CN107266750A - It is a kind of for rubber composition of tire tread and preparation method thereof - Google Patents
It is a kind of for rubber composition of tire tread and preparation method thereof Download PDFInfo
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- CN107266750A CN107266750A CN201610218624.XA CN201610218624A CN107266750A CN 107266750 A CN107266750 A CN 107266750A CN 201610218624 A CN201610218624 A CN 201610218624A CN 107266750 A CN107266750 A CN 107266750A
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- styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
- C08L9/08—Latex
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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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
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention provides a kind of rubber composition of modified Nano white carbon filled styrene butadiene rubber for tire tread.The invention is modified using aliphatic diisocyanate to Nano carbon white, then add water soluble polymer progress graft reaction to form a kind of barrier layer of high dispersive structure to prepare modified Nano white carbon in Nano carbon white particle surface, then 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, assigns said composition high abrasion, low friction, anti-slippery performance.Present invention further propose that the preparation method of said composition.
Description
Technical field
The present invention relates to a kind of rubber composition and preparation method thereof, fourth is filled more particularly to a kind of modified white carbon black
Benzene rubber is used for rubber composition of tire tread and preparation method thereof.
Background technology
It is well known that from the point of view of the Expected Results of inorganic powder filling-modified conjunction rubber, the particle diameter chi of inorganic particle particle
The effect of very little smaller modification is also better, but a technology is inevitably run into the application process of ultrafine inorganic powder
Problem, i.e. superfine powder can be improved with the reduction of particle diameter, specific surface area increase, surface, and autohemagglutination ability is stronger, is more difficult to by rubber
Material is mixed into, infiltrates and disperseed.Therefore scattering problem of the ultrafine inorganic powder in rubber, it has also become prepare high-performance rubber material
The bottleneck of material.
With the successive implementation of EU REACH Legislation and tire tag bill, synthetic rubber environmental protection is extremely urgent, then adds
The demand of upper light color article, the application study of white carbon causes the attention of people.It is rubber that nano silicon, which is commonly called as white carbon,
Consumption is only second to the second largest reinforcing agent of carbon black in glue industry.From last century the nineties, white carbon is extensive as reinforced filling
Obvious balance is obtained applied to " devil's triangle " performance of above-mentioned tire tread requirement in tire tread formula, is made.But
Be that Nano carbon white particle diameter is small, bigger than surface, surface can high, surface again with substantial amounts of hydroxyl, cause Nano carbon white easily
Reunite, be difficult to be uniformly dispersed in the mixed process with elastomeric material, so can not only influence filling-modified effect, but also meeting
Damage the performance of elastomeric material.
In the prior art, the research about modified Nano white carbon filled rubber material mainly passes through coupling agent or surface
It is prepared by activating agent, the method for graft polymers coating modification Nano carbon white particle surface filled rubber material.Such as：Qiu Quanfang
(" latex blending method " natural rubber/silicon dioxide nano composite material micro-structure and property control, 2010, University Of Hainan is large
Scholar's paper) study example high-performance NR composites：Natural rubber/silica nanometer composite wood is prepared using latex blending method
Material, first with γ-methacryloxypropyl trimethoxy silane coupling agent (MPS) modified manometer silicon dioxide (SiO2), then
Nano-silicon dioxide particle (the SiO that upper polymethyl methacrylate (PMMA) obtains core shell structure is grafted through emulsion polymerization2-
MPS-PMMA natural rubber/titanium dioxide finally) is made in itself and Heveatex (NR-PMMA) the directly blending being modified with MMA
Silicon nano composite material.Li Wen Ji et al. is prepared for clay/white carbon compounded mix by drying process with atomizing, for substituting portion
Divide white carbon, to strengthen solution polymerized butadiene styrene rubber/butadiene rubber composite jointly.Patent CN 101798473A use many sulphur silicon
Alkane acceptor modified white carbon black, then prepares silica/carbon black compounded mix.Patent CN201305854136A passes through poly- DOPA
Amine modified white carbon black is being kneaded with rubber raw rubber and auxiliary agent, vulcanized, and 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, are modified using graft polymers
During with inorganic material surface coating modification Nano carbon white, there is that reaction time consumption is longer, energy consumption is higher and big for environment pollution, behaviour
The shortcomings of making complicated；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 is again
The shortcomings of easily reuniting again.
The content of the invention
Present invention aims at provide a kind of rubber composition of use modified Nano white carbon filled styrene butadiene rubber, the rubber
Anti-slippery is good, wearability is good, rolling resistance is low when composition is for tire tread.The invention uses aliphatic diisocyanate
Nano carbon white is modified, water soluble polymer progress graft reaction is then added and is formed in Nano carbon white particle surface
A kind of barrier layer of high dispersive structure prepares modified Nano white carbon, is then 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
Also Nano carbon white and rubber matrix adhesion difference are solved and it is scattered uneven the problem of, assign said composition high abrasion, low friction,
Anti-slippery performance.Present invention further propose that the preparation method of said composition.
A kind of rubber composition for tire tread of the invention, the quality using styrene butadiene rubber latex butt matter is percent
Hundred meters, mainly including following component：
(1) styrene butadiene rubber latex (butt matter) 100%
(2) modified Nano white carbon 20~60%
(3) it is grafted styrene-butadiene latex 2~6%
Wherein, described modified Nano white carbon is modified using aliphatic diisocyanate to Nano carbon white, and
Water soluble polymer progress graft reaction is added afterwards forms a kind of barrier layer of high dispersive structure in Nano carbon white particle surface
To prepare.White carbon be selected from it is nano level, its particle diameter is：20~60nm.Aliphatic diisocyanate is selected from hexa-methylene
Diisocyanate (HDI), IPDI (IPDI), the diisocyanate of one 4,4' of dicyclohexyl methyl hydride mono-
(MDI), at least one of methylcyclohexane diisocyanate (HTDI), preferably HDI.During water soluble polymer is molecular structure
Containing polyethylene backbone, side base is the compound of hydrophilic radical, is polyvinyl alcohol, polyethylene glycol (PEG), polyacrylamide
(PAM), polypropylene glycol (PPG), in one kind, preferably PAM, its consumption be 10%~20% (press Nano carbon white mass parts
Meter).Because this kind of high molecular backbone structure is identical with sub-polyethylene minor structure, the spy with non-polar conformations and chain segment length
Point, can effectively hinder Nano carbon white particle because occurring the phenomenon of bonding in collision process with polyhydroxy.
Described grafting styrene-butadiene latex uses the polar monomer graft styrene-butadiene latex of olefin-containing structure.Styrene butadiene rubber latex is
Formed by conjugated diene hydrocarbon compound and aryl ethylene class compound by emulsion polymerization copolymerization.Conjugated diene hydrocarbon compound is C4
Class conjugated diene hydrocarbon compound.Aryl ethylene class compound can be styrene, α-methylstyrene, 2- propenyl benzenes, ethylo benzene
Ethene and their derivative.The wherein solid content 20~45% of styrene-butadiene latex, combinated styrene content content 15~25%, latex granule
50~200nm of footpath.Polar monomer is the compound containing alkene structures in strand, selected from acrylic acid (AA), methacrylic acid
(MAA), one kind in acrylamide (AM), preferably methacrylic acid grafting styrene-butadiene latex (SBR-g-MAA), grafting rate is 1%
~4%.
The preparation of rubber composition of the present invention can be carried out in condensing field, and specific preparation process includes following step
Suddenly：
(1) it is grafted the preparation of styrene-butadiene latex：Based on the mass parts of styrene-butadiene latex (butt matter), it is firstly added in polymeric kettle
100~200 parts of deionized waters and then sequentially add 100 parts of styrene-butadiene latexes, 1~10 part of emulsifying agent, 0.1~1.0 part of molecular weight and adjust
Agent is saved, after nitrogen displacement, 5~10 parts of polar monomer, stirring, heating is and then added, kettle temperature degree to be polymerized reaches 30~
Added at 50 DEG C after 0.1~0.5 part of initiator, 3~5h of reaction, add 0.1~0.5 part of terminator, grafting styrene-butadiene latex is made.
(2) preparation of modified Nano white carbon：Based on the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 200 are taken
~400 parts of deionized waters are added to 10~30min of stirring mixing in polymeric kettle；Then 2~7 parts of isocyanic acids of aliphatic two are added
Ester, 1.0~2.0 parts of catalyst, are warming up to 40~60 DEG C, 1~2hr of stirring reaction generations quilt centered on Nano carbon white powder
The performed polymer that aliphatic diisocyanate is coated；Finally add 10~20 parts of water soluble polymers and 0.5~2.0 part of catalysis
After agent, 2.0~5.0hr of reaction, modified Nano white carbon is made in scrubbed, dehydration, dry, grinding.
(3) it is used for the preparation of the butadiene-styrene rubber composition of tire tread：Based on the mass parts of styrene-butadiene latex (butt matter), take
100 parts of styrene-butadiene latexes and 2~6 parts of grafting styrene-butadiene latexes, 2~5 parts of emulsifying agents, 200~300 parts of deionized waters are added to cohesion
10~30min of stirring mixing, then adds 20~60 parts of modified Nano white carbons in kettle, is 8 with buffer regulation system pH value
~10, when being warming up to 50~70 DEG C, then stirring 30~60min of mixing adds 3~6 parts of flocculating agents and is condensed, most afterwards through washing
Wash, be dehydrated, drying, tire tread butadiene-styrene rubber composition is made in briquetting.
The present invention is not done especially to the emulsifying agent used, flocculating agent, buffer, molecular weight regulator, terminator etc.
Limit, using conven-tional adjuvants generally in the art, its addition is also those skilled in the art can be with according to the consumption of dry glue
Obtained conventional amount used is calculated, 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, described flocculating agent
One or more of mixtures in usually inorganic acid, such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid.
Emulsifying agent of the present invention is known to those skilled in the art, can be anion emulsifier and nonionic Emulsion
One or more in agent.Such as：Selected from fatty acid soaps, RA rosin acid, neopelex, lauryl sodium sulfate,
One or more in polyoxyethylene sorbitol acid anhydride list olein, preferably neopelex.
The one kind of buffer of the present invention in sodium carbonate, sodium acid carbonate, ammoniacal liquor, ammonium hydrogen carbonate, preferably carbonic acid
Hydrogen sodium.
One or more of mixing of the terminator of the present invention in diethyl hydroxylamine, HAS, Sodium Dimethyldithiocarbamate
Thing.
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 can be high, easily occur phase
Mutual agglomeration, is difficult to allow ultrafine particle in rubber only by traditional method of modifying such as mechanical agitation or activating agent surface treatment
Scattered in nanoscale in matrix, Ultrafine effect is difficult to play.In order to solve this problem, first to Nano carbon white particle surface
Carry out functional modification, particle surface formed it is a kind of using anchoring group cyanic acid ester group (NCO) be the back of the body and Polyethylene Chain as
Tail, and both pass through " covalent bond effect " the close high dispersive structure for connecting into an entirety (see accompanying drawing 1).Due to modified Nano
The Polyethylene Chain molecular structure of white carbon particle surface is different from butadiene-styrene rubber molecular structure, and modified Nano hard charcoal black track producing particle is not allowed
Easily it is distributed in styrene-butadiene latex.It is a certain amount of in styrene-butadiene latex Surface Creation by adding the grafting styrene-butadiene latex of olefin-containing structure
Small molecule it is similar to the Polyethylene Chain structure of Nano carbon white particle surface.Grafting styrene-butadiene latex contains polar group carboxylic in addition
The cyanic acid ester group of base and Nano carbon white particle surface produces strong mutual suction-operated, in both " pole under cooperative effect
The earth improves the compatibility between Nano carbon white particle and styrene-butadiene latex matrix, realizes Nano carbon white particle in styrene-butadiene latex
In be uniformly dispersed.Secondly Nano carbon white particle high dispersive structure is connected by covalent bond, because bond energy of covalent bond is big,
There are enough adsorption strengths, also be difficult to depart under high temperature and shear action, can in rubber blending process
Very stably exist with single particle shape.Present invention efficiently solves the easy agglomeration traits of Nano carbon white, simultaneously
Ensure the dispersiveness in Nano carbon white particle process again.The present invention has operating method simple, and modified cost is low, environment
Pollution is small, the advantages of being adapted to industrialized production.
Brief description of the drawings
Fig. 1 is the ultra-dispersed structure chart of Nano carbon white particle surface.1 is the solvation using Polyethylene Chain as tail in figure
Chain；2 be the anchoring group using cyanic acid ester group as anchor point；3 be hard charcoal black track producing 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
It is only limitted 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, 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.
The measure of grafting rate：About 4g sample is taken with pipette from three-necked bottle in measuring cup, 2~3 are added after weighing
Quinol solution is dripped, dries to constant weight, then above-mentioned sample is placed in Soxhlet extractor, with toluene in 90 DEG C of water-baths
Upper extractive distillation 24h, is then being dried to constant weight.Monomer grafting rate is calculated as follows:
In formula：m0- latex gross mass (g)；The sample quality (g) weighed after m-reaction；mmMonomer is total in-reactant
Quality (g)；mSNRThe quality (g) of natural rubber in-sample；m1The quality (g) of sample after-extraction.
Embodiment 1
(1) it is grafted the preparation of styrene-butadiene latex：Based on styrene-butadiene latex SBR1500 mass parts, it is firstly added in polymeric kettle
120 parts of deionized waters then sequentially add 100 parts of styrene-butadiene latex SBR1500,2.0 parts of neopelexes, 0.3 part ten
Two carbon mercaptan, after nitrogen displacement, and then add 5.5 parts of MAA, stirring, heating, kettle temperature degree to be polymerized add when reaching 35 DEG C
Enter after 0.2 part of ammonium persulfate, reaction 3.5h, add 0.2 part of diethyl hydroxylamine, grafting styrene-butadiene latex (SBR-g-MAA) is made.Take
Sample is analyzed：The grafting rate for measuring SBR-g-MAA is 2.1%.
(2) preparation of modified Nano white carbon：Based on the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 220 are taken
Part deionized water is added to stirring mixing 15min in polymeric kettle；Then 2 parts of hexamethylene diisocyanates (HDI), 1.2 are added
Part sodium hydroxide, stirring is warming up to 45 DEG C, is stirred for reaction 1.2hr generations centered on Nano carbon white powder by aliphatic two
The performed polymer that isocyanates is coated；10 parts of polyacrylamides (PAM) and 0.7 part of sodium hydroxide are finally added, 3.5hr is reacted
Afterwards, modified Nano white carbon is made in scrubbed, dehydration, dry, grinding.
(3) it is used for the preparation of the butadiene-styrene rubber composition of tire tread：By the quality of styrene-butadiene latex SBR1500 (butt matter)
Part meter, takes 100 parts of styrene-butadiene latex SBR1500 and 3.0 parts of SBR-g-MAA (grafting rate is 2.1%), 2.5 parts of detergent alkylate sulphurs
Sour sodium, 230 parts of deionized waters are added to stirring mixing 15min in condensing field, then add 20 parts of modified Nano white carbons, use carbon
Sour hydrogen sodium regulation system pH value is 8.2, when being warming up to 55 DEG C, stirring mixing 35min, then adds 3.0 parts of hydrochloric acid and is condensed,
Tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Mark is made through vulcanization
Quasi- sample, test performance is shown in Table 1.
Embodiment 2
(1) it is grafted the preparation of styrene-butadiene latex：Be the same as Example 1.
(2) preparation of modified Nano white carbon：Be the same as Example 1.
(3) it is used for the preparation of the butadiene-styrene rubber composition of tire tread：By the quality of styrene-butadiene latex SBR1500 (butt matter)
Part meter, takes 100 parts of styrene-butadiene latex SBR1500 and 2.0 parts of SBR-g-MAA (grafting rate is 2.1%), 3.0 parts of detergent alkylate sulphurs
Sour sodium, 230 parts of deionized waters are added to stirring mixing 15min in condensing field, then add 30 parts of modified Nano white carbons, use carbon
Sour hydrogen sodium regulation system pH value is 8.5, when being warming up to 60 DEG C, stirring mixing 40min, then adds 3.5 parts of hydrochloric acid and is condensed,
Tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Standard is made through vulcanization
Sample, test performance is shown in Table 1.
Embodiment 3
(1) it is grafted the preparation of styrene-butadiene latex：Based on styrene-butadiene latex SBR1500 mass parts, it is firstly added in polymeric kettle
150 parts of deionized waters then sequentially add 100 parts of styrene-butadiene latex SBR1500,5.0 parts of neopelexes, 0.5 part ten
Two carbon mercaptan, after nitrogen displacement, and then add 7 parts of MAA, stirring, heating, kettle temperature degree to be polymerized are added when reaching 35 DEG C
After 0.3 part of ammonium persulfate, reaction 3.5h, 0.4 part of diethyl hydroxylamine is added, grafting styrene-butadiene latex (SBR-g-MAA) is made.Sampling
Analysis：The grafting rate for measuring SBR-g-MAA is 2.9%.
(2) preparation of modified Nano white carbon：Based on the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 300 are taken
Part deionized water is added to stirring mixing 20min in polymeric kettle；Then 4 parts of hexamethylene diisocyanates (HDI), 1.4 are added
Part sodium hydroxide, stirring is warming up to 50 DEG C, is stirred for reaction 1.4hr generations centered on Nano carbon white powder by aliphatic two
The performed polymer that isocyanates is coated；15 parts of polyacrylamides (PAM) and 1.2 parts of sodium hydroxides are finally added, 4.2hr is reacted
Afterwards, modified Nano white carbon is made in scrubbed, dehydration, dry, grinding.
(3) it is used for the preparation of the butadiene-styrene rubber composition of tire tread：By the quality of styrene-butadiene latex SBR1500 (butt matter)
Part meter, takes 100 parts of styrene-butadiene latex SBR1500 and 4.0 parts of SBR-g-MAA (grafting rate is 2.9%), 3.0 parts of detergent alkylate sulphurs
Sour sodium, 260 parts of deionized waters are added to stirring mixing 15min in condensing field, then add 40 parts of modified Nano white carbons, use carbon
Sour hydrogen sodium regulation system pH value is 8.5, when being warming up to 55 DEG C, stirring mixing 35min, then adds 4.0 parts of hydrochloric acid and is condensed,
Tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Mark is made through vulcanization
Quasi- sample, test performance is shown in Table 1.
Embodiment 4
(1) it is grafted the preparation of styrene-butadiene latex：Be the same as Example 3.
(2) preparation of modified Nano white carbon：Be the same as Example 3.
(3) it is used for the preparation of the butadiene-styrene rubber composition of tire tread：By the quality of styrene-butadiene latex SBR1500 (butt matter)
Part meter, takes 100 parts of styrene-butadiene latex SBR1500 and 4.5 parts of SBR-g-MAA (grafting rate is 2.9%), 3.5 parts of detergent alkylate sulphurs
Sour sodium, 260 parts of deionized waters are added to stirring mixing 20min in condensing field, then add 45 parts of modified Nano white carbons, use carbon
Sour hydrogen sodium regulation system pH value is 8.6, when being warming up to 60 DEG C, stirring mixing 50min, then adds 5.0 parts of hydrochloric acid and is condensed,
Tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Standard is made through vulcanization
Sample, test performance is shown in Table 1.
Embodiment 5
(1) it is grafted the preparation of styrene-butadiene latex：Based on styrene-butadiene latex SBR1712 mass parts, it is firstly added in polymeric kettle
200 parts of deionized waters then sequentially add 100 parts of styrene-butadiene latex SBR1712,8.0 parts of neopelexes, 0.7 part ten
Two carbon mercaptan, after nitrogen displacement, and then add 9 parts of MAA, stirring, heating, kettle temperature degree to be polymerized are added when reaching 50 DEG C
After 0.4 part of ammonium persulfate, reaction 4.0h, 0.4 part of diethyl hydroxylamine is added, grafting styrene-butadiene latex (SBR-g-MAA) is made.Sampling
Analysis：The grafting rate for measuring SBR-g-MAA is 3.7%.
(2) preparation of modified Nano white carbon：Based on the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 350 are taken
Part deionized water is added to stirring mixing 25min in polymeric kettle；Then 7 parts of hexamethylene diisocyanates (HDI), 1.7 are added
Part sodium hydroxide, stirring is warming up to 52 DEG C, is stirred for reaction 1.8hr generations centered on Nano carbon white powder by aliphatic two
The performed polymer that isocyanates is coated；20 parts of polyacrylamides (PAM) and 1.6 parts of sodium hydroxides are finally added, 4.7hr is reacted
Afterwards, modified Nano white carbon is made in scrubbed, dehydration, dry, grinding.
(3) it is used for the preparation of the butadiene-styrene rubber composition of tire tread：By the quality of styrene-butadiene latex SBR1712 (butt matter)
Part meter, takes 100 parts of styrene-butadiene latex SBR1712 and 5.0 parts of SBR-g-MAA (grafting rate is 3.7%), 4.0 parts of detergent alkylate sulphurs
Sour sodium, 270 parts of deionized waters are added to stirring mixing 20min in condensing field, then add 50 parts of modified Nano white carbons, use carbon
Sour hydrogen sodium regulation system pH value is 8.7, when being warming up to 60 DEG C, stirring mixing 50min, then adds 3.2 parts of sulfuric acid and is condensed,
Tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Mark is made through vulcanization
Quasi- sample, test performance is shown in Table 1.
Embodiment 6
(1) it is grafted the preparation of styrene-butadiene latex：Be the same as Example 5.
(2) preparation of modified Nano white carbon：Be the same as Example 5.
(3) it is used for the preparation of the butadiene-styrene rubber composition of tire tread：By the quality of styrene-butadiene latex SBR1712 (butt matter)
Part meter, takes 100 parts of styrene-butadiene latex SBR1712 and 6.0 parts of SBR-g-MAA (grafting rate is 3.7%), 5.0 parts of detergent alkylate sulphurs
Sour sodium, 300 parts of deionized waters are added to stirring mixing 25min in condensing field, then add 60 parts of modified Nano white carbons, use carbon
Sour hydrogen sodium regulation system pH value is 8.7, when being warming up to 60 DEG C, stirring mixing 50min, then adds 5.5 parts of sulfuric acid and is condensed,
Tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：Standard is made through vulcanization
Sample, test performance is shown in Table 1.
Comparative example 1
(1) it is grafted the preparation of styrene-butadiene latex：Be the same as Example 1.
(2) preparation of modified Nano white carbon：Be the same as Example 1.
(3) it is used for the preparation of the butadiene-styrene rubber composition of tire tread：Other conditions are same as Example 1, difference
The addition for being modified Nano white carbon in preparation process is 15 parts, i.e.,：Take 100 parts of styrene-butadiene latex SBR1500 (butt matter)
Cohesion is added to 3.0 parts of SBR-g-MAA (grafting rate is 2.1%), 2.5 parts of neopelexes, 230 parts of deionized waters
Stirring mixing 15min, then adds 15 parts of modified Nano white carbons in kettle, is 8.2 with sodium acid carbonate regulation system pH value, heating
During to 55 DEG C, mixing 35min is stirred, 3.0 parts of hydrochloric acid is then added and is condensed, last scrubbed, dehydration, dry, briquetting system
Obtain tire tread butadiene-styrene rubber composition.Sampling analysis：Standard specimen is made through vulcanization, test performance is shown in Table 1.
Comparative example 2
(1) preparation of modified Nano white carbon：Be the same as Example 1.
(2) it is used for the preparation of the butadiene-styrene rubber composition of tire tread：Other conditions are same as Example 2, difference
It is to be not added with SBR-g-MAA (grafting rate is 2.1%) in preparation process, i.e.,：Take 100 parts of styrene-butadiene latex SBR1500 (butt matter),
3.0 parts of neopelexes, 230 parts of deionized waters are added to stirring mixing 15min in condensing field, then add 30 parts and change
Property Nano carbon white, with sodium acid carbonate regulation system pH value be 8.5, when being warming up to 60 DEG C, stirring mixing 40min, then add
3.5 parts of hydrochloric acid are condensed, and 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 in Table 1.
Comparative example 3
(1) it is grafted the preparation of styrene-butadiene latex：Be the same as Example 1.
(2) preparation of modified Nano white carbon：Be the same as Example 1.
(3) it is used for the preparation of the butadiene-styrene rubber composition of tire tread：Other conditions are same as Example 3, difference
The addition for being SBR-g-MAA in preparation process (grafting rate is 2.9%) is 1.0 parts, i.e.,：Take 100 parts of styrene-butadiene latexes
SBR1500 (butt matter) and 1.0 parts of SBR-g-MAA (grafting rate is 2.9%), 3.0 parts of neopelexes, 260 parts go
Ionized water is added to stirring mixing 15min in condensing field, then adds 40 parts of modified Nano white carbons, body is adjusted with sodium acid carbonate
It is that pH value is 8.5, when being warming up to 55 DEG C, then stirring mixing 35min adds 4.0 parts of hydrochloric acid and be condensed, finally scrubbed,
Tire tread butadiene-styrene rubber composition is made in dehydration, dry, briquetting.Sampling analysis：Standard specimen, testability is made through vulcanization
1 can be shown in Table.
Comparative example 4
Preparation for the butadiene-styrene rubber composition of tire tread：Other conditions are same as Example 4, and difference is
Modified Nano white carbon is not added with preparation process, but adds unmodified Nano carbon white, its addition is 45 parts, i.e.,：Take
100 parts of styrene-butadiene latex SBR1500 (butt matter) and 4.5 parts of SBR-g-MAA (grafting rate is 2.9%), 3.5 parts of detergent alkylate sulphurs
Sour sodium, 260 parts of deionized waters are added to stirring mixing 20min in condensing field, then add 45 parts of unmodified Nano carbon whites, use
Sodium acid carbonate regulation system pH value is 8.6, when being warming up to 60 DEG C, stirring mixing 50min, then adds 5.0 parts of hydrochloric acid and is coagulated
Poly-, tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：It is made through vulcanization
Standard specimen, test performance is shown in Table 1.
Comparative example 5
(1) it is grafted the preparation of styrene-butadiene latex：Be the same as Example 5.
(2) preparation of modified Nano white carbon：Other conditions are same as Example 5, and difference is in preparation process
HDI is not added with, i.e.,：100 parts of Nano carbon whites (40nm) and 350 parts of deionized waters are taken to be added to stirring mixing 25min in polymeric kettle；
Then 1.7 parts of sodium hydroxides are added, stirring is warming up to 52 DEG C, is stirred for reaction 1.8hr and generates using Nano carbon white powder in
The performed polymer that the heart is coated by aliphatic diisocyanate；Finally add 20 parts of polyacrylamides (PAM) and 1.6 parts of hydroxides
After sodium, reaction 4.7hr, modified Nano white carbon a is made in scrubbed, dehydration, dry, grinding.
(3) it is used for the preparation of the butadiene-styrene rubber composition of tire tread：Other conditions are same as Example 5, difference
It is to be not added with modified Nano white carbon in preparation process, but adds modified Nano white carbon a, its addition is 50 parts, i.e.,：Take
100 parts of styrene-butadiene latex SBR1712 (butt matter) and 5.0 parts of SBR-g-MAA (grafting rate is 3.7%), 4.0 parts of detergent alkylate sulphurs
Sour sodium, 270 parts of deionized waters are added to stirring mixing 20min in condensing field, then add 50 parts of modified Nano white carbon a, use
Sodium acid carbonate regulation system pH value is 8.7, when being warming up to 60 DEG C, stirring mixing 50min, then adds 3.2 parts of sulfuric acid and is coagulated
Poly-, tire tread butadiene-styrene rubber composition is made in last scrubbed, dehydration, dry, briquetting.Sampling analysis：It is made through vulcanization
Standard specimen, test performance is shown in Table 1.
Comparative example 6
(1) it is grafted the preparation of styrene-butadiene latex：Other conditions are same as Example 5, and difference is MAA in preparation process
Addition is 3.0 parts, i.e.,：200 parts of deionized waters are firstly added in polymeric kettle and then 100 parts of styrene-butadiene latexes are sequentially added
SBR1712,8.0 parts of neopelexes, 0.7 part of DDM dodecyl mercaptan, after nitrogen displacement, and then add 3.0 parts
MAA, stirring, heating, kettle temperature degree to be polymerized is added when reaching 50 DEG C after 0.4 part of ammonium persulfate, reaction 4.0h, adds 0.4 part two
Ethylhydroxyl amine, is made grafting styrene-butadiene latex (SBR-g-MAA).Sampling analysis：The grafting rate for measuring SBR-g-MAA is 0.8%.
(2) preparation of modified Nano white carbon：Be the same as Example 5.
(3) it is used for the preparation of the butadiene-styrene rubber composition of tire tread：Other conditions are same as Example 6, difference
It is to be not added with SBR-g-MAA (grafting rate is 3.7%) in preparation process, but adds SBR-g-MAA (grafting rate is 0.8%),
6.0 parts of its addition, i.e.,：Taking 100 parts of styrene-butadiene latex SBR1712 (butt matter) and 6.0 parts of SBR-g-MAA, (grafting rate is
3.7%), 5.0 parts of neopelexes, 300 parts of deionized waters are added to stirring mixing 25min, Ran Houjia in condensing field
Enter 60 parts of modified Nano white carbons, be 8.7 with sodium acid carbonate regulation system pH value, when being warming up to 60 DEG C, stirring mixing 50min,
Then add 5.5 parts of sulfuric acid to be condensed, last scrubbed, dehydration, dry, briquetting are made tire tread and combined with butadiene-styrene rubber
Thing.Sampling analysis：Standard specimen is made through vulcanization, test performance is shown in Table 1.
The performance of the tire tread of table 1 butadiene-styrene rubber composition
As shown in Table 1：0 DEG C of tan δ of embodiment is higher than comparative example, illustrates that the wet-sliding resistant performance for tire preparation is good；Embodiment
60 DEG C of fissipation factors (tan δ) and wear volume it is all lower than comparative example, illustrate for tire prepare rolling resistance is low, wearability is good.
Claims (23)
1. a kind of rubber composition for tire tread, in terms of the mass parts of styrene butadiene rubber latex butt matter, it is main include with
Lower component：
(1) styrene butadiene rubber latex 100%
(2) modified Nano white carbon 20~60%
(3) it is grafted styrene-butadiene latex 2~6%
Characterized in that, described modified Nano white carbon is modified using aliphatic diisocyanate to Nano carbon white,
Then add after water soluble polymer carries out graft reaction and be prepared from.
2. rubber composition as claimed in claim 1, it is characterised in that the particle diameter of the modified Nano white carbon is：20~
60nm。
3. the rubber composition as described in any one of claim 1 or 2, it is characterised in that the aliphatic diisocyanate choosing
From hexamethylene diisocyanate, IPDI, the diisocyanate of one 4,4' of dicyclohexyl methyl hydride mono-, methyl ring
One or more of mixtures in hexane diisocyanate.
4. rubber composition as claimed in claim 3, it is characterised in that the aliphatic diisocyanate is hexa-methylene two
Isocyanates.
5. rubber composition as claimed in claim 1, it is characterised in that the water soluble polymer is contained in molecular structure
Polyethylene backbone, side base is the compound of hydrophilic radical, selected from polyvinyl alcohol, polyethylene glycol, polyacrylamide, polypropylene glycol
In one kind.
6. rubber composition as claimed in claim 5, it is characterised in that the water soluble polymer is polyacrylamide.
7. rubber composition as claimed in claim 5, it is characterised in that based on the mass parts of Nano carbon white, described water-soluble
Property macromolecule consumption be 10%~20%.
8. rubber composition as claimed in claim 1, it is characterised in that the grafting styrene-butadiene latex is using olefin-containing structure
Polar monomer graft styrene-butadiene latex.
9. rubber composition as claimed in claim 8, it is characterised in that the polar monomer is selected from acrylic acid, metering system
One kind in acid, acrylamide.
10. rubber composition as claimed in claim 9, it is characterised in that the polar monomer is methacrylic acid.
11. rubber composition as claimed in claim 8, it is characterised in that the grafting rate of the grafting styrene-butadiene latex is 1%~
4%.
12. rubber composition as claimed in claim 1, it is characterised in that the styrene butadiene rubber latex is by conjugated diene
Compound and aryl ethylene class compound are formed by emulsion polymerization copolymerization.
13. rubber composition as claimed in claim 12, it is characterised in that the conjugated diene hydrocarbon compound is C4Class is conjugated
Diolefin compound.
14. rubber composition as claimed in claim 12, it is characterised in that the aryl ethylene class compound is selected from benzene second
One kind in alkene, α-methylstyrene, 2- propenyl benzenes, ethyl styrene and their derivative.
15. the rubber composition as described in any one of claim 12~14, it is characterised in that the styrene butadiene rubber latex is consolidated
Content is 20~45%, and combinated styrene content content is 15~25%, and latex particle size is 50~200nm.
16. the preparation method of the rubber composition for tire tread as described in one of claim 1~15, its feature exists
In comprising the following steps：
(1) in terms of the mass parts of styrene-butadiene latex butt matter, 100 parts of styrene-butadiene latex butt matter and 2~6 parts of grafting styrene-butadiene latexes, 2 are taken
~5 parts of emulsifying agents, 200~300 parts of deionized waters are added to 10~30min of stirring mixing in condensing field；
(2) 20~60 parts of modified Nano white carbons are added in condensing field, is 8~10 with buffer regulation system pH value, is warming up to
At 50~70 DEG C, 30~60min of stirring mixing；
(3) add 3~6 parts of flocculating agents in condensing field to be condensed, tire is made in last scrubbed, dehydration, dry, briquetting
Face butadiene-styrene rubber composition.
17. method as claimed in claim 16, it is characterised in that the flocculating agent is in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid
One or more of mixtures.
18. method as claimed in claim 16, it is characterised in that the emulsifying agent is anion emulsifier and non-ionic emulsifier
One or more of mixtures in agent.
19. method as claimed in claim 18, it is characterised in that the emulsifying agent is selected from fatty acid soaps, RA rosin acid, 12
One or more of mixtures in sodium alkyl benzene sulfonate, lauryl sodium sulfate, polyoxyethylene sorbitol acid anhydride list olein.
20. method as claimed in claim 19, it is characterised in that the emulsifying agent is neopelex.
21. method as claimed in claim 16, it is characterised in that the buffer is selected from sodium carbonate, sodium acid carbonate, hydroxide
One kind in sodium, ammoniacal liquor, ammonium hydrogen carbonate.
22. method as claimed in claim 21, it is characterised in that the buffer is sodium hydroxide.
23. the method as described in any one of claim 16~22, it is characterised in that the terminator be selected from diethyl hydroxylamine,
One or more of mixtures in HAS, Sodium Dimethyldithiocarbamate.
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