CN102050973B - Tread rubber composite material and preparation method thereof - Google Patents
Tread rubber composite material and preparation method thereof Download PDFInfo
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- CN102050973B CN102050973B CN2009102359272A CN200910235927A CN102050973B CN 102050973 B CN102050973 B CN 102050973B CN 2009102359272 A CN2009102359272 A CN 2009102359272A CN 200910235927 A CN200910235927 A CN 200910235927A CN 102050973 B CN102050973 B CN 102050973B
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Abstract
The invention provides a tread rubber composite material and a preparation method thereof, relating to the technical field of tyres, wherein the tread rubber composite material is prepared from 100 parts by weight of rubber and 2-30 parts by weight of composite powder. The composite powder comprises inorganic particles and rubber particles, wherein the weight ratio of the rubber particles to the inorganic particles is 1:6 to 6: 1. The composite powder is prepared by uniformly mixing and drying raw materials including irradiated synthetic rubber latex and slurry liquid of the inorganic particles. The composite powder can excellently reinforce the rubber so that the tread rubber composite material has the advantages of better mechanical property after aging, lower abrasion consumption, lower fatigue compression themogenesis and higher slippery-resistant performance and higher tearing intensity. Meanwhile, the preparation method of the tread rubber composite material has the advantages of simple process, easiness for operation and industrialization, low cost and wide use range.
Description
Technical field
The present invention relates to the tire field, say further, relate to a kind of tire tread glue matrix material and preparation method thereof.
Background technology
Rolling resistance, anti-slippery and wear resistance are tire " three big rideabilities ", influence each other, restrict between three performances, are difficult to realize the balance optimizing between the three, so the title of tyre performance " Magic triangle " is arranged.The ideal tread rubber should possess the comprehensive premium propertiess such as wear resistance that low rolling resistance, high anti-slippery are become reconciled.Traditional method of modifying of tread rubber is the prescription of adjustment tread rubber matrix material, like novel rubber raw materials of Application and Development and new packing etc.Nanometer inorganic fillers such as application WHITE CARBON BLACK prepare the focus that green tread rubber matrix material is current tread rubber matrix material research, visible " rubber nano composite material progress " (Yan Zhiyun, the Judd people of pertinent literature; The Guangdong chemical industry, 2005,32 (3): 34-37,53), and " application of high dispersion gel-free white carbon black in tire tread glue " (Yu Huaying, Liu Rong, tire industry, 2006,26 (1): 32-35).But the agglomeration power of nano grade inorganic particle is strong, and the poor processability of filler gum is difficult to be dispersed in the rubber matrix.Realize the nano-dispersed of nano grade inorganic filler in rubber external phase, improve the interface binding power between nano inoganic particle and rubber, become a difficult problem of preparation high-performance tire tread rubber nano composite material.
Summary of the invention
For solving the problem that the nano inoganic particle that exists in the prior art is difficult to be dispersed in rubber matrix, the invention provides a kind of tire tread glue matrix material that adopts rubber particles and the nano inorganic particle compounded composite powder that becomes to prepare.
One of the object of the invention provides a kind of tire tread glue matrix material.
Tire tread glue matrix material of the present invention comprises following component: rubber and composite powder, and rubber raw rubber is in 100 parts of weight parts, and the composite powder parts by weight are 2～30 parts, are preferably 4～20 parts, more preferably 5～15 parts.
Composite powder includes rubber particles and inorganic particulate, and the weight ratio of rubber particles and inorganic particulate is 1: 6～6: 1, and preferred 1: 4～4: 1, more preferably 1: 3～3: 1.
Wherein himself gel content of the rubber particles that contains of composite powder is 60% weight or higher, preferred 75% weight or higher.The kind of said rubber particles is selected from least a in the following rubber kind: styrene-butadiene rubber(SBR), carboxylic styrene-butadiene rubber, paracril, carboxy nitrile rubber, cis-1,4-polybutadiene rubber, Zylox, esters of acrylic acid rubber.
The inorganic particulate that wherein contains in the composite powder comprises one or more in metallic salt, carbon black, WHITE CARBON BLACK and the clay; The preferred lime carbonate of wherein said metallic salt.Inorganic particulate particle median size is 1～100nm; Preferred 10～80nm.
Composite powder in the rubber combination of the present invention can adopt according to the method that provides among the Chinese patent ZL03109108.3 (CN1239587C) and prepare.Promptly through will be, by required dry weight mixed and stir, then through dry prepared composite powder through irradiated synthetic rubber latex and inorganic particulate slurries etc.
Specifically, said composite powder is got by the method preparation that includes one of following steps:
A. adding or not adding under the situation of crosslinking coagent, adopt the high-energy radiation line source to carry out radiation vulcanization synthetic rubber latex;
B. again with the slurries of the above inorganic particulate, mix with synthetic rubber latex behind the above-mentioned irradiation, obtain mixed emulsion;
C. again that above-mentioned mixed emulsion is dry.
The ratio of the weight (dry weights of the slurries of inorganic particulate) of contained inorganic particulate is 1: 6～6: 1 in the slurries of weight of the rubber that above-described synthetic rubber latex is contained (being the solid content of rubber latex dry weight or rubber latex) and inorganic particulate, is preferably 1: 4～4: 1.
Among preparing method's step a of the above composite powder, used synthetic rubber emulsion liquid can be selected from SBR emulsion, carboxylic styrene-butadiene rubber emulsion, acrylonitrile-butadiene rubber latex, carboxy nitrile rubber emulsion, cis-1,4-polybutadiene rubber emulsion, Zylox emulsion, esters of acrylic acid rubber latex etc.
Among preparing method's step a of said composite powder, to the irradiance method of the irradiance method of rubber latex (comprise energetic ray line source that crosslinking coagent, irradiation dose, irradiation are used etc.) with preparation fully vulcanized powder rubber in Chinese patent ZL00816450.9 (WO01/40356) and the Chinese patent 01801656.1 (WO 01/98395).Crosslinking coagent can be do not used in rubber latex, also crosslinking coagent can be used.Used crosslinking coagent is selected from simple function group crosslinking coagent, two functional group's crosslinking coagents, trifunctional crosslinking coagent, four-functional group crosslinking coagent or polyfunctional group crosslinking coagent and arbitrary combination thereof.The instance of described simple function group crosslinking coagent includes, but is not limited to: (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) glycidyl acrylate; The instance of described two functional group's crosslinking coagents includes, but is not limited to: 1; 4-butyleneglycol two (methyl) propenoate, 1,6-pinakon two (methyl) propenoate, Diethylene Glycol two (methyl) propenoate, triethylene glycol two (methyl) propenoate, NSC 6366 two (methyl) propenoate, Vinylstyrene; The instance of described trifunctional crosslinking coagent includes, but is not limited to: trimethylolpropane tris (methyl) propenoate, tetramethylolmethane three (methyl) propenoate; The instance of described four-functional group crosslinking coagent includes, but is not limited to: tetramethylolmethane four (methyl) propenoate, ethoxyquin tetramethylolmethane four (methyl) propenoate; The instance of described polyfunctional group crosslinking coagent includes, but is not limited to: Dipentaerythritol five (methyl) propenoate.In this article, " (methyl) propenoate " refers to propenoate or methacrylic ester.These crosslinking coagents can use with the mode of arbitrary combination, as long as they help sulfuration under irradiation.
The add-on of the above crosslinking coagent is generally 0.1～10% weight of dried glue weight in the emulsion with the kind and different variation of prescription of rubber latex.Be preferably 0.5～9% weight, more preferably 0.7～7% weight.
The energetic ray source is selected from cobalt source, ultraviolet or high-energy electron accelerator among preparing method's step a of described composite powder, preferred cobalt source.The dosage of irradiation can be 0.1～30Mrad, preferred 0.5～20Mrad.The dosage of irradiation is relevant with prescription with the kind of rubber latex.Generally speaking, irradiation dose should make the gel content behind the rubber latex radiation vulcanization reach 60% weight or higher, preferred 75% weight or higher, more preferably 80% weight or higher.
Behind the irradiation that above method steps a obtains in the synthetic rubber latex median size of rubber particles be 50～200nm, be preferably 50～150nm.
The slurries of inorganic particulate described in the above method steps b are the suspension-s of said inorganic particulate in water; Can directly adopt commercial slurries product; With need before rubber latex is mixed to disperse through common dispersing apparatus (like high-shear emulsifying agent, colloidal mill etc.), can in water, be uniformly dispersed to guarantee the solids in the slurries.If inorganic particulate does not have the slurries of commercial grade, also can make by oneself, promptly adopt conventional dispersing apparatus to make inorganic particulate and an amount of water form steady suspension, mix with rubber latex then.
Among the step b, can make it to mix through fully stirring described in the above method in the synthetic rubber latex behind the equilateral stirring of slurries limit adding a kind of (or multiple) irradiation of a kind of (or multiple) inorganic particulate.The solid content (drc) of rubber latex and the solid content (dry weights of the slurries of inorganic particulate) of inorganic particulate are not limited especially.
The drying means that is adopted in the drying process of step c described in the above method can adopt the common drying means of prior art, like co-precipitation drying, spraying drying etc.Drying means during preferably with Chinese patent ZL00816450.9 (WO 01/40356) and the middle preparation of Chinese patent 01801656.1 (WO 01/98395) fully vulcanized powder rubber; Be that drying process can be carried out with spray-dryer; Inlet temperature can be controlled at 100～200 ℃, and temperature out can be controlled at 20～80 ℃.By the contained rubber content of the composite powder of above two kinds of method gained in step a with irradiation after synthetic rubber latex in rubber gels content consistent.
Another object of the present invention is the preparation method of tire tread rubber composite.
The preparation method of tire tread rubber composite of the present invention is: rubber raw rubber and the said composite powder that will comprise said kind in interior component by the mixing rubber combination that makes of said amount.In rubber raw rubber is 100 parts by weight, and composite powder weight is 2～30 parts by weight, is preferably 4～20 parts by weight.Said rubber raw rubber comprises a kind of in tree elastomer, styrene-butadiene rubber(SBR) and the cis-1,4-polybutadiene rubber, or presses the epoxy glue of two or more said rubber raw rubber that arbitrary proportion forms.
The calendering process that the present invention prepares the tire tread rubber composite adopts existing rubber mixing-milling technique in the prior art.Employed mixing facilities is the general blending equipment of rubber and plastic processing industry kind, can make mill, Banbury mixer, single screw extrusion machine or twin screw extruder etc.
The present invention prepares the influence that the tire tread rubber composite does not receive vulcanization system, can in the sulfur cross-linking system of routine or non-sulfur cross-linking system, vulcanize.The present invention prepares the influence that rubber combination does not receive sulfuration process, can compression molding, injection sulfurization, sulfurizing pot vulcanization, individual vulcanizer sulfuration, the sulfuration of congruent melting salt, fluidized bed vulcanization, microwave vulcanization and energetic ray sulfuration etc.
Owing to contain rubber particles in the tire tread rubber composite, can improve the deficiency of rubber raw materials performance, owing to contain inorganic particulate in the tire tread rubber composite, can substitute the carbon black reinforced rubber simultaneously.Rubber particles and inorganic particulate compound makes tread rubber matrix material of the present invention have lower abrasion, lower compression heat generation and higher anti-slippery; Good aging back mechanical property, and keep higher draw tensile strength, tensile yield and tear strength simultaneously.Preparing method's technology that must this rubber combination provided by the present invention is simple, easy handling, and cost is low, use is wide, is easy to industriallization.
Tire tread glue matrix material among the present invention contains Synergist S-421 95s such as black-reinforced system, preventing aging system, vulcanization system, identical among the adding method of above Synergist S-421 95 and consumption and the common tread rubber preparation technology.
In the mixing process of said composite powder and rubber raw rubber; With the rubber particles particle in the composite powder serves as to disperse to drive carrier; Can realize that rubber particles particle and the nano grade inorganic particle particle nano level in rubber matrix disperses, increase the interface interaction power between rubber external phase and the disperse phase such as rubber particles and nano inoganic particle, the effect of performance nanoparticle; The over-all properties of tread rubber matrix material can be improved, and the sooty consumption can be reduced in right amount.
Tire tread glue matrix material of the present invention can be realized the nano-dispersed of rubber particles in tread rubber; Also can realize the nano-dispersed of nano inoganic particle in tread rubber; Give full play to the effect that improves the tire tread glue performance of rubber particles and nano inoganic particle; The rolling resistance of balance optimizing tire tread glue, anti-slippery and wear resistance comprehensively improve the performance of tire tread glue.
Embodiment
Below in conjunction with embodiment, further specify the present invention.
Embodiment 1
The composite powder preparation:
With solid content is that (Shanghai Gaoqiao petro-chemical corporation produces, and the trade mark: butylbenzene-5050) 4kg places container, stirs on the limit to drip Viscoat 295 54g down, after being added dropwise to complete, continues stirring one hour for the commercially available SBR emulsion of 45% weight.Use cobalt-60 radiosterilize afterwards, dosage is 0.5Mrad, and dose rate is 50Gy/min, obtains the irradiation SBR emulsion, and wherein the gel content of rubber particles is 85%, and average particle size is 100nm.With Nano carbon white (SiO
2, Shandong Zibo Hai Nagaoke Materials Co., Ltd produces, and particle size range is 20-40nm) mix by the concentration of 5% weight with water, disperse through the high-shear dispersion machine, place for some time.Irradiation SBR emulsion and above-mentioned WHITE CARBON BLACK slurries are cooperated in 50: 50 ratios of dry weight separately; Stirred one hour; Then mixed solution is passed through the spray-dryer spraying drying; The inlet temperature of spray-dryer is 140～160 ℃, and temperature out is 40～60 ℃, in cyclonic separator, collects dried styrene-butadiene rubber(SBR)/WHITE CARBON BLACK composite powder (UFPR/SiO
2).
The preparation of tire tread rubber composite:
With the above-mentioned composite powder UFPR/SiO for preparing
2With styrene-butadiene rubber(SBR) (SBR; ESBR-1502; Rubber plant of Qilu Petrochemical company) and tree elastomer (NR, NR5 standard glue, limited-liability company of Hainan tree elastomer industrial group) after two roller mills mix; It is mixing to evenly to press the continuation of common process adding vulcanization system, obtains the compsn of composite powder and rubber thus.Press sulfurizing time T down at 160 ℃ then
90Vulcanize, obtain the vulcanized rubber print of tire tread glue matrix material, then the vulcanized rubber print is processed the standard batten, carry out each item Mechanics Performance Testing, its result is as shown in table 2.
More than each set of dispense ratio see table 1, except styrene-butadiene rubber(SBR) and tree elastomer weight ratio are 80: 20, other each components are that the parts by weight of 100 parts by weight are represented in styrene-butadiene rubber(SBR) and tree elastomer gross weight all.Its related vulcanization system auxiliary agent: silane coupling agent (Si-69), solid paraffin, zinc oxide (ZnO), Triple Pressed Stearic Acid (Hst), accelerant CZ, anti-aging agent RD, anti-aging agent 4020, carbon black N330, Yellow Protopet 2A and sulphur are commercially available and get.
Comparative example 1
Styrene-butadiene rubber(SBR) (with embodiment 1) and tree elastomer (with embodiment 1) after two roller mills mix, are pressed common process and added vulcanization system and continue mixingly to evenly, obtain the compsn of composite powder and rubber thus.Each set of dispense ratio is seen table 1, and sulfuration process and other conditions are with embodiment 1.Then the vulcanized rubber print is processed the standard batten, carry out each item Mechanics Performance Testing, its result is as shown in table 2.
Comparative example 2
Need not prepare composite powder.Remove the styrene-butadiene rubber(SBR) in the tire tread glue/WHITE CARBON BLACK composite powder (UFPR/SiO
2) replace with outside the WHITE CARBON BLACK (with embodiment 1), all the other technologies and condition are all with embodiment 1.Each set of dispense ratio is seen table 1.The vulcanized rubber print is processed the standard batten, carry out each item Mechanics Performance Testing, its result is as shown in table 2.
Comparative example 3
Remove styrene-butadiene rubber(SBR)/WHITE CARBON BLACK composite powder (UFPR/SiO
2) replace with full sulfuration butylbenzene powdered rubber (UFPR; Method for making is that the irradiation SBR emulsion that embodiment 1 is obtained gets through carrying out drying with the identical technology of embodiment 1 drying process) and outside WHITE CARBON BLACK (with embodiment 1) added respectively, all the other technologies and condition were all with embodiment 1.Each set of dispense ratio is seen table 1.The vulcanized rubber print is processed the standard batten, carry out each item Mechanics Performance Testing, its result is as shown in table 2.
Table 1
Table 2
Find out that by table 1 embodiment 1, comparative example 1, comparative example 2 and comparative example 3 are to be the tread rubber matrix material of tread rubber matrix preparation with NR and SBR.Table 2 shows; Compare with the tread rubber matrix material of comparative example 1 (reinforcement system is 50 parts of carbon black N330), comparative example 2 (having dosed 10 parts of Nano carbon whites in the reinforcement system) and comparative example 3 (having dosed 5 parts of fully vulcanized powder rubbers and 5 parts of Nano carbon whites in the reinforcement system); The tread rubber matrix material of embodiment 1 (having dosed 10 parts of ultra-fine form of finely divided powder, mehtod styrene-butadiene rubber(SBR)/Nano carbon white nano composite powder systems) has lower abrasion, lower compression heat generation and higher anti-slippery (10 ℃ time tan δ value), and keeps higher draw tensile strength, tensile yield and tear strength simultaneously.
Embodiment 2
The composite powder preparation:
The irradiation SBR emulsion is with embodiment 1.Lime carbonate (median size is 40nm for CaCO3, Beijing University of Chemical Technology) is mixed by the concentration of 5% weight with water, disperse, place for some time through the high-shear dispersion machine.Irradiation SBR emulsion and above-mentioned calcium carbonate serosity are cooperated in 50: 50 ratios of dry weight separately; Stirred one hour; Then mixed solution is passed through the spray-dryer spraying drying; The inlet temperature of spray-dryer is 140～160 ℃, and temperature out is 40～60 ℃, in cyclonic separator, collects dried styrene-butadiene rubber(SBR)/lime carbonate composite powder (UFPR/CaCO
3).
The preparation of tire tread rubber composite:
With the above-mentioned UFPR/CaCO for preparing
3With styrene-butadiene rubber(SBR) (with embodiment 1) and cis-1,4-polybutadiene rubber (rubber plant of Qilu Petrochemical company produces for BR, BR-9000) after two roller mills mix, press common process and add vulcanization system and continue mixingly to even, obtain the compsn of composite powder and rubber thus.Each set of dispense ratio is seen table 2, and sulfuration process and other conditions are with embodiment 1.Then the vulcanized rubber print is processed the standard batten, carry out each item Mechanics Performance Testing, its result is as shown in table 4.
Comparative example 4
Styrene-butadiene rubber(SBR) (with embodiment 1) and cis-1,4-polybutadiene rubber (with embodiment 2) after two roller mills mix, are pressed common process and added vulcanization system and continue mixingly to evenly, obtain the compsn of composite powder and rubber thus.Each set of dispense ratio is seen table 2, and sulfuration process and other conditions are processed the standard batten with the vulcanized rubber print then with embodiment 1, carry out each item Mechanics Performance Testing, and its result is as shown in table 4.
Comparative example 5
Need not prepare composite powder.Remove the styrene-butadiene rubber(SBR) in the tire tread glue/lime carbonate composite powder (UFPR/CaCO
3) replace with outside the lime carbonate (with embodiment 2), all the other technologies and condition are all with embodiment 1.Each set of dispense ratio is seen table 2.The vulcanized rubber print is processed the standard batten, carry out each item Mechanics Performance Testing, its result is as shown in table 4.
Comparative example 6
Remove styrene-butadiene rubber(SBR)/lime carbonate composite powder (UFPR/CaCO
3) replace with full sulfuration butylbenzene powdered rubber (UFPR; Method for making is that the irradiation SBR emulsion that embodiment 1 is obtained gets through carrying out drying with the identical technology of embodiment 1 drying process) and outside lime carbonate (with embodiment 2) added respectively, all the other technologies and condition were all with embodiment 1.Each set of dispense ratio is seen table 2.The vulcanized rubber print is processed the standard batten, carry out each item Mechanics Performance Testing, its result is as shown in table 4.
Find out that by table 3 embodiment 2, comparative example 4, comparative example 5 and comparative example 6 are to be the tread rubber matrix material of tread rubber matrix preparation with BR and SBR.Table 4 shows; Compare with the tread rubber matrix material of comparative example 4 (reinforcement system is 50 parts of carbon black N330), comparative example 5 (having dosed 10 parts of nano-calcium carbonates in the reinforcement system) and comparative example 6 (having dosed 5 parts of ultra-fine fully vulcanized powder rubbers and 5 parts of nano-calcium carbonates in the reinforcement system); The tread rubber matrix material of embodiment 2 (having dosed 10 parts of ultra-fine form of finely divided powder, mehtod styrene-butadiene rubber(SBR)/lime carbonate composite powder systems) has preferably aging back mechanical property, lower tired compression heat generation and higher anti-slippery, also has higher tear strength.
Table 3
Table 4
* annotate: adopt hot air aging, experimental temperature is 100 ℃, and the time is 48 hours, reference standard GB/T 3512-2001.
Claims (10)
1. tire tread glue matrix material, include following component: rubber and composite powder are 100 parts by weight in rubber wherein, and the consumption of composite powder is 2～30 parts by weight;
Said rubber is one or more of tree elastomer, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber;
Said composite powder includes rubber particles and inorganic particulate, and wherein the weight ratio of rubber particles and inorganic particulate is 1: 6～6: 1; Said composite powder is prepared by the method that comprises following steps:
A. adding or not adding under the situation of crosslinking coagent, adopt the high-energy radiation line source to carry out radiation vulcanization synthetic rubber latex;
B. again with the slurries of inorganic particulate, mix with synthetic rubber latex behind the above-mentioned irradiation, obtain mixture slurry;
C. again that above-mentioned gained mixture slurry is dry;
Above-described inorganic particulate slurries are the suspension-s of inorganic particulate in water; Described inorganic particulate comprises one or more in metallic salt, carbon black, WHITE CARBON BLACK and the clay; Its inorganic particulate particle median size is 1～100nm;
The weight ratio of contained inorganic particulate is 1: 6～6: 1 in the weight of the rubber that described synthetic rubber latex is contained and the slurries of inorganic particulate.
2. tire tread glue matrix material as claimed in claim 1 is characterized in that:
In rubber is 100 parts by weight, and said composite powder is 4～20 parts by weight.
3. tire tread glue matrix material as claimed in claim 1 is characterized in that:
The rubber particles that said composite powder comprises and the weight ratio of inorganic particulate are 1: 4～4: 1; The weight ratio of contained inorganic particulate is 1: 4～4: 1 in the weight of the rubber that synthetic rubber latex described in the preparation method of said composite powder is contained and the slurries of inorganic particulate.
4. tire tread glue matrix material as claimed in claim 1 is characterized in that:
The gel content of rubber particles is more than the 60%wt in the said composite powder.
5. tire tread glue matrix material as claimed in claim 4 is characterized in that:
The gel content of the rubber particles in the said composite powder is more than the 75%wt.
6. tire tread glue matrix material as claimed in claim 1 is characterized in that:
The median size of rubber particles is 50～200nm in the synthetic rubber latex among the said composite powder preparation method behind the irradiation.
7. tire tread glue matrix material as claimed in claim 1 is characterized in that:
Metallic salt in the said inorganic particulate is a lime carbonate.
8. tire tread glue matrix material as claimed in claim 1 is characterized in that:
Said inorganic particulate particle median size is 10～80nm.
9. tire tread glue matrix material as claimed in claim 1 is characterized in that:
Said synthetic rubber latex is a kind of in SBR emulsion, carboxylic styrene-butadiene rubber emulsion, acrylonitrile-butadiene rubber latex, carboxy nitrile rubber emulsion, esters of acrylic acid rubber latex, cis-1,4-polybutadiene rubber emulsion, the Zylox emulsion.
10. preparation method who prepares each described tire tread glue matrix material of claim 1～9 is characterized in that:
To comprise the rubber raw rubber of said kind and said composite powder is mixing by said amount in interior component, sulfuration makes described tire tread glue matrix material.
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| CN1754907A (en) * | 2004-09-29 | 2006-04-05 | 中国石油化工股份有限公司 | Enhanced full vulcanizing polyolefine thermoplastic elastomer and preparation process thereof |
| CN101215390A (en) * | 2007-12-28 | 2008-07-09 | 北京化工大学 | High-performance engineering tire tread sizing material |
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