CN116355152B - Highly transparent block-type solution-polymerized styrene-butadiene rubber and preparation method thereof - Google Patents
Highly transparent block-type solution-polymerized styrene-butadiene rubber and preparation method thereof Download PDFInfo
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- CN116355152B CN116355152B CN202111618950.7A CN202111618950A CN116355152B CN 116355152 B CN116355152 B CN 116355152B CN 202111618950 A CN202111618950 A CN 202111618950A CN 116355152 B CN116355152 B CN 116355152B
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- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 80
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 28
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 21
- -1 alkyl lithium Chemical compound 0.000 claims abstract description 21
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 22
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- DKVHRWSACAQVKF-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxymethyl]oxolane Chemical compound CC(C)(C)OCC1CCCO1 DKVHRWSACAQVKF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 8
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 7
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- OFBSTYYRPIFDPM-UHFFFAOYSA-N 2,2-di-2-furylpropane Chemical compound C=1C=COC=1C(C)(C)C1=CC=CO1 OFBSTYYRPIFDPM-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 claims 1
- 238000013461 design Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229920003051 synthetic elastomer Polymers 0.000 abstract description 2
- 239000005061 synthetic rubber Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- 238000009826 distribution Methods 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 10
- 239000005060 rubber Substances 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- VUFKMYLDDDNUJS-UHFFFAOYSA-N 2-(ethoxymethyl)oxolane Chemical compound CCOCC1CCCO1 VUFKMYLDDDNUJS-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- 239000011115 styrene butadiene Substances 0.000 description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 125000003158 alcohol group Chemical group 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241001441571 Hiodontidae Species 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 229920004939 Cariflex™ Polymers 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012648 alternating copolymerization Methods 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/42—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using short-stopping agents
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to the technical field of synthetic rubber, in particular to high-transparency block type solution polymerized styrene-butadiene rubber and a preparation method thereof, wherein the high-transparency block type solution polymerized styrene-butadiene rubber is prepared by the following steps of firstly, adding a styrene monomer, a 1, 3-butadiene monomer, a hydrocarbon solvent, a first structure regulator and a second structure regulator into a polymerization kettle under the protection of nitrogen, and adding an initiator alkyl lithium at the temperature of 40-60 ℃ to initiate reaction; and secondly, continuously reacting for 20min to 2.5h at the temperature of 90 ℃ to 125 ℃, and then adding a required amount of terminator into a polymerization kettle to terminate the reaction, thus obtaining the high-transparency block-type solution polymerized styrene-butadiene rubber. The preparation method of the high-transparency block-type solution polymerized styrene-butadiene rubber has the advantages of simple process, easy design of polymer molecular weight, easy control of polymer microstructure, suitability for industrial mass production, and excellent transparency.
Description
Technical Field
The invention relates to the technical field of synthetic rubber, in particular to high-transparency block type solution polymerized styrene-butadiene rubber and a preparation method thereof.
Background
The development of solution polymerized styrene-butadiene rubber can be divided into three generations, wherein the first generation of products are developed by Phillips and Firestone company in the 60 th century, and the rebound resilience, wear resistance and hysteresis loss performance of the products are better than those of ESBR, but the processability and wet skid resistance are poor. The second generation SSBR produced in the beginning of the 80 th century is applied on a large scale by modifying chain ends including coupling and reasonably adjusting the content and sequence distribution of styrene and vinyl chain links, and has rolling resistance and wet skid resistance of rubber, and represents products such as Cariflex S-1215 of Shell company and SL series tin-coupled SSBR of JSR company. The third generation SSBR is regarded as a generalized concept, and the comprehensive performance of the rubber is improved to the greatest extent by applying the concept of integrated rubber and optimizing the combination of molecular design and chain structure. The current third generation of SSBR has ① styrene-isoprene-butadiene terpolymer gum (SIBR) with isoprene chain ends incorporated into the macromolecular chain. ② The SSBR containing block sequence structure distribution is essentially capable of improving the comprehensive performance of rubber to the greatest extent through the optimized combination of molecular design and chain structure.
Copolymerization refers to the reaction of polymerizing two or more compounds into one species under certain conditions. Binary and ternary polymerization are carried out according to the types of monomers, and random copolymerization, block copolymerization, alternating copolymerization and graft copolymerization are carried out according to the molecular structures of polymers. Random copolymerization refers to random arrangement of monomers on a macromolecular chain, the monomers are randomly distributed on a main chain, and no one monomer can form a separate longer chain segment on the molecular chain. A block copolymer, also known as a mosaic copolymer, is a special polymer prepared by joining together two or more polymer segments of different properties, a block polymer having a specific structure will exhibit properties different from those of a simple linear polymer, and a mixture of many random copolymers and even homopolymers. At present, in the field of butadiene-styrene series rubber synthesis, block rubber products mainly relate to thermoplastic elastomers SBS and block solution polymerized styrene butadiene rubber. Wherein SBS is mainly prepared by adopting a two-step method, a coupling method or a three-step method through changing the feeding sequence, and the obtained polymer is a thermoplastic elastomer. In recent years, research hot spots of domestic solution polymerized styrene-butadiene rubber SSBR mainly focus on research of novel initiator, regulator, functionalization, end group modification and molecular structure design, and general development trend of foreign SSBR technology is environmental protection, high performance and special material.
The traditional plastic modification and sole material can not meet the current demands, and the development of the traditional plastic modification and sole material is towards more functionalization, light weight, intellectualization and environmental protection in the future. With the continuous development of synthetic technology, new materials with more excellent properties, such as solution polymerized styrene butadiene rubber (SSBR), have emerged in recent years. One of the research directions of the current solution polymerized styrene-butadiene rubber preparation technology is to synthesize block-type solution polymerized styrene-butadiene rubber with adjustable sequence structure distribution. The block type solution polymerized styrene-butadiene rubber is widely applied to shoe making, plastic modification and other rubber product industries by virtue of the unique properties. For the synthesis of block-soluble polybutylece copolymers, the initiator employed by most research institutions is butyllithium and the solvent is cyclohexane. As can be seen from the study on the performance of the block styrene-butadiene polymer, the main microstructure indexes of the block styrene-butadiene polymer have larger differences in combination with the styrene content, the vinyl content, the block styrene content and the like due to different structure regulators, different feeding sequences and different synthesis process parameters adopted by various study institutions. However, the presently disclosed literature and patents lack descriptions and studies of the preparation technology of solution polymerized styrene-butadiene rubber with high transparency. In addition, the block type solution polymerized styrene-butadiene rubber is characterized in that the comprehensive performance of the rubber is improved to the greatest extent through the optimized combination of molecular design and chain structure, but the effective control of the content of the block styrene is realized within a certain vinyl content range, and the sequential structure regulation and control based on a proper structure regulator is a key technical problem to be solved urgently at present.
Disclosure of Invention
The invention provides a high-transparency block-type solution polymerized styrene-butadiene rubber and a preparation method thereof, which overcome the defects of the prior art, and can effectively solve the problems that the transparency of the existing block-type solution polymerized styrene-butadiene rubber is not high, and the existing block-type solution polymerized styrene-butadiene rubber synthesis method lacks effective control of the styrene content of the block.
One of the technical schemes of the invention is realized by the following measures: A high-transparency block-type solution polymerized styrene-butadiene rubber is prepared by the following steps:
The preparation method comprises the steps of adding a styrene monomer, a1, 3-butadiene monomer, a hydrocarbon solvent, a first structure regulator and a second structure regulator into a polymerization kettle under the protection of nitrogen, adding an initiator alkyl lithium at the temperature of 40-60 ℃ to initiate reaction, continuously reacting for 20min to 2.5h at the temperature of 90-125 ℃, and then adding a required amount of terminator into the polymerization kettle to terminate the reaction to obtain the high-transparency block-type solution polymerized styrene-butadiene rubber.
The following are further optimizations and/or improvements to one of the above-described inventive solutions:
The hydrocarbon solvent is one of cyclopentane, cyclohexane, n-pentane and n-hexane, the mass ratio of the styrene monomer to the 1, 3-butadiene monomer is 4:6-5:5, and the ratio of the total amount of the styrene monomer and the 1, 3-butadiene monomer to the hydrocarbon solvent is 1:9-2:8.
The initiator alkyllithium is one of n-butyllithium, sec-butyllithium and tert-butyllithium, and the amount of alkyllithium is 0.5mmol to 1.2mmol per 100g total amount of styrene monomer and 1, 3-butadiene monomer.
The first structural regulator is one of tetrahydrofuran, 2, 5-dimethyl furan and 2, 2-di (2-furyl) propane, and the mass ratio of the first structural regulator to the hydrocarbon solvent is 0.2:1000-3:1000.
The structure regulator II is one of tetrahydrofurfuryl ethyl ether, 2-tert-butyloxymethyl tetrahydrofuran and sodium dodecyl benzene sulfonate, and the molar ratio of the structure regulator II to the initiator alkyl lithium is 1:10 to 1:1.
The terminating agent is an alcohol substance or a silicon-halogen bond compound, and the molar ratio of the adding amount of the terminating agent to the alkyl lithium is 1:1-2:1.
The alcohol is one of ethanol, glycol, glycerol and isopropanol.
The structural general formula of the silicon-halogen bond compound is SiXM 3, wherein X is one of F, cl, br, I, and M is one of methyl, ethyl and isopropyl.
In the high-transparency block-type solution polymerized styrene-butadiene rubber, the combined styrene content accounts for 40 to 50 percent of the total weight of the polymer, the vinyl content accounts for 20 to 40 percent of the total weight of 1, 3-butadiene in the polymer, the block styrene content accounts for 4 to 20 percent of the total weight of the polymer, the Mooney viscosity is 10 to 110, and the molecular weight is 8 to 20 ten thousand.
The second technical scheme of the invention is realized by the following measures that the preparation method of the high-transparency block type solution polymerized styrene-butadiene rubber, which is used for implementing the first technical scheme, is carried out according to the following steps:
firstly, adding a styrene monomer, a1, 3-butadiene monomer, a hydrocarbon solvent, a first structure regulator and a second structure regulator into a polymerization kettle under the protection of nitrogen, and adding an initiator alkyl lithium at the temperature of 40-60 ℃ to initiate a reaction;
And secondly, continuously reacting for 20min to 2.5h at the temperature of 90 ℃ to 125 ℃, and then adding a required amount of terminator into a polymerization kettle to terminate the reaction, thus obtaining the high-transparency block-type solution polymerized styrene-butadiene rubber.
The preparation method of the high-transparency block-type solution polymerized styrene-butadiene rubber has the advantages of simple process, easy design of polymer molecular weight, easy control of polymer microstructure, suitability for industrial mass production, and excellent transparency.
Drawings
FIG. 1 is a gel permeation chromatogram of a high transparent block type solution polymerized styrene-butadiene rubber prepared in example 3 of the present invention, wherein the abscissa represents time and the ordinate represents molecular weight.
FIG. 2 is a nuclear magnetic resonance 1 H-NMR spectrum of the high-transparency block-type solution polymerized styrene-butadiene rubber prepared in example 4 of the present invention.
FIG. 3 is a graph showing the transparency test of the high transparent block type solution polymerized styrene-butadiene rubber, the commercial block type solution polymerized styrene-butadiene rubber and the thermoplastic elastomer SBS prepared in example 3 of the present invention, wherein the abscissa indicates the wavelength and the ordinate indicates the light transmittance.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments can be determined according to the technical scheme and practical situations of the present invention. The chemical reagents and chemical supplies mentioned in the invention are all commonly used chemical reagents and chemical supplies known in the prior art unless specified otherwise, the percentages in the invention are all mass percentages unless specified otherwise, and the normal temperature and the room temperature in the invention generally refer to the temperature of 15 ℃ to 25 ℃ and are generally defined as 25 ℃.
The invention is further described below with reference to examples:
Example 1 the high transparent block type solution polymerized styrene-butadiene rubber was obtained as follows:
firstly, adding a styrene monomer, a1, 3-butadiene monomer, a hydrocarbon solvent, a first structure regulator and a second structure regulator into a polymerization kettle under the protection of nitrogen, and adding an initiator alkyl lithium at the temperature of 40-60 ℃ to initiate a reaction;
And secondly, continuously reacting for 20min to 2.5h at the temperature of 90 ℃ to 125 ℃, and then adding a required amount of terminator into a polymerization kettle to terminate the reaction, thus obtaining the high-transparency block-type solution polymerized styrene-butadiene rubber.
The hydrocarbon solvent is one of cyclopentane, cyclohexane, n-pentane and n-hexane, the mass ratio of the styrene monomer to the 1, 3-butadiene monomer is 4:6-5:5, and the ratio of the total amount of the styrene monomer and the 1, 3-butadiene monomer to the hydrocarbon solvent is 1:9-2:8.
The initiator alkyllithium is one of n-butyllithium, sec-butyllithium and tert-butyllithium, and the amount of alkyllithium is 0.5mmol to 1.2mmol per 100g total amount of styrene monomer and 1, 3-butadiene monomer.
The first structural regulator is one of tetrahydrofuran, 2, 5-dimethyl furan and 2, 2-di (2-furyl) propane, and the mass ratio of the first structural regulator to the hydrocarbon solvent is 0.2:1000-3:1000.
The structure regulator II is one of tetrahydrofurfuryl ethyl ether, 2-tert-butyloxymethyl tetrahydrofuran and sodium dodecyl benzene sulfonate, and the molar ratio of the structure regulator II to the initiator alkyl lithium is 1:10 to 1:1.
The terminating agent is an alcohol substance or a silicon-halogen bond compound, and the molar ratio of the adding amount of the terminating agent to the alkyl lithium is 1:1-2:1.
The alcohol is one of ethanol, glycol, glycerol and isopropanol.
The structural general formula of the silicon-halogen bond compound is SiXM 3, wherein X is one of F, cl, br, I, and M is one of methyl, ethyl and isopropyl.
In the high-transparency block-type solution polymerized styrene-butadiene rubber, the combined styrene content accounts for 40 to 50 percent of the total weight of the polymer, the vinyl content accounts for 20 to 40 percent of the total weight of 1, 3-butadiene in the polymer, the block styrene content accounts for 4 to 20 percent of the total weight of the polymer, the Mooney viscosity is 10 to 110, and the molecular weight is 8 to 20 ten thousand.
According to the invention, hydrocarbon substances are used as solvents, 1, 3-butadiene monomers and styrene monomers are used as raw materials, alkyl lithium is used as an initiator, under the double regulation action of two structure regulators with different polarities, an intermittent polymerization mode is adopted, and the optimization of molecular design and chain structure is realized by controlling the feeding quantity and proportion within a wide temperature range, so that the high-transparency block-type solution polymerized styrene-butadiene rubber is prepared.
The invention selects two types of structure regulators, wherein the first structure regulator is aprotic ether with medium polarity, and the second structure regulator has stronger polarity and larger steric hindrance. The structure regulator has the main functions of ① to raise solvent polarity, ② to regulate the reactivity ratio of styrene and butadiene, change the copolymerization mode of two monomers, ③ to make alkyl lithium initiator produce polarization and solvation effect, lower the association degree of lithium ion in alkyl lithium and ④ to raise polymerization rate. The structure modifier I and the structure modifier II interact in the synthesis process, wherein the structure modifier I is aprotic ether with medium polarity, can change the polarity of a solvent, has limited regulation capacity on vinyl groups, tends to produce block copolymers, and can be beneficial to the formation of blocks to a certain extent in a low vinyl group range. The structure regulator II has larger steric hindrance and stronger polarity, can lead the initiator alkyl lithium to be dissociated, can be complexed with an active polybutadiene lithium chain ([ PBLi ]) to form a pi-allyl lithium structure, promotes the active species to be dissociated, and quickens the polymerization reaction speed. For example, 2-t-butoxymethyl tetrahydrofuran has a large volume and forms a large steric hindrance when complexed with [ PBLi ], which makes it easier for 1, 3-butadiene monomers to form 1, 2-structured products when intercalating between C-Li bonds. Therefore, the structural regulator II can not only improve the polymerization reaction rate, but also improve the vinyl content in the polymer.
The invention adopts the anionic polymerization chain end active termination technology to terminate the polymerization reaction, and adopts the alcohol substance or the silicon-halogen bond compound as the terminator, thereby effectively terminating the chain end active center, and further avoiding the generation of coupled macromolecules caused by contacting with substances such as water, air, esters, phenols and the like.
Example 2 As an optimization of the above example, the high transparent block type solution polymerized styrene-butadiene rubber was obtained as follows:
The preparation method comprises the steps of adding a styrene monomer, a1, 3-butadiene monomer, a hydrocarbon solvent, a first structure regulator and a second structure regulator into a polymerization kettle under the protection of nitrogen, adding an initiator alkyl lithium at the temperature of 40 ℃ or 60 ℃ to initiate reaction, continuously reacting for 20 minutes or 2.5 hours at the temperature of 90 ℃ or 125 ℃, and then adding a terminator with the required amount into the polymerization kettle to terminate the reaction to obtain the high-transparency block-type solution polymerized styrene-butadiene rubber.
The hydrocarbon solvent is one of cyclopentane, cyclohexane, n-pentane and n-hexane, the mass ratio of the styrene monomer to the 1, 3-butadiene monomer is 4:6 or 5:5, and the ratio of the total amount of the styrene monomer and the 1, 3-butadiene monomer to the hydrocarbon solvent is 1:9 or 2:8.
The initiator alkyllithium is one of n-butyllithium, sec-butyllithium and tert-butyllithium, and the amount of alkyllithium is 0.5mmol or 1.2mmol per 100g total amount of styrene monomer and 1, 3-butadiene monomer.
The first structural regulator is one of tetrahydrofuran, 2, 5-dimethyl furan and 2, 2-di (2-furyl) propane, and the mass ratio of the first structural regulator to hydrocarbon solvent is 0.2:1000 or 3:1000.
The structure regulator II is one of tetrahydrofurfuryl ethyl ether, 2-tert-butyloxymethyl tetrahydrofuran and sodium dodecyl benzene sulfonate, and the molar ratio of the structure regulator II to the initiator alkyl lithium is 1:10 or 1:1.
The terminating agent is an alcohol substance or a silicon-halogen bond compound, and the molar ratio of the adding amount of the terminating agent to the alkyl lithium is 1:1 or 2:1.
The alcohol is one of ethanol, glycol, glycerol and isopropanol.
The structural general formula of the silicon-halogen bond compound is SiXM 3, wherein X is one of F, cl, br, I, and M is one of methyl, ethyl and isopropyl.
In the high-transparency block-type solution polymerized styrene-butadiene rubber, the combined styrene content is 40% or 50% of the total weight of the polymer, the vinyl content is 20% or 40% of the total amount of 1, 3-butadiene in the polymer, the block styrene content is 4% or 20% of the total weight of the polymer, the Mooney viscosity is 10 or 110, and the molecular weight is 80000 or 200000.
Example 3 the high transparent block type solution polymerized styrene-butadiene rubber was obtained as follows:
Firstly, under the protection of nitrogen, 162g of styrene monomer, 190g of 1, 3-butadiene monomer, 2000g of cyclopentane, 2.0g of tetrahydrofuran and 0.37g of 2-t-butoxymethyl tetrahydrofuran (the mol ratio of the 2-t-butoxymethyl tetrahydrofuran to the n-butyllithium is 4:5) are added into a polymerization kettle, and 2.93mmol of initiator n-butyllithium is added at the temperature of 50 ℃ to initiate reaction;
And secondly, continuously reacting for 2 hours at the temperature of 90 ℃, and then adding a terminator ethanol 0.16 g (the molar ratio of ethanol to n-butyllithium is 6:5) into a polymerization kettle to terminate the reaction, thus obtaining the high-transparency block type solution polymerized styrene-butadiene rubber.
And drying and weighing the prepared high-transparency block-type solution polymerized styrene-butadiene rubber. The monomer conversion was determined and calculated to be about 95%, the number average molecular weight Mn was 11.5 ten thousand, the molecular weight distribution index Mw/Mn was 1.03, and the Mooney viscosity was 44.1. The high transparent block type solution polymerized styrene-butadiene rubber had a bound styrene content of 45.5% by weight (based on the total weight of the polymer), a block styrene content of 14.2% by weight (based on the total weight of the polymer) and a vinyl content of 34.6% by weight (based on the total amount of polymerized 1, 3-butadiene).
Example 4 the high transparent block type solution polymerized styrene-butadiene rubber was obtained as follows:
Firstly, 162g of styrene monomer, 190g of 1, 3-butadiene monomer, 2000g of cyclopentane, 3.0 g g of 2, 2-di (2-furyl) propane and 0.22g of ethyl tetrahydrofurfuryl ether (the molar ratio of the ethyl tetrahydrofurfuryl ether to the n-butyllithium is 3:5) are added into a polymerization kettle under the protection of nitrogen, and 2.8mmol of initiator n-butyllithium is added at the temperature of 50 ℃ to initiate reaction;
and secondly, continuously reacting for 2 hours at the temperature of 90 ℃, and then adding a terminator triethylchlorosilane 0.64 g (the mole ratio of triethylchlorosilane to n-butyllithium is 6:5) into a polymerization kettle to terminate the reaction, thus obtaining the high-transparency block-type solution polymerized styrene-butadiene rubber.
And drying and weighing the prepared high-transparency block-type solution polymerized styrene-butadiene rubber. The monomer conversion was determined and calculated to be about 98%, the number average molecular weight Mn was 12.5 ten thousand, the molecular weight distribution index Mw/Mn was 1.03, and the Mooney viscosity was 45.2. The high transparent block type solution polymerized styrene-butadiene rubber had a bound styrene content of 45.1% by weight (based on the total weight of the polymer), a block styrene content of 12.6% by weight (based on the total weight of the polymer) and a vinyl content of 31.2% by weight (based on the total amount of polymerized 1, 3-butadiene).
Example 5 the high transparent block type solution polymerized styrene-butadiene rubber was obtained as follows:
Firstly, under the protection of nitrogen, 162g of styrene monomer, 190g of 1, 3-butadiene monomer, 2000g of cyclopentane, 4.0g of 2, 5-dimethyl furan and 0.36g of sodium dodecyl benzene sulfonate (the molar ratio of ethyl tetrahydrofurfuryl ether to sec-butyllithium is 2:5) are sequentially added into a polymerization kettle, and an initiator sec-butyllithium is added at the temperature of 50 ℃ for 2.59mmol to initiate reaction;
And secondly, continuously reacting for 2 hours at the temperature of 90 ℃, and then adding a terminator ethanol 0.15 g (the molar ratio of ethanol to sec-butyllithium is 6:5) into a polymerization kettle to terminate the reaction, thus obtaining the high-transparency block type solution polymerized styrene-butadiene rubber.
And drying and weighing the prepared high-transparency block-type solution polymerized styrene-butadiene rubber. The monomer conversion was determined and calculated to be about 98%, the number average molecular weight Mn was 13.6 ten thousand, the molecular weight distribution index Mw/Mn was 1.02, and the Mooney viscosity was 50. The high transparent block type solution polymerized styrene-butadiene rubber had a bound styrene content of 45.80% by weight (based on the total weight of the polymer), a block styrene content of 9.2% by weight (based on the total weight of the polymer) and a vinyl content of 28.9% by weight (based on the total amount of polymerized 1, 3-butadiene).
Example 6 the high transparent block type solution polymerized styrene-butadiene rubber was obtained as follows:
Firstly, under the protection of nitrogen, 3500g of styrene monomer, 4100g of 1, 3-butadiene monomer, 43000g of n-hexane, 107.5g of tetrahydrofuran and 2.43 g g of 2-t-butoxymethyl tetrahydrofuran (the mol ratio of the 2-t-butoxymethyl tetrahydrofuran to the t-butyllithium is 1:5) are added into a polymerization kettle, and 50.39mmol of initiator t-butyllithium is added at the temperature of 45 ℃ to initiate reaction;
and secondly, continuously reacting for 1h at the temperature of 110 ℃, and then adding 3.25g of a terminator ethanol (the molar ratio of the ethanol to the tertiary butyl lithium is 7:5) into a polymerization kettle to terminate the reaction, thereby obtaining the high-transparency block type solution polymerized styrene-butadiene rubber.
And drying and weighing the prepared high-transparency block-type solution polymerized styrene-butadiene rubber. The monomer conversion was determined and calculated to be about 98%, the number average molecular weight Mn was 15.1 ten thousand, the molecular weight distribution index Mw/Mn was 1.02, and the Mooney viscosity was 56. The high transparent block type solution polymerized styrene-butadiene rubber had a bound styrene content of 45.9% by weight (based on the total weight of the polymer), a block styrene content of 15.7% by weight (based on the total weight of the polymer) and a vinyl content of 30.7% by weight (based on the total amount of polymerized 1, 3-butadiene).
The high transparent block type solution-polymerized styrene-butadiene rubber prepared in examples 3 to 6 of the present invention was tested by Gel Permeation Chromatography (GPC) for number average molecular weight Mn and molecular weight distribution index (Mw/Mn), the high transparent block type solution-polymerized styrene-butadiene rubber was tested by fourier infrared spectrometer (FTIR) for combined styrene content and vinyl content, and the block styrene content was analyzed and tested by nuclear magnetic vibration 1 H-NMR for mooney viscosity and mooney viscosimeter for mooney viscosimeter.
FIG. 1 is a gel permeation chromatogram of a high transparent block type solution polymerized styrene-butadiene rubber prepared in example 3 of the present invention. As can be seen from FIG. 1, the gel permeation chromatogram of the high transparent block type solution polymerized styrene-butadiene rubber prepared in example 3 shows unimodal molecular weight distribution, has symmetrical peak shape, only contains a very small amount of double coupling peaks, has narrow molecular weight distribution, indicates that the side reaction is less, and effectively avoids coupled macromolecules generated by the polymer contacting with substances such as water, air, esters, phenols and the like in the reaction.
FIG. 2 is a 1 H-NMR spectrum of a high-transparency block-type solution polymerized styrene-butadiene rubber prepared in example 4 of the present invention, which is calculated by a calculation method provided by the literature "microstructure adjustment of styrene-butadiene copolymer and design synthesis of solution polymerized styrene-butadiene (SSBR)" (Zhao Fangyuan. Microstructure adjustment of styrene-butadiene copolymer and design synthesis of solution polymerized styrene-butadiene (SSBR) [ D ]. Beijing university), to obtain a high-transparency block-type solution polymerized styrene-butadiene rubber with a randomness R of 74.2% and a block styrene content of 12.6%.
Transparency test:
The high transparent block type solution polymerized styrene-butadiene rubber, the commercially available block type solution polymerized styrene-butadiene rubber and the thermoplastic elastomer SBS prepared in example 3 were cut into 1mm thick sheets, and the direct light transmittance (the light transmittance at each wavelength was repeatedly measured 4 times to average value) test results thereof in the wavelength range of 380nm to 810nm were tested using a visible spectrometer, as shown in FIG. 3. As can be seen from FIG. 3, the high transparent block-type solution polymerized styrene-butadiene rubber of the present invention has a higher transparency than the commercial block-type solution polymerized styrene-butadiene rubber, and has a direct light transmittance of more than 45% in the wavelength range of 380nm to 810nm and a direct light transmittance of more than 60% in the wavelength range of 600nm to 810 nm. Therefore, the high-transparency block-type solution polymerized styrene-butadiene rubber can be widely applied to shoe industry, and the transparency and glossiness of shoe products are improved, so that the development of domestic high-end shoe industry is driven, and the high-transparency block-type solution polymerized styrene-butadiene rubber can be popularized and applied to other rubber products or plastic modification, and the unique application value of the high-transparency block-type solution polymerized styrene-butadiene rubber is brought into play.
In conclusion, the preparation method of the high-transparency block-type solution polymerized styrene-butadiene rubber has the advantages of simple process, easy design of polymer molecular weight, easy control of polymer microstructure and suitability for industrial mass production. The prepared transparent block type solution polymerized styrene-butadiene rubber has excellent transparency, can be widely applied to the shoe industry, and can obviously improve the transparency of rubber products.
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