Credit New materials Co Ltd
N-butyl lithium, 98% purity Nanjing Tongtiang chemical Co., Ltd
Aluminum sesquiethylate chloride, 98% pure Profenor technologies Ltd
Chemical Co., Ltd of Yangzhou Haichen with a purity of 99% for 1,3, 5-trichlorobenzene
Other reagents are all commercial products
(2) The analysis and test method comprises the following steps:
determination of the degree of unsaturation: the magnetic field strength was measured at room temperature (25 ℃ C.) using an AVANCE300 nuclear magnetic resonance apparatus from Bruker, a CDC13 solvent and TMS as an internal standard, at a magnetic field strength of 9.20 Tesla.
Determination of Mooney viscosity: the measurement was carried out by using a Mooney viscometer model GT-7080-S2 manufactured by Taiwan high-speed railway.
The Mooney relaxation time, determined with a large rotor at 125 ℃ C (1+8) according to the method of GB/T1232.1-2000, is 120 s.
Determination of vulcanization characteristics: the measurement was carried out by using a rotor-less vulcanizer model GT-M2000A manufactured by Taiwan high-speed railway company according to the method specified in GB/T16584-1996.
Measurement of the extrusion swell ratio: adopting RH2000 type capillary rheometer manufactured by British Marvin company at 100 deg.C, length-diameter ratio of 16:1 and shear rate of 10-1000S-1Is measured within the interval of (1).
Measurement of airtightness: the permeability was determined using an automated air tightness tester according to ISO 2782:1995 with a test gas of N2The test temperature is 23 ℃, and the test sample is a circular sea piece with the diameter of 8cm and the thickness of 1 mm.
300% stress at definite elongation: 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 3 times, sequentially adding 3100g of cyclohexane, 920g of isoprene and 1.3g of THF into the polymerization kettle, heating to 40 ℃, adding 15.5mmo1 n-butyllithium to start reaction, reacting for 50min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 50min, and heating at the speed of 0.6 ℃/min to form an IR chain segment with wide molecular weight distribution; then, 1540g of cyclohexane, 320g of styrene and 0.7g of THF are sequentially added into the polymerization kettle, the temperature is raised to 70 ℃, and the reaction is carried out for 60min to form an-IR-PS-chain segment; then adding 31g of butadiene into the polymerization kettle, and carrying out end capping reaction for 10min to form a random block-IR-PS-B-chain segment; and finally, heating to 80 ℃, adding 16.5mmo 11, 3, 5-trichlorobenzene, reacting for 70min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the binary three-arm star-structured copolymer grafting agent [ -IR-PS-B- ] nPh (Mn is 11560, Mw/Mn is 5.31).
(2) Preparation of medium Mooney viscosity, low saturation 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, 450g of cyclohexane and 10.2g of [ -IR-PS-B- ] nPh grafting agent into the polymerization kettle, and stirring and dissolving for 30min until the grafting agent is completely dissolved; and then cooling to-65 ℃, sequentially adding 430g of methane chloride, 256g of isobutene and 5.5g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then adding 75g of methane chloride, 1.21g of sesquiethylaluminum chloride and 0.021g of HCl into the polymerization system for stirring and aging for 20min at-85 ℃, stirring and reacting for 2.0hr, discharging, condensing, washing and drying to obtain the butyl rubber product with medium Mooney viscosity and low saturation. 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 gas into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3200g of cyclohexane, 940g of isoprene and 1.4g of THF into the polymerization kettle, heating to 40 ℃, adding 16.8mmo1 n-butyllithium to start reaction for 60min, reacting for 60min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 60min, and heating at the speed of 0.5 ℃/min to form an IR chain segment with wide molecular weight distribution; then, 1730g of cyclohexane, 370g of styrene and 0.9g of THF are sequentially added into the polymerization kettle, the temperature is raised to 70 ℃, and the reaction is carried out for 65min to form an-IR-PS-chain segment; then adding 35g of butadiene into the polymerization kettle, and carrying out end capping reaction for 15min to form a random block-IR-PS-B-chain segment; and finally, heating to 82 ℃, adding 20.5mmo 11, 3, 5-trichlorobenzene, reacting for 75min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the binary three-arm star-structured copolymer grafting agent [ -IR-PS-B- ] nPh (Mn is 23560, Mw/Mn is 5.76).
(2) Preparation of medium Mooney viscosity, low saturation butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 560g of methane chloride, 480g of cyclohexane and 13.5g of [ -IR-PS-B- ] nPh grafting agent into the polymerization kettle, stirring and dissolving for 33min until the grafting agent is completely dissolved; and then cooling to-70 ℃, sequentially adding 450g of methane chloride, 265g of isobutene and 7.8g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-92 ℃, then adding 80g of methane chloride, 1.41g of aluminum sesquiethylate chloride and 0.034g of HCl into the polymerization system for stirring and reacting for 3.0 hours after mixing and aging for 23 minutes under the condition of-87 ℃, discharging, condensing, washing and drying to obtain a butyl rubber product with medium Mooney viscosity and low saturation. 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 3300g of cyclohexane, 970g of isoprene and 1.7g of THF into the polymerization kettle, heating to 40 ℃, adding 18.5mmo1 n-butyllithium to start reaction for 60min, reacting for 60min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 60min, and heating at the speed of 0.5 ℃/min to form an IR chain segment with wide molecular weight distribution; then, 1780g of cyclohexane, 390g of styrene and 1.1g of THF are sequentially added into a polymerization kettle, the temperature is raised to 70 ℃, and the reaction is carried out for 70min, so as to form an-IR-PS-chain segment; then adding 40g of butadiene into the polymerization kettle, and carrying out end capping reaction for 18min to form a random block-IR-PS-B-chain segment; and finally, heating to 85 ℃, adding 29.5 mmols 11, 3, 5-trichlorobenzene, reacting for 80min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the binary three-arm star-structured copolymer grafting agent [ -IR-PS-B- ] nPh (the Mn is 36520, and the Mw/Mn is 5.92).
(2) Preparation of medium Mooney viscosity, low saturation butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 530g of methane chloride, 510g of cyclohexane and 17.5g of [ -IR-PS-B- ] nPh grafting agent into the polymerization kettle, stirring and dissolving for 37min until the grafting agent is completely dissolved; and then cooling to-75 ℃, sequentially adding 460g of methane chloride, 272g of isobutene and 8.2g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then adding 85g of methane chloride, 1.53g of sesquiethylaluminum chloride and 0.041g of HCl into the polymerization system for stirring and reacting for 3.5 hours after mixing and aging for 27 minutes, discharging, condensing, washing and drying to obtain a butyl rubber product with medium Mooney viscosity and low saturation. 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 3500g of cyclohexane, 1030g of isoprene and 1.9g of THF into the polymerization kettle, heating to 40 ℃, adding 18.5mmo1 n-butyllithium to start reaction for 70min, gradually heating from 40 ℃ to 70 ℃ within 70min, and heating at a speed of 0.5 ℃/min to form an IR chain segment with wide molecular weight distribution; then, 1800g of cyclohexane, 430g of styrene and 1.3g of THF are sequentially added into a polymerization kettle, the temperature is raised to 75 ℃, and the reaction is carried out for 72min to form an-IR-PS-chain segment; then adding 45g of butadiene into the polymerization kettle, and carrying out end capping reaction for 20min to form a random block-IR-PS-B-chain segment; and finally, heating to 85 ℃, adding 36.5mmo 11, 3, 5-trichlorobenzene, reacting for 82min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the binary three-arm star-structured copolymer grafting agent [ -IR-PS-B- ] nPh (the Mn is 39820 and the Mw/Mn is 6.23).
(2) Preparation of medium Mooney viscosity, low saturation butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 500g of methane chloride, 530g of cyclohexane and 20.5g of [ -IR-PS-B- ] nPh grafting agent into the polymerization kettle, and stirring and dissolving for 40min until the grafting agent is completely dissolved; then cooling to-75 ℃, sequentially adding 480g of methane chloride, 278g of isobutene and 9.3g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then adding 88g of methane chloride, 1.74g of sesquiethylaluminum chloride and 0.045g of HCl into the polymerization system for stirring and aging for 26min under the condition of-87 ℃, stirring and reacting for 4.0hr, discharging, condensing, washing and drying to obtain a butyl rubber product with medium Mooney viscosity and low saturation. 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 3600g of cyclohexane, 1060g of isoprene and 2.1g of THF into the polymerization kettle, heating to 40 ℃, adding 20.5mmo1 n-butyllithium to start reaction for 70min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 70min, and heating at the speed of 0.5 ℃/min to form an IR chain segment with wide molecular weight distribution; then 1870g cyclohexane, 450g styrene and 1.5g THF are sequentially added into the polymerization kettle, the temperature is raised to 75 ℃, and the reaction is carried out for 72min, so as to form an-IR-PS-chain segment; then adding 48g of butadiene into the polymerization kettle, and carrying out end capping reaction for 23min to form a random block-IR-PS-B-chain segment; and finally, heating to 87 ℃, adding 46.5mmo 11, 3, 5-trichlorobenzene, reacting for 85min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the binary three-arm star-structured copolymer grafting agent [ -IR-PS-B- ] nPh (the Mn is 42320, and the Mw/Mn is 6.59).
(2) Preparation of medium Mooney viscosity, low saturation butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 480g of methane chloride, 550g of cyclohexane and 23.5g of [ -IR-PS-B- ] nPh grafting agent into the polymerization kettle, and stirring and dissolving for 45min until the grafting agent is completely dissolved; and then cooling to-77 ℃, sequentially adding 500g of methyl chloride, 280g of isobutene and 10.5g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then adding 90g of methyl chloride, 1.81g of sesquiethylaluminum chloride and 0.051g of HCl into the polymerization system for stirring and reacting for 4.2 hours after mixing and aging for 25 minutes, discharging, condensing, washing and drying to obtain the butyl rubber product with medium Mooney viscosity and low saturation. 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 3700g of cyclohexane, 1100g of isoprene and 2.3g of THF into the polymerization kettle, heating to 40 ℃, adding 22.5mmo1 n-butyllithium to start reaction for 80min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 80min, and heating at a speed of 0.4 ℃/min to form an IR chain segment with wide molecular weight distribution; then 1900g of cyclohexane, 470g of styrene and 1.7g of THF are sequentially added into the polymerization kettle, the temperature is raised to 77 ℃, and the reaction is carried out for 75min to form an-IR-PS-chain segment; then adding 50g of butadiene into the polymerization kettle, and carrying out end capping reaction for 25min to form a random block-IR-PS-B-chain segment; and finally, heating to 87 ℃, adding 50.5mmo 11, 3, 5-trichlorobenzene, reacting for 87min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the binary three-arm star-structured copolymer grafting agent [ -IR-PS-B- ] nPh (Mn is 47260, Mw/Mn is 6.78).
(2) Preparation of medium Mooney viscosity, low saturation butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 450g of methane chloride, 550g of cyclohexane and 25.5g of [ -IR-PS-B- ] nPh grafting agent into the polymerization kettle, and stirring and dissolving for 48min until the grafting agent is completely dissolved; then cooling to-80 ℃, sequentially adding 510g of methyl chloride, 283g of isobutene and 12.5g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then adding 93g of methyl chloride, 1.89g of sesquiethylaluminum chloride and 0.065g of HCl into the polymerization system for stirring and reacting for 4.5 hours after mixing and aging for 27 minutes, discharging, condensing, washing and drying to obtain a butyl rubber product with medium Mooney viscosity and low saturation. 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 3900g of cyclohexane, 1200g of isoprene and 2.5g of THF into the polymerization kettle, heating to 40 ℃, adding 24.5mmo1 n-butyllithium to start reaction for 80min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 80min, and heating at a speed of 0.4 ℃/min to form an IR chain segment with wide molecular weight distribution; then adding 1950g of cyclohexane, 500g of styrene and 1.9g of THF into the polymerization kettle in sequence, heating to 80 ℃, and reacting for 80min to form an-IR-PS-chain segment; then adding 60g of butadiene into the polymerization kettle, and carrying out end capping reaction for 30min to form a random block-IR-PS-B-chain segment; and finally, heating to 90 ℃, adding 67.5mmo 11, 3, 5-trichlorobenzene, reacting for 90min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the binary three-arm star-structured copolymer grafting agent [ -IR-PS-B- ] nPh (Mn is 49660 and Mw/Mn is 7.02).
(2) Preparation of medium Mooney viscosity, low saturation butyl rubber: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 415g of methane chloride, 580g of cyclohexane and 28.0g of [ -IR-PS-B- ] nPh grafting agent into the polymerization kettle, stirring and dissolving for 50min until the grafting agent is completely dissolved; and then cooling to-85 ℃, sequentially adding 530g of methane chloride, 284g of isobutene and 14.5g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then adding 100g of methane chloride, 2.15g of sesquiethylaluminum chloride and 0.109g of HCl into the polymerization system for stirring and reacting for 5.0 hours after mixing and aging for 30 minutes, discharging, condensing, washing and drying to obtain the butyl rubber product with medium Mooney viscosity and low saturation. 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 same as in example 1.
(2) Preparation of medium Mooney viscosity, low saturation butyl rubber: the other conditions were the same as in example 1, except that the amount of the grafting agent [ -IR-PS-B- ] nPh added during the synthesis was 2.5g, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 590g of methane chloride, 450g of cyclohexane and 2.5g of [ -IR-PS-B- ] nPh grafting agent into the polymerization kettle, and stirring and dissolving for 30min until the grafting agent is completely dissolved; and then cooling to-65 ℃, sequentially adding 430g of methane chloride, 256g of isobutene and 5.5g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-90 ℃, then adding 75g of methane chloride, 1.21g of sesquiethylaluminum chloride and 0.021g of HCl into the polymerization system for stirring and aging for 20min at-85 ℃, stirring and reacting for 2.0hr, discharging, condensing, washing and drying to obtain the butyl rubber product with medium Mooney viscosity and low saturation. 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: without the addition of monomeric styrene, no-PS-segment could be formed, i.e.: firstly, introducing argon gas into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3200g of cyclohexane, 940g of isoprene and 1.4g of THF into the polymerization kettle, heating to 40 ℃, adding 16.8mmo1 n-butyllithium to start reaction for 60min, reacting for 60min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 60min, and heating at the speed of 0.5 ℃/min to form an IR chain segment with wide molecular weight distribution; then 1730g of cyclohexane and 0.9g of THF are sequentially added into the polymerization kettle, the temperature is raised to 70 ℃, and the reaction is carried out for 65 min; then adding 35g of butadiene into the polymerization kettle, and carrying out end capping reaction for 15min to form a random block-IR-B-chain segment; and finally, heating to 82 ℃, adding 20.5mmo 11, 3, 5-trichlorobenzene, reacting for 75min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the binary three-arm star-structured copolymer grafting agent of [ IR-B- ] nPh (Mn is 15160, Mw/Mn is 3.86).
(2) Preparation of medium Mooney viscosity, low saturation butyl rubber: the other conditions were the same as in example 2 except that: the grafting agent [ -IR-PS-B- ] nPh is not added in the synthesis process, but the grafting agent [ -IR-B- ] nPh is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 560g of methane chloride and 13.5g of cyclohexane and 13.5g of [ -IR-B- ] nPh grafting agent into the polymerization kettle, stirring and dissolving for 33min until the grafting agent is completely dissolved; and then cooling to-70 ℃, sequentially adding 450g of methane chloride, 265g of isobutene and 7.8g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-92 ℃, then adding 80g of methane chloride, 1.41g of aluminum sesquiethylate chloride and 0.034g of HCl into the polymerization system for stirring and reacting for 3.0 hours after mixing and aging for 23 minutes under the condition of-87 ℃, discharging, condensing, washing and drying to obtain the butyl rubber product with medium Mooney viscosity and low saturation. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 3
(1) Preparation of grafting agent: the other conditions were the same as in example 3 except that: without addition of monomeric isoprene, no-IR-segment is formed, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3300g of cyclohexane and 1.7g of THF into the polymerization kettle, heating to 40 ℃, adding 18.5mmo1 n-butyllithium to start reaction for 60min, reacting for 60min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 60min, and heating at the speed of 0.5 ℃/min; then, 1780g of cyclohexane, 390g of styrene and 1.1g of THF are sequentially added into the polymerization kettle, the temperature is raised to 70 ℃, and the reaction is carried out for 70min, so as to form a-PS-chain segment; then adding 40g of butadiene into the polymerization kettle, and carrying out end capping reaction for 18min to form a random block-IR-PS-B-chain segment; and finally, heating to 85 ℃, adding 29.5 mmols 11, 3, 5-trichlorobenzene, reacting for 80min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the binary three-arm star-structured copolymer grafting agent [ -PS-B- ] nPh (Mn is 20100 and Mw/Mn is 2.92).
(2) Preparation of medium Mooney viscosity, low saturation butyl rubber: the other conditions were the same as in example 3 except that: in the synthesis process, a grafting agent [ -IR-PS-B- ] nPh is not added, but a grafting agent [ -PS-B- ] nPh is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 530g of methane chloride, 510g of cyclohexane and 17.5g of [ -PS-B- ] nPh grafting agent into the polymerization kettle, stirring and dissolving for 37min until the grafting agent is completely dissolved; and then cooling to-75 ℃, sequentially adding 460g of methane chloride, 272g of isobutene and 8.2g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then adding 85g of methane chloride, 1.53g of sesquiethylaluminum chloride and 0.041g of HCl into the polymerization system for stirring and reacting for 3.5 hours after mixing and aging for 27 minutes, discharging, condensing, washing and drying to obtain the butyl rubber product with medium Mooney viscosity and low saturation. 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: the polymerization process of the grafting agent does not adopt temperature-variable polymerization, and the monomer isoprene reacts only under the constant temperature condition of 40 ℃, namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 3500g of cyclohexane, 1030g of isoprene and 1.9g of THF into the polymerization kettle in sequence, heating to 40 ℃, adding 18.5mmo1 n-butyllithium to start reaction, and reacting for 70min to form IR1A chain segment; then, 1800g of cyclohexane, 430g of styrene and 1.3g of THF are sequentially added into the polymerization kettle, the temperature is raised to 75 ℃, and the reaction is carried out for 72min to form-IR1-a PS-segment; then is further polymerizedAdding 45g of butadiene into the synthesis kettle, and carrying out end capping reaction for 20min to form a random block-IR-PS-B-chain segment; finally heating to 85 ℃, adding 36.5mmo 11, 3, 5-trichlorobenzene, reacting for 82min, treating the coupled reaction mixture with water after the reaction is finished, and carrying out wet coagulation and drying on the glue solution to obtain the binary three-arm star-structure copolymer grafting agent [ -IR1-PS-B-]nPh (Mn 36750, Mw/Mn 3.21).
(2) Preparation of medium Mooney viscosity, low saturation butyl rubber: the other conditions were the same as in example 4 except that: no grafting agent [ -IR-PS-B-]nPh, but a grafting agent [ -IR ] is added1-PS-B-]nPh, namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced for 3 times for replacement, and 500g of methane chloride, 530g of cyclohexane and [ -IR ] are added into a polymerization kettle1-PS-B-]nPh g grafting agent, stirring and dissolving for 40min until the grafting agent is completely dissolved; then cooling to-75 ℃, sequentially adding 480g of methane chloride, 278g of isobutene and 9.3g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then adding 88g of methane chloride, 1.74g of sesquiethylaluminum chloride and 0.045g of HCl into the polymerization system for stirring and aging for 26min under the condition of-87 ℃, stirring and reacting for 4.0hr, discharging, condensing, washing and drying to obtain a butyl rubber product with medium Mooney viscosity and low saturation. 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: in the synthesis process, no coupling agent 1,3, 5-trichlorobenzene is added, namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3600g of cyclohexane, 1060g of isoprene and 2.1g of THF into the polymerization kettle, heating to 40 ℃, adding 20.5mmo1 n-butyllithium to start reaction for 70min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 70min, and heating at the speed of 0.5 ℃/min to form an IR chain segment with wide molecular weight distribution; then 1870g cyclohexane, 450g styrene and 1.5g THF are sequentially added into the polymerization kettle, the temperature is raised to 75 ℃, and the reaction is carried out for 72min, so as to form an-IR-PS-chain segment; then adding 48g of butadiene into the polymerization kettle, and carrying out end capping reaction for 23min to form a random block-IR-PS-B-chain segment; and (3) coagulating and drying the glue solution by a wet method to prepare a binary-structure random block copolymer grafting agent [ -IR-PS-B- ] n (Mn is 31250, Mw/Mn is 1.89).
(2) Preparation of medium Mooney viscosity, low saturation butyl rubber: the other conditions were the same as in example 5 except that: in the synthesis process, a grafting agent [ -IR-PS-B- ] nPh is not added, but a grafting agent [ -IR-PS-B- ] n is added, namely: firstly, introducing nitrogen into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, adding 480g of methane chloride, 550g of cyclohexane and 23.5g of [ -IR-PS-B- ] n grafting agent into the polymerization kettle, and stirring and dissolving for 45min until the grafting agent is completely dissolved; and then cooling to-77 ℃, sequentially adding 500g of methyl chloride, 280g of isobutene and 10.5g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-93 ℃, then adding 90g of methyl chloride, 1.81g of sesquiethylaluminum chloride and 0.051g of HCl into the polymerization system for stirring and reacting for 4.2 hours after mixing and aging for 25 minutes under the condition of-87 ℃, discharging, condensing, washing and drying to obtain the butyl rubber product with medium Mooney viscosity and low saturation. 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 other conditions were the same as in example 6 except that: the amount of monomeric isoprene added was 300g, i.e.: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3700g of cyclohexane, 300g of isoprene and 2.3g of THF into the polymerization kettle, heating to 40 ℃, adding 22.5mmo1 n-butyllithium to start reaction for 80min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 80min, and heating at the speed of 0.4 ℃/min to form IR with wide molecular weight distribution2A chain segment; then 1900g of cyclohexane, 470g of styrene and 1.7g of THF are sequentially added into the polymerization kettle, the temperature is raised to 77 ℃, and the reaction is carried out for 75min to form an-IR-PS-chain segment; then 50g of butadiene was added to the polymerization vessel, and after termination reaction for 25min, random block-formed-IR was obtained2-a PS-B-segment; finally, the temperature is raised to 87 ℃, 50.5mmo 11, 3, 5-trichlorobenzene is added for reaction for 87min, the reaction mixture after coupling is treated by water after the reaction is finished, and the glue solution is coagulated and dried by a wet method to prepare the binary three-arm star-shapedStructural copolymer grafting agent [ -IR2-PS-B-]nPh (Mn 41300, Mw/Mn 5.52).
(2) Preparation of medium Mooney viscosity, low saturation butyl rubber: the other conditions were the same as in example 6 except that: no grafting agent [ -IR-PS-B-]nPh, but a grafting agent [ -IR ] is added2-PS-B-]nPh, namely: firstly, nitrogen gas is introduced into a 4L stainless steel reaction kettle with a jacket for replacement for 3 times, and 450g of methane chloride, 550g of cyclohexane and [ -IR ] are added into a polymerization kettle2-PS-B-]nPh grafting agent 25.5g, stirring to dissolve for 48min until the grafting agent is completely dissolved; then cooling to-80 ℃, sequentially adding 510g of methyl chloride, 283g of isobutene and 12.5g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then adding 93g of methyl chloride, 1.89g of sesquiethylaluminum chloride and 0.065g of HCl into the polymerization system for stirring and reacting for 4.5 hours after mixing and aging for 27 minutes, discharging, condensing, washing and drying to obtain a butyl rubber product with medium Mooney viscosity and low saturation. 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: 1, 3-benzene dichloride is added instead of 1,3, 5-benzene trichloride in the synthesis process, namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 3900g of cyclohexane, 1200g of isoprene and 2.5g of THF into the polymerization kettle, heating to 40 ℃, adding 24.5mmo1 n-butyllithium to start reaction for 80min, gradually increasing the temperature from 40 ℃ to 70 ℃ within 80min, and heating at a speed of 0.4 ℃/min to form an IR chain segment with wide molecular weight distribution; then adding 1950g of cyclohexane, 500g of styrene and 1.9g of THF into the polymerization kettle in sequence, heating to 80 ℃, and reacting for 80min to form an-IR-PS-chain segment; then adding 60g of butadiene into the polymerization kettle, and carrying out end capping reaction for 30min to form a random block-IR-PS-B-chain segment; finally heating to 90 ℃, adding 67.5mmo 11, 3-benzene dichloride, reacting for 90min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on the glue solution to obtain the binary two-arm star-structured copolymer grafting agent [ -IR-PS-B-]nPh1(Mn of 45120, Mw/Mn of 3.92).
(2) Preparation of medium Mooney viscosity, low saturation butyl rubber: the other conditions were the same as in example 7 except that: no grafting agent [ -IR-PS-B-]nPh, but the grafting agent [ -IR-PS-B-]nPh1Namely: firstly, in a 4L stainless steel reaction kettle with a jacket, nitrogen is introduced for 3 times for replacement, 415g of monochloromethane, 580g of cyclohexane, [ -IR-PS-B-]nPh128.0g of grafting agent is stirred and dissolved for 50min until the grafting agent is completely dissolved; and then cooling to-85 ℃, sequentially adding 530g of methane chloride, 284g of isobutene and 14.5g of isoprene, stirring and mixing until the temperature of a polymerization system is reduced to-95 ℃, then adding 100g of methane chloride, 2.15g of sesquiethylaluminum chloride and 0.109g of HCl into the polymerization system for stirring and reacting for 5.0 hours after mixing and aging for 30 minutes, discharging, condensing, washing and drying to obtain the butyl rubber product with medium Mooney viscosity and low saturation. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
TABLE 1 Properties of Mooney viscosity, low saturation butyl rubber
Figure BDA0002555919030000211
Figure BDA0002555919030000221
As can be seen from Table 1: the medium Mooney viscosity and low saturation butyl rubber has lower Mooney viscosity and higher unsaturation degree and has higher scorching time (T)10) Long, positive cure time (T)90) Short, and shows good vulcanization characteristic and mixing processability; meanwhile, the rubber has good air tightness, low extrusion swelling ratio and high 300% stress at definite elongation, which shows that the butyl rubber with medium Mooney viscosity and low saturation shows good vulcanization characteristic and mixing processability while maintaining excellent physical and mechanical properties.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.

Claims (10)

1. The preparation method of the butyl rubber with medium Mooney viscosity and low saturation is characterized by comprising the following steps:
firstly, styrene and isoprene are taken as reaction monomers, alkyl lithium is taken as an initiator, and trihalogenated benzene is taken as a coupling agent to couple to prepare a binary three-arm star-structured copolymer [ -IR-PS-B- ] nPh;
then, under a catalyst system compounded by Lewis acid and protonic acid, taking the binary three-arm star-shaped copolymer [ -IR-PS-B- ] nPh as a grafting agent to carry out cationic polymerization with isobutene and isoprene to prepare the butyl rubber with medium Mooney viscosity and low saturation;
the number average molecular weight of the binary three-arm star-structure copolymer [ -IR-PS-B- ] nPh is 10000-50000, and the ratio of the weight average molecular weight to the number average molecular weight is 5.23-7.06; the content of isoprene in the binary three-arm star-structure copolymer [ -IR-PS-B- ] nPh is 60% -80%, and the content of styrene is 20% -40%; wherein Ph is a benzene ring; IR is an isoprene homopolymer block with wide molecular weight distribution; PS is a styrene homopolymer block; b is terminated butadiene, n is 1-3, and the general formula is as follows:
Figure FDA0002555919020000011
2. the method according to claim 1, wherein the binary three-arm star-structured copolymer [ -IR-PS-B- ] n is prepared by the following steps:
according to the total mass percentage of reaction monomers, firstly, under the atmosphere of inert gas, sequentially adding 200-300% of solvent, 60-80% of isoprene and 0.05-0.2% of structure regulator into a polymerization kettle, heating to 50-70 ℃, adding an initiator to start reaction, wherein the reaction is variable temperature polymerization, the temperature is gradually increased from 40 ℃ to 70 ℃ within 50-80 min, the temperature rise is a continuous gradual change process, and the reaction is carried out for 50-80 min to form an IR chain segment with wide molecular weight distribution; then, sequentially adding 100-200% of solvent, 20-40% of styrene and 0.01-0.1% of structure regulator into a polymerization kettle, heating to 70-80 ℃, and reacting for 60-80 min to form an-IR-PS-chain segment; then adding 2-5% of butadiene into the polymerization kettle for end capping, and reacting until no free monomer exists; and finally, heating to 80-90 ℃, adding a coupling agent for coupling reaction for 70-90 min, treating the coupled reaction mixture with water after the reaction is finished, and performing wet coagulation and drying on a glue solution to obtain the binary three-arm star-structured copolymer [ -IR-PS-B- ] nPh.
3. The method of claim 1, wherein said medium mooney viscosity, low saturation butyl rubber is prepared by the following steps:
according to the total mass percentage of reaction monomers, firstly, 200-300 percent of diluent and solvent are added into a polymerization kettle in an inert gas atmosphere, and the volume ratio of the diluent to the solvent is 60-40: 40-60 percent of mixed solvent, wherein 1-7 percent of binary three-arm star-structure copolymer [ -IR-PS-B- ] nPh 1-7 percent is stirred and dissolved for 30-50 min until the grafting agent is completely dissolved; and then cooling to-65 to-85 ℃, sequentially adding 100 to 200 percent of diluent, 85 to 95 percent of isobutene and 2 to 5 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 0.05 to 3.0 percent of co-initiator into the polymerization system for stirring and reacting for 2.0 to 5.0 hours after mixing and aging for 20 to 30 minutes at-95 to-85 ℃, discharging and coagulating, washing and drying to obtain the butyl rubber product with medium Mooney viscosity and low saturation.
4. The method of claim 2, 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.
5. The method of claim 2, wherein the initiator is selected from the group consisting of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, lithium naphthalide, cyclohexyllithium, and dodecyllithium.
6. The method of claim 2, wherein the coupling agent is one of 1,3, 5-trichlorobenzene and 1,3, 5-tribromobenzene, and the molar ratio of the coupling agent to the initiator is 1.0-3.0.
7. The method of claim 3, wherein the diluent is one of methyl chloride, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloropropane, heptachloropropane, monofluoromethane, difluoromethane, tetrafluoroethane, carbon hexafluoride, and fluorobutane.
8. The method according to claim 3, wherein the co-initiator is a combination of an alkyl aluminum halide and a protonic acid, and the molar ratio of the protonic acid to the alkyl aluminum halide is 0.01:1 to 0.1: 1.
9. The method of claim 8, wherein the alkyl aluminum halide is selected from at least one of diethylaluminum monochloride, diisobutylaluminum monochloride, methylaluminum dichloroide, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, n-propylaluminum dichloride, diisopropylaluminum dichloride, dimethylaluminum chloride and ethylaluminum chloride.
10. The method of claim 8, wherein the protic acid is selected from the group consisting of HCl, HF, HBr, H2SO4、H2CO3、H3PO4Or HNO3One kind of (1).
CN202010589742.8A 2020-06-24 2020-06-24 Preparation method of middle-Mooney viscosity and low-saturation butyl rubber Active CN113831470B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010589742.8A CN113831470B (en) 2020-06-24 2020-06-24 Preparation method of middle-Mooney viscosity and low-saturation butyl rubber

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010589742.8A CN113831470B (en) 2020-06-24 2020-06-24 Preparation method of middle-Mooney viscosity and low-saturation butyl rubber

Publications (2)

Publication Number Publication Date
CN113831470A true CN113831470A (en) 2021-12-24
CN113831470B CN113831470B (en) 2023-08-22

Family

ID=78964715

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010589742.8A Active CN113831470B (en) 2020-06-24 2020-06-24 Preparation method of middle-Mooney viscosity and low-saturation butyl rubber

Country Status (1)

Country Link
CN (1) CN113831470B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024066778A1 (en) * 2022-09-26 2024-04-04 中国石油天然气集团有限公司 Multicomponent copolymer, preparation method therefor, and use thereof, and halogenated branched butyl rubber, preparation method therefor, and use thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040127645A1 (en) * 2002-12-12 2004-07-01 Korea Kumho Petrochemical Co., Ltd. Radial copolymer prepared from mixed coupling agent
CN103160056A (en) * 2011-12-15 2013-06-19 中国石油天然气股份有限公司 Preparation method for high performance butadiene-styrene-isoprene powder polymer
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040127645A1 (en) * 2002-12-12 2004-07-01 Korea Kumho Petrochemical Co., Ltd. Radial copolymer prepared from mixed coupling agent
CN103160056A (en) * 2011-12-15 2013-06-19 中国石油天然气股份有限公司 Preparation method for high performance butadiene-styrene-isoprene powder polymer
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024066778A1 (en) * 2022-09-26 2024-04-04 中国石油天然气集团有限公司 Multicomponent copolymer, preparation method therefor, and use thereof, and halogenated branched butyl rubber, preparation method therefor, and use thereof

Also Published As

Publication number Publication date
CN113831470B (en) 2023-08-22

Similar Documents

Publication Publication Date Title
CN113493548B (en) Preparation method of branched butyl rubber
CN113831470B (en) Preparation method of middle-Mooney viscosity and low-saturation butyl rubber
CN113831458B (en) Preparation method of middle-Mooney viscosity and low-saturation butyl rubber
CN113831474B (en) Preparation method of hyperbranched wide-distribution butyl rubber
CN113493549B (en) Preparation method of high-width distribution and high-branching butyl rubber
CN113831476B (en) Preparation method of low-saturation butyl rubber
CN113831469B (en) Preparation method of hyperbranched butyl rubber
CN113831477B (en) Preparation method of low-Mooney-viscosity low-saturation butyl rubber
CN113831473B (en) Preparation method of ultra-wide molecular weight distribution and hyperbranched butyl rubber
CN113493546B (en) Preparation method of butyl rubber with wide molecular weight distribution
CN113831475B (en) Preparation method of low-saturation butyl rubber
CN113831471B (en) Preparation method of low-Mooney-viscosity low-saturation butyl rubber
CN113831466B (en) Preparation method of hyperbranched ultra-wide molecular weight distribution butyl rubber
CN113493551B (en) Preparation method of branched butyl rubber
CN113831467B (en) Preparation method of hyperbranched wide-distribution butyl rubber
CN113831472B (en) Preparation method of ultra-wide molecular weight distribution and hyperbranched butyl rubber
CN113831468B (en) Preparation method of hyperbranched ultra-wide molecular weight distribution butyl rubber
CN113493552B (en) Preparation method of wide-distribution butyl rubber
CN113493550B (en) Preparation method of high-width distribution high-branching butyl rubber
CN113493553B (en) Preparation method of hyperbranched butyl rubber
CN113493556B (en) Preparation method of hyperbranched butyl rubber
CN113493547B (en) Preparation method of hyperbranched butyl rubber
CN114478950B (en) Three-arm comb-shaped star-shaped branched butyl rubber and preparation method thereof, and preparation method of three-arm star-shaped nucleating agent
CN114478953B (en) Preparation method of three-arm comb-shaped star-branched butyl rubber
CN114163586B (en) Preparation method of four-arm comb-shaped star-branched butyl rubber

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant