CN101885862A - Rubber nano short fiber composite material for automobile tire and preparation method thereof - Google Patents
Rubber nano short fiber composite material for automobile tire and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a rubber nano short fiber composite material for an automobile tire and a preparation method thereof. By modifying needle-like silicate through a CO2 supercritical method, the needle-like silicate is dissociated into nano short fiber in the process of mixing with a rubber matrix, and soft carbon black is added. The prepared composite material is used as an automobile tire apex, and has the characteristics of high hardness, high modulus, low heat generation, and excellent processability.
Description
Technical field:
The present invention relates to a kind of rubber nano short fiber composite material for automobile tire and preparation method thereof, be applied to the triangle glue of doughnut, can obviously improve the hardness and the modulus of triangle glue.
Background technology:
Current China doughnut, particularly tyres for passenger cars all are radial, and in use suffered stress is rather complicated, requires tyre bead portion to have high intensity and fatigue performance.Triangular shape core glue (being called for short triangle glue) is the tyre bead portion important components, plays a part to fill, locate, meet with stresses, and its hardness directly influences the rigidity of tyre bead portion.Triangle glue is positioned at Steel Traveler upper end, plays a part to fill and reinforced bead, not only plays an important role to improving the distribution of radial lateral rigidity, and while and sidewall district rigid-flexibility transition are will all even subduing property good.Favorable rigidity (high rigidity, high-modulus) is the necessary performance requriements of tyre triangular glue.
Has high modulus and hardness in order to ensure triangle glue, art methods is to add in rubber: the hard (carbon) black and the soft carbon of (1) high consumption, (2) resol, high styrene resin, cobalt salt etc. increase hard agent, (3) staple fibre, or (4) high sulphur dosage improves the hardness and the modulus of material.
High consumption uses carbon black to remain the main stream approach of triangle glue preparation field, though yet the carbon black of high consumption can improve the Young's modulus of triangle glue effectively, but also can obviously improve the loss tangent of material, like this in vehicle traveling process, triangle glue generates heat easily, its thermal fatigue can have a strong impact on the weather resistance of tire, reduces the work-ing life of tire.In addition, carbon black improves being limited in scope of rubber vulcanizate module, uses carbon black can't satisfy the needed high-modulus performance of tyre triangular glue separately.Because the limited and environmental problem of petroleum resources, the feed rate of oil reduces year by year again, and price improves year by year, and carbon black etc. will be subjected to serious restriction from the starting material of petroleum resources so.
Compare with the carbon black reinforced rubber modulus is low, cut-fiber reinforcement rubber composite material had both had the elasticity of rubber, had kept the strength and stiffness of fiber simultaneously again, and goods have high strength, high-modulus, premium properties such as tear-resistant.Yet micron staple fibre, as nylon, polyester, terylene, the virtue staple fibre etc. that sinks, though the modulus of matrix material is increased substantially, but because its length is longer, fiber is difficult to be dispersed in uniformly in the rubber matrix, processing characteristics is relatively poor, and the modulus of matrix material can descend behind the dynamic heat build up, so still can not well satisfy the needed performance requriements of tyre triangular glue.
The patent of Koji Ishiguchi (CODEN:JKXXAF JP 07330962 A 19951219Heisei) discloses a kind of technology, this technology is not used carbon black, but adopt polyolein fiber to prepare the triangle glue matrix material of low mooney viscosity, the fibre-reinforced thermoplastic composite of preparation comprises polyolefine, vulcanized rubber, contains thermoplastic resin, the polyolein fiber of amide group, and the tensile strength of material can be up to 283kg/cm
2, but performances such as its processing characteristics, dynamic heat build up performance, driving stability are not fully improved.
Nano short fiber not only has the distinctive strength and stiffness of fiber, also has characteristics such as easy dispersion, processing characteristics be good.Fibrillar silicate is a kind of moisture rich zeopan mineral of natural stratiform that include nano short fiber, in China river, Zhejiang, area, Anhui contains abundant.Its chemical structure is: Mg
5Si
8O
20(HO)
2(OH
2)
44H
2O.People such as Tian Ming disclose a kind of method for preparing rubber/fibrillar silicate matrix material in " preparation method of a kind of nano silicate fiber and rubber composite " (publication number CN1775836A), use the rubber/fibrillar silicate matrix material of this method preparation can make fibrillar silicate reach the rank of nano-dispersed, play the effect of nano short fiber enhanced.Fibrillar silicate after the surface modification is the energy homodisperse in rubber matrix, and combines well with rubber surface, thereby makes rubber/fibrillar silicate matrix material have good mechanical performance and anisotropic properties.Yet this inventive method is abundant inadequately to the modification of fibrillar silicate, under the situation of high consumption, fibrillar silicate can not be dissociated into nanofiber fully, can there be more aggregate, so that the tensile strength of matrix material and stress at definite elongation improve lower, greatly reduce the reinforced effects of fibrillar silicate.
Summary of the invention:
The purpose of this invention is to provide a kind of rubber nano short fiber composite material for automobile tire and preparation method thereof, pass through CO
2Supercritical methanol technology is carried out modification to fibrillar silicate, with the mixing process of rubber matrix in be dissociated into nano short fiber, add soft carbon simultaneously, prepare high rigidity and high-modulus matrix material.
A kind of rubber nano short fiber composite material for automobile tire provided by the invention, it is formed and mass fraction is:
100 parts of diene series rubber matrixes,
30～100 parts of modified acicular silicate,
Median size is 20～60 parts of the soft carbons of 31～200nm,
0～10 part of paraffin oil,
6～10 parts of promoting agents,
0.5～4 part in anti-aging agent,
1～4 part of vulcanization accelerator,
1～5 part of Sulfur;
Wherein the diene series rubber matrix is a kind of epoxy glue of forming with 4: 1～9: 1 mass ratio in natural rubber or natural rubber and epoxy natural rubber, styrene-butadiene rubber(SBR) or the cis-1,4-polybutadiene rubber.The rubber of any single variety all has such or such shortcoming, in order to satisfy the many-sided technical requirements of triangle glue, rubber matrix of the present invention is based on natural rubber (NR), select to add other rubber of part, by suitable cooperation, to learn from other's strong points to offset one's weaknesses, profit is asked the reasonable balance that makes between performance and performance, performance and the cost, fully reduce rolling resistance, improve hardness, improve weather resistance and resistance to fatigue, prepare to have and meet the vulcanized rubber that triangle glue various aspects of performance requires.
Modified acicular silicate adopts granularity to be not less than the natural fibrillar silicate of 1000 purposes through CO
2Supercritical methanol technology modification and getting, concrete method of modifying is: is 3～24: 1～8 with silane coupling agent, trolamine and fibrillar silicate with mass ratio: 30～100 ratio, add in the reactor, and add dry ice then, under the agitation condition, the airtight temperature that is heated to of reactor is 40 ℃～100 ℃, and pressure 10～14MPa reacted 1～2 hour, after reaction finishes, with the reactor atmospheric pressure state that reduces pressure, to be cooled, obtain modified acicular silicate.
Described silane coupling agent is vinyltriethoxysilane, γ-(2,3 epoxies, third oxygen) propyl trimethoxy silicane, two-[γ-(triethoxysilicane) propyl group] tetrasulfide, vinyltriethoxysilane or γ-methacryloxypropyl trimethoxy silane.
Described soft carbon is selected the product of the following trade mark: N539, N550, N660, N642 or N770 for use.
The above-mentioned doughnut of the present invention preparation method of nano short fiber rubber composite, comprise the following steps: at first in Banbury mixer, to add rubber, modified acicular silicate successively, mix 10～15min at 130～150 ℃, add promoting agent, vulcanization accelerator, anti-aging agent, soft carbon, paraffin oil then, be cooled to 40～50 ℃ at last, add Sulfur and mix, sulfuration obtains rubber composite.
Fibrillar silicate (FS) chemical structure is: Mg
5Si
8O
20(HO)
2(OH
2)
44H
2O, its crystalline structure is: each unit layer has the double-stranded wafer of upper and lower 2 silicon-oxy tetrahedrons, 5 aluminum-oxygen tetrahedrons of therebetween, each unit layer connects into the crystalline structure of duct formula each other by oxygen, form fibrous monocrystalline (being straight needle-like, bar-shaped or fibrous), single crystal diameter mostly is the 10-25 nanometer greatly more, and length is generally the 100-1500 nanometer, monocrystalline length even reach tens microns in the FS kind that has depends on the ore deposit point.The FS monocrystalline generally can closely be arranged in parallel, and becomes brilliant the bundle, and brilliant bundle is assembled and the FS particle of formation micron level again mutually.Because monocrystalline inside is pore passage structure, simultaneously, also formed numerous Parallel Tunnel spaces between the nano crystal fiber that is arranged in parallel naturally, thereby the intragranular void volume of the FS of micron level accounts for more than 30% of particle cumulative volume, inside has huge surface-area.On the other hand, FS is dispersed in the liquid easily, is dissociated into fibrous particle and scatters interlacing anyhow gelinite, rich thixotropic behavior.
Under supercritical state, because supercutical fluid has very high spread coefficient, some reactions for being subjected to spreading restriction can improve the scope of reaction greatly, make reaction more abundant.At supercritical CO
2Under the fluidic effect, FS fully is dissociated into fibrous particle and is dispersed in CO
2In the fluid, be dissolved in CO
2Properties-correcting agent in the fluid then can infiltrate the FS crystals, fully contact with FS, make the FS surface produce more Si-O-Si key, not only effectively reduce the cohesive force between the FS fiber, stop secondary to be assembled, it is tightr in follow-up sulfidation FS to be combined with rubber interface.
Fibrillar silicate is as a kind of polar mineral filler, can obviously improve the modulus of matrix material, but and the affinity between the nonpolar organic polymer is poor, the interpolation silane coupling agent can improve fibrillar silicate and combine with the interface of rubber, the dispersiveness of raising in matrix, thus reinforced effects improved.The present invention adopts granularity to be not less than 1000 purpose fibrillar silicates through CO
2Supercritical methanol technology is handled, and properties-correcting agent fully is immersed in the fibrillar silicate crystal duct, and the active hydroxyl generation chemical reaction on properties-correcting agent and fibrillar silicate surface forms the Si-O-Si key.So not only reduce the interfibrous cohesive force of fibrillar silicate, improved the dispersion of fibrillar silicate in rubber, also make fibrillar silicate surface generate more Si-O-Si key, improved with the interface of rubber matrix and combine, improve the matrix material reinforced effects.
Compare with traditional reinforcing filler-particulate state carbon black, micron fibrillar silicate particle is dissociated into nanofiber and is dispersed in the rubber, matrix material shows the mechanical characteristic (as Gao Dingshen under the low strain, high-tear strength and tangible anisotropy) and the high rigidity of cut-fiber reinforcement rubber composite material, and the raising to the stress at definite elongation of matrix material, hardness, modulus obviously is better than carbon black especially.On the other hand, the absolute length of nano short fiber is little, and its processing characteristics and apparent property are much better than a micron cut-fiber reinforcement rubber composite material.Therefore, rubber/FS nano composite material is particularly suitable for preparing tyre triangular glue.
The carbon black that the present invention adopts is the soft carbon of median size at 31～200nm, have the high stress at definite elongation of HMF high modulus furnace black concurrently, the excellent machinability of fast extruding furnace black, the high resilience of semi-reinforcing furnace black and the flexible resistance of FF fine furnace black, thereby it has higher structure, particle is thin slightly, easily disperse in sizing material, the tensile strength of cross-linked rubber, tearing toughness and stress at definite elongation are higher, and are out of shape little, it is low to give birth to heat, and elasticity and flexible resistance are good.In matrix material,, not only can improve hardness, modulus, processing characteristics, the surface tackiness of material, can also keep the mechanical property of material to have anisotropy, better meet the each side requirement of triangle glue rubber performance with FS and usefulness.
Used promoting agent, anti-aging agent, the vulcanization accelerator of the present invention all be the Rubber processing field commonly used with known.Promoting agent can be selected zinc oxide and stearic mixture for use.Anti-aging agent can be selected antioxidant 4010NA, anti-aging agent RD or anti-aging agent 4020 for use.Vulcanization accelerator can be selected vulcanization accelerator NS, vulcanizating accelerant NOBS, vulcanization accelerator TT, accelerator CZ or accelerator DM for use.
Preparation method of the present invention does not relate to the organic solvent of rubber, needn't require rubber that the existence of water miscible liquid form is arranged, and the scope of application is wider, and technological process is simple.Compare with adding the micron staple fibre, matrix material of the present invention has good processability, the good characteristics of apparent property.Compare with adding hard (carbon) black, the inorganic fibre rigidity is higher, and modulus is higher, and especially the high temperature dynamic modulus is higher.
Can observe the deployment conditions of modified acicular silicate in rubber matrix by sem observation stretching section.Adopt the matrix material of method for preparing of the present invention, from accompanying drawing 1, can observe modified acicular silicate and be dissociated into the nanofiber of diameter less than 100nm, and be uniformly dispersed, fiber is extracted not obvious, this explanation modified acicular silicate combines well with rubber matrix, plays the effect of nanofiber enhanced.Adopt the mechanical property of Instron electronic universal tester according to national standard test compound material, matrix material has shown good reinforced effects, and the anisotropy of matrix material is obvious, and shore a hardness is more than 85, processing characteristics (mooney viscosity) excellence.Use the triangle glue material of this matrix material, have excellent mechanical property and anisotropy thereof, processing characteristics and high-modulus, high rigidity, can improve the work-ing life of triangle glue, reduce preparation cost as automobile.
The present invention adopts fibrillar silicate (FS), after surface modification treatment, with the rubber manufacturing machinery blend, fibrillar silicate is dissociated into nano short fiber is dispersed in the rubber, prepare a kind of NR/FS nano-fiber composite material with high rigidity, high-modulus, low-heat-generation and good processing properties.The present invention uses fibrillar silicate and uses a spot of soft carbon, that can prepare meets the matrix material that the triangle colloidality can require, the characteristics that not only have high-modulus, high rigidity, the while can obviously be reduced the dynamic heat build up of matrix material, improves the work-ing life of tire.
Description of drawings:
To be the present invention be dispersed in stretching profile scanning electron micrograph in the natural rubber to embodiment 4 CO 2 supercritical method modification FS to Fig. 1.
Fig. 2 is that Comparative Examples 1 conventional dry modification processing FS of the present invention is dispersed in the stretching profile scanning electron micrograph in the natural rubber.
Among Fig. 2 shown in the circled, a large amount of FS is dissociated into brilliant bundle (aggregate that nanofiber is arranged in parallel) or the micron particle shape aggregate (nanofiber brilliant bundle pile up formation) more much smaller than original size is dispersed in the rubber matrix, have only FS seldom to be dissociated into nano short fiber, the existence of these FS aggregates, mean that its a large amount of nanofibers that include are not released, reinforced effects is relatively poor.And the FS of use CO 2 supercritical method modification, as Fig. 1, almost whole FS are dissociated into nanofiber and are dispersed in the rubber matrix, and the fibrous termination number obviously increases, as seen the modification FS of the present invention's employing has good dispersiveness in rubber, can produce good reinforced effects.
Embodiment:
Embodiment 1
Doughnut triangle glue nano short fiber rubber composite, the mass fraction of each component is:
80 parts of natural rubber matrixes;
20 parts of epoxy natural rubber matrixes;
69.6 parts of polygorskites after the modification;
40 parts of soft carbon N660;
2 parts of paraffin oils;
2 parts of stearic acid;
6 parts in zinc oxide;
6 parts of Sulfurs;
2 parts of anti-aging agent: 4010NA;
2 parts of vulcanization accelerator: NS;
The method of modifying of polygorskite: 60 part of 1250 purpose polygorskite, 7.2 parts of silane coupling agent γ-(2,3 epoxies, third oxygen) propyl trimethoxy silicanes and 2.4 parts of trolamines are added in the reactor, add dry ice then, put into magnetic stirring bar simultaneously, reactor is airtight and heat in constant temperature oil bath, temperature is 80 ℃, arrive 13MPa up to pressure, open magnetic stirring apparatus, stirred 1 hour, reaction finishes the back valve-off atmospheric pressure state that slowly reduces pressure, product is taken out in question response still cooling, promptly obtains the fibrillar silicate after the modification.
Composite material and preparation method thereof: polygorskite, 80 parts of natural rubbers, 20 parts of epoxy natural rubber matrixes, 40 parts of soft carbon N660 after Banbury mixer adds 69.6 parts of modifications at first successively, mix 10min at 150 ℃, add 2 parts of stearic acid, 6 parts of zinc oxide, 2 parts of vulcanization accelerator NSs, 2 parts of antioxidant 4010NAs, 2 parts of paraffin oils then, being cooled to 6 parts of linking agent Sulfurs of 45 ℃ of addings at last mixes, obtain rubber unvulcanizate, through rolling orientation, sulfuration obtains rubber composite under 142 ℃, and its mechanical property sees Table 1.
Embodiment 2
Doughnut triangle glue nano short fiber rubber composite, the mass fraction of each component is:
85 parts of natural rubber matrixes;
15 parts of styrene-butadiene rubber(SBR) matrixes;
92 parts of polygorskites after the modification;
30 parts of soft carbon N642;
4 parts of paraffin oils;
3 parts of stearic acid;
6 parts in zinc oxide;
2 parts of Sulfurs;
4 parts of anti-aging agent: RD;
4 parts of vulcanization accelerator: CZ;
The method of modifying of polygorskite: 80 part of 1250 purpose polygorskite, 9 parts of vinyltriethoxysilanes and 3 parts of trolamines are added in the reactor, add dry ice then, put into magnetic stirring bar simultaneously, reactor is airtight and heat in constant temperature oil bath, temperature is 100 ℃, arrive 13.5MPa up to pressure, open magnetic stirring apparatus, stirred 1.5 hours, reaction finishes the back valve-off atmospheric pressure state that slowly reduces pressure, product is taken out in question response still cooling, promptly obtains the fibrillar silicate after the modification.
Composite material and preparation method thereof: polygorskite, 85 parts of natural rubbers, 15 parts of styrene-butadiene rubber(SBR) matrixes, 30 parts of soft carbon N642 after Banbury mixer adds 92 parts of modifications at first successively, mix 10min at 150 ℃, add 3 parts of stearic acid, 6 parts of zinc oxide, 4 parts of accelerator CZs, 4 parts of anti-aging agent RDs, 4 parts of paraffin oils then, being cooled to 2 parts of linking agent Sulfurs of 45 ℃ of addings at last mixes, obtain rubber unvulcanizate, through rolling orientation, sulfuration obtains rubber composite under 145 ℃, and its mechanical property sees Table 1.
Embodiment 3
Doughnut triangle glue nano short fiber rubber composite, the mass fraction of each component is:
90 parts of natural rubber matrixes;
10 parts of cis-1,4-polybutadiene rubber matrixes;
38 parts of polygorskites after the modification;
60 parts of soft carbon N539;
3 parts of paraffin oils;
2 parts of stearic acid;
5 parts in zinc oxide;
5 parts of Sulfurs;
Anti-aging agent: 4,020 3 parts;
3 parts of vulcanization accelerator: DM;
The method of modifying of polygorskite: 30 part of 1250 purpose polygorskite, 6 parts of two-[γ (triethoxysilicane) propyl group] tetrasulfides and 2 parts of trolamines are added in the reactor, add dry ice then, put into magnetic stirring bar simultaneously, reactor is airtight and heat in constant temperature oil bath, temperature is 40 ℃, arrive 10MPa up to pressure, open magnetic stirring apparatus, stirred 1.5 hours, reaction finishes the back valve-off atmospheric pressure state that slowly reduces pressure, product is taken out in question response still cooling, promptly obtains the fibrillar silicate after the modification.
Composite material and preparation method thereof: polygorskite, 90 parts of natural rubbers, 10 parts of cis-1,4-polybutadiene rubber matrixes, 60 parts of soft carbon N539 after Banbury mixer adds 38 parts of modifications at first successively, mix 10min at 150 ℃, add 2 parts of stearic acid, 5 parts of zinc oxide, 3 parts of accelerator DMs, 4020,3 parts of paraffin oils of 3 parts of anti-aging agent then, being cooled to 5 parts of linking agent Sulfurs of 45 ℃ of addings at last mixes, obtain rubber unvulcanizate, through rolling orientation, sulfuration obtains rubber composite under 145 ℃, and its mechanical property sees Table 1.
Embodiment 4
Doughnut triangle glue nano short fiber rubber composite, the mass fraction of each component is:
100 parts of natural rubber matrixes;
69.6 parts of polygorskites after the modification;
40 parts of soft carbon N550;
5 parts of paraffin oils;
2 parts of stearic acid;
6 parts in zinc oxide;
6 parts of Sulfurs;
Anti-aging agent: 4,020 1.5 parts;
2 parts of vulcanization accelerator: NS;
The method of modifying of polygorskite: with 60 part of 1250 order polygorskite, 7.2 parts of silane coupling agents two-[γ-(triethoxysilicane) propyl group] tetrasulfide and 2.4 parts of trolamines add in the reactor, add dry ice then, put into magnetic stirring bar simultaneously, reactor is airtight and heat in constant temperature oil bath, temperature is 60 ℃, arrive 12MPa up to pressure, open magnetic stirring apparatus, reacted 1 hour, reaction finishes the back valve-off atmospheric pressure state that slowly reduces pressure, product is taken out in question response still cooling, promptly obtains the fibrillar silicate after the modification.
Composite material and preparation method thereof: polygorskite, 100 parts of natural rubbers, 40 parts of soft carbon N550 after Banbury mixer adds 69.6 parts of modifications at first successively, mix 10min at 150 ℃, add 2 parts of stearic acid, 6 parts of zinc oxide, 2 parts of vulcanization accelerator NSs, 4020,5 parts of paraffin oils of 1.5 parts of anti-aging agent then, being cooled to 6 parts of linking agent Sulfurs of 45 ℃ of addings at last mixes, obtain rubber unvulcanizate, through rolling orientation, sulfuration obtains rubber composite under 142 ℃, and its mechanical property sees Table 1.
Comparative Examples 1
Doughnut triangle glue nano short fiber rubber composite, the mass fraction of each component is:
100 parts of natural rubber matrixes;
69.6 parts of modified paligorskites;
40 parts of soft carbon N550;
5 parts of paraffin oils;
2 parts of stearic acid;
6 parts in zinc oxide;
6 parts of Sulfurs;
Anti-aging agent: 4,020 1.5 parts;
2 parts of vulcanization accelerator: NS;
The method of modifying of polygorskite: with 7.2 parts of properties-correcting agent of 4.8 parts of alcohol dilutions two-[γ-(triethoxysilicane) propyl group] tetrasulfide and 2.4 parts of trolamines, stir.With the first pre-mixing 3 minutes in homogenizer of 60 part of 1250 purpose polygorskite, make its fluffyization, add the properties-correcting agent after the dilution, brute force mixed 10 minutes again, properties-correcting agent and polygorskite are fully soaked into, mix, take out polygorskite in 80 ℃ of baking ovens dry 4 hours.
Composite material and preparation method thereof: polygorskite, 100 parts of natural rubbers, 40 parts of soft carbon N550 after Banbury mixer adds 69.6 parts of modifications at first successively, mix 10min at 150 ℃, add 2 parts of stearic acid, 6 parts of zinc oxide, 2 parts of vulcanization accelerator NSs, 4020,5 parts of paraffin oils of 1.5 parts of anti-aging agent then, being cooled to 6 parts of linking agent Sulfurs of 45 ℃ of addings at last mixes, obtain rubber unvulcanizate, through rolling orientation, sulfuration obtains rubber composite under 142 ℃, and its mechanical property sees Table 1.
The performance of table 1 embodiment of the invention and Comparative Examples relatively
| Performance | Hardness | 100% stress at definite elongation | Tensile strength | Elongation at break | Tear strength | Curing time | Dynamic elastic modulus E ' | Dynamic loss factor Tan δ |
| Unit | Shao Er A | ??MPa | ??MPa | ??％ | ??kN/m | ??min | ??×10 8Pa | |
| Embodiment 1 | ??88 | ??9.7 | ??20.1 | ??231 | ??50 | ??12 | ??4.9 | ??0.108 |
| Embodiment 2 | ??90 | ??12.7 | ??19.2 | ??202 | ??55 | ??9 | ??5.4 | ??0.11 |
| Embodiment 3 | ??85 | ??10.5 | ??18.8 | ??267 | ??48 | ??10 | ??5.0 | ??0.10 |
| Embodiment 4 | ??89 | ??11.9 | ??19.9 | ??221 | ??42 | ??13 | ??5.3 | ??0.12 |
| Comparative Examples 1 | ??80 | ??6.3 | ??15.7 | ??300 | ??30 | ??12 | ??2.8 | ??0.31 |
Claims (4)
1. rubber nano short fiber composite material for automobile tire, it is formed and mass fraction is:
100 parts of diene series rubber matrixes,
30～100 parts of modified acicular silicate,
Median size is 20～60 parts of the soft carbons of 31～200nm,
0～10 part of paraffin oil,
6～10 parts of promoting agents,
0.5～4 part in anti-aging agent,
1～4 part of vulcanization accelerator,
1～6 part of Sulfur;
Wherein the diene series rubber matrix is a kind of epoxy glue of forming with 4: 1～9: 1 mass ratio in natural rubber or natural rubber and epoxy natural rubber, styrene-butadiene rubber(SBR) or the cis-1,4-polybutadiene rubber;
Modified acicular silicate adopts granularity to be not less than the natural fibrillar silicate of 1000 purposes through CO
2Supercritical methanol technology modification and getting, concrete method of modifying is: is 3～24: 1～8 with silane coupling agent, trolamine and fibrillar silicate with mass ratio: 30～100 ratio, add in the reactor, and add dry ice then, under the agitation condition, the airtight temperature that is heated to of reactor is 40 ℃～100 ℃, and pressure 10～14MPa reacted 1～2 hour, after reaction finishes, with the reactor atmospheric pressure state that reduces pressure, to be cooled, obtain modified acicular silicate.
2. rubber nano short fiber composite material for automobile tire according to claim 1 is characterized in that: described silane coupling agent is vinyltriethoxysilane, γ-(2,3 epoxies, third oxygen) propyl trimethoxy silicane, two-[γ-(triethoxysilicane) propyl group] tetrasulfide or γ-methacryloxypropyl trimethoxy silane.
3. rubber nano short fiber composite material for automobile tire according to claim 1 is characterized in that: soft carbon is selected the product of the following trade mark: N539, N550, N660, N642 or N770 for use.
4. claim 1 or 2 or 3 described doughnuts are with the preparation method of nano short fiber rubber composites, comprise the following steps: successively at first to add rubber, modified acicular silicate to Banbury mixer, mix 10～15min at 130～150 ℃, add promoting agent, vulcanization accelerator, anti-aging agent, soft carbon, paraffin oil then, be cooled to 40～50 ℃ of adding Sulfurs at last and mix, sulfuration obtains rubber composite.
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| CN108192156A (en) * | 2017-12-06 | 2018-06-22 | 福建省海安橡胶有限公司 | Triangle rubber sizing material and preparation method under a kind of all-steel giant-scale engineering radial |
| CN110087899A (en) * | 2016-10-26 | 2019-08-02 | 倍耐力轮胎股份公司 | The elastomeric material and tire for tyre element comprising modified Portland fiber |
| CN110382255A (en) * | 2016-12-23 | 2019-10-25 | 倍耐力轮胎股份公司 | The elastic composition of the silicate fiber with needle-shaped pattern containing nano-scale and vehicle tyre including them |
| CN111516164A (en) * | 2020-05-08 | 2020-08-11 | 山东玲珑轮胎股份有限公司 | Preparation method of rubber nano short fiber composite material for apex |
| CN113563562A (en) * | 2021-08-23 | 2021-10-29 | 无锡安睿驰科技有限公司 | Disc-type self-repairing safety tire rubber material and preparation method thereof |
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| CN107667016B (en) * | 2015-04-29 | 2020-06-26 | 倍耐力轮胎股份公司 | Vulcanisable elastomeric material for tyre components comprising modified silicate fibres and tyre thereof |
| CN107667016A (en) * | 2015-04-29 | 2018-02-06 | 倍耐力轮胎股份公司 | The vulcanizable elastomeric material and its tire for tyre element comprising modified Portland fiber |
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| CN110382255A (en) * | 2016-12-23 | 2019-10-25 | 倍耐力轮胎股份公司 | The elastic composition of the silicate fiber with needle-shaped pattern containing nano-scale and vehicle tyre including them |
| CN110382255B (en) * | 2016-12-23 | 2021-07-16 | 倍耐力轮胎股份公司 | Elastomeric compositions containing nanosized silicate fibers having acicular morphology and vehicle tires comprising them |
| CN108192156A (en) * | 2017-12-06 | 2018-06-22 | 福建省海安橡胶有限公司 | Triangle rubber sizing material and preparation method under a kind of all-steel giant-scale engineering radial |
| CN111516164A (en) * | 2020-05-08 | 2020-08-11 | 山东玲珑轮胎股份有限公司 | Preparation method of rubber nano short fiber composite material for apex |
| CN111516164B (en) * | 2020-05-08 | 2022-02-11 | 山东玲珑轮胎股份有限公司 | Preparation method of rubber nano short fiber composite material for apex |
| CN113563562A (en) * | 2021-08-23 | 2021-10-29 | 无锡安睿驰科技有限公司 | Disc-type self-repairing safety tire rubber material and preparation method thereof |
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Application publication date: 20101117 Assignee: BEIJING TIANCHENG LINGLONG TYRE CO., LTD. Assignor: Beijing University of Chemical Technology Contract record no.: 2013990000119 Denomination of invention: Rubber nano short fiber composite material for automobile tire and preparation method thereof Granted publication date: 20111221 License type: Exclusive License Record date: 20130327 |
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