CN103539898B - Preparation method of easy-to-emulsify powder rubber for modified asphalt - Google Patents
Preparation method of easy-to-emulsify powder rubber for modified asphalt Download PDFInfo
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- CN103539898B CN103539898B CN201210241561.1A CN201210241561A CN103539898B CN 103539898 B CN103539898 B CN 103539898B CN 201210241561 A CN201210241561 A CN 201210241561A CN 103539898 B CN103539898 B CN 103539898B
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- butadiene
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 46
- 239000005060 rubber Substances 0.000 title claims abstract description 46
- 239000000843 powder Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000010426 asphalt Substances 0.000 title abstract description 13
- 239000004816 latex Substances 0.000 claims abstract description 64
- 229920000126 latex Polymers 0.000 claims abstract description 64
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 58
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 54
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002174 Styrene-butadiene Substances 0.000 claims abstract description 43
- 239000011115 styrene butadiene Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002562 thickening agent Substances 0.000 claims abstract description 27
- 150000002148 esters Chemical class 0.000 claims abstract description 25
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 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 30
- 239000011734 sodium Substances 0.000 claims description 30
- 229910052708 sodium Inorganic materials 0.000 claims description 30
- 238000007334 copolymerization reaction Methods 0.000 claims description 29
- 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 28
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 26
- 239000003921 oil Substances 0.000 claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 26
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 238000009833 condensation Methods 0.000 claims description 18
- 230000005494 condensation Effects 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000004945 emulsification Methods 0.000 claims description 11
- 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 10
- 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 10
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 10
- 239000000344 soap Substances 0.000 claims description 10
- 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 10
- 238000000227 grinding Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 239000008394 flocculating agent Substances 0.000 claims description 6
- 239000011280 coal tar Substances 0.000 claims description 5
- 239000005662 Paraffin oil Substances 0.000 claims description 3
- 150000007942 carboxylates Chemical group 0.000 claims description 3
- -1 hydroxylPropyl Chemical group 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 229920003091 Methocel™ Polymers 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 3
- 239000011295 pitch Substances 0.000 description 18
- 235000001014 amino acid Nutrition 0.000 description 17
- 150000001413 amino acids Chemical class 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 241001441571 Hiodontidae Species 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 6
- 235000019795 sodium metasilicate Nutrition 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- 229920003086 cellulose ether Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- UQJQVUOTMVCFHX-UHFFFAOYSA-L nabam Chemical compound [Na+].[Na+].[S-]C(=S)NCCNC([S-])=S UQJQVUOTMVCFHX-UHFFFAOYSA-L 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical class [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 2
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 244000286663 Ficus elastica Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- AQLLBJAXUCIJSR-UHFFFAOYSA-N OC(=O)C[Na] Chemical compound OC(=O)C[Na] AQLLBJAXUCIJSR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000318 alkali metal phosphate Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- VMSRVIHUFHQIAL-UHFFFAOYSA-N sodium;dimethylcarbamodithioic acid Chemical compound [Na+].CN(C)C(S)=S VMSRVIHUFHQIAL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a preparation method of special powder rubber for modified asphalt, which comprises the following steps: the thickening agent, styrene and butadiene are graft copolymerized to prepare copolymerized styrene-butadiene latex, then the copolymerized styrene-butadiene latex is grafted with ester to prepare graft latex, and finally the graft latex is coagulated to prepare powdered styrene-butadiene rubber, wherein the prepared powdered styrene-butadiene rubber has the following characteristics: the particle size of the particles is 0.5-1.50 mm, the mass percentage of the combined styrene is 23.5-40.0, the Mooney viscosity ML (1+4) is 40-60 at 100 ℃, the water content is less than or equal to 1.0 percent, and the powder forming rate is more than or equal to 99.5 percent.
Description
Technical field
The present invention relates to the preparation method of powdered rubber, particularly relate to a kind of preparation of modified pitch special powder butadiene-styrene rubberMethod.
Background technology
Rubber powder modified asphalt is a kind of novel high-quality composite. By absorbing, resin in pitch etc. is multiple to be had rubber powderMachine matter, through a series of physical and chemical changes, makes rubber powder moistening, expands, and viscosity increases, and softening point improves, and holds concurrentlyTurn round and look at the viscosity of rubber and pitch, toughness, elasticity, thus improve the pavement performance of pitch.
Ester plasticizer can improve the performance of rubber, reduces its glass transition temperature, expands range of application. Rubber oil canImprove dispersion and the mixed effect of compounding ingredient in rubber, oil-extended styrene buadiene rubber has that good processability, heat-dissipating are low, low temperature is subduedThe feature that life-span is long, has excellent hauling ability and abrasion performance during for tread rubber, and owing to having filled cheap oilCut, has not only reduced cost, and has improved output.
CN201010172912.9 modified asphalt composition with high content of rubber powder, comprises rubber powder, 2,4,7,9-tetramethyl-5-decine-4,7-glycol, pitch. CN201010280827.4 modifying rubber powder emulsified asphalt and preparation method thereof andThe CA mortar making thus, comprises pitch, rubber powder, coupling agent, thickener, dilution dispersant, emulsifying agent, emulsificationAuxiliary agent, water, by dilution stir, the step such as shearing makes modifying rubber powder emulsified asphalt, then adds cement, sand, multipleClose other materials such as swelling agent, gas tracting subtractive agent, polypropylene fibre, defoamer, can further be made into CA mortar.CN200910191814.7 polymer composite modified asphalt relates to road, bridge and tunnel pavement material. Comprise matrix dropGreen grass or young crops, butadiene-styrene rubber, thermoplastic styrene butadiene rubber, plasticizer, stabilizing agent, high-temperature viscosity reducer. CN200910188107.2 carriesSupply a kind of method that improves butadiene-styrene rubber modified pavement asphalt serviceability. Select the mixing and emulsifying equipment of high shear force,At 100～200 DEG C of temperature, polymer is evenly spread in basic asphalt, then add and account for pitch total amount 0.01%～5%Reaction promoter (comprising crosslinking agent, promoter), be prepared into polymer modification road asphalt. CN93115289.5 is novelButadiene-styrene rubber asphalt modifier, mixes with butadiene-styrene rubber and high aromatic hydrocarbons petroleum distillate organic solvent.
US5854322A is used for doing the modified coal tar pitch of roof Material, comprises coal tar asphalt and acrylonitrile-butadiene rubber, by rubberRubber powder is added in the coal tar asphalt under uniform temperature. JP61019671A corrosion-resistant coating composition, comprises modified epoxy treeFat, bituminous material and liquid synthetic rubber. JP61111361A has introduced a kind of method that rubber is mixed with pitch.Mono-kind of JP63010665A is sticky also free of contamination modified pitch neither, carrys out modified pitch by macromolecular material as rubber.GB2378919, GB653414 (A) have introduced the polymer that contains rubber and pitch.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of modified pitch special powder rubber, adopt direct coacervation preparationModified pitch special powder rubber.
The preparation method of powdered rubber of the present invention is:
In polymeric kettle, add successively water, styrene, emulsifying agent, molecular weight regulator, with after nitrogen replacement, add fourth twoAlkene, thickener, agitating heating adds initator in the time that polymeric kettle temperature reaches 30～60 DEG C, 30～60 DEG C of polymerization temperatureUnder degree, react and add terminator after 5～8 hours, make copolymerization styrene-butadiene latex; Copolymerization styrene-butadiene latex is added to another polymerizationIn still, with after nitrogen replacement, add ester, in the time that polymeric kettle temperature reaches 30～60 DEG C, add initator, at 30～60 DEG CUnder polymerization temperature, react after 5～8 hours and add 0.1～0.5 part of terminator, make graft latex; Getting graft latex addsCohesion still, under 40～80 DEG C of condensation temperatures, adds rubber oil, interleaving agent, dispersant, flocculating agent that emulsification is good, stirsMix and mix, be warmed up to 70～100 DEG C of slakings 4～6 hours, then make powder butylbenzene through separating, dewater, being driedRubber.
In the present invention, thickener is cellulose ether, as sodium carboxymethylcellulose pyce, hydroxypropyl methylcellulose sodium, carboxymethyl celluloseSodium, sodium hydroxyethyl cellulose, preferably carboxymethyl cellulose sodium.
The ester of grafting of the present invention is carboxylate or inorganic oxygen-containing acid esters etc., as methacrylate, and ethyl propylene acid esters etc., excellentSelect methacrylate.
Rubber oil of the present invention is paraffin oil, aromatic naphtha, naphthenic oil and coal tar wet goods, preferred aromatic hydrocarbons oil.
The present invention also provides the concrete preparation method of described powder styrene butadiene rubber, is specially:
1) preparation of copolymerization styrene-butadiene latex: taking butadiene styrene total amount as 100 mass parts, add successively in polymeric kettleEnter 50～150 parts of water, 30～50 parts of styrene, 2～10 parts of emulsifying agents, 0.1～1.2 part of molecular weight regulator, use nitrogenAfter displacement, add 50～70 parts of butadiene, 0.4～1 part of thickener, stir, heating, treat polymeric kettle temperature reach 30～60 DEG C time, add 0.1～0.4 part of initator, stir 0.8～1h, then, under 30～60 DEG C of polymerization temperatures, react 5～8Hour, add 0.1～0.5 part of terminator, make copolymerization styrene-butadiene latex;
2) latex grafting: taking copolymerization styrene-butadiene latex as 100 mass parts, in polymeric kettle, add successively 50～150 parts, water,100 parts of copolymerization styrene-butadiene latexes, with after nitrogen replacement, add 5～40 parts of esters, stir, heat, and treat that polymeric kettle temperature reaches30～60 DEG C time, add 0.1～0.4 part of initator, stir 0.8～1h, then, under 30～60 DEG C of polymerization temperatures, react 5～8 hours, add 0.1～0.5 part of terminator, make graft latex;
3) condensation powdering: get 100 parts of graft latexes and add cohesion still, add 20～100 parts of WATER AS FLOW MEDIUM, at 40～80 DEG CUnder condensation temperature, add 2～10 parts of the rubber oils that emulsification is good, stir 20～40min; Add 5～20 portions of interleaving agents, 5～20 parts of dispersants, 4～16 parts of flocculating agents, are fully uniformly mixed, and are warmed up to 70～100 DEG C of slakings 4～6 hours,Then make powder styrene butadiene rubber through separating, dewater, being dried.
In the present invention, thickener, before adding polymeric kettle, is preferably in thickener and adds water to dissolve, the consumption of water and increasingThe mass ratio of the addition of thick dose is 100: (0.5～1), and for making thickener form chelation structure, the consumption of preferred water and thickeningThe mass ratio 100 of the addition of agent: (0.6～0.8). For thickener is dissolved faster, need to be heated to 50～80 DEG C, excellentSelect 70～80 DEG C.
Emulsifying agent of the present invention is Sulfates, Sulfonates, preferably disproportionated rosin soap; Be 2～10 parts, preferably 4～6Part.
Molecular weight regulator used in the present invention is selected from tert-dodecyl mercaptan, uncle's ten carbon mercaptan, uncle's 14 carbon mercaptan, uncle tenSix carbon mercaptan, preferred tertiary DDM dodecyl mercaptan; Be 0.1～1.2 part, preferably 0.4～0.6 part.
The thickener of copolymerization styrene-butadiene latex of the present invention is 0.4～1 part, preferably 0.5～0.8 part.
30～60 DEG C of the polymerization temperatures of styrene-butadiene latex of the present invention, preferably 40～50 DEG C.
Initator of the present invention adopts azo amino-compound or persulfate, and preferably azo amino-compound, as azo aminoAcid sodium; Be 0.1～0.4 part, preferably 0.2～0.3 part.
Terminator used in the present invention is selected from SDD, quinhydrones. It is 0.1～0.5 part, preferably0.2～0.3 part.
The ester of grafting of the present invention is carboxylate or electrodeless esters of oxyacids etc., as methacrylate, and ethyl propylene acid esters etc., excellentSelect methacrylate.
The ester of grafting of the present invention is 5～40 parts, preferably 10～15 parts.
Condensation temperature of the present invention is 40～80 DEG C, preferably 60～80 DEG C.
Rubber oil of the present invention is paraffin oil, aromatic naphtha, naphthenic oil and coal tar wet goods, preferred aromatic hydrocarbons oil.
Rubber oil of the present invention is 2～10 parts, preferably 4～6 parts.
Dispersant of the present invention is that inorganic dispersant has silicate and alkali metal phosphate class, and preferably silicate, as silicic acidSodium etc.
Dispersant of the present invention is 5～20 parts, preferably 5～10 parts.
Interleaving agent of the present invention is inorganic salts, as sodium chloride, magnesium sulfate etc., and preferably sodium chloride.
Interleaving agent of the present invention is 5～20 parts, preferably 10～15 parts.
Flocculating agent of the present invention is inorganic acids, as sulfuric acid, hydrochloric acid etc., and preferably sulfuric acid.
Flocculating agent of the present invention is 4～16 parts of flocculating agents, preferably 10～15 parts.
The prepared powder styrene butadiene rubber of the inventive method has following feature: grain diameter 0.5～1.50mm, and in conjunction with benzene secondAlkene quality percentage composition 23.5～40.0, mooney viscosity ML(1+4) 100℃40～60, moisture content≤1.0%, powder formation rate >=99.5%.
Butylbenzene resemble process is prepared in emulsion polymerisation process involved in the present invention and traditional emulsion polymerisation, with traditional powder fourthBenzene rubber phase has the following advantages than tool:
(1) cellulose ether is the product that the hydrogen of hydroxyl in cellulose macromolecule is replaced by alkyl. Cellulose ether and butadiene,Styrene copolymerized, because cellulose ether is as a kind of protecting colloid, " parcel " lives latex particle, and forms at its outer surfaceOne deck lubricating film, makes latex have better stability and heat resistance.
(2) dissolve cellulose ether form chelation structure, with butadiene, styrene effect, can improve rubber cold resistance,Processing characteristics and mechanical property, have good strengthening action to rubber.
(3) ester is grafted in rubber, can improve the cryogenic property of rubber, or reduces its glass transition temperature (Tg). GlueCondensation powdering modified pitch after breast and ester glycerol polymerization, can improve resistance to water and the solvent resistance of pitch.
(4) rubber oil is the Plasticising system that rubber is good. In rubber, add a certain amount of filling oil, large to reduce rubberFrictional resistance when molecular motion, improves plasticity, reduces heat-dissipating, improves cryogenic subduing flexibility energy, life-extending. In cohesionIn add rubber oil, operating process is simple, and the adding of rubber oil, and has increased the compatibility of rubber powder and pitch, makes moreEasily emulsification.
(5) the one-tenth powder operating procedure of rubber powder is simply controlled, and modified pitch process is more prone to operation, better improves dropBlue or green performance.
Detailed description of the invention
Further illustrate the present invention below in conjunction with embodiment, but and the scope of unrestricted the claims in the present invention protection. EmbodimentAll refer to mass parts with " part " described in comparative example.
Raw material sources:
Butadiene, styrene: synthetic rubber plant of Petrochina Lanzhou Petrochemical Company provides; Sodium carboxymethylcellulose pyce, carboxymethyl fibreTie up other reagent such as plain sodium and be commercially available industrial goods; Naphthenic oil: Liaohe River petro-chemical corporation; Aromatic naphtha: Kelamayi petrochemical industry.
Embodiment 1
1. the dissolving of thickener: in reaction bulb, add 100 parts of water, be heated to 50 DEG C, add 0.5 part of methylcelluloseSodium, startup agitator is stirred to sodium carboxymethylcellulose pyce and dissolves completely. 2. the preparation of copolymerization styrene-butadiene latex: in polymeric kettle successivelyAdd 100 parts of water, 30 parts of styrene, 4 parts of disproportionated rosin soaps, 0.3 part of tert-dodecyl mercaptan, with after nitrogen replacement, addEnter the sodium carboxymethylcellulose pyce of 70 parts of butadiene, 0.4 part of dissolving, stir, heat, in the time that polymeric kettle temperature reaches 40 DEG C, addEnter 0.2 part of azo amino acid sodium, stir 1h, then, under 40 DEG C of polymerization temperatures, react 8 hours, add 0.3 part of diformazanBase nabam, makes copolymerization styrene-butadiene latex; 3. latex grafting: in polymeric kettle, add successively 50 parts, water,100 parts of copolymerization styrene-butadiene latexes, with after nitrogen replacement, add 10 parts of methacrylates, stir, heat, and treat polymeric kettleTemperature adds 0.2 part of azo amino acid sodium while reaching 40 DEG C, stir 1h, and then, under 40 DEG C of polymerization temperatures, reaction 5 is littleTime, add 0.3 part of SDD, make graft latex. 4. condensation powdering: get 100 parts of Graft AdhesiveBreast adds cohesion still, adds 80 parts of WATER AS FLOW MEDIUM, under 40 DEG C of condensation temperatures, adds 6 parts of the naphthenic oils that emulsification is good, stirs40min; Add 10 parts of sodium chloride, 10 parts of sodium metasilicate, 5 parts of sulfuric acid, are fully uniformly mixed, be warmed up to 80 DEG C ripeChange 4 hours, then make powder styrene butadiene rubber through separating, dewater, being dried. Adopt classical way test sample structure and propertyCan, result is as follows: grain diameter 0.5～1.50mm, and in conjunction with styrene quality percentage composition 23.5 ± 1, mooney viscosityML(1+4) 100℃40, moisture content≤1.0%, powder formation rate >=99.5%.
Comparative example 1
Experimental condition, with embodiment 1, does not just add thickener sodium carboxymethylcellulose pyce, to grafting ester after styrene-butadiene latex polymerization,Then carry out oil-filled cohesion. Result is as follows: grain diameter 1.00～2.00mm, and in conjunction with styrene quality percentage composition 23.5± 1, mooney viscosity ML(1+4) 100℃25, moisture content≤1.5%, powder formation rate >=95%.
Embodiment 2
1. the dissolving of thickener: in reaction bulb, add 100 parts of water, be heated to 80 DEG C, add 0.7 part of methylcelluloseSodium, startup agitator is stirred to sodium carboxymethylcellulose pyce and dissolves completely. 2. the preparation of copolymerization styrene-butadiene latex: in polymeric kettle successivelyAdd 100 parts of water, 40 parts of styrene, 10 parts of disproportionated rosin soaps, 1.0 parts of tert-dodecyl mercaptans, with after nitrogen replacement, addEnter the sodium carboxymethylcellulose pyce of 60 parts of butadiene, 0.6 part of dissolving, stir, heat, in the time that polymeric kettle temperature reaches 60 DEG C, addEnter 0.4 part of azo amino acid sodium, stir 1h, then, under 60 DEG C of polymerization temperatures, react 5 hours, add 0.5 part of diformazanBase nabam, makes copolymerization styrene-butadiene latex; 3. latex grafting: in polymeric kettle, add successively 100 parts, water,100 parts of copolymerization styrene-butadiene latexes, with after nitrogen replacement, add 20 parts of ethyl propylene acid esters, stir, heat, and treat polymeric kettleTemperature adds 0.2 part of azo amino acid sodium while reaching 60 DEG C, stir 0.8h, then, under 60 DEG C of polymerization temperatures, reacts 6Hour, add 0.3 part of SDD, make graft latex. 4. condensation powdering: get 100 parts of graftingLatex adds cohesion still, adds 60 parts of WATER AS FLOW MEDIUM, under 60 DEG C of condensation temperatures, adds 8 parts of the naphthenic oils that emulsification is good, stirsMix 40min; Add 20 parts of magnesium sulfate, 15 parts of sodium metasilicate, 15 parts of hydrochloric acid, are fully uniformly mixed, and are warmed up to 80DEG C slaking 6 hours, then through separating, dehydration, the dry powder styrene butadiene rubber that makes. Adopt classical way test sample structureAnd performance, result is as follows: grain diameter 0.5～1.50mm, and in conjunction with styrene quality percentage composition 30, mooney viscosityML(1+4) 100℃50, moisture content≤1.0%, powder formation rate >=99.5%.
Comparative example 2
Experimental condition, with embodiment 2, does not just add thickener sodium carboxymethylcellulose pyce, to grafting ester after styrene-butadiene latex polymerization,Then carry out oil-filled cohesion. Result is as follows: grain diameter 0.5～2.50mm, and in conjunction with styrene quality percentage composition 20,Mooney viscosity ML(1+4) 100℃30, moisture content≤1.4%, powder formation rate >=90%.
Embodiment 3
1. the dissolving of thickener: in reaction bulb, add 100 parts of water, be heated to 60 DEG C, add 0.6 part of carboxymethyl celluloseElement sodium, startup agitator is stirred to sodium carboxymethylcellulose and dissolves completely. 2. the preparation of copolymerization styrene-butadiene latex: in polymeric kettleAdd successively 80 parts of water, 50 parts of styrene, 5 parts of disproportionated rosin soaps, 0.5 part of tert-dodecyl mercaptan, with after nitrogen replacement,Add the sodium carboxymethylcellulose of 50 parts of butadiene, 1 part of dissolving, stir, heat, in the time that polymeric kettle temperature reaches 40 DEG CAdd 0.2 part of azo amino acid sodium, stir 1h, then, under 40 DEG C of polymerization temperatures, react 6 hours, add 0.3 part twoSodium dimethyldithiocar-bamate (SDDC), makes copolymerization styrene-butadiene latex; 3. latex grafting: add successively water 150 in polymeric kettle100 parts of part, copolymerization styrene-butadiene latexes, with after nitrogen replacement, add 30 parts of methacrylates, stirs, heats, and waits to gatherClose when still temperature reaches 40 DEG C and add 0.1 part of azo amino acid sodium, stir 1h, then, under 40 DEG C of polymerization temperatures, react7 hours, add 0.3 part of SDD, make graft latex. 4. condensation powdering: get 100 parts and connectBranch latex adds cohesion still, adds 40 parts of WATER AS FLOW MEDIUM, under 50 DEG C of condensation temperatures, adds 5 parts of the naphthenic oils that emulsification is good,Stir 30min; Add 15 parts of sodium chloride, 10 parts of sodium metasilicate, 8 parts of hydrochloric acid, are fully uniformly mixed, and are warmed up to 70 DEG CSlaking 5 hours, then makes powder styrene butadiene rubber through separating, dewater, being dried. Adopt classical way test sample structure andPerformance, result is as follows: grain diameter 0.5～1.50mm, in conjunction with styrene quality percentage composition 40, mooney viscosityML(1+4) 100℃45, moisture content≤1.0%, powder formation rate >=99.5%.
Comparative example 3
Other experimental condition is with embodiment 3, and difference is directly by styrene-butadiene latex grafting thickener sodium carboxymethylcelluloseAfter carry out grafting with methacrylate again. Be the preparation of styrene-butadiene latex grafting sodium carboxymethylcellulose: in polymeric kettle successivelyAdd 80 parts of water, 100 parts of styrene-butadiene latexes, 5 parts of disproportionated rosin soaps, 0.5 part of tert-dodecyl mercaptan, with after nitrogen replacement,Add the sodium carboxymethylcellulose of 1 part of dissolving, stir, heat, in the time that polymeric kettle temperature reaches 40 DEG C, add 0.2 part of idolNitrogen amino acid sodium, stirs 1h, then, under 40 DEG C of polymerization temperatures, reacts 6 hours, adds 0.3 part of DMDS generationCarbamic acid sodium, makes butylbenzene grafting sodium carboxymethylcellulose latex; Then carry out the reaction of grafting methacrylate, then enterThe oil-filled cohesion of row. Result is as follows: grain diameter 1.00～2.50mm, in conjunction with styrene quality percentage composition 30, Mooney is glutinousDegree ML(1+4) 100℃32, moisture content≤2.0%, powder formation rate >=90%.
Embodiment 4
1. the dissolving of thickener: in reaction bulb, add 100 parts of water, be heated to 80 DEG C, add 1.0 parts of carboxymethyl cellulosesElement sodium, startup agitator is stirred to sodium carboxymethylcellulose and dissolves completely. 2. the preparation of copolymerization styrene-butadiene latex: in polymeric kettleAdd successively 150 parts of water, 30 parts of styrene, 4 parts of disproportionated rosin soaps, 0.8 part of tert-dodecyl mercaptan, with after nitrogen replacement,Add the sodium carboxymethylcellulose of 70 parts of butadiene, 0.5 part of dissolving, stir, heat, treat that polymeric kettle temperature reaches 30 DEG CTime add 0.2 part of azo amino acid sodium, stir 0.8h, then, under 30 DEG C of polymerization temperatures, react 6 hours, add 0.2Part SDD, makes thickening type copolymerization styrene-butadiene latex; 3. latex grafting: add successively in polymeric kettleEnter 100 parts, water, 100 parts of copolymerization styrene-butadiene latexes, with after nitrogen replacement, add 15 parts of ethyl propylene acid esters, stir, addHeat adds 0.2 part of azo amino acid sodium in the time that polymeric kettle temperature reaches 40 DEG C, stirs 0.84h, then 40 DEG C of polymerization temperatureUnder degree, react 5 hours, add 0.3 part of SDD, make graft latex. 4. condensation powdering:Get 100 parts of graft latexes and add cohesion still, add 50 parts of WATER AS FLOW MEDIUM, under 60 DEG C of condensation temperatures, add the virtue that emulsification is good5 parts of hydrocarbon ils, stir 40min; Add 10 parts of sodium sulphate, 15 parts of sodium metasilicate, 16 parts of sulfuric acid, are fully uniformly mixed,Be warmed up to 100 DEG C of slakings 4 hours, then make powder styrene butadiene rubber through separating, dewater, being dried. Employing classical way is surveyedTest agent structure and performance, result is as follows: grain diameter 0.5～1.20mm, in conjunction with styrene quality percentage composition 23.5,Mooney viscosity ML(1+4) 100℃40, moisture content≤1.0%, powder formation rate >=99.5%.
Comparative example 4
Other experimental condition is with embodiment 4, and difference is directly by styrene-butadiene latex grafting thickener sodium carboxymethylcelluloseAfter carry out grafting with methacrylate again. Be the preparation of styrene-butadiene latex grafting sodium carboxymethylcellulose: in polymeric kettle successivelyAdd 150 parts of water, 100 parts of styrene-butadiene latexes, 4 parts of disproportionated rosin soaps, 0.8 part of tert-dodecyl mercaptan, with after nitrogen replacement,Add the sodium carboxymethylcellulose of 0.5 part of dissolving, stir, heat, in the time that polymeric kettle temperature reaches 30 DEG C, add 0.2 part of idolNitrogen amino acid sodium, stirs 0.8h, then, under 30 DEG C of polymerization temperatures, reacts 6 hours, adds 0.2 part of DMDS generationCarbamic acid sodium, makes butylbenzene grafting sodium carboxymethylcellulose latex; Then carry out the reaction of grafting methacrylate, then enterThe oil-filled cohesion of row makes powder styrene butadiene rubber. Result is as follows: grain diameter 0.5～2.50mm, and in conjunction with styrene quality percentageContent 20, mooney viscosity ML(1+4) 100℃30, moisture content≤2.0%, powder formation rate >=90%.
Embodiment 5
1. the dissolving of thickener: in reaction bulb, add 100 parts of water, be heated to 70 DEG C, add 0.7 part of carboxymethyl celluloseElement sodium, startup agitator is stirred to sodium carboxymethylcellulose and dissolves completely. 2. the preparation of copolymerization styrene-butadiene latex: in polymeric kettleAdd successively 100 parts of water, 40 parts of styrene, 2 parts of disproportionated rosin soaps, 0.3 part of tert-dodecyl mercaptan, with after nitrogen replacement,Add the sodium carboxymethylcellulose of 60 parts of butadiene, 0.6 part of dissolving, stir, heat, treat that polymeric kettle temperature reaches 50 DEG CTime add 0.4 part of azo amino acid sodium, stir 0.8h, then, under 50 DEG C of polymerization temperatures, react 7 hours, add 0.5Part SDD, makes copolymerization styrene-butadiene latex; 3. latex grafting: add successively water in polymeric kettle100 parts of 60 parts, copolymerization styrene-butadiene latex, with after nitrogen replacement, add 5 parts of methacrylates, stirs, heating, treatsPolymeric kettle temperature adds 0.1 part of azo amino acid sodium while reaching 40 DEG C, stir 0.8h, then under 40 DEG C of polymerization temperatures,React 5 hours, add 0.1 part of SDD, make graft latex. 4. condensation powdering: get 100Part graft latex adds cohesion still, adds 90 parts of WATER AS FLOW MEDIUM, under 50 DEG C of condensation temperatures, adds the aromatic naphtha 7 that emulsification is goodPart, stir 30min; Add 8 parts of sodium sulphate, 12 parts of sodium metasilicate, 10 parts of sulfuric acid, are fully uniformly mixed, and heat upTo 70 DEG C of slakings 5 hours, then make powder styrene butadiene rubber through separating, dewater, being dried. Adopt classical way test specimensProduct structure and performance, result is as follows: grain diameter 0.5～1.20mm, in conjunction with styrene quality percentage composition 23.5, doorBuddhist nun's viscosity ML(1+4) 100℃45, moisture content≤1.0%, powder formation rate >=99.5%.
Comparative example 5
Other experimental condition is with embodiment 5, and difference is not carry out copolyreaction, directly by methacrylate, increasingThick agent carboxymethyl sodium cellulosate is grafted on styrene-butadiene latex. Be latex grafting: in polymeric kettle, add successively 60 parts, water, fourth100 parts, benzene latex, with after nitrogen replacement, adds the sodium carboxymethylcellulose of 5 parts of methacrylates, 0.6 part of dissolving,Stir, heat, in the time that polymeric kettle temperature reaches 40 DEG C, add 0.1 part of azo amino acid sodium, stir 0.8h, then at 40 DEG CUnder polymerization temperature, react 5 hours, add 0.1 part of SDD, make graft latex; Then fillOil cohesion makes powder styrene butadiene rubber. Result is as follows: grain diameter 0.5～2.00mm, and in conjunction with styrene quality percentage composition20, mooney viscosity ML(1+4) 100℃30, moisture content≤1.5%, powder formation rate >=95%.
Embodiment 6
1. the dissolving of thickener: in reaction bulb, add 100 parts of water, be heated to 80 DEG C, add 1.0 parts of methylcelluloseSodium, startup agitator is stirred to sodium carboxymethylcellulose pyce and dissolves completely. 2. the preparation of copolymerization styrene-butadiene latex: in polymeric kettle successivelyAdd 90 parts of water, 30 parts of styrene, 7 parts of disproportionated rosin soaps, 0.5 part of tert-dodecyl mercaptan, with after nitrogen replacement, addThe sodium carboxymethylcellulose pyce of 70 parts of butadiene, 0.7 part of dissolving, stirs, heats, and in the time that polymeric kettle temperature reaches 30 DEG C, adds0.2 part of azo amino acid sodium, stirs 1h, then, under 30 DEG C of polymerization temperatures, reacts 5 hours, adds 0.5 part of diformazanBase nabam, makes copolymerization styrene-butadiene latex; 3. latex grafting: in polymeric kettle, add successively 150 parts, water,100 parts of copolymerization styrene-butadiene latexes, with after nitrogen replacement, add 30 parts of ethyl propylene acid esters, stir, heat, and treat polymeric kettleTemperature adds 0.2 part of azo amino acid sodium while reaching 60 DEG C, stir 1h, and then, under 60 DEG C of polymerization temperatures, reaction 5 is littleTime, add 0.2 part of SDD, make graft latex. 4. condensation powdering: get 100 parts of Graft AdhesiveBreast adds cohesion still, adds 70 parts of WATER AS FLOW MEDIUM, under 70 DEG C of condensation temperatures, adds 6 parts of the aromatic naphtha that emulsification is good, stirs40min; Add 17 parts of sodium chloride, 13 parts of sodium metasilicate, 11 parts of hydrochloric acid, are fully uniformly mixed, be warmed up to 80 DEG C ripeChange 6 hours, then make powder styrene butadiene rubber through separating, dewater, being dried. Adopt classical way test sample structure and propertyCan, result is as follows: grain diameter 0.5～1.00mm, and in conjunction with styrene quality percentage composition 23.5, mooney viscosityML(1+4) 100℃50, moisture content≤1.0%, powder formation rate >=99.5%.
Comparative example 6
Experimental condition, with embodiment 6, does not just carry out copolyreaction, directly by ethyl propylene acid esters, thickener methyl fiberElement sodium is grafted on styrene-butadiene latex. Be latex grafting: in polymeric kettle, add successively 150 parts, water, 100 parts of styrene-butadiene latexes,With after nitrogen replacement, add the sodium carboxymethylcellulose pyce of 30 parts of ethyl propylene acid esters, 0.7 part of dissolving, stir, heat, wait to gatherClose when still temperature reaches 60 DEG C and add 0.2 part of azo amino acid sodium, stir 1h, then, under 60 DEG C of polymerization temperatures, react5 hours, add 0.2 part of SDD, make graft latex; Then oil-filled cohesion makes powder fourthBenzene rubber. Result is as follows: grain diameter 0.5～2.50mm, and in conjunction with styrene quality percentage composition 21, mooney viscosityML(1+4) 100℃28, moisture content≤1.5%, powder formation rate >=90%.
Claims (8)
1. a preparation method for powdered rubber, is characterized in that being specially:
1) preparation of copolymerization styrene-butadiene latex: taking butadiene styrene total amount as 100 mass parts, in polymeric kettle successivelyAdd 50～150 parts of water, 30～50 parts of styrene, 2～10 parts of emulsifying agents, 0.1～1.2 part of molecular weight regulator, useAfter nitrogen replacement, add 50～70 parts of butadiene, 0.4～1 part of thickener, stir, heat, treat that polymeric kettle temperature reachesDuring to 30～60 DEG C, add 0.1～0.4 part of initator, stir 0.8～1h, then under 30～60 DEG C of polymerization temperatures,React 5～8 hours, add 0.1～0.5 part of terminator, make copolymerization styrene-butadiene latex; Wherein, described thickener isCellulose ether;
2) latex grafting: taking copolymerization styrene-butadiene latex as 100 mass parts, add successively water 50～150 in polymeric kettle100 parts of part, copolymerization styrene-butadiene latexes, with after nitrogen replacement, add 5～40 parts of esters, stirs, heats, and treats polymeric kettle temperatureDegree adds 0.1～0.4 part of initator while reaching 30～60 DEG C, stirs 0.8～1h, then under 30～60 DEG C of polymerization temperatures,React 5～8 hours, add 0.1～0.5 part of terminator, make graft latex;
3) condensation powdering: get 100 parts of graft latexes and add cohesion still, add 20～100 parts of WATER AS FLOW MEDIUM, 40～80Under DEG C condensation temperature, add 2～10 parts of the rubber oils that emulsification is good, stir 20～40min; Add 5～20 portions of interleaving agents,5～20 parts of dispersants, 4～16 parts of flocculating agents, are fully uniformly mixed, and are warmed up to 70～100 DEG C of slakings 4～6 littleTime, then make powder styrene butadiene rubber through separating, dewater, being dried.
2. preparation method as claimed in claim 1, is characterized in that described thickener is sodium carboxymethylcellulose pyce, hydroxylPropyl methocel sodium, sodium carboxymethylcellulose or sodium hydroxyethyl cellulose.
3. preparation method as claimed in claim 1, is characterized in that described ester is carboxylate or inorganic oxygen-containing acid esters.
4. preparation method as claimed in claim 1, is characterized in that described ester is methacrylate or ethyl propyleneAcid esters.
5. preparation method as claimed in claim 1, is characterized in that described rubber oil is paraffin oil, aromatic naphtha, ringAlkane oil or coal tar.
6. preparation method as claimed in claim 1, is characterized in that thickener is before adding polymeric kettle, adds water to enterRow dissolves, and the mass ratio of the consumption of water and the addition of thickener is 100: (0.5～1).
7. preparation method as claimed in claim 1, is characterized in that described emulsifying agent is disproportionated rosin soap.
8. preparation method as claimed in claim 1, is characterized in that the addition of described thickener is 0.5～0.8 part.
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| US4298654A (en) * | 1980-04-28 | 1981-11-03 | The B. F. Goodrich Company | Powdered elastomers and process therefor |
| US6369158B1 (en) * | 1999-12-22 | 2002-04-09 | The Goodyear Tire & Rubber Company | Dibenzyltrithiocarbonate molecular weight regulator for emulsion polymerization |
| CN101077902A (en) * | 2007-06-28 | 2007-11-28 | 上海东升新材料有限公司 | Butylbenzene emulsion and its preparing method and application |
| CN101173106A (en) * | 2007-09-30 | 2008-05-07 | 江苏博特新材料有限公司 | Rubber powder-asphalt emulsion for concrete asphalt mortar and method for producing the same |
| CN101367897A (en) * | 2008-10-08 | 2009-02-18 | 中国石油集团工程技术研究院 | Synthesis of modified styrene butadiene rubber latex special for well cementing cement paste for oil-gas field |
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| US4298654A (en) * | 1980-04-28 | 1981-11-03 | The B. F. Goodrich Company | Powdered elastomers and process therefor |
| US6369158B1 (en) * | 1999-12-22 | 2002-04-09 | The Goodyear Tire & Rubber Company | Dibenzyltrithiocarbonate molecular weight regulator for emulsion polymerization |
| CN101077902A (en) * | 2007-06-28 | 2007-11-28 | 上海东升新材料有限公司 | Butylbenzene emulsion and its preparing method and application |
| CN101173106A (en) * | 2007-09-30 | 2008-05-07 | 江苏博特新材料有限公司 | Rubber powder-asphalt emulsion for concrete asphalt mortar and method for producing the same |
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