CN101735419B - Star-shaped high styrene rubber and preparation method thereof - Google Patents
Star-shaped high styrene rubber and preparation method thereof Download PDFInfo
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- CN101735419B CN101735419B CN2008102266269A CN200810226626A CN101735419B CN 101735419 B CN101735419 B CN 101735419B CN 2008102266269 A CN2008102266269 A CN 2008102266269A CN 200810226626 A CN200810226626 A CN 200810226626A CN 101735419 B CN101735419 B CN 101735419B
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 229920001971 elastomer Polymers 0.000 title claims abstract description 69
- 239000005060 rubber Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 105
- 239000000178 monomer Substances 0.000 claims abstract description 89
- 239000007822 coupling agent Substances 0.000 claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 238000005859 coupling reaction Methods 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 48
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 19
- 239000005977 Ethylene Substances 0.000 claims description 19
- 230000035484 reaction time Effects 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 230000008878 coupling Effects 0.000 claims description 12
- 238000010168 coupling process Methods 0.000 claims description 12
- 230000007704 transition Effects 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000012190 activator Substances 0.000 claims description 8
- -1 metals ion Chemical class 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 125000001979 organolithium group Chemical group 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- 230000009257 reactivity Effects 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 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 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical group CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- MCHYIMAQVBCMAP-UHFFFAOYSA-N [Li]C(C)CCC Chemical compound [Li]C(C)CCC MCHYIMAQVBCMAP-UHFFFAOYSA-N 0.000 claims description 2
- ZEDXYOJKIFJKHK-UHFFFAOYSA-N [Li]CCCCC1=CC=CC=C1 Chemical compound [Li]CCCCC1=CC=CC=C1 ZEDXYOJKIFJKHK-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- LEKSIJZGSFETSJ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li]C1CCCCC1 LEKSIJZGSFETSJ-UHFFFAOYSA-N 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- FVLCOZJIIRIOQU-UHFFFAOYSA-N lithium;dodecane Chemical compound [Li+].CCCCCCCCCCC[CH2-] FVLCOZJIIRIOQU-UHFFFAOYSA-N 0.000 claims description 2
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002900 organolithium compounds Chemical class 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000005049 silicon tetrachloride Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 238000007639 printing Methods 0.000 abstract description 4
- 229920005604 random copolymer Polymers 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 239000005062 Polybutadiene Substances 0.000 abstract 5
- 229920002857 polybutadiene Polymers 0.000 abstract 5
- 229920002223 polystyrene Polymers 0.000 abstract 5
- 244000043261 Hevea brasiliensis Species 0.000 abstract 1
- 229920003052 natural elastomer Polymers 0.000 abstract 1
- 229920001194 natural rubber Polymers 0.000 abstract 1
- 229920003051 synthetic elastomer Polymers 0.000 abstract 1
- 239000005061 synthetic rubber Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 28
- 239000000047 product Substances 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 16
- 238000010792 warming Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000006073 displacement reaction Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000003292 glue Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000004816 latex Substances 0.000 description 7
- 229920000126 latex Polymers 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002449 FKM Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- ANJLMAHUPYCFQY-UHFFFAOYSA-N 4-phenyl-1h-benzimidazole-2-sulfonic acid Chemical class C=12NC(S(=O)(=O)O)=NC2=CC=CC=1C1=CC=CC=C1 ANJLMAHUPYCFQY-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 241000270666 Testudines Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000005728 strengthening Methods 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
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides star-shaped high styrene rubber and a preparation method thereof. The structural formula of the star high styrene rubber is represented as follows: y- [ B1→S1-B2/S2]4Wherein Y is Si or Sn; b is1→S1Is a polystyrene and polybutadiene tapered copolymer; b is2/S2The polystyrene and polybutadiene random copolymer is a polystyrene and polybutadiene random copolymer, the polystyrene and polybutadiene gradual change section in the structural formula is 40-75 wt%, and the mass fraction of the polystyrene and polybutadiene random section is 25-60 wt%; the star-shaped high styrene rubber polymer contains 45-75 wt% of styrene and 25-55 wt% of butadiene. The preparation method of the star high styrene rubber comprises the steps of adding the initiator once, adding the monomers into a polymerization system twice according to a certain sequence, and adding the coupling agent for coupling reaction after the polymerization is finished. The high styrene rubber has the characteristics of high hardness and good strength, can improve the performances of rigidity, hardness, wear resistance, shrinkage reduction and the like of rubber products when being used together with various synthetic rubbers or natural rubbers, and can be widely applied to the shoe manufacturing industry, the tire industry, the printing industry and other industries.
Description
Technical field
The present invention relates to a kind of star copolymer and preparation method thereof, star high styrene rubber of particularly a kind of high rigidity, high firmness, high abrasion and preparation method thereof.
Background technology
The multipolymer that divinyl and vinylbenzene are formed is if combined styrene content is high, with obtaining little and the resin copolymer that plasticity is bigger of elasticity; Otherwise, then obtain the big less rubbery copolymer of plasticity of elasticity.Usually call high styrene rubber to the multipolymer of vinylbenzene binding capacity between 45%～70% in the molecular structure.The distinguishing feature of high styrene rubber is that hardness own is high, intensity is good; And the physicals that has rubber again; With multiple viton or tree elastomer and time spent; Can improve the performances such as rigidity, hardness, wear resistance, reduction shrinking percentage of rubber item, can be widely used in shoemaking industry, tire industry, Printing industry and other industry, and extremely pay attention to.
CN 1224733 has announced a kind of " graft-blending high-phenylethylene rubber and method of manufacture thereof "; It is main raw material that waste polystyrene foam and styrene-butadiene rubber(SBR) or cis-1,4-polybutadiene rubber are adopted in this invention; Blend graft under effects such as linking agent, initiator; Form high styrene rubber, have cost low, improve environmental pollution, advantage such as ME is simple.CN 1271740 disclosed " working method of high-phenylethylene ", its product high-phenylethylene is a kind of rubber and plastic product, as elastomeric strengthening agent; Can with the various viton except that butyl rubber, tree elastomer and usefulness are improved the tensile strength of rubber; Tear strength, the hardness of raising rubber, wear resistance and electrical insulating property; Be used to make high firmness; The goods that specific density is little, the high styrene resin emulsion is got through letex polymerization by divinyl, vinylbenzene, and itself and SBR-1502 latex are carried out common cohesion, dehydration, granulation by the combined styrene content requirement.Advantages such as this product has the hardness height, and mooney viscosity is big, the production technology operation of this invention, control easily.CN 1544522 said " preparation method of high styrene rubber " this patent is to produce with high styrene resin and high styrene latex blending.It is emulsifying agent that patent is calculated soap, alkyl-sulphate, phenylbenzimidazole sulfonic acid salt etc. with fatty acid soaps, rosin; With the superoxide is initiator, is regulator with mercaptan, adds ionogen commonly used; Under 40-80 ℃; Make the styrene emulsion copolymerization of divinyl and the 75-95% of 5-25%, in 5-12h, transformation efficiency>prepared high styrene resin under 98.5% the condition; Use aforesaid method synthetic high styrene resin emulsion again,, be prepared into high styrene rubber with the SBR-1502 latex that contains vinylbenzene 23.5 ± 1% or SBR-1500 latex blending, cohesion altogether.It is short to have the reaction times, control easily, constant product quality, distinguishing feature such as energy consumption is low.
See from result for retrieval; Though it is more to produce the document patent of high styrene rubber both at home and abroad; But adopt latex condensation technique altogether mostly, this technological process can access the high styrene rubber of better performances, but the subject matter that this method exists is: at first on technology; Need synthetic respectively earlier SBR-1500 or SBR-1502 latex and high styrene resin emulsion; Mix again by a certain percentage analyzing two kinds of qualified emulsions, obtain high styrene rubber through the cohesion drying then, its technical process relatively length need twice the synthesis procedures such as preparation and the degassing of water, oil phase, initiator; Secondly on production cost; Because synthetic SBR-1500 or SBR-1502 latex monomer transformation efficiency only 70%; Unreacted monomer accounts for 30%; And this part monomer is difficult to reclaim in the production equipment of middle and small scale, causes production cost is higher and polymerization process is required equipment, auxiliary material, personnel, time, the energy more relatively; On the production cycle, because the synthesis temperature of high styrene resin emulsion is high temperature polymerization, polymeric kettle inner structure gel is more in addition, and used polymeric kettle is produced 10 batches of needs usually and carried out once clear still operation, so plant factor is lower.
Adopt the synthetic high styrene rubber of method of solution polymerization, compare with emulsion polymerization technology, have cost low, improve environmental pollution, advantage such as ME is simple.CN96118387.X has reported styrene-butadiene block copolymer and method of manufacture thereof, and it mainly is a preparation SBS thermoplastic elastomer, and product is a block structure, and no transition does not have the variation of contents of ethylene simultaneously yet.Patent CN1264714 has reported that to cause preparation low by 1 by containing many huge legendary turtles type organolithium, alkoxyl group potassium or sodium alkylate, polar additive, and the 2-structure is gripped the method for diene and single ethene aromatic hydrocarbons random copolymers altogether.Wherein gripping diolefinic monomer altogether is 1,3-butadiene, and single ethene aromatic monomer is a vinylbenzene, and the content of gripping diolefinic monomer altogether is 50～85%, and the content of single ethene aromatic monomer is 15～50%.Alkoxyl group potassium is 0.01～0.6 with the mol ratio that adds the initiator system organic single-lithium, is 0.025-0.5 preferably, and polar additive is 0～1 with the mol ratio that adds the initiator system organic single-lithium.Polar additive is a THF, and polymerization temperature is 0～150 ℃, is preferably 50～80 ℃, uses tin tetrachloride to carry out linked reaction as coupling agent, and coupling agent is 0.1～0.2 with the mol ratio of the organic single-lithium that adds initiator system.This product is a block structure, does not have random section.US4367325 has reported the preparation method of a kind of high-vinyl-content divinyl, styrenerubber; The synthetic high-vinyl styrene-butadiene rubber(SBR) with gradual change vinyl structure of the method for alternating temperature is adopted in polymerization; Contents of ethylene in the divinyl microscopic units >=70%; Product has the better dynamic mechanical property, but this polymkeric substance does not have transition.Patent US 4519431 has reported a kind of preparation method of solution method high styrene rubber; Adopt monomer once to add; Initiator once adds the high styrene rubber of the synthetic hub-and-spoke configuration of method of coupling then; The reinforced number of times of this technology is less, simple to operate, but the divinyl microscopic units is a homogeneous structural in the product.Above-mentioned polymkeric substance all exists product tensile strength and the not high enough shortcoming of hardness.
Summary of the invention
In order to solve the existing in prior technology problem; The invention provides a kind of star high styrene rubber and preparation method thereof; Product of the present invention has the advantages that tensile strength is good, hardness is high; Be fit to do reinforcement and high hardness material, can be widely used in shoemaking industry, tire industry, Printing industry and other industry.
A kind of star high styrene rubber, its structural formula is represented as follows: Y-[B
1→ S
1-B
2/ S
2]
4, wherein Y is Si or Sn; B
1→ S
1Be PS and polyhutadiene transition multipolymer; B
2/ S
2Be PS and random section multipolymer of polyhutadiene, PS and polyhutadiene transition massfraction are 40～75% in the structural formula, and random section massfraction of PS and polyhutadiene is 25～60%; Be 100% in total monomer weight in this star high styrene rubber polymkeric substance, styrene content is 45～75wt%, and butadiene content is 25～55wt%.
Wherein in PS and the polyhutadiene transition multipolymer in the butadiene unit contents of ethylene be 5～15wt%; In random section multipolymer of PS and polyhutadiene in the butadiene unit contents of ethylene be 20～50wt%.
Cinnamic parts by weight are preferably 50～70wt% in the star high styrene rubber multipolymer of the present invention, and the parts by weight of divinyl are preferably 30～50wt%.
The molecular weight of star high styrene rubber of the present invention is 100000～400000, and molecular weight distributing index is 1.2～5.
Specifically, multipolymer of the present invention can obtain through following mode: initiator is once added, and monomer joins paradigmatic system at twice in certain sequence, after the finishing polymerization, adds coupling agent again and carries out linked reaction and make, and its order of addition(of ingredients) is following:
The I step: add vinylbenzene that accounts for monomer total amount 27～45wt% and the divinylic monomer mixture that accounts for monomer total amount 15～33wt%; Polymerization under the effect of organic lithium initiator; Because vinylbenzene is different with the reactivity ratio of divinyl, form divinyl and cinnamic transition in the polymerization process: polymkeric substance can be expressed as: B
1→ S
1-Me, (Me is the metals ion of initiator), temperature of reaction is 50 ℃～80 ℃; Reaction pressure is 0.1MPa～0.25MPa, and the reaction times is 20min～80min, and the contents of ethylene of butadiene unit is 5～15wt% in the product; At this moment, no free monomer exists in the polyreaction;
The II step: add vinylbenzene that accounts for monomer total amount 18～30wt% and the divinylic monomer mixture that accounts for monomer total amount 10～22wt%; Add polar activator simultaneously; The reactivity ratio that act as adjusting vinylbenzene and divinyl of polar activator; Make the two random copolymerization, regulate the contents of ethylene of divinyl simultaneously, form living chain P:B
1→ S
1-B
2/ S
2-Me; Temperature of reaction is 50 ℃～80 ℃, and reaction pressure is 0.1MPa～0.25MPa, and the reaction times is 30min～100min, and the butadiene unit contents of ethylene is 20～50wt% in the product, and at this moment, no free monomer exists in the polyreaction;
The III step: add coupling agent Y, form: Y-[B
1→ S
1-B
2/ S
2]
4, the mol ratio of coupling agent consumption and organolithium is 0.1～1.0,60 ℃～100 ℃ of coupling temperature, time 40min～80min.
After reacting completely, polymers soln is used water treatment, the consumption of water is generally 100～300 times of initiator amount, is preferably 150～250 times.Take this just to have made high-phenylethylene content, high firmness, attrition resistant star high styrene rubber.
In order to make polymkeric substance have excellent performance, the invention provides its best preparation method, the preparation process is narrated as follows:
At first will account for monomer total amount 30～40wt% vinylbenzene and join polymerization system, initiation reaction under the initiator effect with the mixture that accounts for monomer total amount 18～30wt% divinylic monomer mixture and varsol.Temperature of reaction is at 50～80 ℃, and the reaction times is 30～80min, does not have free monomer this moment and exists, and polymkeric substance can be expressed as B
1→ S
1-Me, contents of ethylene is 5～15wt% in this section butadiene unit; The vinylbenzene that will account for monomer total amount 20～30wt% again adds paradigmatic system with the divinylic monomer mixture that accounts for monomer total amount 12～20wt%, adds polar activator simultaneously, forms living chain P:B
1/ S
1-B
2S
2-Me, contents of ethylene is 20～50wt% in this section butadiene unit, and temperature of reaction is 50 ℃～80 ℃, and reaction pressure is 0.1MPa～0.25MPa, and the reaction times is 30min～80min; Carry out coupling with a kind of tin or silicide as coupling agent at last, linked reaction is lasted 40～80min and can be accomplished under 60～100 ℃.
The polar organic compound that needs in the paradigmatic system according to the invention to add 0.01～0.1phm is as promoting agent; Make alkyl lithium initiator produce polarization or solvation effect; Reduce its degree of association, improve the initiation reaction speed of positive initiator such as n-Butyl Lithium, acvator can also be regulated the reactivity ratio of vinylbenzene and divinyl; Make the two random copolymerization, acvator can improve the content of vinyl in the butadiene unit simultaneously.This type polar organic compound comprises diethylene glycol dimethyl ether (2G), THF (THF), ether, ethyl methyl ether, methyl-phenoxide, phenyl ether, glycol dimethyl ether (DME), triethylamine, 6-methyl phosphonic triamide etc., preferred diethylene glycol dimethyl ether, THF.The consumption of promoting agent is 0.02～0.08phm preferably.
Polymers soln can add oxidation inhibitor before solvent steams, as 1076,1010,264, and TNP, one or more in the tri-isopropanolamine, add-on is 0.5～5wt%, is preferably 0.5～2wt%.
The separation of polymkeric substance from solution can be adopted traditional steam stripping coacervation method, also available devolatilization type screw extrusion press.
The initiator that uses among the present invention is preferably the organic single-lithium compound, and commonly used is alkyl list lithium compound, i.e. RLi, and wherein R is the compound base of the representative examples of saturated aliphatic alkyl, alicyclic alkyl, aryl or the above-mentioned group that contain 1～20 carbon atom.This organolithium compound comprises n-Butyl Lithium, s-butyl lithium, methylbutyl lithium, phenyl butyl lithium, naphthalene lithium, cyclohexyl lithium, dodecyl lithium etc.The most frequently used is n-Butyl Lithium and s-butyl lithium.The add-on of organolithium is by the molecular weight decision of the polymkeric substance of design.
The used coupling agent of the present invention is coupling agents such as tin tetrachloride, silicon tetrachloride, and adopting many active site coupling agent is the effective measure of preparation star high styrene rubber.The consumption of coupling agent is decided according to the amount of initiator, and the mol ratio of general coupling agent consumption and organolithium is 0.1～1.0.
In the polymerization process according to the invention, coupling agent can once add, and also can add in batches.
Polyreaction according to the invention is preferably in the inert gas environment and carries out in anaerobic, anhydrous.Polymerization process is accomplished in varsol, and varsol comprises straight-chain paraffin, aromatic hydrocarbons and naphthenic hydrocarbon preferably, like pentane, and hexane, octane, heptane, hexanaphthene, benzene, toluene, ethylbenzene and their mixture, preferably hexanaphthene.Add-on is not particularly limited, and uses common polyreaction aequum to get final product, as being 300～800wt% of total monomer weight.
The mechanical property of high styrene rubber is relevant with the monomer ratio and the molecular weight product of vinylbenzene, divinyl among the present invention.In general, styrene content is high, and its hardness is high, and tensile yield is little; Butadiene content is high, and its hardness is low, and tensile yield is high.Simultaneously, the single armed molecular weight of high styrene rubber determines molecular weight product to a certain extent, thereby influences product performance.It is 50000～150000 that the present invention recommends the single armed molecular weight.
The present invention adopts the synthetic high styrene rubber with different contents of ethylene of the method for twice adding of monomer; Because these different gradual changes-random composition is common and interaction; Can promote the cooperate optimization of the various performances of product, improve the hardness and the dynamic properties of product.Star high styrene rubber of the present invention has high firmness; Intensity is good; And the physicals that has rubber again; With multiple viton or tree elastomer and time spent, can improve the performance such as rigidity, hardness, wear resistance, reduction shrinking percentage of rubber item, can be widely used in shoemaking industry, tire industry, Printing industry and other industry.It is simple that the method for this star high styrene rubber of preparation provided by the present invention has technology, and polymerizing condition is gentle, the characteristics that product performance are stable.
Embodiment
In order to further specify details of the present invention, lift some embodiment below, but should not be so limited.Raw material used among the embodiment all adopts industrial polymerization-grade, and use purified back, does not have other special demands.Embodiment and Comparative Examples result list in the table 1.
Embodiment 1:
In having the 15L stainless steel cauldron of chuck, logical argon gas is with system's displacement 3 times.In polymeric kettle, add hexanaphthene 4315g, vinylbenzene 420g (account for monomer total amount 35%), divinyl 280g (account for monomer total amount 23.3%); Add the n-Butyl Lithium of 12.1mmol, be warming up to 50 ℃, polymerization 80min; Again with 4.32g THF; The mixture of 2194g hexanaphthene and 300g vinylbenzene (account for monomer total amount 25%), 200g divinyl (account for monomer total amount 16.7%) is pressed into polymeric kettle and continues reaction 60min, is warming up to 70 ℃ after monomer transforms fully, adds 3.3mmolSncl
4Coupling agent carries out linked reaction, and the reaction times is 60min.With the reaction mixture after the water treatment coupling, add entry 100g after linked reaction is accomplished, antioxidant 1010 [four-(4-hydroxyl-3,5-t-butyl-phenyl propionic acid) pentaerythritol esters] 12g stirs.Glue is through wet method cohesion, oven dry.
Comparative Examples 1:
Other processing condition and raw material add-on are identical with embodiment 1, and difference is: monomer once adds, and react that no free monomer exists to the polyreaction, finally make the star copolymer with random structure.
Embodiment 2:
In having the 15L stainless steel cauldron of chuck, logical argon gas is with system's displacement 3 times.In polymeric kettle, add hexanaphthene 4444g, vinylbenzene 330g (account for monomer total amount 27.5%), divinyl 300g (account for monomer total amount 25%); Accurately add the n-Butyl Lithium of 24.1mmol, be warming up to 60 ℃, polymerization 50min; Again with 8.64g THF; The mixture of 2088g hexanaphthene and 330g vinylbenzene (account for monomer total amount 27.5%), 240g divinyl (account for monomer total amount 20%) is pressed into polymeric kettle and continues reaction 70min, is warming up to 80 ℃ after monomer transforms fully, adds 6.6mmolSncl at twice
4(add Sncl for the first time
480% of total amount adds remaining 20% behind the reaction 15min) coupling agent carries out linked reaction, and the reaction times is 80min.With the reaction mixture after the water treatment coupling, add 1076 oxidation inhibitor 15g after linked reaction is accomplished, stir.Glue is through wet method cohesion, oven dry.
Comparative Examples 2:
Other processing condition and raw material add-on are identical with embodiment 2; Difference is: feed way is different, and styrene monomer adds at twice, and divinyl once adds; Promptly add the part styrene monomer earlier; Add divinylic monomer after reacting completely, add residual styrene at last, make segmented copolymer.
Embodiment 3:
In having the 15L stainless steel cauldron of chuck, logical argon gas is with system's displacement 3 times.In polymeric kettle, add hexanaphthene 2044g, vinylbenzene 324g (account for monomer total amount 27%), divinyl 396g (account for monomer total amount 33%); Add the n-Butyl Lithium of 8.1mmol, be warming up to 60 ℃, polymerization 50min; Again with 2.16g THF; The mixture of 3777g hexanaphthene and 216g (account for monomer total amount 18%) vinylbenzene, 264g (account for monomer total amount 22%) divinyl is pressed into polymeric kettle and continues reaction 70min, is warming up to 80 ℃ after monomer transforms fully, adds 2.2mmolSncl at twice
4(add Sncl for the first time
480% of total amount adds remaining 20% behind the reaction 15min) coupling agent carries out linked reaction, and the reaction times is 80min.With the reaction mixture after the water treatment coupling, add antioxidant 1076 [3,5-di-tert-butyl-4-hydroxy phenylpropionic acid octadecyl ester] 10g after linked reaction is accomplished, 1010 oxidation inhibitor 5g stir, and glue is through wet method cohesion, oven dry.
Comparative Examples 3:
Commercial high styrene rubber on the market; Vinylbenzene, divinyl raw material add-on are identical with embodiment 3; Difference is: polymerization method is different; At first polymerization high styrene resin (phenylethylene/butadiene=80/20) with styrene-butadiene rubber(SBR) (phenylethylene/butadiene=23/77) blending, makes high styrene rubber then at last.
Embodiment 4:
In having the 15L stainless steel cauldron of chuck, logical argon gas is with system's displacement 3 times.In polymeric kettle, add hexanaphthene 2044g, vinylbenzene 540g (account for monomer total amount 45%), divinyl 180g (account for monomer total amount 15%); Add the n-Butyl Lithium of 12.1mmol, be warming up to 60 ℃, polymerization 50min; Again with 2.16g THF; The mixture of 3777g hexanaphthene and 360g (account for monomer total amount 30%) vinylbenzene, 120g (account for monomer total amount 10%) divinyl is pressed into polymeric kettle and continues reaction 70min, is warming up to 80 ℃ after monomer transforms fully, adds 2.2mmolSncl at twice
4(add Sncl for the first time
480% of total amount adds remaining 20% behind the reaction 15min) coupling agent carries out linked reaction, and the reaction times is 80min.With the reaction mixture after the water treatment coupling, add antioxidant 1076 [3,5-di-tert-butyl-4-hydroxy phenylpropionic acid octadecyl ester] 10g after linked reaction is accomplished, 1010 oxidation inhibitor 5g stir, and glue is through wet method cohesion, oven dry.
Comparative Examples 4:
Other processing condition and raw material addition sequence are identical with embodiment 4; Difference is: styrene monomer accounts for the 27wt% of monomer total amount, and vinylbenzene adds 195g for the first time, and divinyl adds 526g for the first time; Residual monomer adds for the second time, makes solution polymerized butadiene styrene rubber at last.
Embodiment 5:
In having the 15L stainless steel cauldron of chuck, logical argon gas is with system's displacement 3 times.In polymeric kettle, add hexanaphthene 2044g; Vinylbenzene 480g (account for monomer total amount 40%), divinyl 240g (account for monomer total amount 20%) is stirring the n-Butyl Lithium that adds 12.1mmol; Be warming up to 80 ℃; Polymerization 20min, again with 0.68g diethylene glycol dimethyl ether (2G), the mixture of 3777g hexanaphthene and 300g (account for monomer total amount 25%) vinylbenzene, 180g (account for monomer total amount 15%) divinyl is pressed into polymeric kettle and continues reaction 40min; It is 60 ℃ that monomer transforms the back controlled temperature fully, adds 2.2mmolSncl
4Coupling agent carries out linked reaction, and the reaction times is 80min.With the reaction mixture after the water treatment coupling, add antioxidant 1076 [3,5-di-tert-butyl-4-hydroxy phenylpropionic acid octadecyl ester] 10g after linked reaction is accomplished, 1010 oxidation inhibitor 5g stir, and glue is through wet method cohesion, oven dry.
Embodiment 6:
In having the 15L stainless steel cauldron of chuck, logical argon gas is with system's displacement 3 times.In polymeric kettle, add hexanaphthene 2044g; Vinylbenzene 360g (account for monomer total amount 30%), divinyl 240g (account for monomer total amount 20%) is stirring the n-Butyl Lithium that adds 12.1mmol; Be warming up to 60 ℃; Polymerization 60min, again with 0.68g diethylene glycol dimethyl ether (2G), the mixture of 3777g hexanaphthene and 360g (account for monomer total amount 30%) vinylbenzene, 240g (account for monomer total amount 20%) divinyl is pressed into polymeric kettle and continues reaction 40min; It is 80 ℃ that monomer transforms the back controlled temperature fully, divides three times and adds 2.2mmolSncl
4(add Sncl for the first time
450% of total amount adds 20% behind the 2min, add remaining 30% behind the 4min) coupling agent carries out linked reaction, and the reaction times is 60min.With the reaction mixture after the water treatment coupling, add 1010 oxidation inhibitor 12g after linked reaction is accomplished, stir, glue is through wet method cohesion, oven dry.
Embodiment 7:
In having the 15L stainless steel cauldron of chuck, logical argon gas is with system's displacement 3 times.In polymeric kettle, add hexanaphthene 2044g, vinylbenzene 420g, divinyl 280g; Add the n-Butyl Lithium of 12.1mmol, be warming up to 80 ℃, polymerization 40min; Again with 4.32g THF; The mixture of 3777g hexanaphthene and 360g vinylbenzene, 240g divinyl is pressed into polymeric kettle and continues reaction 60min, and it is 80 ℃ that monomer transforms the back controlled temperature fully, divides secondary to add 2.2mmolSicl
4(add Sicl for the first time
480% of total amount adds remaining 20% behind the 15min) coupling agent carries out linked reaction, and the reaction times is 60min.With the reaction mixture after the water treatment coupling, add 1010 oxidation inhibitor 12g after linked reaction is accomplished, stir, glue is through wet method cohesion, oven dry.
Embodiment 8:
In having the 15L stainless steel cauldron of chuck, logical argon gas is with system's displacement 3 times.In polymeric kettle, add pentane 2044g, vinylbenzene 480g (account for monomer total amount 40%), divinyl 240g (account for monomer total amount 20%); Add the n-Butyl Lithium of 12.1mmol, be warming up to 80 ℃, polymerization 20min; Again with 4.32g THF; The mixture of 3777g pentane and 300g vinylbenzene (account for monomer total amount 25%), 180g divinyl (account for monomer total amount 15%) is pressed into polymeric kettle and continues reaction 40min, and it is 60 ℃ that monomer transforms the back controlled temperature fully, divides adding 2.2mmolSncl three times
4(add Sncl for the first time
450% of total amount adds 20% behind the 2min, add remaining 30% behind the 4min) coupling agent carries out linked reaction, and the reaction times is 80min.With the reaction mixture after the water treatment coupling, add antioxidant 1010 oxidation inhibitor 15g after linked reaction is accomplished, stir, glue is through wet method cohesion, oven dry.
Table 1 embodiment and Comparative Examples physical and mechanical properties
Last table shows, in the building-up process of high styrene rubber, adopts and feeds in raw material for twice; Regulate the method for divinyl microtexture when for the second time reinforced, high styrene rubber has transition and random section, and the contents of ethylene of butadiene unit is higher than the contents of ethylene of butadiene unit in the transition in random section simultaneously; High styrene rubber of the present invention has the hardness height, the characteristics that tensile strength is good, comprehensive mechanical property balance; Better (tan δ/0 ℃ value is big more for dynamic properties simultaneously; The anti-slippery that shows rubber is good more, and tan δ/60 ℃ value is more little, shows that the rolling resistance of rubber is more little).
Claims (14)
1. star high styrene rubber, its structural formula is represented as follows: [B
1→ S
1B
2/ S
2]
4Y, wherein Y is Si or Sn; B
1→ S
1Be PS and polyhutadiene transition multipolymer; B
2/ S
2Be PS and random section multipolymer of polyhutadiene, PS and polyhutadiene transition massfraction are 40～75% in the structural formula, and random section massfraction of PS and polyhutadiene is 25～60%; Be 100% in total monomer weight in this star high styrene rubber polymkeric substance, styrene content is 45～75wt%, and butadiene content is 25～55wt%.
2. star high styrene rubber as claimed in claim 1 is characterized in that in PS and the polyhutadiene transition multipolymer that contents of ethylene is 5～15wt% in the butadiene unit; In random section multipolymer of PS and polyhutadiene in the butadiene unit contents of ethylene be 20～50wt%.
3. star high styrene rubber as claimed in claim 1 is characterized in that styrene content is 50～70wt% in the described star high styrene rubber multipolymer, and butadiene content is 30～50wt%.
4. star high styrene rubber as claimed in claim 1, the molecular weight that it is characterized in that described star high styrene rubber is 100000～400000, molecular weight distributing index is 1.2～5.
5. the preparation method of a star high styrene rubber as claimed in claim 1; It is characterized in that initiator is once added, monomer joins paradigmatic system at twice in certain sequence, after the finishing polymerization; Add coupling agent again and carry out linked reaction and make, its order of addition(of ingredients) is following:
The I step: add vinylbenzene that accounts for monomer total amount 27～45wt% and the divinylic monomer mixture that accounts for monomer total amount 15～33wt%; Polymerization under the effect of organic lithium initiator; Because vinylbenzene is different with the reactivity ratio of divinyl, form divinyl and cinnamic transition in the polymerization process: polymkeric substance is expressed as: B
1→ S
1-Me, Me are the metals ion of initiator, and temperature of reaction is 50 ℃～80 ℃; Reaction pressure is 0.1MPa～0.25MPa, and the reaction times is 20min～80min, and the contents of ethylene of butadiene unit is 5～15wt% in the product; At this moment, no free monomer exists in the polyreaction;
The II step: add vinylbenzene that accounts for monomer total amount 18～30wt% and the divinylic monomer mixture that accounts for monomer total amount 10～22wt%; Add polar activator simultaneously; The reactivity ratio that act as adjusting vinylbenzene and divinyl of polar activator; Make the two random copolymerization, regulate the contents of ethylene of divinyl simultaneously, form living chain P:B
1→ S
1-B
2/ S
2-Me; Temperature of reaction is 50 ℃～80 ℃, and reaction pressure is 0.1MPa～0.25MPa, and the reaction times is 30min～100min, and the butadiene unit contents of ethylene is 20～50wt% in the product, and at this moment, no free monomer exists in the polyreaction;
The III step: add coupling agent Y, form: [B
1→ S
1-B
2/ S
2]
4-Y, the mol ratio of coupling agent consumption and organolithium is 0.1～1.0,60 ℃～100 ℃ of coupling temperature; Time 40min～80min; After reacting completely, with polymers soln after with water treatment star high styrene rubber, the consumption of water is 100～300 times of initiator amount;
Described polyreaction is carried out in varsol, and varsol comprises straight-chain paraffin, aromatic hydrocarbons and naphthenic hydrocarbon, and add-on is 300～800wt% of monomer total amount.
6. the preparation method of a star high styrene rubber as claimed in claim 5; It is characterized in that at first will accounting for monomer total amount 30～40wt% vinylbenzene and join polymerization system with the mixture that accounts for monomer total amount 18～30wt% divinylic monomer mixture and varsol; Initiation reaction under the initiator effect, temperature of reaction are at 50～80 ℃, and the reaction times is 30～80min; Do not have free monomer this moment and exist, polymkeric substance is expressed as B
1→ S
1-Me, contents of ethylene is 5～15wt% in this section butadiene unit; The vinylbenzene that will account for monomer total amount 20～30wt% again adds paradigmatic system with the divinylic monomer mixture that accounts for monomer total amount 12～20wt%, adds polar activator simultaneously, forms living chain P:B
1→ S
1-B
2/ S
2-Me, contents of ethylene is 20～50wt% in this section butadiene unit, and temperature of reaction is 50 ℃～80 ℃, and reaction pressure is 0.1MPa～0.25MPa, and the reaction times is 30min～80min; Add coupling agent at last and under 60～100 ℃, carry out linked reaction, the reaction times is 40～80min.
7. preparation method like claim 5 or 6 described star high styrene rubbers; It is characterized in that described polar activator comprises diethylene glycol dimethyl ether, THF, ether, ethyl methyl ether, methyl-phenoxide, phenyl ether, glycol dimethyl ether, triethylamine, 6-methyl phosphonic triamide, add-on is 0.01～0.1phm.
8. the preparation method of a star high styrene rubber as claimed in claim 7 is characterized in that described polar activator consumption is 0.02～0.08phm.
9. preparation method like claim 5 or 6 described star high styrene rubbers; It is characterized in that polymers soln can add the oxidation inhibitor that accounts for monomer total amount 0.5～5wt% before solvent steams; Be selected from 1076,1010,264, TNP, one or more in the tri-isopropanolamine.
10. the preparation method of a star high styrene rubber as claimed in claim 9 is characterized in that described oxidation inhibitor is 0.5～2wt%.
11. preparation method like claim 5 or 6 described star high styrene rubbers; It is characterized in that described initiator is the organic single-lithium compound; Be RLi, wherein R is the compound base of the representative examples of saturated aliphatic alkyl that contains 1～20 carbon atom, alicyclic alkyl, aryl or above-mentioned group.
12. the preparation method of a star high styrene rubber as claimed in claim 11 is characterized in that described organolithium compound comprises n-Butyl Lithium, s-butyl lithium, methylbutyl lithium, phenyl butyl lithium, naphthalene lithium, cyclohexyl lithium, dodecyl lithium.
13. the preparation method like claim 5 or 6 described star high styrene rubbers is characterized in that described coupling agent is tin tetrachloride, silicon tetrachloride, the mol ratio of coupling agent consumption and organolithium is 0.1～1.0.
14. the preparation method like claim 5 or 6 described star high styrene rubbers is characterized in that described coupling agent is once to add or add in batches.
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| CN102558465B (en) * | 2010-12-29 | 2015-03-11 | 中国石油化工股份有限公司 | Synthesizing method of solution polymerized styrene butadiene rubber |
| CN103374109A (en) * | 2012-04-24 | 2013-10-30 | 中国石油天然气股份有限公司 | Star-shaped isoprene-styrene copolymer and preparation method thereof |
| BR112015009244A2 (en) * | 2012-10-24 | 2017-08-22 | Michelin Rech Tech | SBR WITH HIGH STYRENE CONTENT IN RUBBER COMPOSITIONS |
| CN104558457B (en) * | 2013-10-29 | 2018-06-01 | 中国石油天然气股份有限公司 | Star-shaped high styrene rubber and preparation method thereof |
| CN105732894B (en) * | 2014-12-11 | 2018-07-13 | 中国石油天然气股份有限公司 | Double-end functionalized high styrene rubber and preparation method thereof |
| CN105837873B (en) * | 2015-01-15 | 2017-10-17 | 中国石油天然气股份有限公司 | Mixed rubber, preparation method and application thereof |
| CN104817731B (en) * | 2015-04-24 | 2018-03-30 | 茂泰(福建)鞋材有限公司 | A kind of Jing Yin comfortable rubber day skin and preparation method thereof |
| CN113527604B (en) * | 2020-04-22 | 2024-06-11 | 中国石油化工股份有限公司 | Asphalt modifier and preparation method and application thereof |
| CN117487076B (en) * | 2023-12-29 | 2024-03-22 | 新***山子石油化工有限公司 | Wide-distribution modified solution polymerized styrene-butadiene rubber and preparation method thereof |
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| US4519431A (en) * | 1981-11-30 | 1985-05-28 | Bridgestone Tire Company Limited | Styrene-butadiene copolymers with high styrene content |
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| CN1524888A (en) * | 2003-09-16 | 2004-09-01 | 中国石化集团巴陵石油化工有限责任公 | Transparent high-impact styrene-butadiene copolymer and preparation method thereof |
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| US4519431A (en) * | 1981-11-30 | 1985-05-28 | Bridgestone Tire Company Limited | Styrene-butadiene copolymers with high styrene content |
| CN1241582A (en) * | 1998-11-05 | 2000-01-19 | 中国石油兰州化学工业公司 | Fragmentation-resisting simplicial spider block copolymer and its preparation |
| CN1524888A (en) * | 2003-09-16 | 2004-09-01 | 中国石化集团巴陵石油化工有限责任公 | Transparent high-impact styrene-butadiene copolymer and preparation method thereof |
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