CN107266745A - Rubber composition of the white carbon containing modified Nano and preparation method thereof - Google Patents
Rubber composition of the white carbon containing modified Nano and preparation method thereof Download PDFInfo
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- CN107266745A CN107266745A CN201610217661.9A CN201610217661A CN107266745A CN 107266745 A CN107266745 A CN 107266745A CN 201610217661 A CN201610217661 A CN 201610217661A CN 107266745 A CN107266745 A CN 107266745A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/14—Coagulation
- C08C1/15—Coagulation characterised by the coagulants used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
Present invention aims at provide a kind of rubber composition of the white carbon containing modified Nano, the invention uses unsaturated carboxylic acid polar monomer and aryl ethylene class monomer, modified Nano white carbon is prepared using situ aggregation method, then directly mixed with styrene butadiene rubber latex, condense to prepare the rubber composition of high-performance tire tread rubber.The invention not only efficiently solves the easy agglomeration traits of Nano carbon white, and solves the problem of Nano carbon white is with rubber matrix adhesion difference and scattered inequality, imparts said composition high abrasion, the performance of low friction.The preparation method of the rubber composition is simple and easy to apply, with low cost, environmentally safe, is adapted to industrialized production.
Description
Technical field
The present invention relates to a kind of rubber composition and preparation method thereof, rubber composition of tire tread and preparation method thereof is used for more particularly to a kind of modified white carbon black filled styrene butadiene rubber.
Background technology
It is well known that with the successive implementation of EU REACH Legislation and tire tag bill, synthetic rubber environmental protection is extremely urgent, along with the demand of light color article, the application study of white carbon causes the attention of people.It is the second largest reinforcing agent that consumption is only second to carbon black in rubber industry that nano silicon, which is commonly called as white carbon,.From last century the nineties, white carbon is widely used in tire tread formula as reinforced filling, " devil's triangle " performance of above-mentioned tire tread requirement is obtained obvious balance.But Nano carbon white particle diameter is small, bigger than surface, the surface high, surface of energy has substantial amounts of hydroxyl again, Nano carbon white is caused easily to be reunited, it is difficult to be uniformly dispersed in the mixed process with elastomeric material, so can not only influences filling-modified effect, but also the performance of elastomeric material can be damaged.
In the prior art, the research about modified Nano white carbon filled rubber material is mainly prepared by the method for coupling agent or surfactant, graft polymers coating modification Nano carbon white particle surface filled rubber material.Such as：Qiu Quanfang (" latex blending method " natural rubber/control of silicon dioxide nano composite material micro-structure and property, 2010, University Of Hainan's Master's thesis) studies example high-performance NR composites：Natural rubber/silicon dioxide nano composite material is prepared using latex blending method, first with γ-methacryloxypropyl trimethoxy silane coupling agent (MPS) modified manometer silicon dioxide (SiO2), then it is grafted the nano-silicon dioxide particle (SiO that upper polymethyl methacrylate (PMMA) obtains core shell structure through emulsion polymerization2- MPS-PMMA) finally by itself and Heveatex (NR-PMMA) the directly blending being modified with MMA, natural rubber/silicon dioxide nano composite material is made.Li Wen Ji et al. is prepared for clay/white carbon compounded mix by drying process with atomizing, for substituting part white carbon, to strengthen solution polymerized butadiene styrene rubber/butadiene rubber composite jointly.Patent CN 101798473A use multi-sulfur silane acceptor modified white carbon black, then prepare silica/carbon black compounded mix.Patent CN201305854136A is being kneaded with rubber raw rubber and auxiliary agent, vulcanized by poly-dopamine modified lithium white carbon, prepares rubber composition.Although the above method improves the compatibility of Nano carbon white and rubber matrix, but these methods still suffer from certain limitation, when being modified using graft polymers with inorganic material surface coating modification Nano carbon white, there is reaction time consumption longer, energy consumption is higher and big for environment pollution, the shortcomings of complex operation；And when utilizing coupling agent or surfactant-modified Nano carbon white, elastomeric material vulcanization delay can be caused, cause cured properties to reduce, vulcanizing agent need to be added and accelerator causes processing cost to improve, next to that dispersion stabilization difference and easily the shortcomings of reunite again.
The content of the invention
Present invention aims at a kind of rubber composition of the white carbon containing modified Nano is provided, the rubber composition is used for having preferable wearability, relatively low rolling resistance during tire tread.The invention uses unsaturated carboxylic acid polar monomer and aryl ethylene class monomer, prepares modified Nano white carbon using situ aggregation method, is then directly mixed with styrene butadiene rubber latex, condenses to prepare the rubber composition of high-performance tire tread rubber.The invention not only efficiently solves the easy agglomeration traits of Nano carbon white, and solves the problem of Nano carbon white is with rubber matrix adhesion difference and scattered inequality, imparts said composition high abrasion, the performance of low friction.Present invention further propose that the preparation method of said composition.
A kind of rubber composition for tire tread of the invention, is counted by a hundred per cent of the quality of styrene butadiene rubber latex butt matter, mainly including following component：
(1) styrene butadiene rubber latex (butt matter) 100%
(2) modified Nano white carbon 15~40%
Wherein, described modified Nano white carbon is to use unsaturated carboxylic acid polar monomer and aryl ethylene class monomer, is prepared under initiator effect by situ aggregation method.White carbon be selected from it is nano level, its particle diameter is：20~60nm.Unsaturated carboxylic acid polar monomer is selected from one kind in acrylic acid (AA), methacrylic acid (MAA), maleic anhydride (MAH), preferably acrylic acid (AA), and its consumption is：1%~5%.One or more of mixtures of the aryl ethylene class monomer in styrene, α-methylstyrene, 2- propenyl benzenes, ethyl styrene and their derivative, optimization styrene.Initiator is water-soluble thermal initiator, selected from ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, 2,2- azos double (2- amidine oxazolines propane) hydrochloride, 2, one or more of mixtures in 2- azos [2- (2- imidazoline -2- bases) propane] dihydrochloride, preferably potassium peroxydisulfate.
Styrene butadiene rubber latex of the present invention is to be formed by conjugated diene hydrocarbon compound and aryl ethylene class compound by emulsion polymerization copolymerization.Conjugated diene hydrocarbon compound is C4Class conjugated diene hydrocarbon compound.Aryl ethylene class compound can be styrene, α-methylstyrene, 2- propenyl benzenes, ethyl styrene and their derivative.The wherein solid content 20~45% of styrene-butadiene latex, combinated styrene content content 15~25%, 50~200nm of latex particle size.
The preparation of rubber composition of the present invention is carried out in condensing field, and specific preparation process comprises the following steps：
(1) preparation of modified Nano white carbon：
A. prepared by monomer pre-emulsion：Based on the mass parts of aryl ethylene class monomer, 100 parts of aryl ethylene class monomers, 2~10 parts of emulsifying agents, 200~300 parts of deionized waters, 1.0~2.0 parts of buffers, 0.01~0.1 part of initiator are put into reactor together, when being warming up to 50~70 DEG C, stirring reaction is prepared into monomer pre-emulsion in 30~60 minutes.
B. the preparation of modified Nano white carbon：Based on the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 1.0~5.0 parts of unsaturated carboxylic acid polar monomers, 300~500 parts of deionized waters, 1~6 part of buffer is taken to be added to 10~30min of stirring mixing in polymeric kettle；Then 1~5 part of emulsifying agent, 1~5 part of monomer pre-emulsion are added, stirring is warming up to 50~70 DEG C, be stirred for the condensate that 10~30min of mixing generations are coated centered on Nano carbon white powder by carboxylic acid polar monomer and aryl ethylene class monomer, and using this as complex emulsions seed；Then add after 20~40 parts of monomer pre-emulsions and 0.05~0.2 part of initiator, 3.0~5.0h of reaction, be eventually adding 0.1~0.5 part of terminator, modified Nano white carbon is made in scrubbed, dehydration, dry, grinding.
(2) preparation of tire tread butadiene-styrene rubber composition：Based on the mass parts of styrene-butadiene latex butt matter, 100 parts of styrene-butadiene latexes (butt matter) and 1~4 part of emulsifying agent, 100~200 parts of deionized waters are taken to be added to 10~30min of stirring mixing in condensing field, then 15~40 parts of modified Nano white carbons are added, it is 8~10 with buffer regulation system pH value, when being warming up to 50~70 DEG C, 30~60min of stirring mixing, then add 3~6 parts of flocculating agents to be condensed, tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.
The present invention is not specially limited to the emulsifying agent used, flocculating agent, buffer, terminator etc., use conven-tional adjuvants generally in the art, its addition is also that those skilled in the art can calculate obtained conventional amount used according to the consumption of dry glue, and the present invention does not also do particular determination.
Cohesion of the present invention, poly- using acid cure, the technology is general for those skilled in the art, and described flocculating agent is usually inorganic acid, one or more of mixtures in such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid.
Emulsifying agent of the present invention is known to those skilled in the art, it is one or more of mixtures in anion emulsifier and nonionic emulsifier, one or more of mixtures in fatty acid soaps, RA rosin acid, neopelex, lauryl sodium sulfate, polyoxyethylene sorbitol acid anhydride list olein, preferably neopelex.
The one kind of buffer of the present invention in sodium carbonate, sodium acid carbonate, sodium hydroxide, ammoniacal liquor, ammonium hydrogen carbonate, preferably sodium hydroxide.
One or more of mixtures of the terminator of the present invention in diethyl hydroxylamine, HAS, Sodium Dimethyldithiocarbamate.
The particle diameter for the Nano carbon white that the present invention is used is small, the specific surface area of particle is big, surface energy is high, easily occurs mutual agglomeration, it is difficult to allow ultrafine particle to disperse in rubber matrix in nanoscale only by traditional method of modifying such as mechanical agitation or activating agent surface treatment, Ultrafine effect is difficult to play.In order to solve this problem, first to Nano carbon white particle surface carry out functional modification, nanoparticle surface by " hydrogen bond action " form it is a kind of using anchoring group carboxylic acid be the back of the body and aryl ethylene class compound as tail a kind of high dispersive structure (seeAccompanying drawing 1).One of steric hindrance very big separation layer is formed between nano-particle because this high dispersive structure contains benzene ring structure, the mutual suction-operated of particle surface silicone hydroxyl can significantly be reduced, the mutual reunion between particle is hindered, can realize and stably exist with single particle shape.Secondly, modified Nano white carbon particle surface it is identical with butadiene-styrene rubber molecular chain structure as the aryl ethylene class compound of solvent chain, according to similar compatibility principle, there is good compatibility between modified Nano hard charcoal black track producing particle and styrene-butadiene latex matrix, it is modified again without any later stage and is achieved that Nano carbon white particle being uniformly dispersed in styrene-butadiene latex, so that the tire tread for obtaining high comprehensive performance butadiene-styrene rubber composition.
Finally, in preparation process of the tire tread with butadiene-styrene rubber composition, Nano carbon white particle does not carry out mixing and banburying to process by mill and banbury, but is directly prepared with styrene-butadiene latex blending, cohesion.This avoid the problems such as the skidding of sizing material work in-process appearance, incipient scorch, scattered inequality.Its preparation method is simple and easy to apply, with low cost, environmentally safe, is adapted to industrialized production.
Brief description of the drawings
Figure 1For the high dispersive structure of Nano carbon white particle surfaceFigure。In figure1 is the solvent chain using vinylaromatic polymer chain as tail；2 be the anchoring group using carboxylic acid group as anchor point；3 be Nano carbon white particle.
Embodiment
Following examples and comparative example is enumerated to illustrate the invention effect of the present invention, but protection scope of the present invention is not limited in these embodiments and comparative example." part " described in embodiment and comparative example each means mass parts.
(1) raw material sources：
(2) analysis test method：
0 DEG C and 60 DEG C of fissipation factors：Analyzed using the DMA Q800 types dynamic thermomechanical analysis apparatus of TA companies,
From double cantilever chucks.In -150 DEG C~100 DEG C temperature programmings, heating rate is 3 DEG C/min, and amplitude is 10 μm, and test frequency is respectively 1Hz, 5Hz, 10Hz, dynamic force 1N.
Carbon black dispension degree：Method in execution standard GB/T6030-1985.
Akron abrasion volume；Method in execution standard GB/T 25262-2010.
Embodiment 1
(1) preparation of modified Nano white carbon：
A. the preparation of monomer pre-emulsion：In terms of the mass parts of styrene, 100 parts of styrene, 2.5 parts of neopelexes, 200 parts of deionized waters, 1.2 parts of sodium hydroxides, 0.03 part of potassium peroxydisulfate are put into reactor together, when being warming up to 60 DEG C, stirring reaction is prepared into styrene pre-emulsion a for 35 minutes.
B. the preparation of modified Nano white carbon：In terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 2.0 parts of acrylic acid (AA), 300 parts of deionized waters, 1.0 parts of sodium hydroxides are taken to be added to stirring mixing 20min in polymeric kettle；Then 1.2 parts of neopelexes, 1.5 parts of styrene pre-emulsion a are added, stirring is warming up to 65 DEG C, is stirred for mixing the seed of complex emulsions of the 20min generations centered on Nano carbon white powder；Then add after 25 parts of styrene pre-emulsion a and 0.07 part of potassium peroxydisulfate, reaction 3.0h, be eventually adding 0.1 part of diethyl hydroxylamine, modified Nano white carbon is made in scrubbed, dehydration, dry, grinding.
(2) preparation of tire tread butadiene-styrene rubber composition：In terms of the mass parts of styrene-butadiene latex, 100 parts of styrene-butadiene latex SBR1500 (butt matter) and 1.5 parts of neopelexes, 150 parts of deionized waters are taken to be added to stirring mixing 15min in condensing field, then 17 parts of modified Nano white carbons are added, it is 8.5 with sodium hydroxide regulation system pH value, when being warming up to 60 DEG C, mixing 35min is stirred, 3.5 parts of sulfuric acid is then added and is condensed, tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Standard specimen is made through vulcanization, test performance is shown inTable 1。
Embodiment 2
(1) preparation of modified Nano white carbon：
A. the preparation of monomer pre-emulsion：Be the same as Example 1.
B. the preparation of modified Nano white carbon：In terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 1.0 parts of acrylic acid (AA), 350 parts of deionized waters, 2.0 parts of sodium hydroxides are taken to be added to stirring mixing 20min in polymeric kettle；Then 2.5 parts of neopelexes, 2.0 parts of styrene pre-emulsion a are added, stirring is warming up to 65 DEG C, is stirred for mixing the seed of complex emulsions of the 25min generations centered on Nano carbon white powder；Then add after 20 parts of styrene pre-emulsion a and 0.09 part of potassium peroxydisulfate, reaction 4.0h, be eventually adding 0.2 part of diethyl hydroxylamine, modified Nano white carbon is made in scrubbed, dehydration, dry, grinding.Sampling analysis：Standard specimen is made, performance is shown in after testedTable 1。
(2) preparation of tire tread butadiene-styrene rubber composition：In terms of the mass parts of styrene-butadiene latex, 100 parts of styrene-butadiene latex SBR1500 (butt matter) and 1.0 parts of neopelexes, 120 parts of deionized waters are taken to be added to stirring mixing 10min in condensing field, then 15 parts of modified Nano white carbons are added, it is 8.6 with sodium hydroxide regulation system pH value, when being warming up to 60 DEG C, mixing 40min is stirred, 3.0 parts of sulfuric acid is then added and is condensed, tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Standard specimen is made through vulcanization, test performance is shown inTable 1。
Embodiment 3
(1) preparation of modified Nano white carbon：
A. the preparation of monomer pre-emulsion：In terms of the mass parts of styrene, 100 parts of styrene, 5 parts of neopelexes, 240 parts of deionized waters, 1.5 parts of sodium hydroxides, 0.05 part of potassium peroxydisulfate are put into reactor together, when being warming up to 55 DEG C, stirring reaction is prepared into styrene pre-emulsion b for 40 minutes.
The preparation of b modified Nano white carbons：In terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 2.5 parts of acrylic acid (AA), 370 parts of deionized waters, 2.5 parts of sodium hydroxides are taken to be added to stirring mixing 25min in polymeric kettle；Then 3 parts of neopelexes, 2.5 parts of styrene pre-emulsion b are added, stirring is warming up to 65 DEG C, is stirred for mixing the seed of complex emulsions of the 25min generations centered on Nano carbon white powder；Then add after 30 parts of styrene pre-emulsion b and 0.12 part of potassium peroxydisulfate, reaction 4.0h, be eventually adding 0.25 part of diethyl hydroxylamine, modified Nano white carbon is made in scrubbed, dehydration, dry, grinding.
(2) preparation of tire tread butadiene-styrene rubber composition：In terms of the mass parts of styrene-butadiene latex, 100 parts of styrene-butadiene latex SBR1500 (butt matter) and 2.0 parts of neopelexes, 160 parts of deionized waters are taken to be added to stirring mixing 20min in condensing field, then 25 parts of modified Nano white carbons are added, it is 8.9 with sodium hydroxide regulation system pH value, when being warming up to 60 DEG C, mixing 45min is stirred, 4.0 parts of sulfuric acid is then added and is condensed, tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Standard specimen is made through vulcanization, test performance is shown inTable 1。
Embodiment 4
(1) preparation of modified Nano white carbon：
The preparation of a monomer pre-emulsions：Be the same as Example 3.
The preparation of b modified Nano white carbons：In terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 3.0 parts of acrylic acid (AA), 380 parts of deionized waters, 2.7 parts of sodium hydroxides are taken to be added to stirring mixing 25min in polymeric kettle；Then 4 parts of neopelexes, 3.8 parts of styrene pre-emulsion b are added, stirring is warming up to 65 DEG C, is stirred for mixing the seed of complex emulsions of the 25min generations centered on Nano carbon white powder；Then add after 32 parts of styrene pre-emulsion b and 0.14 part of potassium peroxydisulfate, reaction 4.0h, be eventually adding 0.27 part of diethyl hydroxylamine, modified Nano white carbon is made in scrubbed, dehydration, dry, grinding.
(2) preparation of tire tread butadiene-styrene rubber composition：In terms of the mass parts of styrene-butadiene latex, 100 parts of styrene-butadiene latex SBR1500 (butt matter) and 3.0 parts of neopelexes, 170 parts of deionized waters are taken to be added to stirring mixing 25min in condensing field, then 30 parts of modified Nano white carbons are added, it is 8.7 with sodium hydroxide regulation system pH value, when being warming up to 65 DEG C, mixing 50min is stirred, 4.5 parts of hydrochloric acid is then added and is condensed, tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Standard specimen is made through vulcanization, test performance is shown inTable 1。
Embodiment 5
(1) preparation of modified Nano white carbon：
A. prepared by monomer pre-emulsion：In terms of the mass parts of α-methylstyrene, 100 parts of α-methylstyrenes, 10 parts of neopelexes, 300 parts of deionized waters, 1.8 parts of sodium hydroxides, 0.1 part of ammonium persulfate are put into reactor together, when being warming up to 70 DEG C, stirring reaction is prepared into α-methylstyrene pre-emulsion in 60 minutes.
B. the preparation of modified Nano white carbon：In terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 4.5 parts of maleic anhydrides (MAH), 400 parts of deionized waters, 2.8 parts of sodium hydroxides are taken to be added to stirring mixing 25min in polymeric kettle；Then 4.5 parts of neopelexes, 4.2 parts of α-methylstyrene pre-emulsion c are added, stirring is warming up to 65 DEG C, is stirred for mixing the seed of complex emulsions of the 30min generations centered on Nano carbon white powder；Then add after 37 parts of α-methylstyrene pre-emulsions and 0.17 part of ammonium persulfate, reaction 4.0h, be eventually adding 0.29 part of diethyl hydroxylamine, modified Nano white carbon is made in scrubbed, dehydration, dry, grinding.
(2) preparation of tire tread butadiene-styrene rubber composition：In terms of the mass parts of styrene-butadiene latex, 100 parts of styrene-butadiene latex SBR1502 (butt matter) and 3.5 parts of neopelexes, 190 parts of deionized waters are taken to be added to stirring mixing 25min in condensing field, then 35 parts of modified Nano white carbons are added, it is 9.2 with sodium hydroxide regulation system pH value, when being warming up to 65 DEG C, mixing 55min is stirred, 5.0 parts of hydrochloric acid is then added and is condensed, tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Standard specimen is made through vulcanization, test performance is shown inTable 1。
Embodiment 6
(1) preparation of modified Nano white carbon：
A. prepared by monomer pre-emulsion：Be the same as Example 6
B. the preparation of modified Nano white carbon：In terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 5.0 parts of maleic anhydrides (MAH), 500 parts of deionized waters, 6.0 parts of sodium hydroxides are taken to be added to stirring mixing 30min in polymeric kettle；Then 5.0 parts of neopelexes, 5.0 parts of α-methylstyrene pre-emulsion c are added, stirring is warming up to 70 DEG C, is stirred for mixing the seed of complex emulsions of the 30min generations centered on Nano carbon white powder；Then add after 40 parts of α-methylstyrene pre-emulsion c and 0.2 part of ammonium persulfate, reaction 5.0h, be eventually adding 0.5 part of diethyl hydroxylamine, modified Nano white carbon is made in scrubbed, dehydration, dry, grinding.
(2) preparation of tire tread butadiene-styrene rubber composition：In terms of the mass parts of styrene-butadiene latex, 100 parts of styrene-butadiene latex SBR1502 (butt matter) and 4.0 parts of neopelexes, 200 parts of deionized waters are taken to be added to stirring mixing 30min in condensing field, then 40 parts of modified Nano white carbons are added, it is 9.5 with sodium hydroxide regulation system pH value, when being warming up to 70 DEG C, mixing 60min is stirred, 6.0 parts of nitric acid is then added and is condensed, tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Standard specimen is made through vulcanization, test performance is shown inTable 1。
Comparative example 1
(1) preparation of modified Nano white carbon：
The preparation of a monomer pre-emulsions：Be the same as Example 1.
The preparation of b modified Nano white carbons：Be the same as Example 1.
(2) preparation of tire tread butadiene-styrene rubber composition：Other conditions are same as Example 1, and difference is that the addition of modified Nano white carbon in preparation process is 10 parts, i.e.,：100 parts of styrene-butadiene latex SBR1500 (butt matter) and 1.5 parts of neopelexes, 150 parts of deionized waters are taken to be added to stirring mixing 15min in condensing field, then 10 parts of modified Nano white carbons are added, it is 8.5 with sodium hydroxide regulation system pH value, when being warming up to 60 DEG C, stirring mixing 35min, then add 3.5 parts of sulfuric acid to be condensed, tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Standard specimen is made through vulcanization, test performance is shown inTable 1。
Comparative example 2
The preparation of tire tread butadiene-styrene rubber composition：Other conditions are same as Example 2, and difference is to be not added with modified Nano white carbon in preparation process, but is directly added into unmodified Nano carbon white, and its addition is 15 parts, i.e.,：100 parts of styrene-butadiene latex SBR1500 (butt matter) and 1.0 parts of neopelexes, 120 parts of deionized waters are taken to be added to stirring mixing 10min in condensing field, then 15 parts of unmodified Nano carbon whites are added, it is 8.6 with sodium hydroxide regulation system pH value, when being warming up to 60 DEG C, stirring mixing 40min, then add 3.0 parts of sulfuric acid to be condensed, tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Standard specimen is made through vulcanization, test performance is shown inTable 1。
Comparative example 3
(1) preparation of modified Nano white carbon：Other conditions are same as Example 3, and difference is to be not added with styrene pre-emulsion b during in-situ polymerization, i.e.,：100 parts of Nano carbon whites and 2.5 parts of acrylic acid (AA), 370 parts of deionized waters, 2.5 parts of sodium hydroxides are taken to be added to stirring mixing 25min in polymeric kettle；Then 3 parts of neopelexes are added, stirring is warming up to 65 DEG C, is stirred for mixing the seed of complex emulsions of the 25min generations centered on Nano carbon white powder；Then add after 0.12 part of potassium peroxydisulfate, reaction 4.0h, be eventually adding 0.25 part of diethyl hydroxylamine, modified Nano white carbon a is made in scrubbed, dehydration, dry, grinding.
(2) preparation of tire tread butadiene-styrene rubber composition：Other conditions are same as Example 3, and difference is to be not added with modified Nano white carbon in preparation process, but are directly added into modified Nano white carbon a, and its addition is 25 parts, i.e.,：100 parts of styrene-butadiene latex SBR1500 (butt matter) and 2.0 parts of neopelexes, 160 parts of deionized waters are taken to be added to stirring mixing 20min in condensing field, then 25 parts of modified Nano white carbon a are added, it is 8.9 with sodium hydroxide regulation system pH value, when being warming up to 60 DEG C, stirring mixing 45min, then add 4.0 parts of sulfuric acid to be condensed, tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Standard specimen is made through vulcanization, test performance is shown inTable 1。
Comparative example 4
(1) preparation of modified Nano white carbon：
A. prepared by monomer pre-emulsion：Be the same as Example 3.
B. the preparation of modified Nano white carbon：Other conditions are same as Example 4, and difference is to be not added with initiator potassium persulfate during in-situ polymerization, and 1,3- hexadiene pre-emulsion b is that dialogue carbon black particle surface is coated, i.e.,：100 parts of Nano carbon whites and 3.0 parts of acrylic acid (AA), 380 parts of deionized waters, 2.7 parts of sodium hydroxides are taken to be added to stirring mixing 25min in polymeric kettle；Then 4 parts of neopelexes, 3.8 parts of styrene pre-emulsion b are added, stirring is warming up to 65 DEG C, is stirred for mixing the seed of complex emulsions of the 25min generations centered on Nano carbon white powder；Then add after 32 parts of styrene pre-emulsion b, reaction 4.0h, be eventually adding 0.27 part of diethyl hydroxylamine, modified Nano white carbon b is made in scrubbed, dehydration, dry, grinding.
(2) preparation of tire tread butadiene-styrene rubber composition：Other conditions are same as Example 4, and difference is to be not added with modified Nano white carbon in preparation process, but are directly added into modified Nano white carbon b, and its addition is 30 parts, i.e.,：100 parts of styrene-butadiene latex SBR1500 (butt matter) and 3.0 parts of neopelexes, 170 parts of deionized waters are taken to be added to stirring mixing 25min in condensing field, then 30 parts of modified Nano white carbon b are added, it is 8.7 with sodium hydroxide regulation system pH value, when being warming up to 65 DEG C, stirring mixing 50min, then add 4.5 parts of hydrochloric acid to be condensed, tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Standard specimen is made through vulcanization, test performance is shown inTable 1。
Comparative example 5
(1) preparation of modified Nano white carbon：
A. prepared by monomer pre-emulsion：Be the same as Example 5.
B. the preparation of modified Nano white carbon：Other conditions are same as Example 5, and difference is to be not added with maleic anhydride (MAH) in preparation process, i.e.,：100 parts of Nano carbon whites, 400 parts of deionized waters, 2.8 parts of sodium hydroxides are taken to be added to stirring mixing 25min in polymeric kettle；Then 4.5 parts of neopelexes, 4.2 parts of α-methylstyrene pre-emulsion c are added, stirring is warming up to 65 DEG C, is stirred for mixing the seed of complex emulsions of the 30min generations centered on Nano carbon white powder；Then add after 37 parts of α-methylstyrene pre-emulsions and 0.17 part of ammonium persulfate, reaction 4.0h, be eventually adding 0.29 part of diethyl hydroxylamine, modified Nano white carbon c is made in scrubbed, dehydration, dry, grinding.
(2) preparation of tire tread butadiene-styrene rubber composition：Other conditions are same as Example 5, and difference is to be not added with modified Nano white carbon in preparation process, but are directly added into modified Nano white carbon c, and its addition is 35 parts, i.e.,：100 parts of styrene-butadiene latex SBR1502 (butt matter) and 3.5 parts of neopelexes, 190 parts of deionized waters are taken to be added to stirring mixing 25min in condensing field, then 35 parts of modified Nano white carbon c are added, it is 9.2 with sodium hydroxide regulation system pH value, when being warming up to 65 DEG C, stirring mixing 55min, then add 5.0 parts of hydrochloric acid to be condensed, tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Standard specimen is made through vulcanization, test performance is shown inTable 1。
Comparative example 6
The preparation of tire tread butadiene-styrene rubber composition：Other conditions are same as Example 6, and difference is to be not added with modified Nano white carbon in preparation process, but is directly added into unmodified Nano carbon white, and its addition is 40 parts, i.e.,：100 parts of styrene-butadiene latex SBR1502 (butt matter) and 4.0 parts of neopelexes, 200 parts of deionized waters are taken to be added to stirring mixing 30min in condensing field, then 40 parts of unmodified Nano carbon whites are added, it is 9.5 with sodium hydroxide regulation system pH value, when being warming up to 70 DEG C, stirring mixing 60min, then add 6.0 parts of nitric acid to be condensed, tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Standard specimen is made through vulcanization, test performance is shown inTable 1。
Table 1The performance of tire tread butadiene-styrene rubber composition
ByTable 1Understand：0 DEG C of tan δ of embodiment is higher than comparative example, illustrates that the wet-sliding resistant performance for tire preparation is good；The 60 DEG C of fissipation factors (tan δ) and wear volume of embodiment are all lower than comparative example, illustrate that the rolling resistance for tire preparation is low, wearability is good.
Claims (19)
1. the rubber composition of a kind of white carbon containing modified Nano, with the quality of styrene butadiene rubber latex butt matter
Part meter, mainly including following component：
(1) styrene butadiene rubber latex 100%
(2) modified Nano white carbon 15~40%
Characterized in that, the modified Nano white carbon is to use unsaturated carboxylic acid polar monomer and aryl ethylene
Class monomer, is prepared under initiator effect by situ aggregation method.
2. rubber composition as claimed in claim 1, it is characterised in that the modified Nano white carbon
Particle diameter is：20~60nm.
3. the rubber composition as described in any one of claim 1 or 2, it is characterised in that the insatiable hunger
With the one kind of carboxylic acid polar monomer in acrylic acid, methacrylic acid, maleic anhydride.
4. rubber composition as claimed in claim 3, it is characterised in that the unsaturated carboxylic acid polarity
Monomer is acrylic acid.
5. rubber composition as claimed in claim 1, it is characterised in that the aryl ethylene class monomer
One in styrene, α-methylstyrene, 2- propenyl benzenes, ethyl styrene and their derivative
Plant or several mixtures.
6. rubber composition as claimed in claim 5, it is characterised in that the aryl ethylene class monomer
It is styrene.
7. rubber composition as claimed in claim 1, it is characterised in that the initiator is water solubility
Thermal initiator, selected from ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, 2, double (the 2 one amidine azoles of 2 one azos
Quinoline propane) hydrochloride, one kind of 2,2- azos [2- (2- imidazoline -2- bases) propane] dihydrochloride
Or several mixtures.
8. rubber composition as claimed in claim 7, it is characterised in that the initiator is persulfuric acid
Potassium.
9. rubber composition as claimed in claim 1, it is characterised in that the styrene butadiene rubber latex is
Formed by conjugated diene hydrocarbon compound and aryl ethylene class compound by emulsion polymerization copolymerization.
10. rubber composition as claimed in claim 9, it is characterised in that the conjugated diene chemical combination
Thing is C4Class conjugated diene hydrocarbon compound.
11. rubber composition as claimed in claim 9, it is characterised in that the aryl ethylene class chemical combination
Thing is in styrene, α-methylstyrene, 2- propenyl benzenes, ethyl styrene and their derivative
It is a kind of.
12. the rubber composition as described in any one of claim 9~11, it is characterised in that the butylbenzene
The solid content of rubber latex be 20~45%, combinated styrene content content be 15~25%, latex particle size be 50~
200nm。
13. a kind of preparation method of rubber composition as described in one of claim 1~12, including it is as follows
Step：
(1) in terms of the mass parts of styrene-butadiene latex butt matter, take 100 parts of styrene-butadiene latexes and 1~4 part of emulsifying agent,
100~200 parts of deionized waters are added to 10~30min of stirring mixing in condensing field；
(2) 15~40 parts of modified Nano white carbons are added in condensing field, with buffer regulation system pH
It is worth for 8~10, when being warming up to 50~70 DEG C, 30~60min of stirring mixing；
(3) add 3~6 parts of flocculating agents in condensing field to be condensed, last scrubbed, dehydration, dry, pressure
The rubber composition is made in block.
14. method as claimed in claim 13, it is characterised in that the flocculating agent be hydrochloric acid, sulfuric acid,
One or more of mixtures in phosphoric acid, nitric acid.
15. method as claimed in claim 13, it is characterised in that the emulsifying agent is anionic emulsifying
One or more of mixtures in agent and nonionic emulsifier.
16. method as claimed in claim 15, it is characterised in that the emulsifying agent be selected from fatty acid soaps,
RA rosin acid, neopelex, lauryl sodium sulfate, polyoxyethylene sorbitol acid anhydride list olein
In one or more of mixtures.
17. method as claimed in claim 16, it is characterised in that the emulsifying agent is detergent alkylate
Sodium sulfonate.
18. method as claimed in claim 13, it is characterised in that the buffer be selected from sodium carbonate,
One kind in sodium acid carbonate, sodium hydroxide, ammoniacal liquor, ammonium hydrogen carbonate.
19. method as claimed in claim 18, it is characterised in that the buffer is sodium hydroxide.
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