CN107266749B - Rubber composition and preparation method thereof for tire tread - Google Patents
Rubber composition and preparation method thereof for tire tread Download PDFInfo
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- CN107266749B CN107266749B CN201610218621.6A CN201610218621A CN107266749B CN 107266749 B CN107266749 B CN 107266749B CN 201610218621 A CN201610218621 A CN 201610218621A CN 107266749 B CN107266749 B CN 107266749B
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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
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
It is an object of that present invention to provide a kind of rubber compositions for tire tread.The invention utilizes unsaturated carboxylic acid polar monomer and conjugated diene monomer, prepares modified Nano white carbon black by situ aggregation method, then directly mixes, agglomerated to prepare the rubber composition of high-performance tire tread rubber with styrene butadiene rubber latex.The invention not only efficiently solves the problems, such as the easy to reunite of Nano carbon white, but also solves the problems, such as Nano carbon white and rubber matrix binding force difference and dispersion unevenness, imparts the performance of the composition high abrasion, low friction.Preparation method is simple for the rubber composition, low in cost, no pollution to the environment, is suitble to industrialized production.
Description
Technical field
The present invention relates to a kind of rubber compositions and preparation method thereof, fill fourth more particularly to a kind of modified white carbon black
Benzene rubber is used for the rubber composition and preparation method thereof of tire tread.
Background technique
It is well known that with the successive implementation of EU REACH Legislation and tire tag bill, synthetic rubber environmental protection is compeled
The eyebrows and eyelashes, along with the demand of light color article, the application study of white carbon black causes the attention of people.Nano silica is commonly called as white
Carbon black is the second largest reinforcing agent that dosage is only second to carbon black in rubber industry.From last century the nineties, white carbon black is as reinforcement
Filler is widely used in tire tread formula, obtains " devil's triangle " performance of above-mentioned tire tread requirement obvious
Balance.But Nano carbon white partial size is small, specific surface is big, surface energy is high, surface has a large amount of hydroxyl again, leads to a nanometer hard charcoal
It is black easily to reunite, it is not easy to be uniformly dispersed in the mixed process with rubber material, not only will affect filling-modified effect in this way, and
And it can also damage the performance of rubber material.
In the prior art, the research in relation to modified Nano white carbon black filled rubber material mainly passes through coupling agent or surface
Activating agent, graft polymers coating modification Nano carbon white particle surface filled rubber material method prepare.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) have studied high-performance NR composite material: natural rubber/silica nanometer composite wood is prepared using latex blending method
Material first uses γ-methacryloxypropyl trimethoxy silane coupling agent (MPS) modified manometer silicon dioxide (SiO2), then
Upper polymethyl methacrylate (PMMA), which is grafted, through emulsion polymerization obtains the nano-silicon dioxide particle (SiO of core-shell structure2-
MPS-PMMA finally it is directly blended with the modified Heveatex (NR-PMMA) of MMA), natural rubber/silica is made
Nanocomposite.Li Wen Ji et al. is prepared for clay/white carbon black compounded mix by drying process with atomizing, for substituting part
White carbon black, to enhance solution polymerized butadiene styrene rubber/butadiene rubber composite material jointly.Patent CN 101798473A uses multi-sulfur silane
Acceptor modified white carbon black then prepares silica/carbon black compounded mix.Patent CN201305854136A passes through poly-dopamine
Modified white carbon black is being kneaded with rubber raw rubber and auxiliary agent, is being vulcanized, and rubber composition is prepared.Although the above method is improved and is received
The compatibility of off-white carbon black and rubber matrix, but these methods are there are still certain limitation, using graft polymers it is modified and
When inorganic material surface coating modification Nano carbon white, it is longer that there are reaction time consumptions, and energy consumption is higher and causes serious pollution to the environment, operation
The disadvantages of complicated；And when utilizing coupling agent or surfactant-modified Nano carbon white, it will lead to rubber material vulcanization delay, draw
Playing cured properties reduces, and need to add vulcanizing agent and promotor causes processing cost to improve, and followed by dispersion stabilization is poor and easy
Again the disadvantages of reuniting.
Summary of the invention
It is an object of that present invention to provide a kind of rubber composition of white carbon black containing modified Nano, the rubber composition is for taking turns
There are preferable wearability, lower rolling resistance when tire tread.The invention utilizes unsaturated carboxylic acid polar monomer and conjugated diene
Hydrocarbon monomer prepares modified Nano white carbon black by situ aggregation method, then mixes, is agglomerated to prepare high property with styrene butadiene rubber latex
The rubber composition of energy tire tread glue.The invention not only efficiently solves the problems, such as the easy to reunite of Nano carbon white, but also
It solves the problems, such as Nano carbon white and rubber matrix binding force difference and dispersion is uneven, impart the composition high abrasion, low rub
The performance of wiping.Present invention further propose that the preparation method of the composition.
A kind of rubber composition for tire tread of the present invention, it is main in terms of the mass parts of styrene butadiene rubber latex butt matter
To include following component:
Wherein, the modified Nano white carbon black is to use unsaturated carboxylic acid polar monomer and conjugated diene monomer,
It is prepared under initiator effect by situ aggregation method.White carbon black is selected from nanoscale, partial size are as follows: 20~60nm.It is unsaturated
Carboxylic acid polar monomer is selected from one of acrylic acid (AA), methacrylic acid (MAA), maleic anhydride (MAH), preferably metering system
Sour (MAA), dosage are as follows: 1%~5%.Conjugated diene is C4-Cl2Conjugated diene, be selected from 1,3-butadiene；Isoamyl two
Alkene；2,3- dimethyl -1,3 butadiene；2,3- diethyl -1,3 butadiene；2- methyl -3- ethyl -1,3 butadiene；2- chloro- 1,
3- pentadiene；1,3-pentadiene；3- butyl -1,3- octadiene；2- phenyl -1,3-butadiene；One of 1,3- hexadiene or
Several mixtures, preferably 1,3- hexadiene.Initiator is water-soluble thermal initiator, is selected from ammonium persulfate, potassium peroxydisulfate, over cure
Bis- (the 2- amidine oxazoline propane) hydrochlorides of sour sodium, 2,2- azo, 2,2- azo [2- (2- imidazoline -2- base) propane] dihydrochloride
One or more of mixture, initiator system of ammonium persulfate.
Styrene butadiene rubber latex of the present invention is to pass through cream by conjugated diene hydrocarbon compound and aryl ethylene class compound
Liquid polymerization is copolymerized.Conjugated diene hydrocarbon compound is C4Class conjugated diene hydrocarbon compound.Aryl ethylene class compound can be
Styrene, α-methylstyrene, 2- propenyl benzene, ethyl styrene and their derivative.The wherein solid content 20 of styrene-butadiene latex
~45%, combinated styrene content content 15~25%, 50~200nm of latex particle size.
Carboxylic styrene butadiene latex of the present invention is using butadiene, styrene as main monomer, and unsaturated carboxylic acid is function list
Body is obtained through emulsion polymerization, and unsaturated carboxylic acid therein is acrylic acid, methacrylic acid or 2- ethylacrylic acid, preferably propylene
Acid.The solid content 40~55% of carboxylic styrene butadiene latex, 100~170nm of latex particle size.
Water soluble polymer of the present invention is to contain polyethylene backbone in molecular structure, and side group is hydrophilic radical
Compound is stung, polyacrylamide, polyacrylic acid, polymethylacrylic acid, poly- first selected from polyvinylpyrrolidone, 4- polyethylene pyrrole
One of base hydroxy-ethyl acrylate, preferably polyacrylic acid, dosage are 1%~5%.
The preparation of rubber composition of the present invention can carry out in condensing field, and specific preparation process includes following step
It is rapid:
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: in terms of the mass parts of conjugated diene monomer, by 100 parts of conjugated diene monomers, 5
~10 parts of emulsifiers, 150~200 parts of deionized waters, 1.0~2.0 parts of buffers, 0.01~0.1 part of initiator are put into togerther instead
It answers in device, when being warming up to 40~60 DEG C, is stirred to react 30~50 minutes and is prepared into monomer pre-emulsion.
B. in terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 1.0 preparation of modified Nano white carbon black: are taken
~5.0 parts of unsaturated carboxylic acid polar monomers, 200~300 parts of deionized waters, 1~5 part of buffer are added to stir in polymeric kettle and mix
Close 10~30min；Then 1~5 part of emulsifier, 5~10 parts of monomer pre-emulsions is added, stirring is warming up to 50~70 DEG C, then stirs
Mix what 10~30min of mixing generation was coated centered on Nano carbon white powder by carboxylic acid polar monomer and conjugated diene monomer
Condensate, and using this as the seed of multiple emulsion；Then 60~80 parts of monomer pre-emulsions are added and 0.05~0.2 part is drawn
Agent is sent out, after reacting 2.0~5.0h, is eventually adding 0.1~0.3 part of terminator, washed, dehydration, dry, grinding are made modification and receive
Off-white carbon black.
(2) in terms of the mass parts of styrene-butadiene latex butt matter, 100 parts the tire tread preparation of butadiene-styrene rubber composition: are taken
Styrene-butadiene latex (butt matter) and 5~10 parts of carboxylic styrene butadiene latexes, 2~5 parts of emulsifiers, 100~200 parts of deionized waters are added to solidifying
It is stirred 10~20min in poly- kettle, 20~50 parts of modified Nano white carbon blacks and 1~5 part of water soluble polymer is then added, uses
Buffer regulation system pH value is 8~11, when being warming up to 50~60 DEG C, is stirred 30~50min, is then added 3~6 parts and coagulates
Poly- agent is condensed, and tire tread butadiene-styrene rubber composition is made in last washed, dehydration, dry, briquetting.
The present invention is not specially limited used emulsifier, flocculating agent, buffer etc., is all made of generally in the art
Conven-tional adjuvants, additional amount is also the conventional amount used that those skilled in the art can be calculated according to the dosage of dry glue, this
Particular determination is not also done in invention.
Cohesion of the present invention, poly- using acid cure, the technology is general for those skilled in the art, the flocculating agent
Usually inorganic acid, such as the mixture of one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid.
Emulsifier of the present invention is known to those skilled in the art, can be anion emulsifier and nonionic Emulsion
In agent-kind or it is a variety of.Such as: selected from fatty acid soaps, RA rosin acid, neopelex, lauryl sodium sulfate, gathering
The mixture of one or more of ethylene oxide sorbitan monooleate, preferably neopelex.
Buffer of the present invention is selected from one of sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonium hydroxide, ammonium hydrogen carbonate,
It is preferred that sodium hydroxide.
Terminator of the present invention is selected from the mixing of one or more of diethyl hydroxylamine, hydroxyl sulfate, Sodium Dimethyldithiocarbamate
Object.
The particle diameter for the Nano carbon white that the present invention uses is small, and the large specific surface area of particle, surface can be high, easily generation phase
Mutual agglomeration only is difficult to allow ultrafine particle in rubber by traditional method of modifying such as mechanical stirring or activating agent surface treatment
It is in nano-dispersion 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, nanoparticle surface form it is a kind of using anchoring group carboxylic acid be back and conjugated diene as tail
A kind of high dispersive structure (see attached drawing one).This high dispersive structure establishes space stability ultimate load layer between nanoparticle, can
Significantly to reduce the mutual suction-operated of particle surface silicone hydroxyl, the mutual reunion between particle is hindered, can be realized with list
One particle shape steadily exists.
Secondly as the poly-conjugated-diolefin molecular structure of modified Nano white carbon black particle surface and butadiene-styrene rubber molecule knot
Structure is different, is not easy to be distributed in styrene-butadiene latex according to similar compatibility principle modified Nano hard charcoal black track producing particle, by the way that backbone structure is added
Water soluble polymer identical with polymerized conjugated diene molecular structure makes its polar group be evenly dispersed into hard charcoal black track producing particle table
In addition face is added carboxylic styrene butadiene latex on styrene-butadiene latex surface and forms a certain amount of carboxyl, again in the strong of the two polar group
Under mutual suction-operated, the compatibility between particle and styrene-butadiene latex matrix is greatly improved, realizes Nano carbon white particle and exists
Being uniformly dispersed in styrene-butadiene latex, to obtain the tire tread butadiene-styrene rubber composition of high comprehensive performance.
Finally, Nano carbon white particle is not by opening in preparation process of the tire tread with butadiene-styrene rubber composition
Mill and mixer carry out mixing and mixing to process, but directly prepare with styrene-butadiene latex blending, cohesion.This avoid
The skidding of sizing material work in-process appearance, disperses the problems such as uneven at incipient scorch.Preparation method is simple and easy, low in cost, to environment
It is pollution-free, it is suitble to industrialized production.
Detailed description of the invention
Fig. 1 is the high dispersive structure chart of Nano carbon white particle surface.1 is using conjugated diene polymer chain as tail in figure
Solvent chain；2 is using carboxylic acid groups as the anchoring group of anchor point；3 be Nano carbon white particle.
Specific embodiment
Following embodiment and comparative example are enumerated to illustrate invention effect of the invention, but protection scope of the present invention is not
It is only limitted in these embodiment and comparative examples." part " described in embodiment and comparative example each means mass parts.
(1) raw material sources:
Other reagents are commercially available industrial goods
(2) analysis test method:
0 DEG C and 60 DEG C of fissipation factors: being analyzed using the DMA Q800 type dynamic thermomechanical analysis apparatus of TA company,
Select double cantilever chucks.In -150 DEG C~100 DEG C temperature programmings, heating rate is 3 DEG C/min, amplitude 10
μm, test frequency is respectively 1Hz, 5Hz, 10Hz, dynamic force 1N.
Carbon black dispension degree: method in standard GB/T6030-1985 is executed.
Akron abrasion volume；Method in execution standard GB/T 25262-2010.
Embodiment 1
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: with the mass parts meter of 1,3- hexadiene, by 100 parts of 1,3- hexadienes, 6 parts of dodecanes
Base benzene sulfonic acid sodium salt, 160 parts of deionized waters, 1.2 parts of sodium hydroxides, 0.03 part of ammonium persulfate-rise and are put into reactor, are warming up to 40
DEG C when, be stirred to react and be prepared within 35 minutes 1,3- hexadiene pre-emulsion a.
B. in terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 1.5 preparation of modified Nano white carbon black: are taken
Part methacrylic acid (MAA), 220 parts of deionized waters, 1.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 20min；Then
2 parts of neopelexes, 5.5 parts of 1,3- hexadiene pre-emulsion a are added, stirring is warming up to 65 DEG C, is stirred for mixing
25min generates the seed of the multiple emulsion centered on Nano carbon white powder；Then 60 parts of pre- creams of 1,3- hexadiene are added
Change liquid a and 0.07 part of ammonium persulfate, after reacting 3.0h, is eventually adding 0.2 part of diethyl hydroxylamine, washed, dehydration, is ground at drying
Grind to obtain modified Nano white carbon black.
(2) preparation of tire tread butadiene-styrene rubber composition: with the mass parts of styrene-butadiene latex SBR1500 (butt matter)
Meter, takes 100 parts of styrene-butadiene latex SBR1500 and 5 parts of carboxylic styrene butadiene latexes, 2.0 parts of neopelexes, 120 parts of deionizations
Water, which is added in condensing field, is stirred 12min, and 25 parts of modified Nano white carbon blacks and 1.5 parts of polyacrylic acid are then added, use hydrogen
Sodium oxide molybdena regulation system pH value is 8.5, when being warming up to 55 DEG C, is stirred 35min, and 3.5 parts of hydrochloric acid are then added and are condensed,
Tire tread butadiene-styrene rubber composition is made in last washed, dehydration, dry, briquetting.Sampling analysis: standard is made through vulcanization
Sample, test performance are shown in Table 1.
Embodiment 2
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: with embodiment 1.
B. in terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 1.0 preparation of modified Nano white carbon black: are taken
Part methacrylic acid (MAA), 250 parts of deionized waters, 1.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 20min；Then
2 parts of neopelexes, 5.0 parts of 1,3- hexadiene pre-emulsion a are added, stirring is warming up to 55 DEG C, is stirred for mixing
20min generates the seed of the multiple emulsion centered on Nano carbon white powder；Then 65 parts of pre- creams of 1,3- hexadiene are added
Change liquid a and 0.09 part of ammonium persulfate, after reacting 3.5h, is eventually adding 0.15 part of diethyl hydroxylamine, washed, dehydration, is ground at drying
Grind to obtain modified Nano white carbon black.
(2) preparation of tire tread butadiene-styrene rubber composition: with the mass parts of styrene-butadiene latex SBR1500 (butt matter)
Meter, take 100 parts of styrene-butadiene latex SBR1500 and 5.5 parts of carboxylic styrene butadiene latexes, 2.5 parts of neopelexes, 120 parts go from
Sub- water, which is added in condensing field, is stirred 13min, and 20 parts of modified Nano white carbon blacks and 1.0 parts of polyacrylic acid are then added, and uses
Sodium hydroxide regulation system pH value is 8.7, when being warming up to 50 DEG C, is stirred 35min, and 4.0 parts of hydrochloric acid are then added and are coagulated
Poly-, tire tread butadiene-styrene rubber composition is made in last washed, dehydration, dry, briquetting.Sampling analysis: it is made through vulcanization
Standard sample, test performance are shown in Table 1.
Embodiment 3
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: with the mass parts meter of 1,3- hexadiene, by 100 parts of 1,3- hexadienes, 8 parts of dodecanes
Base benzene sulfonic acid sodium salt, 170 parts of deionized waters, 1.4 parts of sodium hydroxides, 0.05 part of ammonium persulfate-rise and are put into reactor, are warming up to 45
DEG C when, be stirred to react and be prepared within 40 minutes 1,3- hexadiene pre-emulsion b.
B. in terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 3.0 preparation of modified Nano white carbon black: are taken
Part methacrylic acid (MAA), 270 parts of deionized waters, 2.5 parts of sodium hydroxides are added in polymeric kettle and are stirred 25min；Then
3 parts of neopelexes, 6.5 parts of 1,3- hexadiene pre-emulsion b are added, stirring is warming up to 65 DEG C, is stirred for mixing
25min generates the seed of the multiple emulsion centered on Nano carbon white powder；Then 70 parts of pre- creams of 1,3- hexadiene are added
Change liquid b and 0.11 part of ammonium persulfate, after reacting 3.0h, is eventually adding 0.25 part of diethyl hydroxylamine, washed, dehydration, is ground at drying
Grind to obtain modified Nano white carbon black.
(2) preparation of tire tread butadiene-styrene rubber composition: with the mass parts of styrene-butadiene latex SBR1500 (butt matter)
Meter, take 100 parts of styrene-butadiene latex SBR1500 and 6.0 parts of carboxylic styrene butadiene latexes, 3.0 parts of neopelexes, 140 parts go from
Sub- water, which is added in condensing field, is stirred 15min, and 30 parts of modified Nano white carbon blacks and 2.0 parts of polyacrylic acid are then added, and uses
Sodium hydroxide regulation system pH value is 8.5, when being warming up to 55 DEG C, is stirred 35min, and 3.5 parts of hydrochloric acid are then added and are coagulated
Poly-, tire tread butadiene-styrene rubber composition is made in last washed, dehydration, dry, briquetting.Sampling analysis: it is made through vulcanization
Standard sample, test performance are shown in Table 1.
Embodiment 4
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: with embodiment 3.
B. in terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 3.5 preparation of modified Nano white carbon black: are taken
Part methacrylic acid (MAA), 270 parts of deionized waters, 2.9 parts of sodium hydroxides are added in polymeric kettle and are stirred 25min；Then
4 parts of neopelexes, 7.5 parts of 1,3- hexadiene pre-emulsion b are added, stirring is warming up to 65 DEG C, is stirred for mixing
25min generates the seed of the multiple emulsion centered on Nano carbon white powder；Then 72 parts of pre- creams of 1,3- hexadiene are added
Change liquid b and 0.12 part of ammonium persulfate, after reacting 3.0h, is eventually adding 0.25 part of diethyl hydroxylamine, washed, dehydration, is ground at drying
Grind to obtain modified Nano white carbon black.
(2) preparation of tire tread butadiene-styrene rubber composition: with the mass parts of styrene-butadiene latex SBR1500 (butt matter)
Meter, take 100 parts of styrene-butadiene latex SBR1500 and 7.5 parts of carboxylic styrene butadiene latexes, 3.5 parts of neopelexes, 150 parts go from
Sub- water, which is added in condensing field, is stirred 15min, and 35 parts of modified Nano white carbon blacks and 3.0 parts of polyacrylic acid are then added, and uses
Sodium hydroxide regulation system pH value is 8.9, when being warming up to 55 DEG C, is stirred 35min, and 4.0 parts of hydrochloric acid are then added and are coagulated
Poly-, tire tread butadiene-styrene rubber composition is made in last washed, dehydration, dry, briquetting.Sampling analysis: it is made through vulcanization
Standard sample, test performance are shown in Table 1.
Embodiment 5
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: with embodiment 3.
B. in terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 3.8 preparation of modified Nano white carbon black: are taken
Part methacrylic acid (MAA), 280 parts of deionized waters, 2.9 parts of sodium hydroxides are added in polymeric kettle and are stirred 28min；Then
4.5 parts of neopelexes, 8.5 parts of 1,3- hexadiene pre-emulsion b are added, stirring is warming up to 65 DEG C, is stirred for mixing
30min generates the seed of the multiple emulsion centered on Nano carbon white powder；Then 74 parts of pre- creams of 1,3- hexadiene are added
Change liquid b and 0.15 part of ammonium persulfate, after reacting 3.0h, is eventually adding 0.25 part of diethyl hydroxylamine, washed, dehydration, is ground at drying
Grind to obtain modified Nano white carbon black.
(2) preparation of tire tread butadiene-styrene rubber composition: with the mass parts of styrene-butadiene latex SBR1500 (butt matter)
Meter, take 100 parts of styrene-butadiene latex SBR1500 and 8.0 parts of carboxylic styrene butadiene latexes, 4.0 parts of neopelexes, 170 parts go from
Sub- water, which is added in condensing field, is stirred 17min, and 40 parts of modified Nano white carbon blacks and 4.0 parts of polyacrylic acid are then added, and uses
Sodium hydroxide regulation system pH value is 9.1, when being warming up to 55 DEG C, is stirred 35min, and 4.5 parts of hydrochloric acid are then added and are coagulated
Poly-, tire tread butadiene-styrene rubber composition is made in last washed, dehydration, dry, briquetting.Sampling analysis: it is made through vulcanization
Standard sample, test performance are shown in Table 1.
Embodiment 6
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: in terms of the mass parts of isoprene, by 100 parts of isoprene, 9 parts of detergent alkylates
Sodium sulfonate, 195 parts of deionized waters, 1.5 parts of sodium hydroxides, 0.07 part of potassium peroxydisulfate-rise and are put into reactor, are warming up to 45 DEG C
When, it is stirred to react and is prepared within 40 minutes isoprene pre-emulsion c.
B. in terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 4.0 preparation of modified Nano white carbon black: are taken
Part maleic anhydride (MAH), 280 parts of deionized waters, 3.0 parts of sodium hydroxides are added in polymeric kettle and are stirred 28min；Then plus
Enter 3.5 parts of neopelexes, 9.0 parts of isoprene pre-emulsion c, stirring is warming up to 65 DEG C, is stirred for mixing 30min
Generate the seed of the multiple emulsion centered on Nano carbon white powder；Then add 75 parts of isoprene pre-emulsion c and
0.15 part of potassium peroxydisulfate after reacting 4.0h, is eventually adding 0.29 part of diethyl hydroxylamine, and washed, dehydration, dry, grinding are made
Modified Nano white carbon black.
(2) preparation of tire tread butadiene-styrene rubber composition: with the mass parts of styrene-butadiene latex SBR1502 (butt matter)
Meter, takes 100 parts of styrene-butadiene latex SBR1502 and 10 parts of carboxylic styrene butadiene latexes, 5.0 parts of neopelexes, 200 parts of deionizations
Water, which is added in condensing field, is stirred 20min, and 50 parts of modified Nano white carbon blacks and 4.0 parts of polyacrylamides are then added, and uses
Sodium hydroxide regulation system pH value is 9.0, when being warming up to 55 DEG C, is stirred 35min, and 5.5 parts of sulfuric acid are then added and are coagulated
Poly-, tire tread butadiene-styrene rubber composition is made in last washed, dehydration, dry, briquetting.Sampling analysis: it is made through vulcanization
Standard sample, test performance are shown in Table 1.
Embodiment 7
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: with embodiment 6.
B. in terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 5.0 preparation of modified Nano white carbon black: are taken
Part maleic anhydride (MAH), 300 parts of deionized waters, 4.0 parts of sodium hydroxides are added in polymeric kettle and are stirred 28min；Then plus
Enter 3.5 parts of neopelexes, 10 parts of isoprene pre-emulsion c, stirring is warming up to 65 DEG C, is stirred for mixing 30min
Generate the seed of the multiple emulsion centered on Nano carbon white powder；Then add 80 parts of isoprene pre-emulsion c and
0.2 part of potassium peroxydisulfate after reacting 4.0h, is eventually adding 0.3 part of diethyl hydroxylamine, and washed, dehydration, dry, grinding are made and change
Property Nano carbon white.
(2) preparation of tire tread butadiene-styrene rubber composition: with the mass parts of styrene-butadiene latex SBR1502 (butt matter)
Meter, take 100 parts of styrene-butadiene latex SBR1502 and 9.0 parts of carboxylic styrene butadiene latexes, 4.5 parts of neopelexes, 200 parts go from
Sub- water, which is added in condensing field, is stirred 15min, and 45 parts of modified Nano white carbon blacks and 5.0 parts of polyacrylamides are then added,
It is 9.0 with sodium hydroxide regulation system pH value, when being warming up to 55 DEG C, is stirred 35min, 6.0 parts of sulfuric acid is then added and carry out
Tire tread butadiene-styrene rubber composition is made in cohesion, last washed, dehydration, dry, briquetting.Sampling analysis: it is made through vulcanization
At standard sample, test performance is shown in Table 1.
Comparative example 1
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: with embodiment 1.
B. the preparation of modified Nano white carbon black: with embodiment 1.
(2) preparation of tire tread butadiene-styrene rubber composition: other conditions are same as Example 1, the difference is that
The additional amount of modified Nano white carbon black is 15 parts in preparation process, it may be assumed that takes 100 parts of styrene-butadiene latex SBR1500 (butt matter) and 5 parts
Carboxylic styrene butadiene latex, 2.0 parts of neopelexes, 120 parts of deionized waters are added in condensing field and are stirred 12min,
Then 15 parts of modified Nano white carbon blacks and 1.5 parts of polyacrylic acid are added, is 8.5 with sodium hydroxide regulation system pH value, is warming up to
At 55 DEG C, it is stirred 35min, 3.5 parts of hydrochloric acid are then added and are condensed, last washed, dehydration, dry, briquetting are made
Tire tread butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Comparative example 2
The preparation of tire tread butadiene-styrene rubber composition: other conditions are same as Example 2, the difference is that preparation
Modified Nano white carbon black is not added in the process, but is directly added into unmodified Nano carbon white, additional amount is 20 parts, it may be assumed that is taken
100 parts of styrene-butadiene latex SBR1500 (butt matter) and 5.5 parts of carboxylic styrene butadiene latexes, 2.5 parts of neopelexes, 120 parts go
Ionized water, which is added in condensing field, is stirred 13min, and 20 parts of unmodified Nano carbon whites and 1.0 parts of polypropylene are then added
Acid, with sodium hydroxide regulation system pH value be 8.7, when being warming up to 50 DEG C, be stirred 35min, then be added 4.0 parts of hydrochloric acid into
Tire tread butadiene-styrene rubber composition is made in row cohesion, last washed, dehydration, dry, briquetting.Sampling analysis: through vulcanizing
Standard sample is made, test performance is shown in Table 1.
Comparative example 3
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: with embodiment 3.
B. the preparation of modified Nano white carbon black: with embodiment 3.
(2) preparation of tire tread butadiene-styrene rubber composition: other conditions are same as Example 3, the difference is that
Carboxylic styrene butadiene latex is not added in preparation process, it may be assumed that take 100 parts of styrene-butadiene latex SBR1500 (butt matter), 3.0 parts of detergent alkylates
Sodium sulfonate, 140 parts of deionized waters are added in condensing field and are stirred 15min, be then added 30 parts of modified Nano white carbon blacks and
2.0 parts of polyacrylic acid are 8.5 with sodium hydroxide regulation system pH value, when being warming up to 55 DEG C, are stirred 35min, are then added
3.5 parts of hydrochloric acid are condensed, and tire tread butadiene-styrene rubber composition is made in last washed, dehydration, dry, briquetting.Sampling
Analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Comparative example 4
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: with embodiment 3.
B. the preparation of modified Nano white carbon black: with embodiment 4.
(2) preparation of tire tread butadiene-styrene rubber composition: other conditions are same as Example 4, the difference is that
Polyacrylic acid is not added, it may be assumed that take 100 parts of styrene-butadiene latex SBR1500 (butt matter) and 7.5 parts of carboxylic styrene butadiene latexes, 3.5 parts of dodecanes
Base benzene sulfonic acid sodium salt, 150 parts of deionized waters are added in condensing field and are stirred 15min, and 35 parts of modified Nano hard charcoals are then added
It is black, with sodium hydroxide regulation system pH value be 8.9, when being warming up to 55 DEG C, be stirred 35min, then be added 4.0 parts of hydrochloric acid into
Tire tread butadiene-styrene rubber composition is made in row cohesion, last washed, dehydration, dry, briquetting.Sampling analysis: through vulcanizing
Standard sample is made, test performance is shown in Table 1.
Comparative example 5
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: with embodiment 3.
B. the preparation of modified Nano white carbon black: other conditions are same as Example 5, the difference is that in-situ polymerization process
In initiator ammonium persulfate is not added, 1,3- hexadiene pre-emulsion b is that dialogue carbon black particle surface is coated, it may be assumed that takes 100
Part Nano carbon white (40nm) and 3.8 parts of methacrylic acids (MAA), 280 parts of deionized waters, 2.9 parts of sodium hydroxides are added to poly-
It closes in kettle and is stirred 28min；Then 4.5 parts of neopelexes, 8.5 parts of 1,3- hexadiene pre-emulsion b are added, stir
It mixes and is warming up to 65 DEG C, be stirred for the seed that mixing 30min generates the multiple emulsion centered on Nano carbon white powder；Then again
74 parts of 1,3- hexadiene pre-emulsion b are added, after reacting 3.0h, are eventually adding 0.25 part of diethyl hydroxylamine, washed, dehydration,
Modified Nano white carbon black a is made in dry, grinding.
(2) preparation of tire tread butadiene-styrene rubber composition: other conditions are same as Example 5, the difference is that
Modified Nano white carbon black is not added in preparation process, but is directly added into modified Nano white carbon black a, additional amount is 40 parts, it may be assumed that is taken
100 parts of styrene-butadiene latex SBR1500 (butt matter) and 8.0 parts of carboxylic styrene butadiene latexes, 4.0 parts of neopelexes, 170 parts go
Ionized water, which is added in condensing field, is stirred 17min, and 40 parts of modified Nano white carbon black a and 4.0 parts of polyacrylic acid are then added,
It is 9.1 with sodium hydroxide regulation system pH value, when being warming up to 55 DEG C, is stirred 35min, 4.5 parts of hydrochloric acid is then added and carry out
Tire tread butadiene-styrene rubber composition is made in cohesion, last washed, dehydration, dry, briquetting.Sampling analysis: it is made through vulcanization
At standard sample, test performance is shown in Table 1.
Comparative example 6
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: with embodiment 6.
B. the preparation of modified Nano white carbon black: with embodiment 6.
(2) preparation of tire tread butadiene-styrene rubber composition: other conditions are same as Example 6, the difference is that
The additional amount of carboxylic styrene butadiene latex is 4 parts in preparation process, it may be assumed that takes 100 parts of styrene-butadiene latex SBR1502 (butt matter) and 4 parts of carboxylics
Base styrene-butadiene latex, 5.0 parts of neopelexes, 200 parts of deionized waters are added in condensing field and are stirred 20min, so
50 parts of modified Nano white carbon blacks and 4.0 parts of polyacrylamides are added afterwards, is 9.0 with sodium hydroxide regulation system pH value, is warming up to
At 55 DEG C, it is stirred 35min, 5.5 parts of sulfuric acid are then added and are condensed, last washed, dehydration, dry, briquetting are made
Tire tread butadiene-styrene rubber composition.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
Comparative example 7
(1) preparation of modified Nano white carbon black:
A. prepared by monomer pre-emulsion: with embodiment 6.
B. the preparation of modified Nano white carbon black: with embodiment 7.
(2) preparation of tire tread butadiene-styrene rubber composition: the difference is that in preparation process acrylamide plus
Entering amount is 0.8 part, it may be assumed that takes 100 parts of styrene-butadiene latex SBR1502 (butt matter) and 9.0 parts of carboxylic styrene butadiene latexes, 4.5 parts of dodecanes
Base benzene sulfonic acid sodium salt, 200 parts of deionized waters are added in condensing field and are stirred 15min, and 45 parts of modified Nano hard charcoals are then added
Black and 0.8 part of polyacrylamide is 9.0 with sodium hydroxide regulation system pH value, when being warming up to 55 DEG C, is stirred 35min, so
6.0 parts of sulfuric acid are added afterwards to be condensed, last washed, dehydration, dry, briquetting are made tire tread and are combined with butadiene-styrene rubber
Object.Sampling analysis: standard sample is made through vulcanization, test performance is shown in Table 1.
The performance of table 1 tire tread butadiene-styrene rubber composition
As shown in Table 1: 0 DEG C of tan δ of embodiment is higher than comparative example, illustrates that prepare wet-sliding resistant performance good for tire；Implement
The 60 DEG C of fissipation factors (tan δ) and wear volume of example are lower than comparative example, illustrate that the rolling resistance for tire preparation is low, wear-resisting
Property is good.
Claims (22)
1. a kind of rubber composition for tire tread, in terms of the mass parts of styrene butadiene rubber latex butt matter, mainly include with
Lower component:
It is characterized in that, the modified Nano white carbon black is prepared by following methods:
A. prepared by monomer pre-emulsion: in terms of the mass parts of conjugated diene monomer, by 100 parts of conjugated diene monomers, 5~10
Part emulsifier, 150~200 parts of deionized waters, 1.0~2.0 parts of buffers, 0.01~0.1 part of initiator are put into togerther reactor
In, when being warming up to 40~60 DEG C, it is stirred to react 30~50 minutes and is prepared into monomer pre-emulsion.
B. in terms of the mass parts of Nano carbon white, 100 parts of Nano carbon whites and 1.0~5.0 preparation of modified Nano white carbon black: are taken
Part unsaturated carboxylic acid polar monomer, 200~300 parts of deionized waters, 1~5 part of buffer are added in polymeric kettle and are stirred 10
~30min；Then 1~5 part of emulsifier, 5~10 parts of monomer pre-emulsions is added, stirring is warming up to 50~70 DEG C, is stirred for mixing
It closes 10~30min and generates the polymerization coated centered on Nano carbon white powder by carboxylic acid polar monomer and conjugated diene monomer
Body, and using this as the seed of multiple emulsion；Then 60~80 parts of monomer pre-emulsions and 0.05~0.2 part of initiation are added
Agent after reacting 2.0~5.0h, is eventually adding 0.1~0.3 part of terminator, and modified Nano is made in washed, dehydration, dry, grinding
White carbon black.
The carboxylic styrene butadiene latex is using butadiene, styrene as main monomer, and unsaturated carboxylic acid is function monomer through emulsion polymerization
It obtains, solid content is 40~55%, and latex particle size is 100~170nm, and the unsaturated carboxylic acid is acrylic acid, methyl-prop
One of olefin(e) acid or 2- ethylacrylic acid；
The water soluble polymer is to contain polyethylene backbone in molecular structure, and side group is the compound of hydrophilic radical, is selected from
Polyvinylpyrrolidone, 4- polyvinyl pyridine, polyacrylamide, polyacrylic acid, polymethylacrylic acid, polymethylacrylic acid hydroxyl second
One of ester.
2. rubber composition as described in claim 1, which is characterized in that the partial size of the modified Nano white carbon black are as follows: 20~
60nm。
3. rubber composition as described in claim 1, which is characterized in that the unsaturated carboxylic acid polar monomer is selected from propylene
One of acid, methacrylic acid, maleic anhydride.
4. rubber composition as claimed in claim 3, which is characterized in that the unsaturated carboxylic acid polar monomer is metering system
Acid.
5. rubber composition as described in claim 1, which is characterized in that the conjugated diene is carbon atom number from C4~Cl2
Conjugated diene, be selected from 1,3-butadiene；Isoprene；2,3- dimethyl -1,3 butadiene；2,3- diethyl -1,3 fourths two
Alkene；2- methyl -3- ethyl -1,3 butadiene；The chloro- 1,3-pentadiene of 2-；1,3-pentadiene；3- butyl -1,3- octadiene；2- benzene
Base -1,3-butadiene；The mixture of one or more of 1,3- hexadiene.
6. rubber composition as claimed in claim 5, which is characterized in that the conjugated diene is 1,3- hexadiene.
7. rubber composition as described in claim 1, which is characterized in that the initiator is water-soluble thermal initiator, is selected from
Bis- (the 2- amidine oxazoline propane) hydrochlorides of ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, 2,2- azo, 2,2- azo [2- (2- imidazoles
Quinoline -2- base) propane] dihydrochloride one or more of mixtures.
8. rubber composition as claimed in claim 7, which is characterized in that the initiator is ammonium persulfate.
9. rubber composition as described in claim 1, which is characterized in that the styrene butadiene rubber latex is by conjugated diene hydrocarbonylation
It closes object and aryl ethylene class compound is copolymerized by emulsion polymerization.
10. rubber composition as claimed in claim 9, which is characterized in that the conjugated diene hydrocarbon compound is C4Class conjugation two
Olefin(e) compound.
11. rubber composition as claimed in claim 9, which is characterized in that the aryl ethylene class compound be selected from styrene,
One of α-methylstyrene, 2- propenyl benzene, ethyl styrene and their derivative.
12. such as the described in any item rubber compositions of claim 9~11, which is characterized 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.
13. rubber composition as described in claim 1, which is characterized in that the unsaturated carboxylic acid is acrylic acid.
14. rubber composition as described in claim 1, which is characterized in that the water soluble polymer is polyacrylic acid.
15. the method as described in claim 1, which is characterized in that the terminator be selected from diethyl hydroxylamine, hydroxyl sulfate,
The mixture of one or more of Sodium Dimethyldithiocarbamate.
16. the preparation method of rubber composition as described in claim 1, which comprises the following steps:
(1) in terms of the mass parts of styrene-butadiene latex butt matter, 100 parts of styrene-butadiene latexes and 5~10 parts of carboxylic styrene butadiene latexes, 2~5 parts are taken
Emulsifier, 100~200 parts of deionized waters are added in condensing field and are stirred 10~20min；
(2) 20~50 parts of modified Nano white carbon blacks and 1~5 part of water soluble polymer are added, with buffer regulation system pH value
It is 8~11, when being warming up to 50~60 DEG C, is stirred 30~50min；
(3) 3~6 parts of flocculating agents are added to be condensed, tire tread is made with butylbenzene rubber in last washed, dehydration, dry, briquetting
Glue composition.
17. the method described in claim 16, which is characterized in that the flocculating agent is hydrochloric acid, in sulfuric acid, phosphoric acid, nitric acid
One or more of mixtures.
18. the method described in claim 16, which is characterized in that the emulsifier is anion emulsifier and non-ionic emulsifier
The mixture of one or more of agent.
19. method as claimed in claim 18, which is characterized in that the emulsifier is selected from fatty acid soaps, RA rosin acid, 12
The mixture of one or more of sodium alkyl benzene sulfonate, lauryl sodium sulfate, polyoxyethylene sorbitol acid anhydride list olein.
20. method as claimed in claim 19, which is characterized in that the emulsifier is neopelex.
21. the method described in claim 16, which is characterized in that the buffer is selected from sodium carbonate, sodium bicarbonate, hydroxide
One of sodium, ammonium hydroxide, ammonium hydrogen carbonate.
22. method as claimed in claim 21, which is characterized in that the buffer is sodium hydroxide.
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| JP2002080642A (en) * | 2000-09-08 | 2002-03-19 | Sumitomo Rubber Ind Ltd | Rubber composition for tread, and tire obtained using the same |
| CN1437635A (en) * | 2000-05-22 | 2003-08-20 | 米其林技术公司 | Composition for tyre running tread and method for preparing same |
| CN102558627A (en) * | 2011-12-23 | 2012-07-11 | 北京化工大学 | Preparation method of white carbon black modified styrene-butadiene rubber facing green tires and product thereof |
| CN103509159A (en) * | 2013-09-23 | 2014-01-15 | 北京石油化工学院 | Grafting modification method for solution-polymerized styrene-butadiene rubber with low gel rate |
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|---|---|---|---|---|
| CN1437635A (en) * | 2000-05-22 | 2003-08-20 | 米其林技术公司 | Composition for tyre running tread and method for preparing same |
| JP2002080642A (en) * | 2000-09-08 | 2002-03-19 | Sumitomo Rubber Ind Ltd | Rubber composition for tread, and tire obtained using the same |
| CN102558627A (en) * | 2011-12-23 | 2012-07-11 | 北京化工大学 | Preparation method of white carbon black modified styrene-butadiene rubber facing green tires and product thereof |
| CN103509159A (en) * | 2013-09-23 | 2014-01-15 | 北京石油化工学院 | Grafting modification method for solution-polymerized styrene-butadiene rubber with low gel rate |
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