CN104262698A - Rubber composition and tire same - Google Patents
Rubber composition and tire same Download PDFInfo
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- CN104262698A CN104262698A CN201410452008.1A CN201410452008A CN104262698A CN 104262698 A CN104262698 A CN 104262698A CN 201410452008 A CN201410452008 A CN 201410452008A CN 104262698 A CN104262698 A CN 104262698A
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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
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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
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to a rubber composition and a tire containing the same, providing a rubber composition. The rubber composition comprises the following raw materials in parts by weight: 100 parts of diene rubber, 20-120 parts of white carbon black, 0-50 parts of carbon black and 2-30 parts of surface-modified carbon nanotubes, wherein the molecule of a modified group at least contains an unsaturated carbon-carbon double bond or triple bond; the number of carbon atoms of the molecule is greater than or equal to 2; and the unsaturated carbon-carbon double bond or triple bond is on a main chain or a branch chain. The invention also provides the tire containing the rubber composition.
Description
Technical field
The invention belongs to rubber for tire field, relate to a kind of rubber combination for tire, more particularly, relate to and a kind ofly comprise the rubber combination of the carbon nanotube (CNT) of specific surface modification and comprise its tire.
Background technology
Now, people thirst for providing a kind of tire integrating low-rolling-resistance, short wetland braking distance, long life, good processing property and high anti-damage performance very much.To start the nineties at twentieth century, it is found that white carbon black can improve rolling resistance, wet braking distance and tear resistance, but but can produce many adverse influences after introducing white carbon black, this is because white carbon black is electric poor conductor, and this just needs to introduce a conduction chimney in the tread and realizes electric charge to derive to realize anti-electrostatic.And conduct electricity the introducing of chimney and can increase facility investment and improve production cost.
Simultaneously for the requirement of environment protection, the rolling resistance of tire or hysteresis quality must reduce.The technology of current reduction hysteresis quality is the loading level of reduction filler or uses white carbon black and other LR low reinforcing fillers.The thermal conductivity which results in sizing material reduces, thus causes thermal accumlation and thermal ageing effect.Meanwhile, the tear strength of low filling and vulcanization glue and wear resisting property all can reduce.
In order to overcome the disadvantageous effect that filling white carbon black causes, low-heat-generation design (especially new packing and chemical additive) development rapidly.Carbon nanotube has the character of many uniquenesses, such as: very large length-to-diameter ratio, very high tensile strength, excellent electrical and thermal conductivity performance etc.The performance of these uniquenesses makes carbon nanotube have more applied research in field of compound material, the mechanical property that carbon nanotube is good can it can be used as the wild phase of matrix material, and its excellent electricity and thermal property can give the special performance of material in electric heating while raising material mechanical performance.Because carbon nanotube has nano-grade size, less on heat-dissipating impact while it can improve the rigidity of rubber.Such as, but carbon nanotube has many difficulties in the application, bad dispersibility, the entanglement between carbon nanotube and high-specific surface area and the mooney viscosity caused is higher, processing characteristics is poor.
Following prior art document describes this area for trial carbon nanotube being applied to rubber combination, wherein:
Patent documentation
Patent documentation 1 EP2338697 B1
Patent documentation 2 EP2514606 A1
Patent documentation 3 US2011/0146859 A1
(this patent relates to solid special company of the U.S. and is applied in by 1 to 10 parts of carbon nanotubes in tire composition to improve conductivity patent documentation 4 CN102101919 B.)
(document relates to a kind of carbon nanotube disclosed in Florida State Univ. and strengthens the preparation method of nano material patent documentation 5 US20130264521 A1, and the method adopts the carbon nanotube of a certain amount of 1% to 10% functionalization to carry out reinforced composite.)
Patent documentation 6 WO2003/102073
Patent documentation 7 JP2010-265363
Patent documentation 8 JP2010-065163
Patent documentation 9 JP2010-059303
Patent documentation 10 JP2009-185146
Patent documentation 11 JP2009-179809
Patent documentation 12 JP2009-179808
Patent documentation 13 JP2007-217459
Patent documentation 14 JP2007-217458
Patent documentation 15 JP2004-203350
Patent documentation 16 JP2004-203342
Patent documentation 17 JP2004-130885
(document relates to BRIDGESTONE company and pays close attention to heat conductivility to improve the endurance quality of tire patent documentation 18 JP2004-010689.)
Patent documentation 19 JP2010-024414
(document relates to Sumitomo company about the application of run-flat tire that still can travel after gas leakage and carbon nanotube thermal treatment to patent documentation 20 JP2009-046547.)
Non-patent literature
Non-patent literature 1 Z.Spitalsky, D.Tasis, K.Papagelis, C.Galiotis, Carbon nanotube-polymer composites:Chemistry, processing, mechanical and electrical properties, Progress in Polymer Science, Vol.35, issue 3, p357-401 (" carbon nano tube-polymer mixture: chemistry, processing, machinery and electrical property ", polymer chemistry is in progress, the 35th volume, theme 3,357-401 page)
Non-patent literature 2 N.Wu, CNT filled tire shoulder compound for improved performance, Bachelor degree thesis No.2007000468, Beijing University of Chemical Technology, Carboxylated MWCNT shows better performances (" the tire shoulder compound that the CNT for improving SNR fills ", undergraduate degree paper No.2007000468, Beijing University of Chemical Technology, Carboxylation MWCNT shows better properties)
Non-patent literature 3 T.Clancy, T.Gates, Modeling of interfacial modification effects on thermal conductivity of carbon nanotube composites, Polymer, vol.47, issue 16, p5990-5996 (" model that the interface modification for the thermal conductivity of carbon mano-tube composite affects ", polymkeric substance, the 47th volume, theme 16,5990-5996 page).
But the scheme that above-mentioned prior art document proposes all fails to provide the rubber composition for tire of the advantage simultaneously with the volume specific resistance not changing tyre mix processing characteristics (mooney viscosity is suitable for), raising heat conductivility and reduce tire.
Summary of the invention
The invention provides a kind of rubber combination of novelty and comprise its tire, thus solving the defect and problem that exist in prior art.
Present inventor finds after extensive and deep research, according to the requirement of tire conductivity and the feature of carbon nanotube self, for tire (tyre surface, crown, sidewall etc., preferred tyre surface) rubber combination in use the carbon nanotube of specific surface modification, heat conductivility and the conductivity of material can be improved, do not changed rubber unvulcanizate processing characteristics, improve heat conductivility, reduce the tire product of the volume specific resistance of tire simultaneously.Based on above-mentioned discovery, the present invention is accomplished.
On the one hand, the invention provides a kind of rubber combination, it comprises:
The polydiene of 100 weight parts;
The white carbon black of 20-120 weight part;
The carbon black of 0-50 weight part; And
The carbon nanotube of the surface modification of 2-30 weight part, wherein, at least containing a unsaturated carbon-carbon double bond or triple bond in the molecule of modified group, its amount of carbon atom >=2, wherein said unsaturated carbon-carbon double bond or triple bond are positioned on main chain or side chain.
In one preferred embodiment, described modified group is the ring texture containing unsaturated carbon-carbon double bond or the linear chain structure containing unsaturated carbon-carbon double bond, and wherein said unsaturated carbon carbon double bond is positioned on main chain or on side chain.
Another preferred embodiment in, described modified group is selected from: dicyclopentadiene, cyclopentadiene and poly cyclopentadiene.
Another preferred embodiment in, the length of the carbon nanotube of described surface modification is less than 2 microns, and diameter is 0.5-200nm.
Another preferred embodiment in, the content of the carbon nanotube of described surface modification is 2-20 weight part, comprises single wall and multi-walled carbon nano-tubes.
Another preferred embodiment in, described polydiene comprises: natural rubber, cis-1,4-polybutadiene rubber, polyisoprene rubber, isoprene-isobutylene rubber, ethylene-propylene rubber(EPR) and styrene-butadiene rubber(SBR).
Another preferred embodiment in, the content of described white carbon black is 30-110 weight part, comprising: thermal silica and precipitated silica.
Another preferred embodiment in, the content of described carbon black is 0-40 weight part.
Another preferred embodiment in, described rubber combination also comprises the softening agent of 0-30 weight part.
On the other hand, the invention provides a kind of tire, it comprises above-mentioned rubber combination, and wherein, according to ASTM D1646-07, characterized by mooney viscosity, the processing characteristics of described tyre mix is identical with carbon black; According to ASTM E1225-09, the thermal conductivity of described tyre mix improves 20%; According to ASTM D257-07, the volume specific resistance of described tyre mix is lower than 1.0 × 10
9ohmm.
Beneficial effect of the present invention is as follows:
Tire product of the present invention does not change rubber unvulcanizate processing characteristics, improve heat conductivility, reduce the volume specific resistance of tire simultaneously, thus can effectively the heat in tire and electrostatic be derived, improve work-ing life and the vehicle security under steam of tire.
Accompanying drawing explanation
According to carrying out following detailed description by reference to the accompanying drawings, object of the present invention and feature will become more obvious, in accompanying drawing:
Fig. 1 is the change curve according to the tyre surface internal temperature in the tire vulcanization process of the embodiment of the present application 7, shows the relation of tyre surface internal temperature and curing time, and wherein curve 1 represents tyre surface formula 7-1, and curve 2 represents tyre surface formula 7-2.
Embodiment
rubber combination
In a first aspect of the present invention, provide a kind of rubber combination, it comprises:
Polydiene;
White carbon black;
Carbon black; And
The carbon nanotube of surface modification.
the carbon nanotube of surface modification
In rubber combination of the present invention, the content of the carbon nanotube of surface modification is 2-30 weight part, preferred 2-20 weight part.
Preferably, the carbon nanotube of described surface modification has the purity of 95% or higher.
Preferably, the carbon nanotube of described surface modification has the diameter of 0.5-200nm.
Preferably, the carbon nanotube of described surface modification has the length being less than 2 μm.
In the present invention, at least containing a unsaturated carbon-to-carbon double bond or carbon carbon triple bond in the molecule of the modified group of surface-modified carbon nanotubes, its amount of carbon atom >=2, wherein said unsaturated carbon-carbon double bond or triple bond can be positioned on main chain or side chain.
Preferably, described modified group is the ring texture containing unsaturated carbon-carbon double bond or the linear chain structure containing unsaturated carbon-carbon double bond, and wherein said unsaturated carbon-carbon double bond can be positioned on main chain or on side chain.
Preferably, described modified group is selected from: dicyclopentadiene, cyclopentadiene and poly cyclopentadiene.
Preferably, the carbon nanotube of described surface modification comprises Single Walled Carbon Nanotube and multi-walled carbon nano-tubes.
polydiene
In rubber combination of the present invention, rubbery system selects polydiene, and polydiene calculates with 100 parts by weight (phr).
In the present invention, polydiene comprises natural rubber and other various synthetic rubber, wherein elastomeric object lesson comprises cis-1,4-polybutadiene rubber (cis-1,4-polyhutadiene), polyisoprene rubber (cis-Isosorbide-5-Nitrae-polyprene), isoprene-isobutylene rubber (comprising conventional butyl rubbers, chlorinated butyl rubber and brominated butyl rubber), styrene-butadiene rubber(SBR) (butadiene/styrene copolymers), ethylene-propylene rubber(EPR) (ethylene/propylene/diene monomer multipolymer).Preferred natural rubber, styrene-butadiene rubber(SBR) and cis-1,4-polybutadiene rubber.
Preferably, the rubber of preferred at least two kinds of dienes.Such as, be preferably the combination of two kinds or more rubber, as cis-Isosorbide-5-Nitrae-polyisoprene rubber (comprises natural rubber and synthesis cis-1,4-polyisoprene), styrene-butadiene rubber(SBR) (butadiene/styrene copolymers), cis-1,4-polybutadiene rubber (cis-1，4-polybutadiene).
Preferably, styrene-butadiene rubber(SBR) can select the butadiene/styrene copolymers of solution polymerization, wherein can select the vinyl containing 10-70 % by weight, can select the vinylbenzene containing 5-40 % by weight, sometimes can select the styrene-butadiene rubber(SBR) that styrene content is higher.
white carbon black
In rubber combination of the present invention, the content of white carbon black is 20-120 weight part, preferred 30-110 weight part, more preferably 60-90 weight part.
Preferably, described white carbon black comprises thermal silica and precipitated silica, preferred precipitated silica.
carbon black
In rubber combination of the present invention, the content of carbon black is 0-50 weight part, preferred 0-40 weight part, more preferably 0-20 weight part.
In the present invention, carbon black can not be used.
In the present invention, the example of carbon black includes, but are not limited to: N110, N121, N134, N220, N231, N234, N242, N293, N299, N315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990, N991.It is the absorption value of 5 to 150g/kg, DBP is 30 to 150cm that these carbon blacks have iodine absorption value
3the feature of/100g.
additive
In rubber combination of the present invention, also can comprise various additive.
In the present invention, described rubber combination also can comprise the softening agent of 0-30 weight part.Softening agent can be added in rubber mix process, also can be contained in rubber.Described softening agent comprises various oil known in the art, comprises the various wet goods of aromatic hydrocarbon oil, naphthenic oil, paraffin oil, department of botany, and various resin known in the art, comprises the various resins etc. of carbon five, carbon nine, department of botany.
In the present invention, described rubber combination also can comprise the additive of 1-50 weight part.Described additive comprises: antioxidant, and its consumption is generally 1-5 weight part; Stearic acid, its consumption is generally 1-5 weight part; Zinc oxide, its consumption is generally 1-8 weight part; And Microcrystalline Wax, its consumption is generally 1-5 weight part.
In the present invention, described rubber combination also can comprise vulcanization accelerator to control time and the temperature of sulfuration, improves processing and the use properties of rubber.Preferably, two kinds of promotor, i.e. primary accelerator and secondary accelerator is used.Wherein the consumption of primary accelerator is generally 0.5-6 weight part, and the consumption of secondary accelerator is less, is generally 0.1-3 weight part.The kind of promotor used in the present invention has thiazoles, thiurams, sulfenamide, dithiocarbamate(s), xanthan acids, guanidine class, Thiourea etc.Preferably, primary accelerator is sulfenamide, and secondary accelerator is guanidine class.
the purposes of rubber combination
In the present invention, described rubber combination can be used in be needed in the various rubber components of the tire of strong mechanical performance, good heat conductivility and low hysteresis loss to conduct heat in tire and electrostatic, described rubber component comprises tyre surface, sidewall, crown, tire shoulder, the string of a hat, band bundle, rim of the mouth, triangle rubber, liner, air retaining wall etc., preferred tyre surface.
tire
In a second aspect of the present invention, provide a kind of tire, it comprises above-mentioned rubber combination, and wherein, according to ASTM D1646-07, characterized by mooney viscosity, the processing characteristics of described tyre mix is identical with carbon black; According to ASTM E1225-09, the thermal conductivity of described tyre mix improves 20%; According to ASTMD257-07, the volume specific resistance of described tyre mix is lower than 1.0 × 10
9(show that tire has the ability of good conducting static electricity, preferably, volume specific resistance is lower than 5.0 × 10 for Ohmm
5ohmm).
Tire of the present invention can be used for tyres for passenger cars, passenger tyre, agricultural tire, racing-car tyre, truck tyre, Off-the-road tire etc.Described tire can be radial or bias tyre.
The curing temperature of tire composition of the present invention is 100-200 DEG C, preferred 130-180 DEG C.Conventional vulcanization process can be used, such as, in water vapour, superheated water, oil bath heating or electrically heated mould, carry out sulfuration.
embodiment
The present invention is set forth further below in conjunction with specific embodiment.The following example only for explaining and the present invention being described, and does not form limitation of the scope of the invention.The test method of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Except as otherwise noted, all per-cent and number are by weight.
the preparation of rubber combination:
Prepare rubber combination by mixing method, describedly mixingly to comprise:
(1) female refining:
Female refining is carried out in X (S) M-1.6 × (0 ~ 180) type Banbury mixer, and starting temperature is 70 DEG C, and rotating speed is 70 turns/min, and pressure is 7 bar.Order of addition(of ingredients) is: solution polymerized butadiene styrene rubber and cis-1,4-polybutadiene rubber are initially adding, and add white carbon black, carbon black, carbon nanotube, coupling agent, anti-aging agent, zinc oxide, Microcrystalline Wax, stearic acid and softening agent after 30s, finally binder removal 150 DEG C time.
(2) refining eventually:
Refining carries out in X (S) M-1.6 × (0 ~ 180) type Banbury mixer eventually, order of addition(of ingredients) is: at the first rubber master batch of beginning, promotor vulkacit D, accelerant N-cyclohexyl-2-benzothiazole sulfonamide and sulphur is added, binder removal after 180s after 20s.
Starting material:
Solution polymerized butadiene styrene rubber (RC2557S, purchased from Sinopec Dushanzi petro-chemical corporation)
Cis-1,4-polybutadiene rubber (BR9000, purchased from Sinopec Dushanzi petro-chemical corporation)
White carbon black (Newsil HD115MP, purchased from Wuxi Que Chenggui company limited)
Carbon black (N234, purchased from American Cabot company limited)
Softening agent (environment-friendly aromatic oil TDAE, holy purchased from the German Chinese)
Non-surface-modified carbon nanotubes (as comparing) (GT-300, purchased from Shandong great Zhan nano material company limited)
The carbon nanotube (GT-30K, purchased from Shandong great Zhan nano material company limited) of surface modification
Coupling agent: two-(γ-triethoxyl silane propyl group)-tetrasulfide, anti-aging agent: N-(1,3-dimethyl) butyl-N'-diphenyl-para-phenylene diamine, Microcrystalline Wax, zinc oxide, stearic acid, promotor: vulkacit D, promotor: N-cyclohexyl-2-benzothiazole sulfonamide, sulphur (commercially available).
The process of surface modification of carbon nanotube:
First carbon nanotube is oxidized, makes its surface produce carboxyl, then utilize the condensation reaction of carboxyl and hydroxyl to connect the chemical group of various structure in carbon nano tube surface.
Modified group only containing a unsaturated link(age), as palmityl alcohol modification:
Modified group containing multiple unsaturated link(age), as α-linolenyl alcohol modification:
Unsaturated link(age) modified group containing aromatic nucleus, as Sorbic Acid and Resorcinol or Ursol D reaction post-modification:
The carbon nanotube of long-chain fat hydrocarbon modification, as stearyl alcohol modification:
Cyclic olefin and polymer modified carbon nano-tube thereof, as cyclopentadiene and dicyclic pentylene modified:
Equipment:
X (S) M-1.6 × (0 ~ 180) type Banbury mixer: height rubber and plastics machine technical equipment company limited of Qingdao section;
XK-200 type mill: height rubber and plastics machine technical equipment company limited of Qingdao section;
XLB-400 type vulcanizing press: height rubber and plastics machine technical equipment company limited of Qingdao section;
MV3000 mooney viscosity instrument: German Montech;
D-MDR3000 rheometer: German Montech;
Z010 universal tensile testing machine: German Zwick;
Xiao A hardness instrument: German Zwick;
DMA+1000 dynamic test machine: French Metravib.
testing standard and instrument:
(i) mooney viscosity: ASTM D1646-2007; Adopt the MV3000 mooney viscosity instrument of German Montech company;
(ii) Xiao A hardness: ASTM D2240-2010; Adopt the Z3130 sclerometer of German Zwick company
(iii) tensile strength index: ASTM D412-2006, sample is dumbbell shape, and test speed is 500mm/min, and test environment temperature is 23 ± 2 DEG C; Adopt German Zwick Z010 tension testing machine.
Wherein, the tensile strength x 100% of the tensile strength/comparative example of tensile strength index=embodiment
(iv) DIN wear index: DIN-53516; Adopt the DIN wear testing machine of GOTECH.
Wherein, the DIN abrasion loss weight x 100% of the DIN abrasion loss weight/embodiment of DIN wear index=comparative example
(v) anti tear index: ASTM D624-2007, adopt square sample, test speed is 500mm/min, and test environment temperature is 23 ± 2 DEG C; Adopt German Zwick Z010 tension testing machine.
Wherein, the tear strength x 100% of the tear strength/comparative example of anti tear index=embodiment
(vi) hysteresis loss Tan δ: use DMA (Dynamic Mechanical Analyzer) test, temperature is 40 DEG C, and frequency is 10Hz, and dynamic deformation is 1-50%, and test pattern is plane shear pattern, gets Tan δ maximum value; The DMA+1000 of Metravib is adopted to test.
(vii) thermal conductivity index: ASTM E1225-09, probe temperature is 373K;
Wherein, the thermal conductivity x 100% of the thermal conductivity/comparative example of thermal conductivity index=embodiment
(viii) volume resistance: ASTM D257-07;
(ix) sulphur load: imbed in all parts of tire by organizing thermopair before tyre vulcanization, the temperature variation of each position of real time record inside tires in the sulfidation of tire more;
(x) tire high-speed performance test: tire specification 255/45R18, GB/T 7034-1998.
embodiment 1-2
Following table 1-2 shows the composition of the rubber combination prepared according to above-mentioned mixing method, and the performance of test, the carbon nanotube (modified group is cyclopentadiene and polymer thereof) of surface modification has carried out the contrast of performance with the carbon nanotube of carbon black and non-surface modification:
Table 1 (carbon nanotube of surface modification has carried out performance comparison with the carbon black of identical addition, and wherein composition 1-1,1-2,1-3,1-4 is as comparing)
As can be seen from upper table 1:
1) carbon nanotube of surface modification can overcome the shortcoming of bad dispersibility and processing difficulties, and it has with the identical mooney viscosity of carbon black, and its tensile strength, tearing toughness, wear resisting property are all good than the carbon black of same amount.
2) hysteresis loss of the carbon nanotube of surface modification is identical with the carbon black of same amount.
3) heat conductivility of the carbon nanotube of surface modification improves 20% than conventional carbon black.
4) when surface-modified carbon nanotubes consumption is 6 weight part, volume specific resistance has started to decline, and when consumption is 10 weight part, volume specific resistance reduces by 5 orders of magnitude.
Table 2 (the performance comparison between the composition of the carbon nanotube of surface modification and the carbon nanotube of non-surface modification, wherein 2-1 is the basic reference formulations not adding carbon nanotube, and 2-2,2-3 and 2-4 are the comparative formula of adding non-surface-modified carbon nanotubes)
As can be seen from upper table 2:
1) interpolation of the carbon nanotube of non-surface modification causes the significantly rising of mooney viscosity, and when its consumption 10 weight part, contrast with reference formulations 2-1, mooney viscosity rises 48 values;
2) dispersiveness of the carbon nanotube of non-surface modification is poor, obviously reduces when its consumption reaches 6 weight part back draft intensity;
3) carbon nanotube of cyclopentadiene and polymer surface modification thereof can overcome the shortcoming of bad dispersibility and processing difficulties, and its tensile strength, tearing toughness, wear resisting property are all than unmodified carbon nanotubes, and its tearing toughness is better.
embodiment 3-5
Following table 3-5 shows the composition of the rubber combination prepared according to above-mentioned mixing method, and the performance of test, come to compare with the reference formulations not adding carbon nanotube by the consumption changing surface-modified carbon nanotubes (modified group is cyclopentadiene and polymer thereof).
Table 3 (wherein 3-1 is reference formulations, and all the other are experiment enforcement formula)
Table 4 (wherein 4-1 is reference formulations, and all the other are experiment enforcement formula)
Table 5 (wherein 5-1 is reference formulations, and all the other are experiment enforcement formula)
Can find out further from table 3-5: for white carbon black consumption in 30-110 weight part and the carbon black loading situation at 3-40 weight part, after adding the carbon nanotube of cyclopentadiene and polymer surface modification thereof, the mooney viscosity of sizing material raises is acceptable, does not affect its processing characteristics; Meanwhile, good mechanics, conduction and heat conductivility can be obtained.
Embodiment 6
Following table 6 shows the composition of the rubber combination prepared according to above-mentioned mixing method, and the performance of test, table 6 be various modified group carry out modification carbon nanotube between contrast, wherein composition 6-1,6-2,6-3,6-4,6-5 is as comparing:
Table 6
As can be seen from upper table 6:
After adding the carbon nanotube of cyclopentadiene and polymer thereof, hydroxyl surface modification, mooney viscosity and hardness all raise, and mooney viscosity and hardness reduce after adding the carbon nanotube of long-chain fat hydrocarbon surface modification, although long-chain fat hydrocarbon modified carbon nano-tube can improve the consistency of itself and rubber and its dispersiveness in rubber, but the contact that longer organic molecule chain hinders carbon nanotube is built bridge, thus reduces the conductivity of sizing material.The dispersiveness of carbon nanotube in rubber of hydroxyl surface modification is poor, and after addition increases, conductivity obviously declines.
The carbon nanotube of cyclopentadiene and polymer modification thereof in processing and sulfidation can with rubber macromolecular chain generation crosslinking reaction, improve dispersiveness, processing characteristics, reinforcing effect and heat-conductivity conducting performance.
embodiment 7
Following table 7 is the experimental result of adding surface-modified carbon nanotubes tire, and wherein 7-1 is reference formulations.
Table 7
As can be seen from upper table 7, add the tensile strength of surface-modified carbon nanotubes postcure glue, tear strength and thermal conductivity and promote all to some extent, hardness does not change substantially simultaneously.In the process of tyre vulcanization, carry out thermometric to tyre surface inside, the sizing material each position heat-up rate adding nano material and the top temperature that can reach all are higher than reference sizing material, and the highest difference is 3 DEG C (as shown in Figure 1); Good heat conductivility can improve curing efficiency and energy-conservation energy consumption.
In the process of cooling of tire, cooling rate is also faster, and this is conducive to reducing tire internal temperature in use, provides the work-ing life of tire.
In addition, add the tire of surface-modified carbon nanotubes, its high speed performance improves a grade.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read foregoing of the present invention, these equivalent changes fall within the application's appended claims limited range equally.
Claims (10)
1. a rubber combination, it comprises:
The polydiene of 100 weight parts;
The white carbon black of 20-120 weight part;
The carbon black of 0-50 weight part; And
The carbon nanotube of the surface modification of 2-30 weight part, wherein, at least containing a unsaturated carbon-carbon double bond or triple bond in the molecule of modified group, its amount of carbon atom >=2, wherein said unsaturated carbon-carbon double bond or triple bond are positioned on main chain or side chain.
2. rubber combination as claimed in claim 1, is characterized in that, described modified group is the ring texture containing unsaturated carbon-carbon double bond or the linear chain structure containing unsaturated carbon-carbon double bond, and wherein said unsaturated carbon carbon double bond is positioned on main chain or on side chain.
3. rubber combination as claimed in claim 1, it is characterized in that, described modified group is selected from: dicyclopentadiene, cyclopentadiene and poly cyclopentadiene.
4. rubber combination as claimed in claim 1, it is characterized in that, the length of the carbon nanotube of described surface modification is less than 2 microns, and diameter is 0.5-200nm.
5. the rubber combination according to any one of claim 1-4, is characterized in that, the content of the carbon nanotube of described surface modification is 2-20 weight part, comprises single wall and multi-walled carbon nano-tubes.
6. the rubber combination according to any one of claim 1-4, is characterized in that, described polydiene comprises: natural rubber, cis-1,4-polybutadiene rubber, polyisoprene rubber, isoprene-isobutylene rubber, ethylene-propylene rubber(EPR) and styrene-butadiene rubber(SBR).
7. the rubber combination according to any one of claim 1-4, is characterized in that, the content of described white carbon black is 30-110 weight part, comprising: thermal silica and precipitated silica.
8. the rubber combination according to any one of claim 1-4, is characterized in that, the content of described carbon black is 0-40 weight part.
9. the rubber combination according to any one of claim 1-4, is characterized in that, described rubber combination also comprises the softening agent of 0-30 weight part.
10. a tire, it comprises the rubber combination according to any one of claim 1-9, and wherein, according to ASTM D1646-07, characterized by mooney viscosity, the processing characteristics of described tyre mix is identical with carbon black; According to ASTM E1225-09, the thermal conductivity of described tyre mix improves 20%; According to ASTMD257-07, the volume specific resistance of described tyre mix is lower than 1.0 × 10
9ohmm.
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| CN111727124A (en) * | 2018-01-12 | 2020-09-29 | 米其林集团总公司 | Method for producing rubber composition using depolymerized carbon nanotubes |
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| US11814523B2 (en) | 2018-01-12 | 2023-11-14 | Compagnie Generale Des Etablissements Michelin | Method for producing rubber compositions with disaggregated carbon nanotubes |
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| CN113024912A (en) * | 2019-12-09 | 2021-06-25 | 北京彤程创展科技有限公司 | Conductive rubber composition and preparation method thereof |
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| CN104262698B (en) | 2017-11-24 |
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