CN103524797B - Diene rubber composition and preparation method thereof - Google Patents
Diene rubber composition and preparation method thereof Download PDFInfo
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- CN103524797B CN103524797B CN201210231660.1A CN201210231660A CN103524797B CN 103524797 B CN103524797 B CN 103524797B CN 201210231660 A CN201210231660 A CN 201210231660A CN 103524797 B CN103524797 B CN 103524797B
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Abstract
The invention discloses a diene rubber composition and a preparation method thereof. The diene rubber composition comprises the following components in parts by weight: 100 parts of main body rubber, 10-60 parts of carbon black and 0.5-3 parts of a vulcanizing agent, wherein based on the mass of the main body rubber being 100%, the main body rubber comprises (1) 10-100% of nano silicon dioxide/poly-conjugated diene modified diene rubber and (2) 0-90% of diene rubber, the nano silicon dioxide/poly-conjugated diene modified diene rubber is prepared by performing graft polymerization on diene rubber latex and nano silicon dioxide/poly-conjugated diene composite emulsion in the presence of an initiating agent, and the mass ratio of the dry basis of the diene rubber latex to the dry basis of the nano silicon dioxide/poly-conjugated diene composite emulsion is 100:(0.1-100); based on 100 parts of the dry basis of the emulsion, the nano silicon dioxide/poly-conjugated diene composite emulsion comprises 0.1-5 parts of surface functional-modified nano silicon dioxide; the particle size of the nano silicon dioxide/poly-conjugated diene composite emulsion is 50-80nm, the number-average molecular weight is 100000-140000, and the molecular weight distribution is 2-3.
Description
Technical field
The present invention relates to a kind of rubber combination and preparation method thereof, relate to a kind of dyene-type rubber composition for tire tread and preparation method thereof in particular.
Background technology
Along with automobile at a high speed, the development in safe, energy-conservation, comfortableization direction, also improve year by year the requirement of tire high performance, this just requires that tire tread has good wet-sliding resistant performance, excellent wear resistance and low rolling resistance.
Nano silicon is commonly called as white carbon black, is the second largest strengthening agent that in rubber industry, consumption is only second to carbon black.From the nineties in last century, white carbon black is widely used in tire tread formula as reinforced filling, and " devil's triangle " performance that above-mentioned tire tread is required obtains significantly balance.
The invention provides a kind of rubber combination for tire tread, nano silicon is incorporated on poly-conjugated-diolefin molecular chain and prepares function and service emulsion, and by preparing the rubber product of modification with latex grafting, the wear resistance of tire, anti-slippery can be improved, and there is lower rolling resistance.
Summary of the invention
The object of this invention is to provide a kind of dyene-type rubber composition for tire tread, have good wear resistance, anti-slippery when this rubber combination is used for tire, and there is lower rolling resistance.Another object of the present invention is to provide the preparation method of the rubber combination of environmental protection.
Rubber combination disclosed in this invention, in each ingredients weight parts, containing 100 parts of main rubbers, 10 ~ 60 parts of carbon blacks, 0.5 ~ 3 part of vulcanizing agent, be 100% calculating with main rubber quality, the polydiene 10 ~ 100% of nano silicon/poly-conjugated-diolefin modification that main rubber comprises (1), (2) polydiene 0 ~ 90%, the polydiene of nano silicon/poly-conjugated-diolefin modification is by the graft polymerization and obtaining under initiator existent condition of polydiene latex and nano silicon/poly-conjugated-diolefin composite emulsion, the mass ratio of polydiene latex butt and nano silicon/poly-conjugated-diolefin composite emulsion butt is 100:0.1 ~ 100, nano silicon/poly-conjugated-diolefin composite emulsion, it is 100 parts in composite emulsion butt, nano silicon containing surface-functionalized modification 0.1 ~ 5 part, nano silicon/poly-conjugated-diolefin composite emulsion particle diameter is 50 ~ 80nm, number-average molecular weight is 100000 ~ 140000, molecular weight distribution is 2 ~ 3.
In rubber combination of the present invention, polydiene is selected from the rubber being mainly usually used in tire tread, be selected from emulsion polymerized styrene butadiene rubber (ESBR), solution polymerized butadiene styrene rubber (SSBR), natural rubber, cis-1,4-polybutadiene rubber, styrene-isoprene-divinyl (SIBR) rubber, polydiene latex is corresponding can be content of polybutadiene rubber latex, natural rubber latex, styrene butadiene rubber latex.
Carbon black of the present invention can be general carbon black, and the present invention preferably uses N2 adsorption specific surface area to be 60 ~ 120m
2g
-1, DBP absorption value is 60 ~ 120cm
3g
-1carbon black.
In order to improve the dispersiveness of silicon-dioxide in emulsion thus improve the performance of functional latex further, the present invention selects coupling agent treatment silicon-dioxide, make silicon-dioxide have reactivity, re-use emulsion polymerization in situ and obtain the nano silicon/poly-conjugated-diolefin composite emulsion had good stability.Nano silicon disclosed in this invention/poly-conjugated-diolefin composite emulsion is 100 parts in emulsion butt, the nano silicon containing surface-functionalized modification 0.1 ~ 5 part; Nano silicon/poly-conjugated-diolefin composite emulsion particle diameter is 50 ~ 80nm, and number-average molecular weight is 100000 ~ 140000, and molecular weight distribution is 2 ~ 3.
The nano silicon of surface-functionalized modification of the present invention refers to that silicon-dioxide adopts coupling agent to be made the nano silicon with response type by surface functionalization process, coupling agent is wherein silane coupling agent, it accounts for 0.1 ~ 50% of surface-functionalized modified manometer silicon dioxide quality, and preferably 10 ~ 30%.
The nano silicon stated belonging to the present invention, as long as nano level, preferably 20 ~ 60nm.
Silane coupling agent of the present invention, can be vinyl silane, one or more in methyl acrylic ester silane, preferred vinyl triethoxyl silane (VTES), vinyltrimethoxy silane (VTMS), vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriacetoxy silane, vinyl tributyl ketoximyl silane, methyl tributanoximo silane, vinyl silane triisopropoxide, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, second diaminopropyl Trimethoxy silane, vinyl trichloro silane, vinyl trimethoxysilane oligomer, γ-methacryloxypropyl trimethoxy silane (MPS), one or more in three (trimethylsiloxy group) methacryloxy propylsilane (MPTS), more preferably one or more in vinyltriethoxysilane, vinyltrimethoxy silane, three (trimethylsiloxy group) methacryloxy propylsilane.
Conjugated diene of the present invention is C
4-C
12conjugated diene, is preferably 1,3-butadiene, isoprene, 2,3-dimethyl-1,3 divinyl, 2,3-diethyl-1,3 divinyl, 2-methyl-3-ethyl-1,3 divinyl, the chloro-1,3-pentadiene of 2-, 1,3-pentadiene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-butadiene, one or more in 1,3-hexadiene, more preferably 1,3-butadiene and/or isoprene.
Rubber combination of the present invention, can contain in the auxiliary agents such as zinc oxide, stearic acid, anti-aging agent, promotor one or more; The kind of these auxiliary agents and add-on are conventionally known to one of skill in the art, and the add-on that the present invention recommends is 100 parts by weight with polydiene, and zinc oxide dosage is 1 ~ 5 part, and stearic acid dosage is 1 ~ 4 part, promotor 0.5 ~ 3 part, 0.5 ~ 2 part, anti-aging agent.
According to the present invention, described anti-aging agent can be N-(1,3-dimethylbutyl)-4-aminodiphenylamine (6PPD), N-phenyl-n-sec.-propyl-Ursol D (3PPD) and poly-(2,2,4-trimethylammonium-1, one or more in 2-dihyaroquinoline (RD), preferred 6PPD, consumption is 0.5 ~ 2 part.
Vulcanizing agent of the present invention can be sulphur and/or morpholine class, preferred sulphur, and consumption is 0.5 ~ 3 part;
According to the present invention, described promotor can be the promotor that various routine is used for rubber combination, and can be such as one or more in thiazole accelerators, sulphenamide accelerators and thiuram accelerator, consumption be 0.5 ~ 3 part.
Thiazole accelerators of the present invention can be dibenzothiazyl disulfide, 2-benzothiazolyl mercaptan, zinc 2-mercaptobenzothiazole salt, 2 (4-morpholinodithio) benzothiazole and N, one or more in N-diethyl-dithio oxygen base benzothiazole, are preferably dithio-bis-benzothiazole.
Sulphenamide accelerators of the present invention can be one or more in N cyclohexyl 2 benzothiazole sulfenamide, N tert butyl benzothiazole 2 sulfenamide, N-oxygen diethyl support group-2-[4-morpholinodithio sulphenamide, N, N-dicyclohexyl-2-[4-morpholinodithio sulphenamide and N-oxygen diethylidene thiocarbamyl-N '-oxygen diethylidene sulphenamide; Be preferably N cyclohexyl 2 benzothiazole sulfenamide.
Thiuram accelerator of the present invention can be one or more in tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, disulfide diisobutyl thiuram, tetra-benzyl thiram disulfide, bis-pentamethylenethiuram tetrasulfide and tetrabutylthiuram disulfide; Be preferably tetramethyl-thiuram disulfide.
Present invention also offers the preparation method of this rubber combination, be specially:
(1) preparing nano silicon/poly-conjugated-diolefin composite emulsion, by seeding emulsion polyerization legal system for nano silicon/poly-conjugated-diolefin composite emulsion, is 100 parts in conjugated diene monomer quality:
Prepared by monomer pre-emulsion: conjugated diene monomer, emulsifying agent, deionized water, buffer reagent, initiator mixing pre-emulsification are prepared into pre-emulsion in 15 ~ 45 minutes; Wherein the ratio of monomer and water is 1:1 ~ 1:2, and emulsifier is 3 ~ 20 parts, and buffer reagent consumption is 0.3 ~ 1 part, and initiator amount is 0.1 ~ 0.8 part;
With surface-functionalized modified manometer silicon dioxide for core prepares nano silicon/poly-conjugated-diolefin composite emulsion: the nano silicon 0.1 ~ 5 part getting surface-functionalized modification joins in the reactor that 0.1 ~ 5 part of emulsifying agent and 10 ~ 50 parts of deionized waters are housed, stirring is warming up to 60 ~ 80 DEG C, then getting 1/20 ~ 1/5 monomer pre-emulsion joins in reactor, controlling temperature of reaction kettle is 60 ~ 80 DEG C, be incubated 0.5 ~ 1 hour, allow conjugated diene monomer by coated for surface-functionalized modified manometer silicon dioxide and be polymerized, and using this seed as composite emulsion, in the reactor that seed emulsion is housed, drip remaining monomer pre-emulsion, and dropwised in 5 ~ 8 hours, finally obtain poly-conjugated-diolefin/nano silicon function and service emulsion,
(2) nano silicon/poly-conjugated-diolefin composite emulsion is joined in polydiene latex, mix, 0.08 ~ 0.12 part of initiator is added under 65 ~ 85 DEG C and agitation condition, carry out graft polymerization reaction 5 ~ 8h, finally the emulsion condensation drying of graft modification is obtained nano silicon/poly-conjugated-diolefin modified rubber;
(3) polydiene, nano silicon/poly-conjugated-diolefin modified rubber, carbon black and vulcanizing agent is blend sulfurized.
In nano silicon of the present invention/poly-conjugated-diolefin composite emulsion preparation process, emulsifying agent used is conventionally known to one of skill in the art, can be one or more in anionic emulsifier and nonionic emulsifying agent.Anionic emulsifier can be metal carboxylate, Sulfates, one or more in Sulfonates emulsifying agent, preferred fatty acid soap, resin acid soaps, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, more preferably sodium lauryl sulphate, nonionic emulsifying agent can be ester class, one or more in ethers, preferred polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitol acid anhydride monopalmitate, polyoxyethylene sorbitan monooleate, alkylphenol polyoxyethylene, polyoxyethylene nonylphenol ether, fatty alcohol-polyoxyethylene ether, more preferably alkylphenol polyoxyethylene.
Buffer reagent used in nano silicon of the present invention/poly-conjugated-diolefin composite emulsion preparation process can be sodium carbonate, sodium bicarbonate, sodium hydroxide, ammoniacal liquor, bicarbonate of ammonia, preferred sodium carbonate or sodium bicarbonate.
Initiator of the present invention is water-soluble thermal initiator, initiator system of ammonium persulfate, Potassium Persulphate, Sodium Persulfate, 2, two (the 2-amidine azoles quinoline propane) hydrochloride, 2 of 2-azo, 2-azo [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride, more preferably Potassium Persulphate or Sodium Persulfate.
The emulsion condensation drying of graft modification of the present invention adopts flocculate and break emulsion, precipitation, the dry processing condition of normal latex, this technology is that those skilled in the art are in common knowledge, and such as " China Synthetic Rubber Industry " 2009 32 volumes the 4th interim " application of latex coprecipitation method styrene-butadiene rubber(SBR)/organic montmorillonite nano composite material in tire tread " just describe these processing condition.The processing condition that the present invention recommends are: one or more adding in the flocculation agent such as sodium-chlor, Repone K, magnesium chloride, calcium chloride, magnesium sulfate, calcium sulfate, hydrochloric acid, sulfuric acid carry out flocculate and break emulsion, coprecipitated plastic emitting, drying.
Surface-functionalized modified manometer silicon dioxide of the present invention adopts coupling agent to be made the nano silicon with response type by surface functionalization process the silicon-dioxide of 20 ~ 60nm, this technology is conventionally known to one of skill in the art, such as, discloses the method for nano-silica surface functional modification in " radiation research and radiation process journal " 25 volumes the 5th phase in 2007 " research of surface modification of silica and radiation initiation grafting GMA "; The present invention is not particularly limited to, the method that the present invention recommends is: take 0.1 ~ 50 part of nano silicon stand-by in oven drying, then with 5 ~ 500 parts of solvent after ultrasonic wave disperse fully, add the coupling agent after 0.1 ~ 50 part of hydrolysis, stir post-heating to 80 ~ 120 DEG C backflow 2 ~ 4 hours, filtration washing.Solvent is toluene, dimethylbenzene or methyl ethyl ketone, and its add-on is 5 ~ 500 parts, preferably 100 ~ 300 parts.
In preparation method disclosed by the invention, when rubber combination contains zinc oxide, stearic acid, anti-aging agent, promotor auxiliary agent, these auxiliary agents add in polydiene, nano silicon/blend sulfurized process of poly-conjugated-diolefin modified rubber, carbon black and vulcanizing agent.
The effect that the present invention is useful:
Graft modification rubber of the present invention is formed by nano silicon and the graft polymerization of poly-conjugated-diolefin composite emulsion, because composite emulsion has satisfactory stability, size tunable, be distributed in 50 ~ 80nm, during direct graft modification rubber latex, there is good dispersiveness, good with rubber latex consistency, and technique is simple, easy to operate.
Nano silicon/poly-conjugated-diolefin the functional materials adopting the present invention to prepare has good dynamic properties simultaneously, and 60 DEG C of dissipation factors (tan δ) are reduced, and illustrate when low for the preparation of rolling resistance during tire.Molecular weight and molecualr weight distribution has important impact to mixing behavior, and the molecular weight and molecualr weight distribution of nano silicon of the present invention/poly-conjugated-diolefin functional materials is suitable for, and time mixing as functional composite material, heat-dissipating is low, mixing behavior good.Graft modification rubber physical mechanical property of the present invention is excellent, and particularly tensile strength can be significantly improved.0 DEG C of tan δ is higher for modified polydiene, illustrates that modified rubber product prepares wet-sliding resistant performance for tire and damping performance is good.The method being used further to graft modification rubber by preparing functional latex effectively solves nano silicon scattering problem of (particularly nonpolar rubber) in rubber matrix, therefore good over-all properties is shown after being applied to tire, its 60 DEG C of dissipation factors (tan δ) reduce, and illustrate when low for the preparation of rolling resistance during tire.0 DEG C of tan δ is higher, illustrates to be used for tire to prepare wet-sliding resistant performance good, and Akron abrasion volume is low, illustrates that to prepare wear resistance for tire good.
In addition, the present invention is raw materials used to be easy to get, preparation process is easy to be easy to control, in functional latex preparation process not with an organic solvent, environmental protection, pollution-free, cost is low, adopts seeding emulsion polyerization method that nano silicon can be made with chemical bonds, can be good be scattered in poly-conjugated-diolefin.
Embodiment:
Effect of the present invention is further illustrated below by embodiment and comparative example.
(1) raw material sources:
Nano silicon (20 ~ 60nm), 99.5%, Weifang Wan Li auxiliary agent company limited produces;
Silane coupling agent VTES, MPS, VTMS, MPTS, gamma-amino propyl trimethoxy silicane, vinyltriacetoxy silane, technical grade, is Qufu City Wanda Chemical Co., Ltd. and produces;
Divinyl, 99.5%, Lanzhou Petrochemical Company synthetic rubber plant produces;
Isoprene, 99.3%, Lanzhou Xin Lan petrochemical complex company limited produces;
Content of polybutadiene rubber latex, solid content 50%, Lanzhou Petrochemical Company is produced;
Styrene butadiene rubber latex: SBR 1500, SBR 1502, combined styrene content 23.5%, solid content 23%, Lanzhou Petrochemical Company is produced;
Carbon black: Wuxi Shuan Cheng carbon black company limited produces;
Polybutadiene rubber BR9100, Jinzhou produces;
Natural rubber, GB 5
#, Yunnan Natural Rubber industry companies produces
Styrene butadiene rubber sbr 1500E, SBR 1502E, Lanzhou Petrochemical Company is produced.
Various unmodified rubber performance is in table 1.
The unmodified rubber product performance of table 1
| Performance/glue kind | SBR 1500 | Natural rubber | SBR 1502 | Polybutadiene rubber |
| Tensile strength, MPa | 24.5 | 16.4 | 22.6 | 17.2 |
| Tensile yield, % | 484 | 554 | 411 | 460 |
| 300% stress at definite elongation, MPa (35min) | 15.8 | 11.2 | 17.1 | 8.94 |
| tanδ(0℃) | 0.158 | 0.152 | 0.172 | 0.148 |
(2) analysis test method:
Molecular weight and distribution thereof: adopt high temperature gel chromatogram analysis method (GPC), GPC tests the GPCV2000 type high temperature gel chromatographic instrument that instrument is WATERS company.Take orthodichlorobenzene as solvent, by sample dissolution, placement filtering at 135 DEG C; Sample size 200 μ L/ post, flow velocity 1ml/min, adopts HT6, HT5, HT4, HT3 post group.
0 DEG C and 60 DEG C of dissipation factors: adopt the DMA Q800 type dynamic thermomechanical analysis apparatus of TA company to analyze, select two cantilever chuck.-150 DEG C ~ 100 DEG C temperature programmings, temperature rise rate is 3 DEG C/min, and amplitude is 10 μm, and test frequency is respectively 1Hz, 5Hz, 10Hz, dynamic force 1N.
Particle diameter: the Zetasizer-3000HSA laser particle analyser adopting Malvern company to produce is tested.
Akron abrasion volume; Method in operative norm GB/T 25262-2010.
Tensile strength, tensile yield and 300% stress at definite elongation: operative norm GB/T528-2009.
Embodiment 1
Nano-silica surface functional modification: take 120g nano silicon in oven drying, then after mixing with 1200g toluene, ultrasonic wave is disperseed fully, add the VTES after 240g hydrolysis, be heated with stirring to 82 DEG C of backflows 2.3 hours, then filter, wash, vacuum-drying.
Prepared by functional latex:
The first step, prepared by monomer pre-emulsion.1,3-butadiene 1200g, Sodium dodecylbenzene sulfonate 120g, deionized water 1800g, sodium hydroxide 12g, Potassium Persulphate 2.4g are mixed pre-emulsification and be prepared into pre-emulsion in 20 minutes.
Second step is that core prepares functional latex with modified manometer silicon dioxide.The nano silicon 3.6g getting surface-functionalized modification joins in the reactor that 60g Sodium dodecylbenzene sulfonate and 480g deionized water are housed, stirring is warming up to 60 DEG C, then getting 313g monomer pre-emulsion joins in reactor, controlling temperature of reaction kettle is 60 DEG C, be incubated 40 minutes, make monomer that nano silicon is coated and be polymerized, and using this seed as composite emulsion.In the reactor that seed emulsion is housed, drip remaining 2821g monomer pre-emulsion, and dropwised in 7.5 hours, obtain poly-1,3-butadiene/nano silicon function and service emulsion.Poly-1,3-butadiene/nano silicon functional composite material is finally obtained with sulfuric acid cohesion drying.
Graft modification rubber: get nano silicon/poly-1, it is in SBR 1500 latex of 980g that 3-divinyl functional latex butt 100g joins butt, fully be uniformly mixed, under 75 DEG C and agitation condition, add 92g Potassium Persulphate carry out graft polymerization reaction 6h, finally carry out flocculate and break emulsion by adding sodium-chlor in the latex of graft modification, coprecipitated plastic emitting, drying obtains SBR 1500 product of nano silicon/poly-1,3-butadiene graft modification.
Prepared by rubber combination
By 1000g natural rubber, 1000g nano silicon/(N2 adsorption specific surface area is 78m for poly-1,3-butadiene graft modification SBR 1500,225g carbon black N326
2g
-1, DBP absorption value is 70cm
3g
-1), 30g anti-aging agent 6PPD and 60g sulphur is blend sulfurized prepares rubber combination.
Embodiment 2
The nano silicon method of surface-functionalized modification is prepared: take 6g nano silicon in 50 DEG C of oven drying 5h according to method disclosed in " radiation research and radiation process journal " 25 volumes the 5th phase in 2007 " research of surface modification of silica and radiation initiation grafting GMA ", dried nano silicon is added in the aqueous solution being dissolved with 96g coupling agent MPS, ultrasonic disperse 1h.After dispersion, mixed solution is stirred 8h at 110 DEG C.After filtration, by modified silicon-dioxide toluene wash, again through surname extraction after products therefrom vacuum filtration, be finally positioned in baking oven dry.
Prepared by functional latex:
The first step, prepared by monomer pre-emulsion.Isoprene 1200g, sodium lauryl sulphate 72g, deionized water 1200g, ammoniacal liquor 6g, ammonium persulphate 9.6g are mixed pre-emulsification and be prepared into pre-emulsion in 15 minutes.
Second step is that core prepares functional latex with modified manometer silicon dioxide.The nano silicon 60g getting surface-functionalized modification joins in the reactor that 3.6g sodium lauryl sulphate and 180g deionized water are housed, stirring is warming up to 65 DEG C, then getting 124g monomer pre-emulsion joins in reactor, controlling temperature of reaction kettle is 75 DEG C, be incubated 20 minutes, make monomer that nano silicon is coated and be polymerized, and using this seed as composite emulsion.In the reactor that seed emulsion is housed, drip remaining 2363g monomer pre-emulsion, and dropwised in 6.5 hours, finally obtain polyisoprene/nano silicon function and service emulsion.Polyisoprene/nano silicon functional composite material is finally obtained with sulfuric acid cohesion drying.
Graft modification rubber: get nano silicon/polyisoprene functional latex butt 230g and join the natural rubber latex Ruzhong that butt is 1000g, fully be uniformly mixed, under 65 DEG C and agitation condition, add 102g Potassium Persulphate carry out graft polymerization reaction 6.5h, finally carry out flocculate and break emulsion by adding magnesium sulfate in the latex of graft modification, coprecipitated plastic emitting, drying obtains the Natural Rubber Products of nano silicon/polyisoprene graft modification.
Prepared by rubber combination
By the natural rubber of 400g SBR 1500,1600g nano silicon/polyisoprene graft modification, 500g carbon black N330, (N2 adsorption specific surface area is 79m
2g
-1, DBP absorption value is 100cm
3g
-1), 10g sulphur is blend sulfurized prepares rubber combination.
Embodiment 3
Nano-silica surface functional modification: take 240g nano silicon stand-by in oven drying, then after mixing with 4800g dimethylbenzene, ultrasonic wave is disperseed fully, add the VTMS after 312g hydrolysis, stir post-heating to 93 DEG C backflow 4 hours, then filter, wash, vacuum-drying.
Prepared by functional latex:
The first step, prepared by monomer pre-emulsion.1,3-pentadiene 1200g, Sodium dodecylbenzene sulfonate 40g, alkylphenol polyoxyethylene 200g, deionized water 1920g, sodium carbonate 9.6g, Sodium Persulfate 9.8g are mixed pre-emulsification and be prepared into pre-emulsion in 30 minutes.
Second step is that core prepares functional latex with modified manometer silicon dioxide.The nano silicon 54g getting surface-functionalized modification joins in the reactor that 54g fatty acid soaps and 456g deionized water are housed, stirring is warming up to 68 DEG C, then getting 676g monomer pre-emulsion joins in reactor, controlling temperature of reaction kettle is 68 DEG C, be incubated 60 minutes, make monomer that nano silicon is coated and be polymerized, and using this seed as composite emulsion.In the reactor that seed emulsion is housed, drip remaining 2703g monomer pre-emulsion, and dropwised in 6 hours, obtain poly-1,3-pentadiene/nano silicon function and service emulsion.Poly-1,3-pentadiene/nano silicon functional composite material is finally obtained with sulfuric acid cohesion drying.
Graft modification rubber: get nano silicon/poly-1, it is in SBR 1502 latex of 660g that 3 pentadiene functional latex butt 300g join butt, fully be uniformly mixed, under 72 DEG C and agitation condition, add 86g Potassium Persulphate carry out graft polymerization reaction 5.8h, finally will add sodium-chlor in the latex of graft modification and sulphuric acid soln carries out flocculate and break emulsion, coprecipitated plastic emitting, drying obtains SBR 1502 product of nano silicon/poly-1,3-pentadiene graft modification.
Prepared by rubber combination
By SBR 1502, the 1000g carbon black N375 of 2000g nano silicon/poly-1,3-pentadiene graft modification, (N2 adsorption specific surface area is 93m
2g
-1, DBP absorption value is 115cm
3g
-1), 70g zinc oxide, 46g stearic acid, 20g promotor dithio-bis-benzothiazole and 20g sulphur is blend sulfurized prepares rubber combination.
Embodiment 4
Nano-silica surface functional modification: take 456g nano silicon stand-by in oven drying, then after mixing with 5040g methyl ethyl ketone, ultrasonic wave is disperseed fully, add the MPTS after 576g hydrolysis, stir post-heating to 80 DEG C backflow 3.2 hours, then filter, wash, vacuum-drying.
Prepared by functional latex:
The first step, prepared by monomer pre-emulsion.2,3-dimethyl-1,3 divinyl 1200g, polyoxyethylene nonylphenol ether 180g, deionized water 1340g, sodium bicarbonate 11.04g, two (2-amidine azoles quinoline propane) the hydrochloride 6g of 2,2-azos are mixed pre-emulsification and be prepared into pre-emulsion in 35 minutes.
Second step is that core prepares functional latex with modified manometer silicon dioxide.The nano silicon 43.2g getting surface-functionalized modification joins in the reactor that 10g polyoxyethylene nonylphenol ether, 20g fatty acid soaps and 120g deionized water are housed, stirring is warming up to 78 DEG C, then getting 560g monomer pre-emulsion joins in reactor, controlling temperature of reaction kettle is 78 DEG C, be incubated 55 minutes, make monomer that nano silicon is coated and be polymerized, and using this seed as composite emulsion.In the reactor that seed emulsion is housed, drip remaining 3176g monomer pre-emulsion, and dropwised in 5.5 hours, obtain poly-2,3-dimethyl-1,3 divinyl/nano silicon function and service emulsion.Poly-2,3-dimethyl-1,3 divinyl/nano silicon functional composite material is finally obtained with sulfuric acid cohesion drying.
Graft modification rubber: get nano silicon/poly-2,3-dimethyl-1, it is in the content of polybutadiene rubber latex of 600g that 3 divinyl functional latex butt 520g join butt, fully be uniformly mixed, under 78 DEG C and agitation condition, add 82g Potassium Persulphate carry out graft polymerization reaction 7.2h, finally carry out flocculate and break emulsion by adding calcium chloride in the latex of graft modification, coprecipitated plastic emitting, drying obtains nano silicon/poly-2, the polybutadiene rubber product of 3-dimethyl-1,3 butadiene graft modification.
Prepared by rubber combination
By the polybutadiene rubber of 1600g SBR 1500,400g nano silicon/poly-2,3-dimethyl-1,3 butadiene graft modification, (N2 adsorption specific surface area is 115m to 600 carbon black N220
2g
-1, DBP absorption value is 106cm
3g
-1), 84g zinc oxide, 80g stearic acid, 24g anti-aging agent 6PPD, 10g accelerant disulfide tetra methylthiuram and 30g sulphur is blend sulfurized prepares rubber combination.
Embodiment 5
Nano-silica surface functional modification: take 540g nano silicon stand-by in oven drying, then after mixing with 3120g toluene, ultrasonic wave is disperseed fully, add the gamma-amino propyl trimethoxy silicane after 468g hydrolysis, stir post-heating to 98 DEG C backflow 3.7 hours, then filter, wash, vacuum-drying.
Prepared by functional latex:
The first step, prepared by monomer pre-emulsion.1,3-hexadiene 1200g, fatty acid soaps 48g, deionized water 1320g, bicarbonate of ammonia 6.96g, 2,2-azos [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride 3.6g are mixed pre-emulsification and be prepared into pre-emulsion in 45 minutes.
Second step is that core prepares functional latex with modified manometer silicon dioxide.The nano silicon 33.6g getting surface-functionalized modification joins in the reactor that 21g alkylphenol polyoxyethylene, 21g fatty alcohol-polyoxyethylene ether and 300g deionized water are housed, stirring is warming up to 80 DEG C, then getting 258g monomer pre-emulsion joins in reactor, controlling temperature of reaction kettle is 80 DEG C, be incubated 45 minutes, make monomer that nano silicon is coated and be polymerized, and using this seed as composite emulsion.In the reactor that seed emulsion is housed, drip remaining 2321g monomer pre-emulsion, and dropwised in 8 hours, obtain poly-1,3-hexadiene/nano silicon function and service emulsion.Poly-1,3-hexadiene/nano silicon functional composite material is finally obtained with sulfuric acid cohesion drying.
Graft modification rubber: get nano silicon/poly-1, it is in SBR 1500 latex of 620g that 3-hexadiene functional latex butt 620g joins butt, fully be uniformly mixed, under 68 DEG C and agitation condition, add 95g ammonium persulphate carry out graft polymerization reaction 7.8h, finally carry out flocculate and break emulsion by adding magnesium sulfate in the latex of graft modification, coprecipitated plastic emitting, drying obtains SBR 1500 product of a meter silicon-dioxide/poly-1,3-hexadiene graft modification.
Prepared by rubber combination
By the natural rubber of 800g, 1200g nano silicon/poly-1,3-hexadiene/SBR 1500 modified rubber, (N2 adsorption specific surface area is 64m to 900g carbon black N351
2g
-1, DBP absorption value is 120cm
3g
-1) and 50g sulphur is blend sulfurized prepares rubber combination.
Comparative example 1
The nano silicon 3.6g of modification in Example 1 to be scattered in 1200g and 1800g cyclohexane solvent ultrasonic disperse 20 minutes; be heated to 60 DEG C; after add 2.4g n-Butyl Lithium as initiator; polyreaction carries out 7.5 hours under nitrogen protection; then product is joined in ethanol and obtain white depositions; filtration drying just obtains poly-1,3-butadiene/nanometer silicon dioxide composite material.
Prepared by rubber combination
By 1000g natural rubber, 93g gathers 1,3-butadiene/nanometer silicon dioxide composite material, (N2 adsorption specific surface area is 78m2g-1, DBP absorption value is 70cm for 907g SBR 1500,225g carbon black N326
3g
-1), 50g zinc oxide, 20g stearic acid, 30g anti-aging agent 6PPD and 60g sulphur is blend sulfurized prepares rubber combination.
In table 2, each embodiment and comparative example test data illustrate, nano silicon of the present invention/poly-conjugated-diolefin composite emulsion performance is more excellent.
In table 4, each embodiment and comparative example dynamic properties test data and abrasion resistance illustrate, building rubber compound physical performance of the present invention is obviously better than the product performance of comparative example.
Comparative example 2
Comparative example 3.Take 240g nano silicon stand-by in oven drying, then after mixing with 4800g dimethylbenzene, ultrasonic wave is disperseed fully, add the VTMS after 312g hydrolysis, stir post-heating to 93 DEG C backflow 4 hours, then the nano silicon butt quality 300g of this organic modification being joined butt quality is in SBR 1502 latex of 660g, fully be uniformly mixed, under 75 DEG C and agitation condition, add 86g Potassium Persulphate carry out graft polymerization reaction 5.8h, finally by the latex sodium-chlor of graft modification and sulphuric acid soln cohesion, coprecipitated plastic emitting, drying obtains SBR 1502 product of white carbon black modification.Obvious white depositions is had, caused by nano silicon sedimentation in coagulation liquid.
Prepared by rubber combination
By the SBR 1502 of 2000g white carbon black modification, 1000g carbon black N375, (N2 adsorption specific surface area is 93m
2g
-1, DBP absorption value is 115cm
3g
-1), 70g zinc oxide, 46g stearic acid, 20g promotor dithio-bis-benzothiazole and 20g sulphur is blend sulfurized prepares rubber combination.
In table 3, the mechanical mechanics property of each embodiment and comparative example styrene-butadiene rubber(SBR) product and dynamic properties test data illustrate, graft modification styrene-butadiene rubber(SBR) product performance of the present invention are obviously better than the product performance of comparative example.
In table 4, each embodiment and comparative example dynamic properties test data and abrasion resistance illustrate, building rubber compound physical performance of the present invention is obviously better than the product performance of comparative example.
Comparative example 3
Prepared by rubber combination
By 2000g SBR 1502,1000g carbon black N375, (N2 adsorption specific surface area is 93m
2g
-1, DBP absorption value is 115cm
3g
-1), 70g zinc oxide, 46g stearic acid, 20g promotor dithio-bis-benzothiazole and 20g sulphur is blend sulfurized prepares rubber combination.
In table 4, each embodiment and comparative example dynamic properties test data and abrasion resistance illustrate, building rubber compound physical performance of the present invention is obviously better than the product performance of comparative example.
Comparative example 4
By 2000g SBR 1502,1000g carbon black N375, (N2 adsorption specific surface area is 93m
2g
-1, DBP absorption value is 115cm
3g
-1), 40g nano silicon, 2gVTMS, 70g zinc oxide, 46g stearic acid, 20g promotor dithio-bis-benzothiazole and 20g sulphur is blend sulfurized prepares rubber combination.
In table 3, each embodiment and comparative example dynamic properties test data and abrasion resistance illustrate, building rubber compound physical performance of the present invention is obviously better than the product performance of comparative example.
Table 2 nano silicon/poly-conjugated-diolefin composite emulsion performance
| Functional latex/material property | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 |
| Particle diameter, nm | 58 | 62 | 55 | 68 | 72 | 50 | - |
| Number-average molecular weight Mn × 10 -4 | 10.2 | 11.2 | 12.5 | 11.6 | 13.4 | 10.8 | 15 |
| Molecular weight distribution mw/mn | 2.81 | 2.65 | 2.23 | 2.58 | 2.69 | 2.75 | 1.78 |
| tanδ(60℃) | 0.254 | 0.286 | 0.273 | 0.269 | 0.243 | 0.238 | 0.316 |
Table 3 graft modification rubber product performance
| Modified rubber product performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example |
| Tensile strength, MPa (145 DEG C, 35min) | 26.8 | 28.9 | 24.8 | 19.1 | 25.9 | 23.5 |
| Tensile yield, % | 462 | 537 | 395 | 441 | 472 | 400 |
| 300% stress at definite elongation, MPa (35min) | 16.8 | 13.6 | 18.4 | 10.1 | 17.8 | 18.1 |
| tanδ(0℃) | 0.332 | 0.315 | 0.347 | 0.304 | 0.341 | 0.258 |
Table 4 building rubber compound physical performance
Claims (17)
1. a dyene-type rubber composition, is characterized in that, in each ingredients weight parts, containing 100 parts of main rubbers, 10 ~ 60 parts of carbon blacks, 0.5 ~ 3 part of vulcanizing agent, be 100% calculating with main rubber quality, the polydiene 10 ~ 100% of nano silicon/poly-conjugated-diolefin modification that main rubber comprises (1), (2) polydiene 0 ~ 90%, the polydiene of nano silicon/poly-conjugated-diolefin modification is by the graft polymerization and obtaining under initiator existent condition of polydiene latex and nano silicon/poly-conjugated-diolefin composite emulsion, the mass ratio of polydiene latex butt and nano silicon/poly-conjugated-diolefin composite emulsion butt is 100:0.1 ~ 100, nano silicon/poly-conjugated-diolefin composite emulsion, it is 100 parts in composite emulsion butt, nano silicon containing surface-functionalized modification 0.1 ~ 5 part, nano silicon/poly-conjugated-diolefin composite emulsion particle diameter is 50 ~ 80nm, number-average molecular weight is 100000 ~ 140000, molecular weight distribution is 2 ~ 3.
2. rubber combination according to claim 1, (2) polydiene that it is characterized in that in main rubber is selected from the one in emulsion polymerized styrene butadiene rubber, solution polymerized butadiene styrene rubber, natural rubber, cis-1,4-polybutadiene rubber, styrene isoprene butadiene rubber (SIBR), and its polydiene of polydiene of the nano silicon in main rubber (1)/poly-conjugated-diolefin modification is introduced with the form of content of polybutadiene rubber latex, natural rubber latex, styrene butadiene rubber latex.
3. rubber combination according to claim 1, is characterized in that carbon black N2 adsorption specific surface area is 60 ~ 120m
2g
-1, DBP absorption value is 60 ~ 120cm
3g
-1.
4. rubber combination according to claim 1, it is characterized in that the nano silicon of surface-functionalized modification refers to that silicon-dioxide adopts silane coupling agent to be made the nano silicon with response type by surface functionalization process, coupling agent is 0.1 ~ 50% of surface-functionalized modified manometer silicon dioxide quality.
5. rubber combination according to claim 4, is characterized in that coupling agent is surface-functionalized modified manometer silicon dioxide quality 10 ~ 30%.
6. rubber combination according to claim 4, is characterized in that silane coupling agent is one or more in vinyl silane, methyl acrylic ester silane.
7. rubber combination according to claim 6, it is characterized in that silane coupling agent be in vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriacetoxy silane, vinyl tributyl ketoximyl silane, vinyl silane triisopropoxide, vinyl trichloro silane, vinyl trimethoxysilane oligomer, γ-methacryloxypropyl trimethoxy silane and three (trimethylsiloxy group) methacryloxy propylsilane one or more.
8. rubber combination according to claim 1, is characterized in that conjugated diene is C
4-C
12conjugated diene.
9. rubber combination according to claim 8, is characterized in that conjugated diene is 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, the chloro-1,3-pentadiene of 2-, 1,3-pentadiene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-divinyl, one or more in 1,3-hexadiene.
10. rubber combination according to claim 1, it is characterized in that rubber combination to contain in zinc oxide, stearic acid, anti-aging agent, promotor one or more, wherein 1 ~ 5 part, zinc oxide, stearic acid 1 ~ 4 part, promotor 0.5 ~ 3 part, 0.5 ~ 2 part, anti-aging agent.
11. rubber combinations according to claim 10, it is characterized in that anti-aging agent is N-(1,3-dimethylbutyl)-4-aminodiphenylamine (6PPD), N-phenyl-n-sec.-propyl-Ursol D (3PPD) and poly-(2,2,4-trimethylammonium-1,2-dihyaroquinoline) one or more in (RD); Promotor is one or more in thiazole accelerators, sulphenamide accelerators and thiuram accelerator; Vulcanizing agent is sulphur and/or morpholine class vulcanizing agent.
12. rubber combinations according to claim 1, it is characterized in that the processing condition of polydiene latex and nano silicon/poly-conjugated-diolefin composite emulsion graft polymerization under initiator existent condition are: nano silicon/poly-conjugated-diolefin composite emulsion joins in polydiene latex, mix, under 65 ~ 85 DEG C and agitation condition, add 0.08 ~ 0.12 part of initiator, carry out graft polymerization reaction 5 ~ 8h.
The preparation method of 13. 1 kinds of compositions according to claim 1, is characterized in that preparation process is:
(1) preparing nano silicon/poly-conjugated-diolefin composite emulsion, by seeding emulsion polyerization legal system for nano silicon/poly-conjugated-diolefin composite emulsion, is 100 parts in conjugated diene monomer quality:
Prepared by monomer pre-emulsion: conjugated diene monomer, emulsifying agent, deionized water, buffer reagent, initiator mixing pre-emulsification are prepared into pre-emulsion in 15 ~ 45 minutes; Wherein the ratio of monomer and water is 1:1 ~ 1:2, and emulsifier is 3 ~ 20 parts, and buffer reagent consumption is 0.3 ~ 1 part, and initiator amount is 0.1 ~ 0.8 part;
With surface-functionalized modified manometer silicon dioxide for core prepares nano silicon/poly-conjugated-diolefin composite emulsion: the nano silicon 0.1 ~ 5 part getting surface-functionalized modification joins in the reactor that 0.1 ~ 5 part of emulsifying agent and 10 ~ 50 parts of deionized waters are housed, stirring is warming up to 60 ~ 80 DEG C, then getting 1/20 ~ 1/5 monomer pre-emulsion joins in reactor, controlling temperature of reaction kettle is 60 ~ 80 DEG C, be incubated 0.5 ~ 1 hour, allow conjugated diene monomer by coated for surface-functionalized modified manometer silicon dioxide and be polymerized, and using this seed as composite emulsion, in the reactor that seed emulsion is housed, drip remaining monomer pre-emulsion, and dropwised in 5 ~ 8 hours, finally obtain nano silicon/poly-conjugated-diolefin composite emulsion,
(2) nano silicon/poly-conjugated-diolefin composite emulsion is joined in polydiene latex, mix, 0.08 ~ 0.12 part of initiator is added under 65 ~ 85 DEG C and agitation condition, carry out graft polymerization reaction 5 ~ 8h, finally the emulsion condensation drying of graft modification is obtained nano silicon/poly-conjugated-diolefin modified rubber;
(3) polydiene, nano silicon/poly-conjugated-diolefin modified rubber, carbon black and vulcanizing agent is blend sulfurized.
14. preparation methods according to claim 13, it is characterized in that emulsifying agent be in anionic emulsifier and/or nonionic emulsifying agent one or more; Buffer reagent be in sodium carbonate, sodium bicarbonate, sodium hydroxide, ammoniacal liquor and bicarbonate of ammonia one or more; Initiator is water-soluble thermal initiator.
15. preparation methods according to claim 14, it is characterized in that anionic emulsifier be in metal carboxylate, Sulfates, Sulfonates emulsifying agent one or more; Nonionic emulsifying agent be in ester class, ethers emulsifying agent one or more; Buffer reagent is sodium carbonate and/or sodium bicarbonate; Water-soluble thermal initiator is ammonium persulphate, Potassium Persulphate, Sodium Persulfate, 2,2-azos two (2-amidine azoles quinoline propane) hydrochloride, 2,2-azos [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride.
16. preparation methods according to claim 15, it is characterized in that anionic emulsifier is sodium lauryl sulphate, nonionic emulsifying agent is polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitol acid anhydride monopalmitate, polyoxyethylene sorbitan monooleate, alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether.
17. preparation methods according to claim 13, it is characterized in that rubber combination contains in zinc oxide, stearic acid, anti-aging agent, promotor auxiliary agent one or more, with the rubber of polydiene, nano silicon/poly-conjugated-diolefin modification, carbon black and the common mixing sulfuration of vulcanizing agent.
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| CN105218899A (en) * | 2014-06-19 | 2016-01-06 | 南港(张家港保税区)橡胶工业有限公司 | A kind of energy-saving tire tyre surface formula |
| CN104262885A (en) * | 2014-10-22 | 2015-01-07 | 华文蔚 | Rubber composition |
| CN104262716A (en) * | 2014-10-22 | 2015-01-07 | 华文蔚 | Rubber composition for tire |
| CN104262705A (en) * | 2014-10-22 | 2015-01-07 | 华文蔚 | Rubber composition |
| CN104629241A (en) * | 2015-01-30 | 2015-05-20 | 柳州市中配橡塑配件制造有限公司 | Oil-extended rubber used for automobile tires |
| CN104629240A (en) * | 2015-01-30 | 2015-05-20 | 柳州市中配橡塑配件制造有限公司 | Oil-extended rubber |
| CN107266716A (en) * | 2016-04-08 | 2017-10-20 | 中国石油天然气股份有限公司 | The method of modifying of Nano carbon white |
| CN106699968A (en) * | 2016-11-23 | 2017-05-24 | 厦门大学 | Method for preparing nanosilicon dioxide modified styrene-butadiene latex |
| CN111073086B (en) * | 2018-10-18 | 2022-03-29 | 中国石油天然气股份有限公司 | Rubber composition for high-wear-resistance green tire and preparation method thereof |
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