CN114316139B - 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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- CN114316139B CN114316139B CN202011056727.3A CN202011056727A CN114316139B CN 114316139 B CN114316139 B CN 114316139B CN 202011056727 A CN202011056727 A CN 202011056727A CN 114316139 B CN114316139 B CN 114316139B
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- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000007822 coupling agent Substances 0.000 claims abstract description 63
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 43
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000009826 distribution Methods 0.000 claims abstract description 27
- 238000005859 coupling reaction Methods 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 125000001979 organolithium group Chemical group 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- VUFKMYLDDDNUJS-UHFFFAOYSA-N 2-(ethoxymethyl)oxolane Chemical compound CCOCC1CCCO1 VUFKMYLDDDNUJS-UHFFFAOYSA-N 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 230000000977 initiatory effect Effects 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 55
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 16
- 230000008878 coupling Effects 0.000 description 10
- 238000010168 coupling process Methods 0.000 description 10
- 238000000034 method Methods 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
- 238000011160 research Methods 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 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
- 238000005096 rolling process Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 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
- 238000009776 industrial production Methods 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 229920005604 random copolymer Polymers 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
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- GPOGLVDBOFRHDV-UHFFFAOYSA-N (2-nonylphenyl) dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(O)O GPOGLVDBOFRHDV-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000007983 Tris buffer Substances 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
- 238000013459 approach Methods 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 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
- 150000001875 compounds Chemical class 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
- 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
- 230000001747 exhibiting effect Effects 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
- 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer 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
- 238000001228 spectrum Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 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 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention 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 organolithium initiator and a structure regulator, polymerizing 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: a portion of the coupling agent was added within 30 minutes after the polymerization reached the peak temperature, and the remaining portion of the coupling agent was added within a range of 10 to 30 minutes after the addition of the portion of the coupling agent. The preparation method can be used for efficiently preparing 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 service performance similar to those of natural rubber, has better wear resistance, heat resistance, aging resistance and vulcanization speed than natural rubber, can be used with natural rubber and various synthetic rubbers, is widely used in the fields of tires, adhesive tapes, rubber tubes, wire and cable, medical appliances, production of various rubber products and the like, is the largest general synthetic rubber variety, and is one of the earliest rubber varieties for realizing industrial production.
The development of green tires is a viable approach for the tire industry to meet increasingly stringent environmental protection requirements, and green tire tread rubber requires low rolling resistance, good wear resistance and good wet skid resistance to ensure long service life, safety and energy conservation of the tire, but these three properties contradict each other and are difficult to meet simultaneously, so the green tire tread rubber is called as a devil triangle. In recent years, the synthesis of novel tread rubber with the balance of 'magic triangle' performance by adopting a molecular structure design method is a development trend, and solution polymerized styrene-butadiene rubber (SSBR) has the comprehensive properties of good wear resistance, crack resistance, wet road gripping performance, heat resistance, flex resistance after long-time exposure at high temperature and the like due to the controllable structure, and becomes an important raw material for developing green tires.
The linear solution polymerized styrene-butadiene rubber and the star-shaped solution polymerized styrene-butadiene rubber are two types of SSBR, and the linear solution polymerized styrene-butadiene rubber is difficult to vulcanize at the molecular chain end and low molecular substances, so that large side groups capable of freely moving are formed in vulcanized rubber, and the rolling resistance of the tire is increased; one end of the star-shaped solution polymerized styrene-butadiene rubber molecular chain is connected with a chemical bond, and the number of the free movable molecular chain ends in the macromolecular network after vulcanization is greatly reduced, so that the rolling resistance of the tire is reduced, and the star-shaped solution polymerized styrene-butadiene rubber molecular chain is more suitable to be used as a tire raw material.
The star-structured solution polymerized styrene-butadiene rubber (namely, star-shaped solution polymerized styrene-butadiene rubber) is a high polymer elastomer material prepared by butadiene and styrene through an anionic polymerization technology, and the preparation process generally comprises the steps of taking organic lithium as an initiator and Lewis base as a structure regulator, polymerizing in an organic solvent (generally, obtaining a linear styrene-butadiene copolymer through polymerization), and then adding a coupling agent for coupling to prepare a star-shaped solution polymerized styrene-butadiene rubber product. Under the production process of the 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 (comprising a larger molecular weight part and a smaller molecular weight part); 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 distribution) can be prepared. Researches show that the star-shaped solution polymerized styrene-butadiene rubber with the trimodal molecular weight distribution has the characteristics of better mechanical property, processability and the like, is more suitable for being used as a green raw material of products such as green tires and the like, so that optimization of the styrene-butadiene rubber synthesis process and flexible control of coupling rate (coupling degree) are realized, and the star-shaped solution polymerized styrene-butadiene rubber products with the trimodal molecular weight distribution are synthesized, and become a key problem facing the green tire raw material production industry gradually.
Xu Wei [1] And the method is characterized in that cyclohexane/hexane is used as a solvent, n-butyllithium is used as an initiator, ethyl tetrahydrofurfuryl ether is used as a structure regulator, dimethyl dichlorosilane and silicon tetrachloride are used as a mixed coupling agent, and butadiene and styrene are subjected to anion (anion) 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 use, and a random copolymer of butylbenzene and its preparation method, wherein the coupling agent is a mixture of benzene ring compound 1 with two vinyl groups and benzene ring compound 2 with one vinyl group and one halogen, and the coupling agent can be used for synthesisTo obtain the styrene-butadiene random copolymer product with trimodal molecular weight distribution.
Although some researches and reports on solution polymerized styrene-butadiene rubber with trimodal molecular weight distribution exist, the preparation of solution polymerized styrene-butadiene rubber with trimodal molecular weight distribution by compounding with various coupling agents is still limited at present. Therefore, optimizing the solution polymerized styrene-butadiene rubber synthesis process to efficiently prepare the solution polymerized styrene-butadiene rubber product with trimodal molecular weight distribution is still an important subject faced by the person skilled in the art.
Related literature:
[1] xu, liang Aimin, wu Yi string, etc. the trimodal high vinyl solution polymerized styrene-butadiene rubber [ J ]. 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 the solution polymerized styrene-butadiene rubber which is prepared by the preparation method, has the molecular weight distributed in a trimodal manner, has good mechanical properties and meets the requirements of green tire raw materials.
The invention also provides application of the styrene-butadiene rubber prepared by the preparation method in the aspect of tires, and the mechanical properties of the tires can be improved.
In one aspect of the present invention, there is provided a method for preparing solution polymerized styrene-butadiene rubber, comprising: in the presence of an organolithium initiator and a structure regulator, polymerizing 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: a portion of the coupling agent was added within 30 minutes after the polymerization reached the peak temperature, and the remaining portion of the coupling agent was added within a range of 10 to 30 minutes after the addition of the portion of the coupling agent.
According to the preparation method of the solution polymerized styrene-butadiene rubber, the star-shaped solution polymerized styrene-butadiene rubber product is synthesized under the condition of anionic polymerization, the coupling degree is regulated and controlled by controlling the adding time of the coupling agent, and the star-shaped solution polymerized styrene-butadiene rubber product with trimodal molecular weight distribution is synthesized.
According to the further research of the invention, the part of the coupling agent (namely the first part of the coupling agent) can be 10-80% of the total amount of the coupling agent, and the condition is more favorable for preparing the solution polymerized styrene-butadiene rubber product with the trimodal molecular weight distribution and the comprehensive characteristics such as mechanical property and the like.
Further, the specific amount (total amount) of the coupling agent can be generally controlled as follows: 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 (corresponding to the molar ratio of the coupling agent to the lithium element in the organolithium initiator being (0.01-0.8): 1), 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 four-arm structure compound coupling agent, for example, may be one or a mixture of two of silicon tetrachloride and tin tetrachloride. In the specific implementation, the same coupling agent (namely a single coupling agent) can be selected, for example, silicon tetrachloride or tin tetrachloride can be selected, and according to the preparation method disclosed by the invention, the 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 invention, the mass content of the styrene in the total monomer composed of the styrene and the butadiene is generally 5-50%, and the balance is butadiene (namely, the mass content of butadiene is correspondingly 50-95%); for example, in one embodiment, the mass content of styrene may be 5-40% or 5-30% or 5-20% or 5-15%.
In the present invention, the amount of the organolithium initiator may be a conventional amount in the art for preparing solution polymerized styrene-butadiene rubber, and in one embodiment of the present invention, the amount of the organolithium initiator may be 0.02 to 0.1 part by weight (i.e., the amount of the organolithium initiator is 0.02 to 0.1% of the total amount (or referred to as the total amount) of styrene and butadiene, for example, may be 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 be generally an alkyllithium. Specifically, the structural formula of the alkyl lithium can be RLi, wherein R is C1-C6 alkyl. In an embodiment, the organolithium initiator may be specifically selected from one or a mixture of several of ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, and the like.
The structure-modifying agent of the present invention may be a Lewis base-based structure-modifying agent commonly used in the art, for example, ethyl tetrahydrofurfuryl ether, tetrahydrofuran, sodium dodecylbenzenesulfonate, etc., and the amount thereof may be a conventional amount in the art, and is not particularly limited. In general, in some preferred embodiments of the present invention, the structure modifier is used in an amount of 0.005 to 0.1 part by weight, further may be 0.01 to 0.1, such as may be 0.02 to 0.09 or 0.03 to 0.07 or 0.04 to 0.05, relative to 100 parts by weight of the total amount of styrene and butadiene.
In the synthesis process of the star-shaped solution polymerized styrene-butadiene rubber, styrene and butadiene monomers are polymerized to reach peak temperature generally, namely, the polymerization reaction of the two monomers is completed, the product is generally mainly a linear styrene-butadiene copolymer, and then 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 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 second part of coupling agent) is added within the range of 10-30 minutes (namely between 10 and 30 minutes) after the part of coupling agent is added, so that the star-shaped solution polymerized styrene-butadiene rubber with trimodal molecular weight distribution can be prepared, and the used coupling agent can be a single coupling agent (namely one coupling agent) or a mixture of two or more coupling agents, and the invention is not limited to the above and has greater practical significance in industry.
In the preparation process, the structure regulator and the styrene and butadiene monomers can be added into the solvent, then the temperature is raised to the initiation temperature, and then the organolithium 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 10-60min. In the practice of the invention, the initiation temperature may generally be from 30 to 45℃and may be, for example, from 35 to 40 ℃. The solvent used may be any solvent known in the art, for example, a solvent oil, and in one embodiment, the solvent may be a carbon five solvent oil.
In the present invention, the coupling reaction conditions may be: the temperature is 0-150 ℃ and the pressure is 0-1.0MPa. In particular, the coupling reaction time may be 20 to 60 minutes, for example, 20 to 50 minutes, or 30 to 40 minutes. 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 of coupling agent within 10-30 minutes after the first part of coupling agent is added, and continuing the coupling reaction to prepare the solution polymerized styrene-butadiene rubber. In the concrete 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 stopped, additives such as an antioxidant and the like can be added according to the requirement, so that the performance of the prepared star-shaped 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-t-butylphenol or the like.
In another aspect, the invention also provides solution polymerized styrene-butadiene rubber, which is prepared by the preparation method.
The solution polymerized styrene-butadiene rubber provided by the invention is prepared by the specific preparation method, has the molecular weight distributed in a trimodal manner, has good mechanical properties, and meets the requirements of green tire materials. In one embodiment, the solution polymerized styrene-butadiene rubber has Mn of (15-19). Times.10 4 About, the coupling efficiency reaches 45% or more and 47% or more, the Mooney viscosity (ML 100℃ 1+4 ) About 60-80 or 65-70.
In still another aspect, the invention further provides an application of the styrene-butadiene rubber prepared by the preparation method in the aspect of tires.
As described above, the styrene-butadiene rubber prepared by the preparation method has the characteristics 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 from the styrene-butadiene rubber has the characteristics of low rolling resistance, good wear resistance, good 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 (in three-peak distribution), and has the advantages of simple preparation system, flexible and controllable process, high efficiency, lower cost and the like, and industrial production and application are utilized.
The solution polymerized styrene-butadiene rubber provided by the invention is prepared by the specific preparation method, has the molecular weight distributed in a trimodal manner, has good mechanical properties, and meets the requirements of green tire materials.
The application of the styrene-butadiene rubber in the aspect of the tire provided by the invention adopts the styrene-butadiene rubber as the raw material of the tire, can improve the comprehensive characteristics of the tire such as mechanical property 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 refractive index of the time difference on the ordinate.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The solution polymerized styrene-butadiene rubber is synthesized by adopting a 10kg/h continuous polymerization test device (a polymerization kettle), and the preparation process is specifically as follows:
adding carbon five 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 content of styrene is 10 percent and the content of butadiene is 90 percent), and when the temperature in the kettle reaches 35 ℃ (initiation temperature), adding 44g of cyclopentane solution of n-butyllithium (the molar concentration of n-butyllithium is about 0.7-0.8 mol/L) into the mixture to initiate polymerization; about 30min after the polymerization reaches the peak temperature, 20g of SiCl is added 4 The coupling reaction was started and after 20min, 4g of SiCl was added 4 (calculated as lithium element, coupling agent SiCl) 4 The molar ratio of total to n-butyllithium was about 0.125: 1) And (3) continuing the coupling reaction for 20min (namely, the interval between the two coupling agent additions is 20min and the coupling reaction is 40 min), 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 4 The coupling efficiency was 47%, the Mooney viscosity (ML 100℃ 1+4 ) 70; the GPC chart of the solution polymerized styrene-butadiene rubber was also shown in FIG. 1, and it showed a trimodal molecular weight distribution.
Example 2
The solution polymerized styrene-butadiene rubber is synthesized by adopting a 15L batch polymerization test device (a polymerization kettle), and the preparation process is specifically as follows:
adding carbon five solvent oil into a polymerization kettle, starting stirring, then adding 0.15g of ethyl tetrahydrofurfuryl ether and 320g of monomer (the total amount of styrene and butadiene is 320g, wherein the styrene content is 10 percent and the butadiene content is 90 percent), and adding 2g of cyclopentane solution of n-butyllithium (the molar concentration of the n-butyllithium is about 1.6 mol/L) into the kettle until the temperature in the kettle reaches 40 ℃ to initiate polymerization; about 30 minutes after the polymerization reaction reaches the peak temperature, 0.9g of SiCl is added 4 The coupling reaction was started and after 15min, 0.2g of SiCl was added 4 (calculated as lithium element, coupling agent SiCl) 4 The molar ratio of total to n-butyllithium was about 0.15: 1) The coupling reaction was continued for 15min (i.e. the interval between the two coupling agent additions was 15min,coupling reactions were carried out for a total of 30 min) followed by addition of trimethylchlorosilane (terminator) and 4- [ (4, 6-dioctylthio-1, 35-triazin-2-yl)]2,6 di-tert-butylphenol (antioxidant), discharging to obtain a solution polymerized styrene-butadiene rubber (having a GPC chart similar to that of the solution polymerized styrene-butadiene rubber of example 1, exhibiting a trimodal molecular weight distribution). The Mn of the solution polymerized styrene-butadiene rubber is 16 multiplied by 10 4 Coupling efficiency was 50%, mooney viscosity (ML 100℃ 1+4 ) 68.
Claims (3)
1. A preparation method of star-shaped solution polymerized styrene-butadiene rubber with trimodal molecular weight distribution is characterized by comprising the following steps: adding a structure regulator, styrene and butadiene into a solvent, heating to an initiation temperature, adding an organic lithium initiator for polymerization reaction, and then adding a coupling agent into a polymerization reaction system for coupling reaction to obtain star-shaped solution polymerized styrene-butadiene rubber with trimodal molecular weight distribution; 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 the range of 10-30 minutes after the part of the coupling agent is added; the part of the coupling agent is 10-80% of the total amount of the coupling agent;
the structure modifier is used in an amount of 0.005 to 0.1 parts by weight relative to 100 parts by weight of the total amount of styrene and butadiene;
the initiation temperature is 35-45 ℃;
the polymerization conditions are as follows: the reaction temperature is 0-150 ℃, the reaction pressure is 0-1.0MPa, and the reaction time is 10-60min;
the coupling reaction conditions are as follows: the temperature is 0-150 ℃ and the pressure is 0-1.0MPa;
the mass content of the styrene is 5-50% in the total monomer composed of the styrene and the butadiene, and the balance is the butadiene;
the structure regulator is selected from one or more of ethyl tetrahydrofurfuryl ether, tetrahydrofuran and sodium dodecyl benzene sulfonate;
the coupling agent is one or a mixture of two of silicon tetrachloride and tin tetrachloride;
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, a step of;
the organolithium initiator is used in an amount of 0.02 to 0.1 parts by weight relative to 100 parts by weight of the total amount of styrene and butadiene;
the coupling agent of the part and the coupling agent of the rest are one coupling agent or a mixture of two or more coupling agents.
2. A star-shaped solution polymerized styrene-butadiene rubber with trimodal molecular weight distribution, which is characterized in that the preparation method of claim 1 is adopted.
3. The use of the star-shaped solution polymerized styrene-butadiene rubber with trimodal molecular weight distribution prepared by the preparation method of claim 1 in the aspect of tires.
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