CN106317517A - SBR/HVPBR rubber composite material and preparation method thereof - Google Patents
SBR/HVPBR rubber composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an SBR/HVPBR rubber composite material and a preparation method thereof, and belongs to the technical field of rubber processing. The composite material comprises, by weight, 10-20 parts of high vinyl polybutadiene rubber and 80-90 parts of carbon nanotube-containing styrene butadiene rubber. The preparation method comprises the following steps: uniformly stirring an aqueous carbon nanotube solution and a salt solution, dropwise adding a styrene butadiene rubber emulsion, and carrying out a coacervation reaction to obtain the carbon nanotube-containing styrene butadiene rubber; and blending the high vinyl polybutadiene rubber and the carbon nanotube-containing styrene butadiene rubber in an internal mixer for 10-15 min, and carrying out co-vulcanization. The carbon nanotubes are applied to the rubber composite material in the invention, so the stress at definite elongation, the tensile strength and the wear resistance of the rubber are enhanced, and the heat conductivity and the electricity conductivity of the rubber are improved.
Description
Technical field
A kind of SBR/HVPBR rubber composite and preparation method thereof, belongs to rubber processing techniques field.
Background technology
High vinyl polybutadiene rubber (HVPBR) is a kind of high-performance rubber with low-rolling-resistance and good anti-slippery, it is better than butadiene rubber with butadiene-styrene rubber (SBR) blended characteristic to be blended with butadiene-styrene rubber, is one of elite clone manufacturing rubber tire tread.For improving wearability and the stress at definite elongation of tire, adding white carbon black in rubber mixing process, white carbon black is the important reinforcing material being widely used in tire, and filling number just has remarkable result more than 40 parts.And white carbon black is often difficult to obtain bigger breakthrough at reinforcing rubber and functionalization two aspect simultaneously.
CNT has another name called Baji-tube, is by the carbon pipe of graphite carbon source sublayer curling.Pipe diameter is generally several nanometer to tens nanometer, and pipe thickness is only several nanometer, the hollow cylindrical " cage type pipe " being rolled into as wire gauze.It is the One-dimensional Quantum material that one has special construction (radial dimension be nanometer scale, axial dimension be that micron dimension, draw ratio be very big, pipe two ends are substantially all sealing).CNT is considered as new function material and the structural material of a kind of excellent performance.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, it is provided that one has heat-conductivity conducting performance, intensity higher SBR/HVPBR rubber composite and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is: this SBR/HVPBR rubber composite, it is characterised in that weight portion composition includes: high vinyl polybutadiene rubber 10
~ 20 parts, 80 ~ 90 parts of the butadiene-styrene rubber of carbon nanotubes.The present invention provides one to have heat-conductivity conducting performance rubber composite, composite is based on butadiene-styrene rubber, add high vinyl polybutadiene rubber regulation material composition so that composite can adapt to the addition of CNT completely, does not affect the mechanical property of composite.CNT has very high-tensile and toughness, lightweight, and has electrical and thermal conductivity.The present invention is applied to rubber composite, is possible not only to strengthen the stress at definite elongation of rubber, hot strength, wearability, and can improve the heat conductivity of rubber, electric conductivity.
In the butadiene-styrene rubber of described carbon nanotubes, the mass fraction shared by CNT is 0.75% ~ 1.2%.CNT content requirement in butadiene-styrene rubber is higher, and in the composite of butadiene-styrene rubber and high vinyl polybutadiene rubber, addition is too high, affects processing characteristics, and addition is too low, affects the heat-conductivity conducting performance of composite.The inventors found that, in the ban CNT is joined the butadiene-styrene rubber obtaining carbon nanotubes in butadiene-styrene rubber, and accurately control CNT content in butadiene-styrene rubber, blend sulfurized with high vinyl polybutadiene rubber again, then less on processing characteristics impact, keep good heat-conductivity conducting performance, and produce more preferable mechanical property.
Described CNT is hydroxyl modification CNT or carboxy-modified CNT.CNT through hydroxyl modification or carboxy-modified after in butadiene-styrene rubber, be easier to dispersion, the combination with rubber is more firm, and heat-conductivity conducting performance is more prominent, and the mechanical property of composite is the most excellent.Preferably CNT is carboxy-modified CNT.
Described high vinyl polybutadiene rubber be contents of ethylene be more than 60%, ML100 DEG C of 1+4 of Mooney viscosity be 55 ~ 95 unformed elastomer.The Main Function of high vinyl polybutadiene rubber is processing characteristics and the mechanical property of the butadiene-styrene rubber of regulation carbon nanotubes, the present invention requiring, high vinyl polybutadiene rubber is that contents of ethylene is more than 60%, ML100 DEG C of 1+4 of Mooney viscosity is 55 ~ 95, the now strand of high vinyl polybutadiene rubber and the entanglement of butadiene-styrene rubber is more easy to occur, crosslinking points is the most uniform, and the mechanical property of composite reaches optimum state.
The preparation method of a kind of above-mentioned SBR/HVPBR rubber composite, it is characterised in that preparation process is:
1) carbon nano-tube aqueous solutions of the preparation mass concentration 4% ~ 7% that CNT is added to the water；
2) preparation mass concentration is that the saline solution of 17 ~ 23% is as flocculation mother solution；
3) by step 2) the flocculation mother solution that obtains joins in condensing field, add carbon nano-tube aqueous solutions 15 ~ 20 parts, SBR emulsion 80 ~ 99 parts is dripped again after stirring, temperature 60 ~ 70 DEG C, be condensed reaction under conditions of speed of agitator 300 ~ 400r/min, obtain the butadiene-styrene rubber of carbon nanotubes after condense；
4) 10 ~ 20 parts of high vinyl polybutadiene rubbers and 80 are weighed
The butadiene-styrene rubber of the carbon nanotubes of ~ 90 parts, is blended after 10 ~ 15min co-vulcanization in banbury and get final product.
Modified carbon nano-tube and butadiene-styrene rubber are flocculated in saline solution by the present invention, so that modified carbon nano-tube is fully included in butadiene-styrene rubber, and is uniformly dispersed；First CNT is made aqueous solution easily and saline solution stirring and evenly mixing, ensure the dispersed of CNT, then SBR emulsion is slowly added in the way of dropping, prevent CNT from reuniting in butadiene-styrene rubber, gradually condense under heating and stirring condition, during modified carbon nano-tube is so that state is included in butadiene-styrene rubber the most equably, the high vinyl polybutadiene rubber being subsequently adding specified quantitative is blend sulfurized, the mechanical property of regulation material and processing characteristics.Make this composite both have good heat conductive electric conductivity, there is again higher mechanical property.
CNT described in step 1) is to utilize the CNT of hydroxyl modification or utilize carboxy-modified CNT.Preferably, described modified carbon nano-tube is to utilize carboxy-modified CNT.It is more preferable that carboxy-modified CNT compares the CNT of hydroxyl modification dispersibility in coacervation process, more preferable to the modified effect of composite.
Described utilizes the CNT of hydroxyl modification for utilizing sodium hydrate aqueous solution that CNT is carried out the CNT of the hydroxyl modification that hydroxyl modification obtains.
The concrete preparation technology of the described CNT utilizing hydroxyl modification is: weighs 2 ~ 3g CNT and joins in the sodium hydrate aqueous solution that 50mL concentration is 1.7 ~ 2.3mol/L and dispersed with stirring；After this carbon nano tube dispersion liquid is poured into autoclave sealing, 175 ~ 185 DEG C of reaction 1.5 ~ 2.5h；Reaction is cooled to room temperature after terminating, and filtering, washing to filter liquor is neutrality, and again with methanol is washed 2 ~ 3 times；Much filtrate vacuum drying obtains hydroxyl modification carbon nanotube powder.
Described utilize carboxy-modified CNT for utilizing the toluene solution of azodiisobutyronitrile that CNT carries out carboxy-modified prepared carboxy-modified CNT.
The described concrete preparation technology utilizing carboxy-modified CNT is,
1) under continual stirring conditions, CNT and azodiisobutyronitrile (AIBN) 1:(1.5 ~ 2.3 in mass ratio) it is added separately in toluene；After logical nitrogen deoxygenation, react 3 ~ 5h at 70 DEG C ~ 78 DEG C；Product toluene 4 ~ 5 times final vacuums of washing are dried to obtain AIBN modified carbon nano tube pipe powder；
2) AIBN modified carbon nano-tube is scattered in the methanol solution of sodium hydroxide, 60 DEG C ~ 65 DEG C backflow 40 ~ 50h；After reaction terminates, with hydrochloric acid, pH value is adjusted to acidity；Product is washed with deionized 4 ~ 5 times, and vacuum drying obtains carboxy-modified carbon nanotube powder.
The hydroxyl of CNT or carboxy-modified method are the most ripe, hydroxyl or the carboxy-modified effect of CNT are more suitable in the coacervation process of butadiene-styrene rubber of the present invention synchronizing dispersion by the above-mentioned process conditions of the present invention, dispersion is more uniform, and agglomeration less occurs.The present invention respectively provides a kind of modified technique satisfactory for result, but utilizes the modified carbon nano-tube that the hydroxyl of traditional CNT or carboxy-modified method obtain if able to strengthen its dispersibility in butadiene-styrene rubber, it is also possible to be applied directly in the present invention.
Step 2) described in saline solution be the one in sodium-chloride water solution, calcium chloride water, aluminum sulfate aqueous solution.The above-mentioned saline solution of the present invention, after mixing with carbon nano-tube aqueous solutions, remains able to ensure the optimal aggregation speed of butadiene-styrene rubber emulsion, it is ensured that CNT fully dispersed.
Compared with prior art, a kind of SBR/HVPBR rubber composite of the present invention and preparation method thereof is had the beneficial effect that so that composite can adapt to the addition of CNT completely, does not affect the mechanical property of composite.The present invention will have very high-tensile and toughness, lightweight, and the CNT possessing electrical and thermal conductivity is applied to rubber composite, based on butadiene-styrene rubber, add high vinyl polybutadiene rubber regulation material composition, not only strengthen the stress at definite elongation of rubber, hot strength, wearability, and the heat conductivity of rubber, electric conductivity can be improved, can apply to thermal conductive tyre, thermal interfacial material etc..
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described, and wherein embodiment 1 is most preferred embodiment.
Embodiment 1
1) 50mg CNT is ultrasonic
(10min) it is scattered in 50mL toluene；The most under continual stirring conditions, the toluene solution (being l.0gAIBN dissolved in 10mL toluene) of 10mL azodiisobutyronitrile (AIBN) is added.After logical nitrogen 0.5h deoxygenation, 75 DEG C of reaction 4h；Product toluene washs 40 DEG C of dried in vacuum overnight after 4 ~ 5 times.Obtain the AIBN modified carbon nano tube pipe powder of black；30mgAIBN modified carbon nano-tube is scattered in (10M) in the methanol solution of 50mL sodium hydroxide, 60 DEG C of backflow 48h；After reaction terminates, with hydrochloric acid, pH value is adjusted to acid pH=3.0；Product is washed with deionized 4 ~ 5 times, 40 DEG C of dried in vacuum overnight；Obtain the carbon nanotube powder that black is carboxy-modified；5 parts of carboxy-modified carbon nanotube powders are dissolved in 95 parts of water, obtain the carboxy-modified carbon nano-tube aqueous solutions of 5%；
2) compound concentration is the sodium chloride solution of 20%, as flocculation mother solution；
3) carboxy-modified carbon nano-tube aqueous solutions 18 parts is weighed, butadiene-styrene rubber (SBR-1500 or SBR-1502) emulsion 90 parts；
4) prepare the butadiene-styrene rubber of carbon nanotubes, condensing field add deionized water, by step 2) the flocculation mother solution that obtains joins in condensing field, and start stirring, add carbon nano-tube aqueous solutions stirring 5min；It is subsequently adding the SBR emulsion of amount of calculation, the butadiene-styrene rubber particle dehydration after having condensed is dried to obtain the butadiene-styrene rubber of carbon nanotubes；Agglutination test controls condensation temperature 60 ~ 70 DEG C, speed of agitator 380r/min；
5) prepared by rubber composite, weigh the 15 parts of molybdenum system high vinyl polybutadiene rubbers (contents of ethylene amorphous elastomer more than 60%, ML100 DEG C of 1+4 of Mooney viscosity is 80) with the butadiene-styrene rubber of the carbon nanotubes of 85 parts, processing aid, after 10 ~ 15min is blended in banbury, co-vulcanization prepares.
Embodiment 2
1) weigh 2.5g CNT and join in the sodium hydrate aqueous solution that 50mL concentration is 2.mol/L and dispersed with stirring；This carbon nano tube dispersion liquid is poured into autoclave and seals rear 180 DEG C of reaction 2h；Reaction is cooled to room temperature after terminating, and filtering, washing to filter liquor is neutrality, and again with methanol is washed 3 times；Much filtrate vacuum drying obtains hydroxyl modification carbon nanotube powder；The carbon nano-tube aqueous solutions of preparation mass concentration 5% that CNT is added to the water；
2) butadiene-styrene rubber of carbon nanotubes is prepared；Condensing field adds deionized water temperature control, at 60 DEG C, to join in condensing field by 20% calcium chloride solution 150ml, start stirring, speed of agitator 400r/min, add 15 parts of step 1) hydroxyl modification carbon nano-tube aqueous solutions stirring 5min；95 parts of SBR-1502 latex are slowly added to, and are dried the butadiene-styrene rubber particle dehydration after having condensed；
3) 10 parts of molybdenum system high vinyl polybutadiene (HVPBR) rubber and 90 parts of steps 2 are weighed) after the butadiene-styrene rubber of carbon nanotubes for preparing plasticates 5 minutes, weigh 10 parts of white carbon blacks, processing aids, in banbury, 15min after cure is blended prepares rubber composite.
Embodiment 3
1) 50mg CNT is ultrasonic
(10min) it is scattered in 50mL toluene；The most under continual stirring conditions, the toluene solution (0.75gAIBN is dissolved in 10mL toluene) of 10mL azodiisobutyronitrile (AIBN) is added；After logical nitrogen 0.5h deoxygenation, 70 DEG C of reaction 5h；Product toluene washs 40 DEG C of dried in vacuum overnight after 4 ~ 5 times；Obtain the AIBN modified carbon nano tube pipe powder of black；30mgAIBN modified carbon nano-tube is scattered in (10M) in the methanol solution of 50mL sodium hydroxide, 60 DEG C of backflow 50h；After reaction terminates, with hydrochloric acid, pH value is adjusted to acid pH=3.0；Product is washed with deionized 4 ~ 5 times, 40 DEG C of dried in vacuum overnight；Obtain the carbon nanotube powder that black is carboxy-modified；5 parts of carboxy-modified carbon nanotube powders are dissolved in 95 parts of water, obtain the carboxy-modified carbon nano-tube aqueous solutions of 5%；
2) butadiene-styrene rubber of carbon nanotubes is prepared, condensing field adds deionized water temperature control, at 65 DEG C, to join in condensing field by 23% calcium chloride solution 200ml, start stirring, speed of agitator 350r/min, adds 20 parts of hydroxyl modification carbon nano-tube aqueous solutions stirring 5min；87 parts of SBR-1502 latex are slowly added to, and are dried the butadiene-styrene rubber particle dehydration after having condensed；
3) 10 parts of molybdenum systems high vinyl polybutadiene (HVPBR) are weighed
Rubber and 90 parts of steps 2) after the butadiene-styrene rubber of carbon nanotubes for preparing plasticates 5 minutes, weigh 26 parts of white carbon blacks, processing aids, in banbury, 15min after cure is blended prepares rubber composite.
Embodiment 4
1) weigh 2g CNT and join in the sodium hydrate aqueous solution that 50mL concentration is 1.7 mol/L and dispersed with stirring；This carbon nano tube dispersion liquid is poured into autoclave and seals rear 185 DEG C of reaction 1.5h；Reaction is cooled to room temperature after terminating, and filtering, washing to filter liquor is neutrality, and again with methanol is washed 3 times；Much filtrate vacuum drying obtains hydroxyl modification carbon nanotube powder；The carbon nano-tube aqueous solutions of preparation mass concentration 6% that CNT is added to the water；
2) butadiene-styrene rubber of carbon nanotubes is prepared.Condensing field adds deionized water temperature control, at 60 DEG C, to join in condensing field by 17% calcium chloride solution 220ml, start stirring, speed of agitator 350r/min, add 20 parts of step 1) hydroxyl modification carbon nano-tube aqueous solutions stirring 5min；95 parts of SBR-1502 latex are slowly added to, and are dried the butadiene-styrene rubber particle dehydration after having condensed；
3) 20 parts of molybdenum systems high vinyl polybutadiene (HVPBR) are weighed
Rubber and the butadiene-styrene rubber of 80 parts of carbon nanotubes prepared for step a), 42 parts of white carbon blacks, a certain amount of processing aids, after 15min being blended in banbury, co-vulcanization prepares rubber composite.
Embodiment 5
1) 50mg CNT is ultrasonic
(10min) it is scattered in 50mL toluene；The most under continual stirring conditions, the toluene solution of 10mL azodiisobutyronitrile (AIBN) is added
(1.15gAIBN is dissolved in 10mL toluene).After logical nitrogen 0.5h deoxygenation, 78 DEG C of reaction 3h；Product toluene washs 40 DEG C of dried in vacuum overnight after 4 ~ 5 times.Obtain the AIBN modified carbon nano tube pipe powder of black；30mgAIBN modified carbon nano-tube is scattered in (10M) in the methanol solution of 50mL sodium hydroxide, 65 DEG C of backflow 40h；After reaction terminates, with hydrochloric acid, pH value is adjusted to acid pH=3.0；Product is washed with deionized 4 ~ 5 times, 40 DEG C of dried in vacuum overnight；Obtain the carbon nanotube powder that black is carboxy-modified；7 parts of carboxy-modified carbon nanotube powders are dissolved in 93 parts of water, obtain the carboxy-modified carbon nano-tube aqueous solutions of 7%；
2) butadiene-styrene rubber of carbon nanotubes is prepared, condensing field adds deionized water temperature control, at 65 DEG C, to join in condensing field by 22% calcium chloride solution 200ml, start stirring, speed of agitator 350r/min, adds 18 parts of hydroxyl modification carbon nano-tube aqueous solutions stirring 5min；80 parts of SBR-1502 latex are slowly added to, and are dried the butadiene-styrene rubber particle dehydration after having condensed；
3) 15 parts of molybdenum systems high vinyl polybutadiene (HVPBR) are weighed
Rubber and 85 parts of steps 2) after the butadiene-styrene rubber of carbon nanotubes for preparing plasticates 5 minutes, weigh 26 parts of white carbon blacks, processing aids, in banbury, 12min after cure is blended prepares rubber composite.
Embodiment 6
1) weigh 3g CNT and join in the sodium hydrate aqueous solution that 50mL concentration is 2.3mol/L and dispersed with stirring；This carbon nano tube dispersion liquid is poured into autoclave and seals rear 175 DEG C of reaction 2.5h；Reaction is cooled to room temperature after terminating, and filtering, washing to filter liquor is neutrality, and again with methanol is washed 2 times；Much filtrate vacuum drying obtains hydroxyl modification carbon nanotube powder；The carbon nano-tube aqueous solutions of preparation mass concentration 4% that CNT is added to the water；
2) butadiene-styrene rubber of carbon nanotubes is prepared.Condensing field adds deionized water temperature control, at 60 DEG C, to join in condensing field by 21% aluminum sulfate solution 150ml, start stirring, speed of agitator 350r/min, add 15 parts of step 1) hydroxyl modification carbon nano-tube aqueous solutions stirring 5min；99 parts of SBR-1502 latex are slowly added to, and are dried the butadiene-styrene rubber particle dehydration after having condensed；
3) 20 parts of molybdenum systems high vinyl polybutadiene (HVPBR) are weighed
Rubber and 80 parts of steps1)The butadiene-styrene rubber of the carbon nanotubes prepared, 42 parts of white carbon blacks, a certain amount of processing aids, after 10min being blended in banbury, co-vulcanization prepares rubber composite.
Comparative example 1
Weigh 90 parts of styrene butadiene rubber sbrs-1502,10 parts of molybdenum system high vinyl polybutadiene (HVPBR) rubber are blended after plasticating 5 minutes in banbury, weighing 50 parts of white carbon blacks, processing aid, after 20min being blended in banbury, co-vulcanization prepares rubber composite.
Comparative example 2
Weighing 85 parts containing mass fraction is the styrene butadiene rubber sbr-1502 of 0.3% CNT; in butadiene-styrene rubber, the interpolation of CNT and modification mode are with embodiment 1; 15 parts of molybdenum system high vinyl polybutadiene (HVPBR) rubber are blended after plasticating 5 minutes in banbury; processing aid, after 20min being blended in banbury, co-vulcanization prepares rubber composite.
Comparative example 3
Weigh 80 parts of styrene butadiene rubber sbrs-1502,20 parts of molybdenum system high vinyl polybutadiene (HVPBR) rubber, are blended in banbury after plasticating 5 minutes, weigh 50 parts of white carbon blacks, processing aid, after 20min being blended in banbury, co-vulcanization prepares rubber composite.
The performance test results of each embodiment and comparative example composite is shown in Table 1.
Table 1 embodiment and the performance test results of comparative example composite
。
Upper table is the project testing situation of embodiment and comparative example.As can be seen from the table, in embodiment, hot strength and stress at definite elongation containing CNT rubber composite are substantially better than comparative example, in embodiment, in resistivity relatively comparative example, resistivity reduces an order of magnitude, show that CNT can significantly improve the electric conductivity of rubber composite, in embodiment, thermal conductivity rises with the increase of content of carbon nanotubes, shows that the heat conductivility of carbon nanotubes rubber composite is better than in comparative example the rubber composite of not carbon nanotubes.Can be seen that, when content of carbon nanotubes is too low, effect is less desirable from comparative example 2, but have certain modified effect.
The above, be only presently preferred embodiments of the present invention, is not the restriction that the present invention makees other form, and any those skilled in the art are changed possibly also with the technology contents of the disclosure above or are modified as the Equivalent embodiments of equivalent variations.But every without departing from technical solution of the present invention content, any simple modification, equivalent variations and remodeling above example made according to the technical spirit of the present invention, still fall within the protection domain of technical solution of the present invention.
Claims (11)
1. a SBR/HVPBR rubber composite, it is characterised in that weight portion composition includes: high vinyl polybutadiene rubber 10
~ 20 parts, the butadiene-styrene rubber 80 of carbon nanotubes
~ 90 parts.
A kind of SBR/HVPBR rubber composite the most according to claim 1, it is characterised in that: in the butadiene-styrene rubber of described carbon nanotubes, the mass fraction shared by CNT is 0.75% ~ 1.2%.
A kind of SBR/HVPBR rubber composite the most according to claim 2, it is characterised in that: described CNT is hydroxyl modification CNT or carboxy-modified CNT.
A kind of SBR/HVPBR rubber composite the most according to claim 1, it is characterised in that: described high vinyl polybutadiene rubber be contents of ethylene be more than 60%, ML100 DEG C of 1+4 of Mooney viscosity be 55 ~ 95 unformed elastomer.
5. the preparation method of SBR/HVPBR rubber composite described in an any one of claim 1 ~ 4, it is characterised in that preparation process is:
1) carbon nano-tube aqueous solutions of the preparation mass concentration 4% ~ 7% that CNT is added to the water；
2) preparation mass concentration is that the saline solution of 17 ~ 23% is as flocculation mother solution；
3) by step 2) the flocculation mother solution that obtains joins in condensing field, add carbon nano-tube aqueous solutions 15 ~ 20 parts, SBR emulsion 80 ~ 99 parts is dripped again after stirring, under conditions of temperature 60 ~ 70 DEG C, speed of agitator 300 ~ 400r/min, it is condensed reaction, after having condensed, obtains the butadiene-styrene rubber of carbon nanotubes；
4) 10 ~ 20 parts of high vinyl polybutadiene rubbers and 80 are weighed
The butadiene-styrene rubber of the carbon nanotubes of ~ 90 parts, is blended after 10 ~ 15min co-vulcanization in banbury and get final product.
The preparation method of a kind of SBR/HVPBR rubber composite the most according to claim 5, it is characterised in that: the CNT described in step 1) is to utilize the CNT of hydroxyl modification or utilize carboxy-modified CNT.
The preparation method of a kind of SBR/HVPBR rubber composite the most according to claim 6, it is characterised in that: described utilizes the CNT of hydroxyl modification for utilizing sodium hydrate aqueous solution that CNT is carried out the CNT of the hydroxyl modification that hydroxyl modification obtains.
The preparation method of a kind of SBR/HVPBR rubber composite the most according to claim 6, it is characterised in that: the concrete preparation technology of the described CNT utilizing hydroxyl modification is: weighs 2 ~ 3g CNT and joins in the sodium hydrate aqueous solution that 50mL concentration is 1.7 ~ 2.3mol/L and dispersed with stirring；After this carbon nano tube dispersion liquid is poured into autoclave sealing, 175 ~ 185 DEG C of reaction 1.5 ~ 2.5h；Reaction is cooled to room temperature after terminating, and filtering, washing to filter liquor is neutrality, and again with methanol is washed 2 ~ 3 times；Much filtrate vacuum drying obtains hydroxyl modification carbon nanotube powder.
The preparation method of a kind of SBR/HVPBR rubber composite the most according to claim 6, it is characterised in that: described utilize carboxy-modified CNT for utilizing the toluene solution of azodiisobutyronitrile that CNT carries out carboxy-modified prepared carboxy-modified CNT.
The preparation method of a kind of SBR/HVPBR rubber composite the most according to claim 6, it is characterised in that: the described concrete preparation technology utilizing carboxy-modified CNT is,
1) under continual stirring conditions, CNT and azodiisobutyronitrile 1:(1.5 ~ 2.3 in mass ratio) it is added separately in toluene；After logical nitrogen deoxygenation, react 3 ~ 5h at 70 DEG C ~ 78 DEG C；Product toluene 4 ~ 5 times final vacuums of washing are dried to obtain AIBN modified carbon nano tube pipe powder；
2) AIBN modified carbon nano-tube is scattered in the methanol solution of sodium hydroxide, 60 DEG C ~ 65 DEG C backflow 40 ~ 50h；After reaction terminates, with hydrochloric acid, pH value is adjusted to acidity；Product is washed with deionized 4 ~ 5 times, and vacuum drying obtains carboxy-modified carbon nanotube powder.
The preparation method of 11. a kind of SBR/HVPBR rubber composites according to claim 5, it is characterised in that: step 2) described in saline solution be the one in sodium-chloride water solution, calcium chloride water, aluminum sulfate aqueous solution.
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