A kind of antistatic low fatigue temperature rise tire tread rubber material of high wet-sliding resistant and its preparation
Method
Technical field
The present invention relates to rubber tyre technical field, more particularly to a kind of antistatic low fatigue temperature rise tire of high wet-sliding resistant
Face glue material and preparation method thereof.
Background technology
In recent years, with the fast development of automobile industry, high-performance tire will become the trend of tyre industry development, high
Performance tire will not only have excellent wearability, but also possess excellent wet-sliding resistant performance, low rolling resistance, low tired
Labor Wen Sheng, the preferable capacity of heat transmission and excellent antistatic property, in order to meet more than performance simultaneously, usual way is
It is blended to use by two kinds and two or more polymer with functional filler.
Chinese invention patent CN200910160511.9 report SUMITOMO CHEMICAL tyre companies (SUMTTOMO) are used along fourth rubber
Glue and epoxy natural rubber make tire, and the wet gripping power of composite material, wear-resisting property improve.However rubbery system and hard charcoal
It is black all cannot be effectively antistatic, therefore in the patent tire antistatic property without reference to.
Chinese invention patent CN105082387A describes a kind of graphene static conductive tire preparation method, in all-purpose tire
The graphene that certain score is added in formula improves the electrostatic conductive performance of tire, however the anti-slippery of tire and rolling resistance
Problem is not solved effectively.
Chinese invention patent CN102911411A describes a kind of antistatic low rolling resistance tyre tread rubber and its preparation
Method, this method is using Butadiene-Styrene Rubber and butadiene rubber as parent, addition graphene raising composite material antistatic property, however its
Fatigue temperature rise performance but without reference to.
Research both at home and abroad finds to be used in combination with solution polymerized butadiene styrene rubber and butadiene rubber, and silane is added by main stuffing of white carbon
Coupling agent can effectively improve the anti-slippery of tire tread, reduce rolling resistance however its antistatic property is poor;Graphene
Material has excellent electric conductivity and heat conductivility, however its contribution of wet-sliding resistant performance to tyre surface glue material is limited.
It was found that replacing part solution polymerized butylbenzene rubber for 0~50% epoxy natural rubber using epoxy content in the present invention
Glue and butadiene rubber, while a small amount of grapheme material is added in, it not only can further solve tread rubber rolling resistance and moisture-resistant
The contradiction of slip, and dispersion of the white carbon in sizing material can be improved, the wearability of tire is improved, reduces the tired of composite material
Labor Wen Sheng promotes the thermal conductivity factor of tire.
Invention content
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of antistatic low fatigue temperature rise tire of high wet-sliding resistant
Tyre surface glue material and preparation method thereof.The present invention improves dispersion in silica compound by adding in epoxy natural rubber,
It improves the anti-slippery of material, reduce rolling resistance and wearability;Add in grapheme material solve tread rubber static conductive and
The problem of heat conduction.60 DEG C of Tan δ≤0.11 of composite material rolling resistance prepared by the present invention, 0 DEG C of Tan δ of wet-sliding resistant performance≤
0.36, fatigue temperature rise reduces by 5 DEG C or so, Ti product electricity Zu≤2.7 × 1010Ω cm, Biao Mian electricity Zu≤5.2 × 108Ω, heat conduction system
Shuo≤0.35W/mk.
In order to solve the above technical problems, the technical solution used in the present invention is as follows.
A kind of antistatic low fatigue temperature rise tire tread rubber material of high wet-sliding resistant, the tire tread rubber material is by following components
It is prepared according to following parts by weight:
90~110 parts of solution polymerized butadiene styrene rubber, 10~20 parts of butadiene rubber;0~50 part of epoxy natural rubber, graphene 1
~10 parts, 50~80 parts of white carbon, 4~6 parts of silane coupling agent, 10~20 parts of carbon black, 0~6 part of environment-friendly rubber oil, zinc oxide 4
~6 parts, 2~3 parts of stearic acid, 2~3 parts of anti-aging agent, 1~8 part of accelerating agent, 1~2 part of sulphur.
Preferably, the oil-filled mass fraction of the solution polymerized butadiene styrene rubber is 20~50%, further preferably 37.5%.
Preferably, the epoxy natural rubber is one kind in the epoxy natural rubber that epoxy content is 0~50%
It is or a variety of.
Preferably, the number of plies of the graphene is individual layer, one or more in few layer or multilayer.Further preferred graphite
The number of plies of alkene is 1~30 layer.
Preferably, the grain size of the white carbon is 10~50nm, and dioxide-containing silica is more than 98%.
Preferably, the carbon black is one or more in super abrasive carbon black, intermediate super abrasion furnace black and high wear-resistant carbon black.
Preferably, solution polymerized butadiene styrene rubber, butadiene rubber, epoxy must be existed simultaneously in the raw material of the tire tread rubber material
Change natural rubber, white carbon and graphene.
Preferably, the mixing method of the graphene and sizing material is dry or wet mixing;The sizing material is solution polymerized butylbenzene rubber
Glue, butadiene rubber and epoxy natural rubber.
The preparation method of the above-described antistatic low fatigue temperature rise tire tread rubber material of a kind of high wet-sliding resistant, including such as
Lower step:
A, one section of mixing:It is room temperature to adjust open mill roller temperature, and circulating cooling roller temperature, it is 1 that regulating roller speed, which compares,:1.3~1:
1.6, then solution polymerized butadiene styrene rubber, butadiene rubber, epoxy natural rubber and graphene are kneaded on a mill uniform;
B, two-stage mixing:Closed-smelting machine rotor rotating speed is 20~50rpm, and presser bar pressure is 0.5~1MP, and one section is kneaded
Sizing material input mixer in, be kneaded 30~80 seconds, by zinc oxide, stearic acid, anti-aging agent input banburying chamber be kneaded 30~80 seconds,
By white carbon, silane coupling agent input banburying chamber is kneaded 60~200 seconds, continues carbon black input banburying chamber being kneaded 60~100 seconds,
Environment-friendly rubber oil input banburying chamber is kneaded 60~240 seconds, dumping;
C, three-stage mixing:Mixer temperature is adjusted to 120~140 DEG C, closed-smelting machine rotor rotating speed is adjusted to 30~50rpm, will
In two-stage mixing glue input banburying chamber, it is heat-treated 100~900 seconds, dumping when sizing material temperature reaches 130~170 DEG C, in air
It is cooled to room temperature;
D, four sections of mixings:It is room temperature to adjust open mill roller temperature, and circulating cooling roller temperature, regulating roller speed is than 1:1.3~1:1.6
Three-stage mixing glue is thin 3~8 times logical in open mill, accelerating agent and sulphur are added in, it is thin to lead to 6~8 slices, finished composition is obtained,
I.e. a kind of antistatic low fatigue temperature rise tire tread rubber material of high wet-sliding resistant.
Preferably, the mixer is meshing mixer.
Compared with prior art, the invention has the advantages that and technique effect:
The tire tread rubber material of the present invention, can effectively improve the anti-slippery of tire, reduce the rolling of tire simultaneously
Resistance reduces fatigue temperature rise, it is often more important that be effectively improved white carbon in rubber by epoxy natural rubber and grapheme material
Dispersibility in glue improves the wearability and heat conductivility of tire.
Specific embodiment
The specific implementation of the present invention is described in further detail, but embodiments of the present invention with reference to embodiments
It is without being limited thereto.
1 following mass parts are 1g.
Comparative example:Anti-slippery tire tread rubber material, mixing ratio are shown in Table 1.
Table 1
The calendering process of anti-slippery tire tread rubber material:
A, one section of mixing:It is room temperature to adjust open mill roller temperature, and circulating cooling roller temperature, it is 1 that regulating roller speed, which compares,:1.45 then
Solution polymerized butadiene styrene rubber (oil-filled mass fraction 37.5%), butadiene rubber are kneaded on a mill uniform.
B, two-stage mixing:Closed-smelting machine rotor rotating speed 30rpm, presser bar pressure 0.7MP put into one section of sizing material being kneaded close
It in mill, is kneaded 30 seconds, zinc oxide, stearic acid, antioxidant 4020 input banburying chamber is kneaded 60 seconds, (grain size is by white carbon
25nm), silane coupling agent Si69 puts into banburying chamber and is kneaded 120 seconds, continues super abrasive carbon black input banburying chamber being kneaded 120 seconds,
Dumping.
C, three-stage mixing:The temperature of mixer is adjusted to 120 DEG C, two-stage mixing glue input banburying chamber is kneaded 360 seconds, glue
Dumping when material temperature degree reaches 150 DEG C, is cooled to room temperature in air.
D, four sections of mixings:It is room temperature to adjust open mill roller temperature, and circulating cooling roller temperature, regulating roller speed is than 1:1.45, by three sections
Rubber compound is thin 6 times logical in open mill, adds in accelerator NS, diphenylguanidine, accelerating agent TT and sulphur, thin to lead to 8 slices, obtains
Finished composition, i.e., anti-slippery tire tread rubber material.
Embodiment 1:The antistatic low fatigue temperature rise tire tread rubber material of high wet-sliding resistant, mixing ratio are shown in Table 2.
Table 2
The calendering process of the antistatic low fatigue temperature rise tire tread rubber material of high wet-sliding resistant:
A, one section of mixing:It is room temperature to adjust open mill roller temperature, and circulating cooling roller temperature, regulating roller speed is than 1:1.45 Ran Hou
By solution polymerized butadiene styrene rubber (oil-filled mass fraction 37.5%), butadiene rubber, epoxy natural rubber, (epoxy content is on open mill
25%) it is kneaded uniformly with graphene.
B, two-stage mixing:Closed-smelting machine rotor rotating speed 30rpm, presser bar pressure 0.7MP put into one section of sizing material being kneaded close
It in mill, is kneaded 30 seconds, zinc oxide, stearic acid, antioxidant 4020 input banburying chamber is kneaded 60 seconds, (grain size is by white carbon
25nm), silane coupling agent Si69 puts into banburying chamber and is kneaded 120 seconds, continues super abrasive carbon black input banburying chamber being kneaded 60 seconds, will
Environment-friendly rubber oil NYTEX4700 inputs banburying chamber is kneaded 120 seconds, dumping.
C, three-stage mixing:Mixer temperature is adjusted to 120 DEG C, closed-smelting machine rotor rotating speed is adjusted to 30rpm, by two-stage mixing glue
It puts into banburying chamber to be kneaded 360 seconds, dumping when sizing material temperature reaches 150 DEG C is cooled to room temperature in air.
D, four sections of mixings:It is room temperature to adjust open mill roller temperature, and circulating cooling roller temperature, regulating roller speed is than 1:1.45, by three sections
Rubber compound is thin 6 times logical in open mill, adds in accelerator NS, diphenylguanidine, accelerating agent TT and sulphur, thin to lead to 8 slices, obtains
The antistatic low fatigue temperature rise tire tread rubber material of finished composition, i.e. high wet-sliding resistant.
Embodiment 2:The antistatic low fatigue temperature rise tire tread rubber material of high wet-sliding resistant, mixing ratio are shown in Table 3.
Table 3
The calendering process of the antistatic low fatigue temperature rise tire tread rubber material of high wet-sliding resistant:
A, one section of mixing:It is room temperature to adjust open mill roller temperature, and circulating cooling roller temperature, regulating roller speed is than 1:1.45 Ran Hou
By solution polymerized butadiene styrene rubber (oil-filled mass fraction 37.5%), butadiene rubber, epoxy natural rubber, (epoxy content is on open mill
40%) it is kneaded uniformly with graphene.
B, two-stage mixing:Closed-smelting machine rotor rotating speed 30rpm, presser bar pressure 0.7MP put into one section of sizing material being kneaded close
It in mill, is kneaded 30 seconds, zinc oxide, stearic acid, antioxidant 4020 input banburying chamber is kneaded 60 seconds, (grain size is by white carbon
25nm), silane coupling agent Si69 puts into banburying chamber and is kneaded 120 seconds, continues super abrasive carbon black input banburying chamber being kneaded 60 seconds, will
Environment-friendly rubber oil NYTEX4700 inputs banburying chamber is kneaded 120 seconds, dumping.
C, three-stage mixing:Mixer temperature is adjusted to 120 DEG C, closed-smelting machine rotor rotating speed is adjusted to 30rpm, by two-stage mixing glue
It puts into banburying chamber to be kneaded 360 seconds, dumping when sizing material temperature reaches 150 DEG C is cooled to room temperature in air.
D, four sections of mixings:It is room temperature to adjust open mill roller temperature, and circulating cooling roller temperature, regulating roller speed is than 1:1.45, by three sections
Rubber compound is thin 6 times logical in open mill, adds in accelerator NS, diphenylguanidine, accelerating agent TT and sulphur, thin to lead to 8 slices, obtains
The antistatic low fatigue temperature rise tire tread rubber material of finished composition, i.e. high wet-sliding resistant.
Embodiment 3:The antistatic low fatigue temperature rise tire tread rubber material of high wet-sliding resistant, mixing ratio are shown in Table 4.
Table 4
The calendering process of the antistatic low fatigue temperature rise tire tread rubber material of high wet-sliding resistant:
A, one section of mixing:It is room temperature to adjust open mill roller temperature, and circulating cooling roller temperature, regulating roller speed is than 1:1.45 Ran Hou
By solution polymerized butadiene styrene rubber (oil-filled mass fraction 37.5%), butadiene rubber, epoxy natural rubber, (epoxy content is on open mill
50%) it is kneaded uniformly with graphene.
B, two-stage mixing:Closed-smelting machine rotor rotating speed 30rpm, presser bar pressure 0.7MP put into one section of sizing material being kneaded close
It in mill, is kneaded 30 seconds, zinc oxide, stearic acid, antioxidant 4020 input banburying chamber is kneaded 60 seconds, (grain size is by white carbon
25nm), silane coupling agent Si69 puts into banburying chamber and is kneaded 120 seconds, continues super abrasive carbon black input banburying chamber being kneaded 60 seconds, will
Environment-friendly rubber oil NYTEX4700 inputs banburying chamber is kneaded 120 seconds, dumping.
C, three-stage mixing:Mixer temperature is adjusted to 120 DEG C, closed-smelting machine rotor rotating speed is adjusted to 30rpm, by two-stage mixing glue
It puts into banburying chamber to be kneaded 360 seconds, dumping when sizing material temperature reaches 150 DEG C is cooled to room temperature in air.
D, four sections of mixings:It is room temperature to adjust open mill roller temperature, and circulating cooling roller temperature, regulating roller speed is than 1:1.45, by three sections
Rubber compound is thin 6 times logical in open mill, adds in accelerator NS, diphenylguanidine, accelerating agent TT and sulphur, thin to lead to 8 slices, obtains
The antistatic low fatigue temperature rise tire tread rubber material of finished composition, i.e. high wet-sliding resistant.
Table 5
Molding vulcanization is carried out to finished composition obtained as above at 150 DEG C, vulcanizate, mechanical property, anti-slippery is made
Can, rolling resistance, wear-resisting property, resistivity, thermal conductivity factor, fatigue temperature rise result are shown in Table 5 respectively.Wherein wet-sliding resistant performance and rolling
Dynamic resistance performance represents that correlative study shows the anti-slippery of 0 DEG C of higher tire of Tan δ values using 0 DEG C and 60 DEG C of Tan δ values
Can be better, the rolling resistance of the lower tire of 60 DEG C of Tan δ values is lower, and smaller then its wearability of DIN abrasion is better, compression fatigue temperature
The heat for rising smaller sizing material is lower, and the capacity of heat transmission of the bigger sizing material of thermal conductivity factor is bigger.