CN114316139A - Solution polymerized styrene-butadiene rubber and preparation method and application thereof - Google Patents
Solution polymerized styrene-butadiene rubber and preparation method and application thereof Download PDFInfo
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- CN114316139A CN114316139A CN202011056727.3A CN202011056727A CN114316139A CN 114316139 A CN114316139 A CN 114316139A CN 202011056727 A CN202011056727 A CN 202011056727A CN 114316139 A CN114316139 A CN 114316139A
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- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000007822 coupling agent Substances 0.000 claims abstract description 57
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 38
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- 238000005859 coupling reaction Methods 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 13
- 125000001979 organolithium group Chemical group 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000005049 silicon tetrachloride Substances 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 25
- 239000000243 solution Substances 0.000 description 48
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 16
- 238000010168 coupling process Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 230000008878 coupling Effects 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- VUFKMYLDDDNUJS-UHFFFAOYSA-N 2-(ethoxymethyl)oxolane Chemical compound CCOCC1CCCO1 VUFKMYLDDDNUJS-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 239000005051 trimethylchlorosilane Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- -1 alkyl lithium Chemical compound 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Images
Classifications
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- 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
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Abstract
The invention provides solution-polymerized styrene-butadiene rubber and a preparation method and application thereof, wherein the preparation method comprises the following steps: in the presence of an organic lithium initiator and a structure regulator, carrying out polymerization reaction on styrene and butadiene, and then adding a coupling agent into a polymerization reaction system for coupling reaction to obtain solution polymerized styrene-butadiene rubber; wherein the adding time of the coupling agent is as follows: adding a part of the coupling agent within 30 minutes after the polymerization reaction reaches the peak temperature, and adding the rest part of the coupling agent within 10-30 minutes after the part of the coupling agent is added. The invention can efficiently prepare the solution polymerized styrene butadiene rubber product with trimodal molecular weight distribution.
Description
Technical Field
The invention relates to a technology for controlling molecular weight distribution of synthetic styrene-butadiene rubber, in particular to solution-polymerized styrene-butadiene rubber with trimodal molecular weight distribution and a preparation method and application thereof.
Background
Styrene Butadiene Rubber (SBR), also known as polystyrene butadiene copolymer, has physical and mechanical properties, processability and product use performance close to natural rubber, has better wear resistance, heat resistance, aging resistance and vulcanization speed than natural rubber, can be used together with natural rubber and various synthetic rubbers, is widely used in the fields of production of tires, adhesive tapes, rubber tubes, electric wires and cables, medical appliances, various rubber products and the like, is the largest general synthetic rubber variety, and is one of the rubber varieties which are originally industrially produced.
The development of green tires is a feasible approach for the tire industry to meet increasingly strict environmental requirements, and the tread rubber of the green tires requires low rolling resistance, good wear resistance and good wet skid resistance so as to ensure the long service life, safety and energy conservation of the tires, but the three performances are mutually contradictory and are difficult to meet at the same time, so the tire is called as a magic triangle. In recent years, the molecular structure design method is a development trend for synthesizing novel tread rubber with balanced magic triangle performance, and solution polymerized styrene butadiene rubber (SSBR) has good wear resistance, crack resistance, wet road gripping performance, heat resistance, flexing resistance after long-time exposure at high temperature and other comprehensive properties due to controllable structure, and becomes an important raw material for developing green tires.
The linear solution polymerized styrene-butadiene rubber and the star solution polymerized styrene-butadiene rubber are two types of SSBR, and the linear solution polymerized styrene-butadiene rubber forms a large side group capable of freely moving in vulcanized rubber because the molecular chain end and low molecular substances of the linear solution polymerized styrene-butadiene rubber are not easy to be vulcanized, so that the rolling resistance of the tire is increased; one end of the star solution polymerized styrene butadiene rubber molecular chain is connected with the chemical bond, the number of the molecular chain terminal which can freely move in the vulcanized macromolecular network is greatly reduced, thereby reducing the rolling resistance of the tire, and being more suitable for being used as the tire raw material.
The star-shaped solution polymerized styrene-butadiene rubber (i.e. star-shaped solution polymerized styrene-butadiene rubber) is a macromolecular elastomer material prepared by butadiene and styrene through an anionic polymerization technology, and the preparation process generally takes organic lithium as an initiator and Lewis base as a structure regulator, and after polymerization (generally linear styrene-butadiene copolymer is obtained through polymerization) in an organic solvent, a coupling agent is added for coupling, so as to prepare a star-shaped solution polymerized styrene-butadiene rubber product. Under the production process of SSBR at the present stage, when a single coupling agent is adopted, the molecular weight of the prepared solution polymerized styrene-butadiene rubber is generally in bimodal distribution (contains a part with larger molecular weight and a part with smaller molecular weight); when the coupling agent is a mixture of two or more coupling agents and the number of coupling functional groups of different coupling agents is different, the solution polymerized styrene-butadiene rubber with trimodal molecular weight distribution (the molecular weight is trimodal). Researches show that the star solution polymerized styrene-butadiene rubber with the trimodal molecular weight distribution has the characteristics of more excellent mechanical property, processability and the like, and is more suitable to be used as a green raw material of products such as green tires, so that the optimization of a styrene-butadiene rubber synthesis process, the flexible control of the coupling rate (coupling degree) and the synthesis of the star solution polymerized styrene-butadiene rubber with the trimodal molecular weight distribution gradually become key problems in the green tire raw material production industry.
Xu Wei[1]Cyclohexane/hexane as solvent, n-butyl lithium as initiator,Ethyl tetrahydrofurfuryl ether is used as a structure regulator, dimethyl dichlorosilane and silicon tetrachloride are used as mixed coupling agents, and butadiene and styrene are subjected to anion (anionic) copolymerization by adopting an intermittent polymerization process to synthesize the high-vinyl SSBR with trimodal distribution. Patent document CN106146734A discloses a coupling agent and its application, and a random styrene-butadiene copolymer and its preparation method, wherein the coupling agent is a mixture of a benzene ring compound 1 with two vinyl groups and a benzene ring compound 2 with one vinyl group and one halogen, and the random styrene-butadiene copolymer with trimodal molecular weight distribution can be synthesized by using the coupling agent.
Although some studies and reports have been made on solution-polymerized styrene-butadiene rubber with trimodal molecular weight distribution, the present invention is still limited to the preparation of solution-polymerized styrene-butadiene rubber with trimodal molecular weight distribution by compounding a plurality of coupling agents. Therefore, optimizing the synthesis process of solution polymerized styrene-butadiene rubber to efficiently prepare solution polymerized styrene-butadiene rubber products with trimodal molecular weight distribution is still an important subject for those skilled in the art.
The related documents are:
[1] xuwe, beam edison, wuyixuan et al, synthesis of trimodal high vinyl solution-polymerized styrene-butadiene rubber [ J ] with mixed coupling agents synthetic rubber industry, 2014,37 (4): 258-262.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of solution polymerized styrene butadiene rubber, which can synthesize a star-shaped solution polymerized styrene butadiene rubber product with trimodal molecular weight distribution by controlling the adding time of a coupling agent and has the advantages of simple preparation process, low cost and the like.
The invention also provides solution-polymerized styrene-butadiene rubber which is prepared by the preparation method, has trimodal distribution of molecular weight, good mechanical property and meets the requirements of green tire raw materials.
The invention also provides the application of the styrene butadiene rubber prepared by the preparation method in the aspect of tires, and the mechanical property and other characteristics of the tires can be improved.
In one aspect of the present invention, a method for preparing solution-polymerized styrene-butadiene rubber is provided, which comprises: in the presence of an organic lithium initiator and a structure regulator, carrying out polymerization reaction on styrene and butadiene, and then adding a coupling agent into a polymerization reaction system for coupling reaction to obtain solution polymerized styrene-butadiene rubber; wherein the adding time of the coupling agent is as follows: adding a part of the coupling agent within 30 minutes after the polymerization reaction reaches the peak temperature, and adding the rest part of the coupling agent within 10-30 minutes after the part of the coupling agent is added.
The preparation method of the solution polymerized styrene-butadiene rubber provided by the invention synthesizes a star-shaped solution polymerized styrene-butadiene rubber product under the condition of anion polymerization, and synthesizes and obtains the star-shaped solution polymerized styrene-butadiene rubber product with trimodal molecular weight distribution by controlling the adding time of the coupling agent and regulating the coupling degree.
According to the further research of the invention, the total amount of the coupling agent (i.e. the first part of coupling agent) can be 10-80%, and the condition is more favorable for preparing solution polymerized styrene-butadiene rubber products with trimodal molecular weight distribution and comprehensive properties such as mechanical property and the like.
Further, the specific amount (total amount) of the coupling agent can be generally controlled to be: the molar ratio of the coupling agent to the organic lithium initiator is (0.01-0.8) calculated by lithium element of the organic lithium initiator: 1 (corresponding to a molar ratio of the coupling agent to the lithium element in the organolithium initiator of (0.01-0.8): 1), and may be, for example, (0.1-0.8): 1 or (0.1-0.7): 1 or (0.1-0.6): 1 or (0.1-0.5): 1 or (0.1-0.4): 1 or (0.1-0.3): 1 or (0.1-0.2): 1.
specifically, the coupling agent may be a compound coupling agent with a four-arm structure, such as one or a mixture of two of silicon tetrachloride and tin tetrachloride. In specific implementation, the same coupling agent (namely a single coupling agent) can be selected, such as silicon tetrachloride or tin tetrachloride, according to the preparation method disclosed by the invention, a star-shaped solution-polymerized styrene-butadiene rubber product with trimodal molecular weight distribution can be prepared, and meanwhile, the process flow can be simplified and the cost can be saved.
In the present invention, in the total amount of monomers consisting of styrene and butadiene, the mass content of styrene may be generally 5 to 50%, the balance being butadiene (i.e., the mass content of butadiene is correspondingly 50 to 95%); for example, in one embodiment, the styrene may be present in an amount of 5-40% by mass, or 5-30% by mass, or 5-20% by mass, or 5-15% by mass.
In the present invention, the organolithium initiator may be used in an amount conventionally used in the preparation of solution-polymerized styrene-butadiene rubber, and in one embodiment of the present invention, the organolithium initiator may be used in an amount of 0.02 to 0.1 parts by weight (i.e., the amount of the organolithium initiator is 0.02 to 0.1% of the total amount (or the total amount) of styrene and butadiene), for example, 0.02 to 0.7, relative to 100 parts by weight of the total amount of styrene and butadiene.
The organolithium initiator of the present invention may be a conventional anionic polymerization initiator, and in the practice of the present invention, may generally be an alkyllithium. Specifically, the alkyl lithium can be RLi, wherein R is C1-C6 alkyl. In one embodiment, the organolithium initiator may be selected from one or more of ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and the like.
The structure modifier of the present invention may be a lewis base structure modifier commonly used in the art, and may be, for example, ethyltetrahydrofurfuryl ether, tetrahydrofuran, sodium dodecylbenzenesulfonate, etc., and the amount thereof may be an amount conventionally used in the art, which is not particularly limited. In general, in some preferred embodiments of the present invention, the structure-regulating agent is used in an amount of 0.005 to 0.1 part by weight, further 0.01 to 0.1 part by weight, for example 0.02 to 0.09 or 0.03 to 0.07 or 0.04 to 0.05 part by weight, relative to 100 parts by weight of the total amount of styrene and butadiene.
In the synthesis process of star-shaped solution polymerized styrene-butadiene rubber, styrene and butadiene monomers are polymerized, the peak temperature is generally reached, namely the polymerization reaction of the two monomers is completed, the product is generally mainly linear styrene-butadiene copolymer, and a coupling agent is added for coupling reaction, so that the star-shaped solution polymerized styrene-butadiene rubber is obtained. According to the research of the invention, a part of coupling agent (or called a first part of coupling agent) is added within 30 minutes after the polymerization reaction reaches the peak temperature to start coupling, and the rest part of coupling agent (or called a second part of coupling agent) is added within 10-30 minutes (namely between 10 and 30 minutes) after the part of coupling agent is added, so that the star solution polymerized styrene-butadiene rubber with the trimodal molecular weight distribution can be prepared.
In the preparation process, the structure regulator, the styrene monomer and the butadiene monomer can be added into the solvent, then the temperature is raised to the initiation temperature, and the organic lithium initiator is added for polymerization reaction. In general, the polymerization conditions may be: the reaction temperature is 0-150 ℃, the reaction pressure is 0-1.0MPa, and the reaction time is 10-60 min. In the practice of the present invention, the initiation temperature may be generally in the range of 30 to 45 deg.C, for example 35 to 40 deg.C. The solvent used may be any solvent conventional in the art, such as solvent oil, and in one embodiment, the solvent may be carbon five solvent oil.
In the present invention, the coupling reaction conditions may be: the temperature is 0-150 ℃, and the pressure is 0-1.0 MPa. In specific implementation, the coupling reaction time can be 20-60min, for example, 20-50min, 30-50min or 30-40 min. And adding a first part of coupling agent within 30 minutes after the polymerization reaction reaches the peak temperature to start the coupling reaction, adding the rest part of coupling agent within 10-30 minutes after the first part of coupling agent is added, and continuing the coupling reaction to obtain the solution polymerized styrene-butadiene rubber. In specific implementation, after the coupling reaction is finished, a terminator can be added to terminate the reaction; when the terminator is added or after the reaction is terminated, additives such as antioxidant and the like can be added according to the requirements, so that the performance of the prepared star solution polymerized styrene-butadiene rubber is further enhanced. The terminator, the antioxidant and the amount thereof used in the present invention may be conventional in the art, and are not particularly limited, and for example, the terminator may be trimethylchlorosilane, ethanol or the like, and the antioxidant may be tris (nonylphenyl) phosphite, 4- [ (4, 6-dioctylthio-1, 35-triazin-2-yl) ] -2, 6-di-tert-butylphenol or the like.
On the other hand, the invention also provides solution-polymerized styrene-butadiene rubber which is prepared by adopting the preparation method.
The solution polymerized styrene-butadiene rubber of the invention,the molecular weight of the tire rubber prepared by the specific preparation method is in trimodal distribution, has good mechanical property, and meets the requirements of green tire materials. In one embodiment, the solution-polymerized styrene-butadiene rubber has a Mn of (15-19). times.104About 45% or more of coupling efficiency and Mooney viscosity (ML)100℃ 1+4) Is about 60-80 or 65-70.
In another aspect of the invention, the invention also provides an application of the styrene butadiene rubber prepared by the preparation method in the aspect of tires.
As mentioned above, the styrene-butadiene rubber prepared by the preparation method has the advantages of trimodal molecular weight distribution, good mechanical properties and the like, and can be used as a tire material (or raw material). According to the research of the invention, the tire prepared by adopting the styrene butadiene rubber has the characteristics of lower rolling resistance, good wear resistance, wet skid resistance and the like, and has higher practical value.
The implementation of the invention has at least the following beneficial effects:
the preparation method of the solution polymerized styrene-butadiene rubber provided by the invention adopts a mode of adding the coupling agent for multiple times to adjust the coupling efficiency, can prepare the solution polymerized styrene-butadiene rubber product with wide molecular weight distribution (trimodal distribution), has the advantages of simple preparation system, flexible and controllable process, high efficiency, lower cost and the like, and utilizes industrial production and application.
The solution polymerized styrene-butadiene rubber is prepared by the specific preparation method, the molecular weight of the solution polymerized styrene-butadiene rubber is in trimodal distribution, the solution polymerized styrene-butadiene rubber has good mechanical property, and the requirements of green tire materials are met.
The application of the styrene butadiene rubber in the aspect of tires provided by the invention adopts the styrene butadiene rubber as the raw material of the tires, can improve the comprehensive properties of the tires such as mechanical properties and the like, and is more beneficial to practical application.
Drawings
FIG. 1 is a Gel Permeation Chromatography (GPC) spectrum of a solution-polymerized styrene-butadiene rubber according to an embodiment of the present invention, with time (min) on the abscissa and time-lapse refractive index on the ordinate.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A10 kg/h continuous polymerization test device (a polymerization kettle) is adopted to synthesize the solution polymerized styrene butadiene rubber, and the preparation process is as follows:
adding carbon solvent oil into a polymerization kettle, starting stirring, then adding 3g of ethyl tetrahydrofurfuryl ether and 7kg of monomers (the total amount of styrene and butadiene is 7kg, wherein the styrene content is 10 percent, and the butadiene content is 90 percent), and adding 44g of cyclopentane solution of n-butyl lithium (the molar concentration of the n-butyl lithium is about 0.7-0.8mol/L) to initiate polymerization when the temperature in the kettle reaches 35 ℃ (initiation temperature); about 30min after the polymerization reaction reaches the peak temperature, 20g SiCl is added4The coupling reaction was started and after a further 20min, 4g of SiCl were added4(coupling agent SiCl calculated as lithium element)4The molar ratio of total amount to n-butyllithium was about 0.125: 1) and continuing the coupling reaction for 20min (namely, the interval between the feeding of the coupling agents for two times is 20min, and the coupling reaction lasts for 40min totally), then adding trimethylchlorosilane (terminator) and tris (nonylphenyl) phosphite (antioxidant), and discharging to obtain the solution polymerized styrene-butadiene rubber.
The Mn of the solution polymerized styrene-butadiene rubber is 15 multiplied by 10 after being tested4Coupling efficiency of 47%, Mooney viscosity (ML)100℃ 1+4) Is 70; the GPC chart of the solution-polymerized styrene-butadiene rubber was also found to show a trimodal molecular weight distribution as shown in FIG. 1.
Example 2
A15L batch polymerization test device (a polymerization kettle) is adopted to synthesize the solution polymerized styrene butadiene rubber, and the preparation process is as follows:
carbowax solvent oil was added to the polymerization kettle, stirring was started, and then 0.15g of ethyl tetrahydrofurfuryl ether and 320g of monomer (total amount of styrene and butadiene: v.) were added320g of a solution containing 10% of styrene and 90% of butadiene, and when the temperature in the reactor reached 40 ℃, 2g of a cyclopentane solution of n-butyllithium (the molar concentration of n-butyllithium was about 1.6mol/L) was added thereto to initiate polymerization; about 30min after the polymerization reaction reaches the peak temperature, 0.9g SiCl is added4The coupling reaction was started and after a further 15min, 0.2g of SiCl were added4(coupling agent SiCl calculated as lithium element)4The molar ratio of total amount to n-butyllithium was about 0.15: 1) continuing the coupling reaction for 15min (i.e. the interval between the two coupling agent additions is 15min, the coupling reaction is 30min totally), then adding trimethylchlorosilane (terminator) and 4- [ (4, 6-dioctylthio-1, 35-triazine-2-yl)]2,6 di-tert-butylphenol (antioxidant), and discharging to obtain the solution polymerized styrene-butadiene rubber (the GPC spectrogram of the solution polymerized styrene-butadiene rubber is similar to that of the solution polymerized styrene-butadiene rubber in example 1, and the solution polymerized styrene-butadiene rubber has a trimodal molecular weight distribution). The Mn of the solution polymerized styrene-butadiene rubber is tested to be 16 multiplied by 104Coupling efficiency of 50%, Mooney viscosity (ML)100℃ 1+4) Is 68.
Claims (10)
1. A preparation method of solution polymerized styrene-butadiene rubber is characterized by comprising the following steps: in the presence of an organic lithium initiator and a structure regulator, carrying out polymerization reaction on styrene and butadiene, and then adding a coupling agent into a polymerization reaction system for coupling reaction to obtain solution polymerized styrene-butadiene rubber; wherein the adding time of the coupling agent is as follows: adding a part of the coupling agent within 30 minutes after the polymerization reaction reaches the peak temperature, and adding the rest part of the coupling agent within 10-30 minutes after the part of the coupling agent is added.
2. The method according to claim 1, wherein the portion of the coupling agent is 10 to 80% of the total amount of the coupling agent.
3. The method according to claim 1, wherein the molar ratio of the coupling agent to the organolithium initiator is (0.01-0.8) based on the lithium element of the organolithium initiator: 1.
4. the process according to any one of claims 1 to 3, wherein the coupling agent is a compound-based coupling agent having a four-arm structure.
5. The method according to claim 4, wherein the coupling agent is one or a mixture of silicon tetrachloride and tin tetrachloride.
6. The production method according to claim 1 or 3, wherein the organolithium initiator is used in an amount of 0.02 to 0.1 part by weight relative to 100 parts by weight of the total amount of styrene and butadiene.
7. The process according to claim 1 or 2, wherein the coupling reaction conditions are: the temperature is 0-150 ℃, and the pressure is 0-1.0 MPa.
8. The production method according to any one of claims 1 to 7, wherein the structure-regulating agent is used in an amount of 0.005 to 0.1 part by weight relative to 100 parts by weight of the total amount of styrene and butadiene.
9. A solution-polymerized styrene-butadiene rubber produced by the production process according to any one of claims 1 to 8.
10. Use of styrene-butadiene rubber obtained by the process according to any one of claims 1 to 8 in tires.
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