CN103539949A - Preparation method of high-performance liquid styrene-butadiene rubber - Google Patents
Preparation method of high-performance liquid styrene-butadiene rubber Download PDFInfo
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- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 54
- 239000007788 liquid Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 71
- 239000011347 resin Substances 0.000 claims abstract description 71
- 239000004816 latex Substances 0.000 claims abstract description 50
- 229920000126 latex Polymers 0.000 claims abstract description 50
- 238000003756 stirring Methods 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000003505 terpenes Chemical class 0.000 claims abstract description 25
- 235000007586 terpenes Nutrition 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002174 Styrene-butadiene Substances 0.000 claims abstract description 15
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000011115 styrene butadiene Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 230000004048 modification Effects 0.000 claims description 20
- 238000012986 modification Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- -1 Xylo-Mucine Chemical compound 0.000 claims description 14
- 229920002678 cellulose Polymers 0.000 claims description 14
- 239000001913 cellulose Substances 0.000 claims description 14
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 13
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 13
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 12
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 12
- 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 claims description 11
- 238000009833 condensation Methods 0.000 claims description 11
- 230000005494 condensation Effects 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical group OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 claims description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 8
- 239000000344 soap Substances 0.000 claims description 8
- 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 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 6
- 238000005189 flocculation Methods 0.000 claims description 5
- 230000016615 flocculation Effects 0.000 claims description 5
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical group CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 30
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000000701 coagulant Substances 0.000 abstract description 3
- 230000015271 coagulation Effects 0.000 abstract 2
- 238000005345 coagulation Methods 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000002562 thickening agent Substances 0.000 abstract 1
- 125000005270 trialkylamine group Chemical group 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 18
- 239000005060 rubber Substances 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 238000013459 approach Methods 0.000 description 13
- 239000012530 fluid Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 8
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000004902 Softening Agent Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000008719 thickening Effects 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- AMYRSDHRQFEUCF-UHFFFAOYSA-N buta-1,3-diene 2-phenylethenol Chemical compound C=CC=C.OC=CC1=CC=CC=C1 AMYRSDHRQFEUCF-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001084 poly(chloroprene) Polymers 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920013649 Paracril Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- DPHPJEIYZKUGGA-UHFFFAOYSA-N [Ca].C(=CC1=CC=CC=C1)S(=O)(=O)O Chemical compound [Ca].C(=CC1=CC=CC=C1)S(=O)(=O)O DPHPJEIYZKUGGA-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 229920001688 coating polymer Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- UZRCGISJYYLJMA-UHFFFAOYSA-N phenol;styrene Chemical compound OC1=CC=CC=C1.C=CC1=CC=CC=C1 UZRCGISJYYLJMA-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to a preparation method of high-performance liquid styrene butadiene rubber, which comprises the following steps: adding ethanol into a reaction bottle, heating to 80-110 ℃, adding terpene resin, stirring until the terpene resin is completely dissolved, adding a dissolved thickening agent, and stirring and mixing uniformly. Sequentially adding water, styrene-butadiene latex, an emulsifier and a molecular weight regulator into a polymerization kettle, replacing with nitrogen, adding modified terpene resin, stirring and heating, adding an initiator when the temperature of the polymerization kettle reaches 30-60 ℃, reacting for 5-8 hours at the polymerization temperature of 30-60 ℃, and adding a terminator to prepare the grafted latex. Adding the grafted latex into a coagulation kettle, adding water, an anti-aging agent and trialkylamine chloride, stirring and heating, adding the coagulant at a coagulation temperature of 20-80 ℃, stirring for 1-3 hours at a temperature of 20-80 ℃ for curing, washing, dehydrating and drying to obtain high-performance liquid butylbenzeneRubber. The prepared high-performance liquid styrene-butadiene rubber has the characteristics that: bound styrene content of 23.5-26.5, number average molecular weight
Description
Technical field
The present invention relates to the preparation method of fluid rubber for coating, particularly relate to a kind of preparation method of high-performance liquid styrene-butadiene rubber(SBR).
Background technology
Fluid rubber is an important kind of rubber, and number-average molecular weight is between 500 ~ 10000.It is reported, the throughput of the various fluid rubbers in the whole world has reached 200kt/a.Fluid rubber is of a great variety, and liquid acrylonitrile butadiene rubber, liquid styrene butadiene rubber and liquid isoprene rubber are all important kinds of fluid rubber, in field separately, has outstanding application advantage.
Liquid styrene butadiene rubber is divinyl and cinnamic low-molecular weight copolymer, and emulsion polymerization liquid styrene-butadiene rubber(SBR) Industrial products have appearred for 1962 in molecular weight 2000～15000 the earliest.Liquid styrene butadiene rubber has excellent electrical insulation capability and physicals, and is insoluble to common organic solvents, heats not melting.The feature of liquid styrene butadiene rubber is good with the intermiscibility of some conventional rubber, so they can blending use, also absorb fillers and oil product simultaneously.Because these blending ingredients are uniformly dispersed, cast good fluidity, so injection moldable produces vulcanite goods, also can be used as the softening agent of styrene-butadiene rubber(SBR), paracril and chloroprene rubber, or as sizing agent, sealing material etc.Terpine resin has that look shallow, high rigidity, high adhesive force, solvability are good, oxidation-resistance and Heat stability is good, there is good consistency with polymkeric substance, when the agent of SBR adhesion rubber, can maintain force of cohesion and good tack, excellent property aspect adhesion fast especially.When terpine resin is grafted to liquid styrene butadiene rubber for coating, greatly improved adhesive performance.
CN200510032745.7 high strong adhesive, this tackiness agent comprises chloroprene rubber, grafted monomer, thickening material, dispersion agent, tackifier, catalyzer, oxidation inhibitor, solvent, filler etc.The method thickening material adds in chloroprene rubber mixing process, adds grafted monomer, dispersion agent, catalyzer etc. in dissolution process, then through again mixing and make high strong adhesive.In the method, thickening material can be carboxymethyl cellulose, and grafted monomer is ester class.CN200310112091.X polyvinyl chloride film adhesive, this tackiness agent is combined by a certain percentage by tackifying resin, VAE emulsion, emulsifying agent, softening agent, thickening material, organic solvent and water.The step of this invention is tackifying resin is mixed with organic solvent and dissolve; Emulsifying agent and softening agent are joined in the tackifying resin solution of the first step gained, be uniformly mixed; Emulsifying agent is sim alkylphenol polyoxy ethyl ether, dodecyl phenenyl sulfate, and softening agent is dibutyl phthalate ester class.By after thickening material and water mixed dissolution, the speed with 10～200ml/min under the agitation condition of 1200～4000r/min joins in second step gained mixture, first forms w/o type emulsion, the rear anti-phase O/W type emulsion that obtains; The 3rd step gained mixture is joined in VAE emulsion, be uniformly mixed, can obtain product.Mono-kind high of CN200910195111.1 holds viscous force glue, natural rubber, oil rubber SIS, naphthenic oil, petroleum resin, natural terpenes resin, rubber accelerator and oxidation inhibitor, consists of.Described in CN201010225123.7, CN201010502113.3, the raw material of coating comprises: terpolymer EP rubber, teflon resin, SBR, terpine resin, SBS, anti-old dispersing auxiliary etc.CN201010106727.X solvent-free polyurethane adhesive for flexible package, at least by A, two kinds of components of B, be mixed and form, A component is the base polyurethane prepolymer for use as that contains terminal isocyanate group end-blocking, and B component is containing the butylbenzene fluid rubber of terminal hydroxy group and/or containing the polyester polyol of the butyronitrile fluid rubber of end carboxyl and the composite composition of polyether glycol.CN201010105813.9 primer coating for extrusion complex of soft package is the mono-component polyurethane polymkeric substance being polymerized by the polyester polyol that contains liquid end hydroxy styrene-butadiene rubber and polyisocyanate solution.In the present invention, the raw material of making effective constituent is consisting of of percentage composition meter by weight: containing the polyester polyol 35%-50% of liquid end hydroxy styrene-butadiene rubber, polyisocyanates 10%-25%, ethyl acetate 30%-50%.CN200410062252.3 waterproof paint, is made by terpolymer EP rubber, styrene-butadiene rubber(SBR), solidifying agent, tenderizer, promotor, vulcanizing agent, antiager and filler.What CN02125508.3, CN02125504.0, CN02125507.5 introduced is the synthetic method of liquid end hydroxy styrene-butadiene rubber, and take divinyl, vinylbenzene is monomer, and organo-peroxide is initiator, organic ketone, C
1-C
6organic Alcohol is solvent, and the free radical polymerisation process carrying out is characterized in that before reaction, having used reaction suppressor, when using reaction suppressor before reaction, after reaction, also can use terminator.
US4448956A has introduced polymeric amide grafting low-molecular-weight liquid paracril etc.JP57042720A has introduced as obtaining a kind of epoxy resin, and by a kind of triphenylphosphine catalyzer, to liquid acrylonitrile butadiene rubber, modification realizes.The foreign patents such as JP57149324A, JP57021427A, JP56106918A have been reported the utilization of fluid rubber.
Both domestic and external be reported as fluid rubber the utilization of different field or by fluid rubber to various polymer modifications, and mostly be liquid acrylonitrile butadiene rubber, liquid isoprene rubber etc.; Or by end group to liquid rubber modified.The present invention utilizes common liquid styrene butadiene rubber emulsion polymerisation process, and to liquid styrene butadiene rubber modification, method is simple, reliable.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high-performance liquid styrene-butadiene rubber(SBR), adopt direct coacervation to prepare a kind of high-performance liquid styrene-butadiene rubber(SBR).
A kind of preparation method of high-performance liquid styrene-butadiene rubber(SBR) is:
In reaction flask, add ethanol, add terpine resin after being heated to 80 ~ 110 ℃, be stirred to it and dissolve completely, add the ether of cellulose of dissolving, be uniformly mixed, make modified terpene resin.In polymeric kettle, add successively water, styrene-butadiene latex, emulsifying agent, molecular weight regulator, with after nitrogen replacement, add modified terpene resin, stirring heating, when polymeric kettle temperature reaches 30～60 ℃, add initiator, under 30～60 ℃ of polymerization temperatures, react 5～8 hours, add terminator, make graft latex.Get graft latex and add cohesion still, 1 adds water, anti-aging agent, trialkyl ammonia chloride, and stirring heating, under 20～80 ℃ of condensation temperatures, add flocculation agent, at 20～80 ℃, stir within 1～3 hour, carry out slaking, then through washing, dehydration, the dry high-performance liquid styrene-butadiene rubber(SBR) that obtains.
In the present invention, the properties-correcting agent of terpine resin is ether of cellulose, as sodium carboxymethylcellulose pyce, Vltra tears sodium, Xylo-Mucine, sodium hydroxyethyl cellulose, preferably carboxymethyl cellulose sodium.
The present invention also provides the best preparation method of described a kind of high-performance liquid styrene-butadiene rubber(SBR), is specially:
1) modification of terpine resin: in reaction flask, add the ethanol that 100 parts of mass percent concentrations are 75%, be heated to 80 ~ 110 ℃, add 0.1～0.6 part of terpine resin, startup agitator is stirred to it and dissolves completely, then adds the ether of cellulose of 0.1～0.5 part of dissolving, is uniformly mixed.
2) preparation of graft latex: add successively 50～150 parts, water, 100 parts, 2～10 parts emulsifying agents of styrene-butadiene latex, 5～15 parts of molecular weight regulators in polymeric kettle, with after nitrogen replacement, add 5～15 parts of modified terpene resins, stir, heat, when polymeric kettle temperature reaches 30～60 ℃, add 0.1～0.4 part of initiator, stir 0.8～1h, then under 30～60 ℃ of polymerization temperatures, react 5～8 hours, add 0.1～0.5 part of terminator, make graft latex.
3) cohesion: get 100 parts of graft latexes and add cohesion still, add 20～100 parts of water, 0.2～0.5 part of anti-aging agent, stirring heating, under 20～80 ℃ of condensation temperatures, add 3～15 parts of flocculation agent, at 20～80 ℃, stir within 1～3 hour, carry out slaking, then through washing, dehydration, the dry high-performance liquid styrene-butadiene rubber(SBR) that obtains.
In the present invention, ether of cellulose, before adding terpine resin, is preferably in water and dissolves, and the mass ratio of the consumption of water and the add-on of ether of cellulose is 100 ︰ (0.1～0.8).Preferably 100 ︰ (0.1～0.3), for it is dissolved faster, need to be heated to 50～80 ℃, preferably 70～80 ℃.
The dissolving of terpine resin in the present invention, need be heated to 80～110 ℃ for terpine resin is comparatively fast dissolved, preferably 90～100 ℃.
In the present invention, in 100 parts of ethanol, the add-on of terpine resin is 0.1～0.6 part, preferably 0.2～0.4 part.
In the present invention, in the modification procedure of terpine resin, the consumption of ether of cellulose is 0.1～0.5 part, preferably 0.1～0.3 part.
In the preparation process of graft latex of the present invention, described emulsifying agent is Sulfates, Sulfonates, in order to guarantee the stability of latex system and to obtain higher percentage of grafting, and preferred disproportionated rosin soap, consumption is 2～10 parts, preferably 4～6 parts.
In the preparation process of graft latex of the present invention, the molecular weight regulator using is selected from tert-dodecyl mercaptan, uncle's ten carbon mercaptan, uncle's 14 carbon mercaptan, uncle's 16 carbon mercaptan, preferred tertiary DDM dodecyl mercaptan, and consumption is 5～15 parts, preferably 7～12 parts.
In the preparation process of graft latex of the present invention, the add-on of modified terpene resin is 5～15 parts, preferably 5 ~ 10 parts.
In the preparation process of graft latex of the present invention, described initiator adopts diazoamino compound or persulphate, preferred diazoamino compound, and as diazoamino acid sodium, consumption is 0.2～1.0 part, preferably 0.2 ~ 0.4 part.
In the present invention, the terminator adopting is selected from Sodium dimethyldithiocarbamate 40min, quinhydrones, and consumption is 0.2～1.0 part, preferably 0.2～0.4 part.
In the preparation process of graft latex of the present invention, polymerization temperature is 30～60 ℃, preferably 40～50 ℃, reacts 5～8 hours.
The anti-aging agent adopting in the present invention is N-Octyl-N '-phenyl-ρ-Ursol D, styrenated phenol etc., optimization styrene phenol.Aging inhibitor dosage is 0.2～0.8 part, preferably 0.3～0.5 part.
In the present invention, emulsion condensation temperature is 20～80 ℃, preferably 20～30 ℃.
The flocculation agent adopting is polymer coagulant, sulfuric acid etc.Described polymer coagulant is selected from acrylamide and styrene sulfonate, ligninsulfonate, vinylformic acid, methacrylic acid etc., as Sodium styrene sulfonate, styrene sulfonic acid calcium etc.
Flocculation agent consumption is 3～15 parts, preferably 5～10 parts.
After graft latex cohesion of the present invention, at curing temperature, be 20～80 ℃, preferably 60～80 ℃.Time is 1～3 hour, preferably 2～3 hours.The high-performance liquid styrene-butadiene rubber(SBR) performance that the inventive method is prepared: combined styrene content 23.5～26.5, number-average molecular weight
viscosity 30 ~ 50(25 ℃) PaS, functionality approaches 2.
With respect to current liquid styrene butadiene rubber preparation, method of modifying, advantage of the present invention has:
(1) terpine resin is applied in styrene-butadiene rubber(SBR) sizing agent, has and maintains force of cohesion and good tack, especially better aspect adhesion fast.And styrene-butadiene latex and terpine resin grafting are as coating, can improve coating polymer cross-linking density, can increase again compactness, snappiness and the sticking power to base material of coating.
(2) ether of cellulose mechanism of modification is that hydrophobic main chain and ambient water molecule, by hydrogen bond association, have improved the fluid volume of polymkeric substance itself, has reduced the space of Particle free activity, thereby has improved system viscosity.
(3) ether of cellulose modified terpene resin, both interact, and the webbed chelation structure of shape, makes the performance of terpine resin modification butadiene-styrene rubber better.
(4) ether of cellulose modified terpene resin reinforcement liquid styrene butadiene rubber is used for doing coating, and the adhesive property of the coating both having strengthened, can reduce costs again.
(5) with respect to the modification of current liquid styrene butadiene rubber end group, this method of modifying is not only simple to operate, reliable, and cost is low.
(6) liquid styrene butadiene rubber is mainly used to do softening agent, sizing agent and sealing material etc. at present, and liquid styrene butadiene rubber of the present invention can be used to do high-grade paint, has expanded its range of application.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention, but and the scope of unrestricted the claims in the present invention protection.
Raw material sources:
Divinyl (B), vinylbenzene (S): CNPC's Lanzhou Petrochemical is produced; Sodium carboxymethylcellulose pyce, Xylo-Mucine: commercially available industrial goods; Terpine resin: commercially available prod; Other auxiliary agent provides by CNPC's Lanzhou Petrochemical.
Embodiment 1
1. the modification of terpine resin: in reaction flask, add 100 parts of water, be heated to 50 ℃, add 0.1 part of sodium carboxymethylcellulose pyce, startup agitator is stirred to sodium carboxymethylcellulose pyce and dissolves completely.In another reaction flask, add the ethanol of 100 parts of mass percent concentrations 75%, be heated to 80 ℃, add 0.1 part of terpine resin, be stirred to it and dissolve completely, then add the sodium carboxymethylcellulose pyce of 0.1 part of dissolving, be uniformly mixed, make modified terpene resin.2. the preparation of graft latex: add successively 50 parts, water, 100 parts, 4 parts disproportionated rosin soaps of styrene-butadiene latex, 5 parts of tert-dodecyl mercaptans in polymeric kettle, with after nitrogen replacement, add 15 parts of modified terpene resins, stir, heat, when polymeric kettle temperature reaches 30 ℃, add 0.3 part of diazoamino acid sodium, stir 1h, then under 30 ℃ of polymerization temperatures, react 8 hours, add 0.5 part of Sodium dimethyldithiocarbamate 40min, make graft latex.3. cohesion: get 100 parts of graft latexes and add cohesion still, add 100 parts of WATER AS FLOW MEDIUM, 0.5 part of styrenated phenol, 0.02 part of trialkyl ammonia chloride, stirring heating, under 80 ℃ of condensation temperatures, add 15 parts of sulfuric acid, at 80 ℃, stir within 3 hours, carry out slaking, then through washing, dehydration, the dry high-performance liquid styrene-butadiene rubber(SBR) that obtains.Adopt classical way specimen, experimental result: combined styrene content 23.5, number-average molecular weight
viscosity 35(25 ℃) PaS, functionality approaches 2.
Comparative example 1
Then experiment condition, with embodiment 1, just not to terpine resin modification, directly condenses styrene-butadiene latex grafting terpine resin experimental result: combined styrene content 23.5, number-average molecular weight
viscosity 26(25 ℃) PaS, functionality approaches 2.
Embodiment 2
1. the modification of terpine resin: in reaction flask, add 100 parts of water, be heated to 80 ℃, add 0.6 part of sodium carboxymethylcellulose pyce, startup agitator is stirred to sodium carboxymethylcellulose pyce and dissolves completely.The quality of ethanol of take is 100 parts, in another reaction flask, the ethanol that adds 100 parts of mass percent concentrations 75%, be heated to 110 ℃, add 0.6 part of terpine resin, be stirred to it and dissolve completely, then add the sodium carboxymethylcellulose pyce of 0.2 part of dissolving, be uniformly mixed, make modified terpene resin.2. the preparation of graft latex: add successively 150 parts, water, 100 parts, 10 parts disproportionated rosin soaps of styrene-butadiene latex, 10 parts of tert-dodecyl mercaptans in polymeric kettle, with after nitrogen replacement, add 5 parts of modified terpene resins, stir, heat, when polymeric kettle temperature reaches 60 ℃, add 0.4 part of diazoamino acid sodium, stir 1h, then under 60 ℃ of polymerization temperatures, react 5 hours, add 0.5 part of Sodium dimethyldithiocarbamate 40min, make graft latex.3. cohesion: get 100 parts of graft latexes and add cohesion still, add 100 parts of WATER AS FLOW MEDIUM, 0.5 part of styrenated phenol, 0.08 part of trialkyl ammonia chloride, stirring heating, under 30 ℃ of condensation temperatures, add 15 parts of sulfuric acid, at 30 ℃, stir within 3 hours, carry out slaking, then through washing, dehydration, the dry high-performance liquid styrene-butadiene rubber(SBR) that obtains.Adopt classical way specimen, experimental result: combined styrene content 23.5, number-average molecular weight
viscosity 50(25 ℃) PaS, functionality approaches 2.
Comparative example 2
Then experiment condition, with embodiment 2, just not to terpine resin modification, directly condenses styrene-butadiene latex grafting terpine resin experimental result: combined styrene content 23.5, number-average molecular weight
viscosity 23(25 ℃) PaS, functionality approaches 2.
Embodiment 3
1. the modification of terpine resin: in reaction flask, add 100 parts of water, be heated to 60 ℃, add 0.3 part of Xylo-Mucine, startup agitator is stirred to Xylo-Mucine and dissolves completely.In another reaction flask, add the ethanol of 100 parts of mass percent concentrations 75%, be heated to 90 ℃, add 0.5 part of terpine resin, be stirred to it and dissolve completely, then add the Xylo-Mucine of 0.3 part of dissolving, be uniformly mixed, make modified terpene resin.2. the preparation of graft latex: add successively 100 parts, water, 100 parts, 6 parts disproportionated rosin soaps of styrene-butadiene latex, 15 parts of tert-dodecyl mercaptans in polymeric kettle, with after nitrogen replacement, add 10 parts of modified terpene resins, stir, heat, when polymeric kettle temperature reaches 40 ℃, add 0.3 part of diazoamino acid sodium, stir 0.8h, then under 40 ℃ of polymerization temperatures, react 8 hours, add 0.2 part of Sodium dimethyldithiocarbamate 40min, make graft latex.3. cohesion: get 100 parts of graft latexes and add cohesion still, add 50 parts of WATER AS FLOW MEDIUM, 0.3 part of styrenated phenol, 0.05 part of trialkyl ammonia chloride, stirring heating, under 50 ℃ of condensation temperatures, add 12 parts of sulfuric acid, at 50 ℃, stir within 2 hours, carry out slaking, then through washing, dehydration, the dry high-performance liquid styrene-butadiene rubber(SBR) that obtains.Adopt classical way specimen, experimental result: combined styrene content 24.5, number-average molecular weight
viscosity 45(25 ℃) PaS, functionality approaches 2.
Comparative example 3
Experiment condition is with embodiment 3, just not to latex grafting, to directly adding in agglomeration process after terpine resin modification.Experimental result: combined styrene content 24.0, number-average molecular weight
viscosity 20(25 ℃) PaS, functionality approaches 2.
Embodiment 4
1. the modification of terpine resin: in reaction flask, add 100 parts of water, be heated to 70 ℃, add 0.4 part of Xylo-Mucine, startup agitator is stirred to Xylo-Mucine and dissolves completely.In another reaction flask, add the ethanol of 100 parts of mass percent concentrations 75%, be heated to 100 ℃, add 0.3 part of terpine resin, be stirred to it and dissolve completely, then add the Xylo-Mucine of 0.4 part of dissolving, be uniformly mixed, make modified terpene resin.2. the preparation of graft latex: add successively 70 parts, water, 100 parts, 8 parts disproportionated rosin soaps of styrene-butadiene latex, 8 parts of tert-dodecyl mercaptans in polymeric kettle, with after nitrogen replacement, add 7 parts of modified terpene resins, stir, heat, when polymeric kettle temperature reaches 50 ℃, add 0.3 part of diazoamino acid sodium, stir 1h, then under 50 ℃ of polymerization temperatures, react 7 hours, add 0.4 part of Sodium dimethyldithiocarbamate 40min, make graft latex.3. cohesion: get 100 parts of graft latexes and add cohesion still, add 80 parts of WATER AS FLOW MEDIUM, 0.4 part of styrenated phenol, 0.03 part of trialkyl ammonia chloride, stirring heating, under 70 ℃ of condensation temperatures, add 13 parts of sulfuric acid, at 70 ℃, stir within 2 hours, carry out slaking, then through washing, dehydration, the dry high-performance liquid styrene-butadiene rubber(SBR) that obtains.Adopt classical way specimen, experimental result: combined styrene content 24.5, number-average molecular weight
viscosity 40(25 ℃) PaS, functionality approaches 2.
Comparative example 4
Experiment condition is with embodiment 4, just not to latex grafting, to directly adding in agglomeration process after terpine resin modification.Experimental result: combined styrene content 24.0, number-average molecular weight
viscosity 20(25 ℃) PaS, functionality approaches 2.
Embodiment 5
1. the modification of terpine resin: in reaction flask, add 100 parts of water, be heated to 60 ℃, add 0.4 part of Xylo-Mucine, startup agitator is stirred to Xylo-Mucine and dissolves completely.In another reaction flask, add the ethanol of 100 parts of mass percent concentrations 75%, be heated to 95 ℃, add 0.4 part of terpine resin, be stirred to it and dissolve completely, then add the Xylo-Mucine of 0.5 part of dissolving, be uniformly mixed, make modified terpene resin.2. the preparation of graft latex: add successively 90 parts, water, 100 parts, 7 parts disproportionated rosin soaps of styrene-butadiene latex, 9 parts of tert-dodecyl mercaptans in polymeric kettle, with after nitrogen replacement, add 9 parts of modified terpene resins, stir, heat, when polymeric kettle temperature reaches 45 ℃, add 0.3 part of diazoamino acid sodium, stir 0.8h, then under 45 ℃ of polymerization temperatures, react 7 hours, add 0.3 part of Sodium dimethyldithiocarbamate 40min, make graft latex.3. cohesion: get 100 parts of graft latexes and add cohesion still, add 80 parts of WATER AS FLOW MEDIUM, 0.4 part of styrenated phenol, 0.07 part of trialkyl ammonia chloride, stirring heating, under 60 ℃ of condensation temperatures, add 8 parts of sulfuric acid, at 60 ℃, stir within 3 hours, carry out slaking, then through washing, dehydration, the dry high-performance liquid styrene-butadiene rubber(SBR) that obtains.Adopt classical way specimen, experimental result: combined styrene content 23.5, number-average molecular weight
viscosity 35(25 ℃) PaS, functionality approaches 2.
Comparative example 5
Experiment condition, with embodiment 5, is the unmodified terpine resin of latex grafting, adds the Xylo-Mucine of dissolving in agglomeration process, in cohesion still, adds after graft latex, adds the Xylo-Mucine of dissolving, then with embodiment 5, condenses.Experimental result: combined styrene content 23.5, number-average molecular weight
viscosity 15(25 ℃) PaS, functionality approaches 2.
Embodiment 6
1. the modification of terpine resin: in reaction flask, add 100 parts of water, be heated to 80 ℃, add 0.5 part of sodium carboxymethylcellulose pyce, startup agitator is stirred to sodium carboxymethylcellulose pyce and dissolves completely.In another reaction flask, add the ethanol of 100 parts of mass percent concentrations 75%, be heated to 85 ℃, add 0.5 part of terpine resin, be stirred to it and dissolve completely, then add the sodium carboxymethylcellulose pyce of 0.3 part of dissolving, be uniformly mixed, make modified terpene resin.2. the preparation of graft latex: add successively 75 parts, water, 100 parts, 9 parts disproportionated rosin soaps of styrene-butadiene latex, 12 parts of tert-dodecyl mercaptans in polymeric kettle, with after nitrogen replacement, add 10 parts of modified terpene resins, stir, heat, when polymeric kettle temperature reaches 35 ℃, add 0.3 part of diazoamino acid sodium, stir 1h, then under 35 ℃ of polymerization temperatures, react 7 hours, add 0.3 part of Sodium dimethyldithiocarbamate 40min, make graft latex.3. cohesion: get 100 parts of graft latexes and add cohesion still, add 60 parts of WATER AS FLOW MEDIUM, 0.3 part of styrenated phenol, 0.06 part of trialkyl ammonia chloride, stirring heating, under 50 ℃ of condensation temperatures, add 11 parts of sulfuric acid, at 50 ℃, stir within 3 hours, carry out slaking, then through washing, dehydration, the dry high-performance liquid styrene-butadiene rubber(SBR) that obtains.Adopt classical way specimen, experimental result: combined styrene content 23.5, number-average molecular weight
viscosity 30(25 ℃) PaS, functionality approaches 2.
Comparative example 6
Experiment condition, with embodiment 6, is the unmodified terpine resin of latex grafting, adds the Xylo-Mucine of dissolving in agglomeration process, in cohesion still, adds after graft latex, adds the Xylo-Mucine of dissolving, then with embodiment 6, condenses.Experimental result: combined styrene content 23.5, number-average molecular weight
viscosity 10(25 ℃) PaS, functionality approaches 2.
Claims (12)
1. a preparation method for liquid styrene butadiene rubber, is characterized in that comprising the steps:
1) modification of terpine resin: in reaction flask, add the ethanol that 100 parts of mass percent concentrations are 75%, be heated to 80 ~ 110 ℃, add 0.1～0.6 part of terpine resin, startup agitator is stirred to it and dissolves completely, then adds the ether of cellulose of 0.1～0.5 part of dissolving, is uniformly mixed; Make modified terpene resin;
2) preparation of graft latex: add successively 50～150 parts, water, 100 parts, 2～10 parts emulsifying agents of styrene-butadiene latex, 5～15 parts of molecular weight regulators in polymeric kettle, with after nitrogen replacement, add 5～15 parts of modified terpene resins, stir, heat, when polymeric kettle temperature reaches 30～60 ℃, add 0.1～0.4 part of initiator, stir 0.8～1h, then under 30～60 ℃ of polymerization temperatures, react 5～8 hours, add 0.1～0.5 part of terminator, make graft latex;
3) cohesion: get 100 parts of graft latexes and add cohesion still, add 20～100 parts of water, 0.2～0.5 part of anti-aging agent, stirring heating, under 20～80 ° of C condensation temperatures, add 3～15 parts of flocculation agent, at 20～80 ℃, stir within 1～3 hour, carry out slaking, then through washing, dehydration, the dry liquid styrene butadiene rubber that obtains.
2. preparation method as claimed in claim 1, is characterized in that described ether of cellulose is sodium carboxymethylcellulose pyce, Vltra tears sodium, Xylo-Mucine, sodium hydroxyethyl cellulose.
3. preparation method as claimed in claim 1, is characterized in that described ether of cellulose, before adding terpine resin, dissolves in water, and the mass ratio of the consumption of water and the add-on of ether of cellulose is 100 ︰ (0.1～0.8).
4. preparation method as claimed in claim 1, the add-on that it is characterized in that terpine resin in 100 parts of ethanol is 0.2～0.4 part.
5. preparation method as claimed in claim 1, is characterized in that in the modification procedure of terpine resin, and the consumption of ether of cellulose is 0.1～0.3 part.
6. preparation method as claimed in claim 1, is characterized in that described emulsifying agent is disproportionated rosin soap, and consumption is 4～6 parts.
7. preparation method as claimed in claim 1, is characterized in that described molecular weight regulator is selected from tert-dodecyl mercaptan, uncle's ten carbon mercaptan, uncle's 14 carbon mercaptan, uncle's 16 carbon mercaptan.
8. preparation method as claimed in claim 1, is characterized in that in the preparation process of described graft latex, the add-on of modified terpene resin is 5～10 parts.
9. preparation method as claimed in claim 1, is characterized in that in the preparation process of graft latex, and described initiator adopts diazoamino compound or persulphate.
10. preparation method as claimed in claim 1, is characterized in that described terminator is selected from Sodium dimethyldithiocarbamate 40min, quinhydrones.
11. preparation methods as claimed in claim 1, is characterized in that, in the preparation process of graft latex, polymerization temperature is 40～50 ℃, react 5～8 hours.
12. preparation methods as claimed in claim 1, is characterized in that the condensation temperature of described graft latex is 20～30 ℃.
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| CN106032427A (en) * | 2015-03-18 | 2016-10-19 | 中国石油化工股份有限公司 | Rubber composition, and vulcanized rubber and preparation method thereof |
| CN111032769A (en) * | 2017-09-01 | 2020-04-17 | 株式会社可乐丽 | Rubber composition for heavy duty tire and tire |
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| CN111032769A (en) * | 2017-09-01 | 2020-04-17 | 株式会社可乐丽 | Rubber composition for heavy duty tire and tire |
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