CN106317517B - A kind of SBR/HVPBR rubber composite materials - Google Patents

A kind of SBR/HVPBR rubber composite materials Download PDF

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CN106317517B
CN106317517B CN201510336420.1A CN201510336420A CN106317517B CN 106317517 B CN106317517 B CN 106317517B CN 201510336420 A CN201510336420 A CN 201510336420A CN 106317517 B CN106317517 B CN 106317517B
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rubber
carbon nanotube
carbon
parts
sbr
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CN201510336420.1A
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CN106317517A (en
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王晓敏
李迎
李静
刘浩
孙丽朋
张桦
刘容德
桂俊杰
王晶
张新华
苏建华
孙培培
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中国石油化工股份有限公司
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Abstract

A kind of SBR/HVPBR rubber composite materials, belong to rubber processing techniques field, and composite material is characterized in that, parts by weight composition includes:80 ~ 90 parts of the butadiene-styrene rubber of 10 ~ 20 parts of high vinyl polybutadiene rubber, carbon nanotubes.Preparation method, which is characterized in that SBR emulsion is added dropwise again and is condensed after carbon nano-tube aqueous solutions are first stirred evenly with salting liquid and reacts, obtains the butadiene-styrene rubber of carbon nanotubes;Again by high vinyl polybutadiene rubber and the butadiene-styrene rubber of carbon nanotubes, co-vulcanization after 10 ~ 15min is blended in mixer.Carbon nanotube is applied to rubber composite material by the present invention, can not only enhance the stress at definite elongation of rubber, tensile strength, wearability, but also can improve the thermal conductivity of rubber, electric conductivity.

Description

A kind of SBR/HVPBR rubber composite materials
Technical field
A kind of SBR/HVPBR rubber composite materials, belong to rubber processing techniques field.
Background technology
High vinyl polybutadiene rubber(HVPBR)It is a kind of high-performance with low-rolling-resistance and good anti-slippery Rubber is blended with butadiene-styrene rubber (SBR) blended characteristic better than butadiene rubber and butadiene-styrene rubber, is the excellent of manufacture rubber tire tread One of different material.To improve the wearability and stress at definite elongation of tire, carbon black is added in rubber mixing process, carbon black is extensively should For the important reinforcing material of tire, and filling number is more than 40 parts and just has remarkable result.And carbon black is often difficult to mend in rubber Obtain the breakthrough of bigger simultaneously with two aspect of functionalization by force.
Carbon nanotube also known as Baji-tube are the carbon pipes formed by the curling of graphite carbon source sublayer.Pipe diameter is generally several receive Rice is to tens nanometers, and pipe thickness is only several nanometers, the hollow cylindrical " cage type pipe " being rolled into as wire netting.It is One kind has special construction(Radial dimension is nanometer scale, axial dimension is that micron dimension, draw ratio be very big, two end group of pipe It is all sealed in sheet)One-dimensional Quantum material.Carbon nanotube is considered as a kind of new function material and structural wood haveing excellent performance Material.
Invention content
The technical problem to be solved by the present invention is to:Overcome the deficiencies of the prior art and provide it is a kind of have thermal conductivity, The higher SBR/HVPBR rubber composite materials of intensity.
The technical solution adopted by the present invention to solve the technical problems is:The SBR/HVPBR rubber composite materials, feature It is, parts by weight composition includes:The butadiene-styrene rubber 80 ~ 90 of 10 ~ 20 parts of high vinyl polybutadiene rubber, carbon nanotubes Part.The present invention, which provides one kind, has thermal conductivity rubber composite material, and composite material adds in Gao Yi based on butadiene-styrene rubber Alkenyl polybutadiene rubber adjusts material composition so that composite material can adapt to the addition of carbon nanotube completely, not influence multiple The mechanical property of condensation material.Carbon nanotube has very high-tensile and toughness, light-weight, and with electrical and thermal conductivity.This hair It is bright to be applied to rubber composite material, it can not only enhance the stress at definite elongation of rubber, tensile strength, wearability, but also can be with Improve thermal conductivity, the electric conductivity of rubber.
Mass fraction in the butadiene-styrene rubber of the carbon nanotubes shared by carbon nanotube is 0.75% ~ 1.2%.Carbon nanometer Content requirement of the pipe in butadiene-styrene rubber is higher, in the composite material of butadiene-styrene rubber and high vinyl polybutadiene rubber, adds It is excessively high to enter amount, influences processing performance, addition is too low, influences the thermal conductivity of composite material.The present inventor It was found that carbon nanotube is added in the ban the butadiene-styrene rubber that carbon nanotubes is obtained in butadiene-styrene rubber, and accurately control carbon nanometer Pipe content in butadiene-styrene rubber, then it is blend sulfurized with high vinyl polybutadiene rubber, then smaller, holding is influenced on processing performance Good thermal conductivity, and generate better mechanical property.
The carbon nanotube is hydroxyl modification carbon nanotube or carboxy-modified carbon nanotube.Carbon nanotube changes through perhydroxyl radical Property or it is carboxy-modified after be easier to disperse in butadiene-styrene rubber, and rubber combination also more securely, thermal conductivity is more prominent Go out, the mechanical property of composite material is also more excellent.Preferred carbon nanotube is carboxy-modified carbon nanotube.
The high vinyl polybutadiene rubber is more than 60%, Mooney viscosity ML for contents of ethylene1+4100 DEG C are 55 ~ 95 unformed elastomer.The main function of high vinyl polybutadiene rubber is the butadiene-styrene rubber for adjusting carbon nanotubes Processing performance and mechanical property require high vinyl polybutadiene rubber to be more than 60%, Mooney for contents of ethylene and glue in of the invention Spend ML1+4100 DEG C are 55 ~ 95, and the entanglement of the strand and butadiene-styrene rubber of high vinyl polybutadiene rubber at this time is more easy to send out Raw, crosslinking points are the most uniform, and the mechanical property of composite material reaches optimum state.
A kind of preparation method of above-mentioned SBR/HVPBR rubber composite materials, which is characterized in that preparation process is:
1)Carbon nanotube is added to the water and prepares the carbon nano-tube aqueous solutions of mass concentration 4% ~ 7%;
2)It prepares the salting liquid that mass concentration is 17 ~ 23% and is used as flocculation mother liquor;
3)By step 2)Obtained flocculation mother liquor is added in condensing field, adds in 15 ~ 20 parts of carbon nano-tube aqueous solutions, stirring Be added dropwise 80 ~ 99 parts of SBR emulsion again after uniformly, temperature under conditions of 60 ~ 70 DEG C, 300 ~ 400r/min of speed of agitator into Row aggregation obtains the butadiene-styrene rubber of carbon nanotubes after the completion of cohesion;
4)The butadiene-styrene rubber of 10 ~ 20 parts of high vinyl polybutadiene rubbers and 80 ~ 90 parts of carbon nanotubes is weighed, In mixer be blended 10 ~ 15min after co-vulcanization to obtain the final product.
Modified carbon nano-tube and butadiene-styrene rubber are flocculated in salting liquid in the present invention, so that modified carbon nano-tube fills Subpackage is contained in butadiene-styrene rubber, and is uniformly dispersed;Carbon nanotube is made aqueous solution first easily to stir and evenly mix with salting liquid, is protected The homodisperse of carbon nanotube is demonstrate,proved, then SBR emulsion is slowly added in a manner of being added dropwise, and prevents carbon nanotube in butylbenzene Reunite in rubber, heating and gradually agglomerated under stirring condition, modified carbon nano-tube is with most equably state is included in butylbenzene rubber In glue, the high vinyl polybutadiene rubber for then adding in specific quantity is blend sulfurized, adjusts the mechanical property and processability of material Energy.So that this composite material not only has good heat conductive electric conductivity, but also with higher mechanical property.
Step 1)Described in carbon nanotube for utilize hydroxyl modification carbon nanotube or utilize carboxy-modified carbon nanometer Pipe.Preferably, the modified carbon nano-tube is to utilize carboxy-modified carbon nanotube.Carboxy-modified carbon nanotube compares hydroxyl Modified carbon nanotube dispersibility in coacervation process is more preferable, also more preferable to the modified effect of composite material.
The carbon nanotube using hydroxyl modification is to carry out hydroxyl to carbon nanotube using sodium hydrate aqueous solution to change The carbon nanotube of hydroxyl modification that property obtains.
The specific preparation process of the carbon nanotube using hydroxyl modification is:2 ~ 3g carbon nanotubes are weighed to be added to In the sodium hydrate aqueous solution of a concentration of 1.7 ~ 2.3mol/L of 50mL and it is dispersed with stirring;The carbon nano tube dispersion liquid is poured into height After pressing reaction kettle sealing, 175 ~ 185 DEG C of 1.5 ~ 2.5h of reaction;It is cooled to room temperature after reaction, is filtered, washed to filter liquor and is Neutrality, again with methanol are washed 2 ~ 3 times;Much filtrate is dried in vacuo to obtain hydroxyl modification carbon nanotube powder.
It is described using carboxy-modified carbon nanotube be using azodiisobutyronitrile toluene solution to carbon nanotube into The carboxy-modified carboxy-modified carbon nanotube obtained of row.
Described is using the specific preparation process of carboxy-modified carbon nanotube,
1)Under continual stirring conditions, carbon nanotube and azodiisobutyronitrile(AIBN)In mass ratio 1:(1.5~2.3)Point It is not added in toluene;After logical nitrogen deoxygenation, 3 ~ 5h is reacted at 70 DEG C ~ 78 DEG C;Vacuum after reaction product washs 4 ~ 5 times with toluene It is dried to obtain AIBN modified carbon nano tube pipe powders;
2)AIBN modified carbon nano-tubes are scattered in the methanol solution of sodium hydroxide, 60 DEG C ~ 65 DEG C 40 ~ 50h of reflux;Instead After answering, pH value is adjusted to acidity with hydrochloric acid;Product is washed with deionized 4 ~ 5 times, and vacuum drying obtains carboxy-modified Carbon nanotube powder.
The hydroxyl of carbon nanotube or carboxy-modified method are more mature, and above-mentioned process conditions of the invention are to carbon nanometer The hydroxyl of pipe or carboxy-modified effect are more suitable in the coacervation process of butadiene-styrene rubber of the present invention synchronous dispersion, and dispersion is more uniform, Agglomeration less occurs.The present invention only respectively provides a kind of effect ideal modified technique, but utilizes traditional carbon nanotube If the obtained modified carbon nano-tube of hydroxyl or carboxy-modified method can enhance its dispersibility in butadiene-styrene rubber, also may be used To be applied directly in the present invention.
Step 2)Described in salting liquid be sodium-chloride water solution, calcium chloride water, one kind in aluminum sulfate aqueous solution. The above-mentioned salting liquid of the present invention remains able to ensure the best solidifying of butadiene-styrene rubber emulsion after mixing with carbon nano-tube aqueous solutions Poly- reaction rate ensures the fully dispersed of carbon nanotube.
Compared with prior art, advantageous effect possessed by a kind of SBR/HVPBR rubber composite materials of the invention is:Make The addition of carbon nanotube can be adapted to completely by obtaining composite material, not influence the mechanical property of composite material.The present invention will have very It is high-tensile and toughness, light-weight, and the carbon nanotube for having electrical and thermal conductivity is applied to rubber composite material, with butylbenzene rubber Based on glue, add in high vinyl polybutadiene rubber and adjust material composition, not only enhance the stress at definite elongation of rubber, tensile strength, Wearability, and the thermal conductivity of rubber, electric conductivity can be improved, it can be applied to thermal conductive tyre, thermal interfacial material etc..
Specific embodiment
With reference to specific embodiment, the present invention will be further described, and wherein embodiment 1 is most preferred embodiment.
Embodiment 1
1)50mg carbon nanotubes ultrasound (10min) is scattered in 50mL toluene;Then under continual stirring conditions, add in 10mL azodiisobutyronitriles(AIBN)Toluene solution(L.0gAIBN it is dissolved in 10mL toluene).After logical nitrogen 0.5h deoxygenations, 75 DEG C of reaction 4h;It is dried in vacuum overnight for 40 DEG C after reaction product washs 4 ~ 5 times with toluene.Obtain the AIBN modified carbon nano tubes of black Pipe powder;30mgAIBN modified carbon nano-tubes are scattered in the methanol solution of 50mL sodium hydroxides(10M), 60 DEG C of reflux 48h;Instead After answering, pH value is adjusted to acid pH=3.0 with hydrochloric acid;Product is washed with deionized 4 ~ 5 times, and 40 DEG C are dried in vacuum overnight; Obtain the carboxy-modified carbon nanotube powder of black;5 parts of carboxy-modified carbon nanotube powders are dissolved in 95 parts of water, obtain 5% Carboxy-modified carbon nano-tube aqueous solutions;
2)Compound concentration is 20% sodium chloride solution, as flocculation mother liquor;
3)Weigh carboxy-modified 18 parts of carbon nano-tube aqueous solutions, butadiene-styrene rubber(SBR-1500 or SBR-1502)Lotion 90 Part;
4)The butadiene-styrene rubber of carbon nanotubes is prepared, deionized water is added in condensing field, by step 2)Obtained flocculation is female Liquid is added in condensing field, starts stirring, adds in carbon nano-tube aqueous solutions stirring 5min;Then the butadiene-styrene rubber of calculation amount is added in Lotion is dried to obtain the butadiene-styrene rubber particle dehydration after the completion of cohesion in the butadiene-styrene rubber of carbon nanotubes;Agglutination test controls 60 ~ 70 DEG C of condensation temperature, speed of agitator 380r/min;
5)Prepared by rubber composite material, weigh 15 parts of molybdenum system high vinyl polybutadiene rubbers(Contents of ethylene is more than 60% amorphous elastomer, Mooney viscosity ML1+4100 DEG C are 80)With the butadiene-styrene rubber of 85 parts of carbon nanotubes, processing helps Agent, co-vulcanization is made after 10 ~ 15min is blended in mixer.
Embodiment 2
1)It weighs 2.5g carbon nanotubes and is added in the sodium hydrate aqueous solution of a concentration of 2.mol/L of 50mL and stirs and divide It dissipates;The carbon nano tube dispersion liquid is poured into 180 DEG C of reaction 2h after autoclave seals;It is cooled to room temperature after reaction, mistake Filter is washed to filter liquor to be neutral, and again with methanol is washed 3 times;Much filtrate is dried in vacuo to obtain hydroxyl modification carbon nanotube powder; Carbon nanotube is added to the water and prepares the carbon nano-tube aqueous solutions of mass concentration 5%;
2)Prepare the butadiene-styrene rubber of carbon nanotubes;The control of deionized water temperature is added in condensing field at 60 DEG C, by 20% chlorine Change calcium solution 150ml to be added in condensing field, start stirring, speed of agitator 400r/min adds in 15 parts of steps 1)Hydroxyl modification Carbon nano-tube aqueous solutions stir 5min;95 parts of SBR-1502 latex are slowly added to, and the butadiene-styrene rubber particle after the completion of cohesion is taken off Water is dried;
3)Weigh 10 parts of molybdenum system high vinyl polybutadienes(HVPBR)Rubber and 90 parts of steps 2)Carbon containing nanometer obtained The butadiene-styrene rubber of pipe is plasticated after five minutes, weighs 10 parts of carbon blacks, processing aids, 15min after cure is blended in mixer, rubber is made Glue composite material.
Embodiment 3
1)50mg carbon nanotubes ultrasound (10min) is scattered in 50mL toluene;Then under continual stirring conditions, add in The toluene solution of 10mL azodiisobutyronitriles (AIBN) (0.75gAIBN is dissolved in 10mL toluene);Logical nitrogen 0.5h deoxygenations Afterwards, 70 DEG C of reaction 5h;It is dried in vacuum overnight for 40 DEG C after reaction product washs 4 ~ 5 times with toluene;Obtain the AIBN carbon modifieds of black Nanotube powder;30mgAIBN modified carbon nano-tubes are scattered in the methanol solution of 50mL sodium hydroxides (10M), 60 DEG C of reflux 50h;After reaction, pH value is adjusted to acid pH=3.0 with hydrochloric acid;Product is washed with deionized 4 ~ 5 times, and 40 DEG C of vacuum are done It is dry overnight;Obtain the carboxy-modified carbon nanotube powder of black;5 parts of carboxy-modified carbon nanotube powders are dissolved in 95 parts of water, Obtain 5% carboxy-modified carbon nano-tube aqueous solutions;
2)The butadiene-styrene rubber of carbon nanotubes is prepared, the control of deionized water temperature is added in condensing field at 65 DEG C, by 23% Calcium chloride solution 200ml is added in condensing field, starts stirring, and speed of agitator 350r/min adds in 20 parts of hydroxyl modification carbon and receives Mitron aqueous solution stirs 5min;87 parts of SBR-1502 latex are slowly added to, and the butadiene-styrene rubber particle dehydration after the completion of cohesion is done It is dry;
3)Weigh 10 parts of molybdenum system high vinyl polybutadiene (HVPBR) rubber and 90 parts of steps 2)Carbon containing nanometer obtained The butadiene-styrene rubber of pipe is plasticated after five minutes, weighs 26 parts of carbon blacks, processing aids, 15min after cure is blended in mixer, rubber is made Glue composite material.
Embodiment 4
1)It weighs 2g carbon nanotubes and is added in the sodium hydrate aqueous solution of a concentration of 1.7 mol/L of 50mL and stirs and divide It dissipates;The carbon nano tube dispersion liquid is poured into 185 DEG C of reaction 1.5h after autoclave seals;It is cooled to room temperature after reaction, It is neutrality to be filtered, washed to filter liquor, and again with methanol is washed 3 times;Much filtrate is dried in vacuo to obtain hydroxyl modification carbon nanotube powders End;Carbon nanotube is added to the water and prepares the carbon nano-tube aqueous solutions of mass concentration 6%;
2)Prepare the butadiene-styrene rubber of carbon nanotubes.The control of deionized water temperature is added in condensing field at 60 DEG C, by 17% chlorine Change calcium solution 220ml to be added in condensing field, start stirring, speed of agitator 350r/min adds in 20 parts of steps 1)Hydroxyl modification Carbon nano-tube aqueous solutions stir 5min;95 parts of SBR-1502 latex are slowly added to, and the butadiene-styrene rubber particle after the completion of cohesion is taken off Water is dried;
3)Weigh carbon containing nanometer made from 20 parts of molybdenum system high vinyl polybutadiene (HVPBR) rubber and 80 parts of step a) The butadiene-styrene rubber of pipe, 42 parts of carbon blacks, a certain amount of processing aid, co-vulcanization is made rubber and answers after 15min is blended in mixer Condensation material.
Embodiment 5
1)50mg carbon nanotubes ultrasound (10min) is scattered in 50mL toluene;Then under continual stirring conditions, add in The toluene solution of 10mL azodiisobutyronitriles (AIBN) (1.15gAIBN is dissolved in 10mL toluene).Logical nitrogen 0.5h deoxygenations Afterwards, 78 DEG C of reaction 3h;It is dried in vacuum overnight for 40 DEG C after reaction product washs 4 ~ 5 times with toluene.Obtain the AIBN carbon modifieds of black Nanotube powder;30mgAIBN modified carbon nano-tubes are scattered in the methanol solution of 50mL sodium hydroxides (10M), 65 DEG C of reflux 40h;After reaction, pH value is adjusted to acid pH=3.0 with hydrochloric acid;Product is washed with deionized 4 ~ 5 times, and 40 DEG C of vacuum are done It is dry overnight;Obtain the carboxy-modified carbon nanotube powder of black;7 parts of carboxy-modified carbon nanotube powders are dissolved in 93 parts of water, Obtain 7% carboxy-modified carbon nano-tube aqueous solutions;
2)The butadiene-styrene rubber of carbon nanotubes is prepared, the control of deionized water temperature is added in condensing field at 65 DEG C, by 22% Calcium chloride solution 200ml is added in condensing field, starts stirring, and speed of agitator 350r/min adds in 18 parts of hydroxyl modification carbon and receives Mitron aqueous solution stirs 5min;80 parts of SBR-1502 latex are slowly added to, and the butadiene-styrene rubber particle dehydration after the completion of cohesion is done It is dry;
3)Weigh 15 parts of molybdenum system high vinyl polybutadiene (HVPBR) rubber and 85 parts of steps 2)Carbon containing nanometer obtained The butadiene-styrene rubber of pipe is plasticated after five minutes, weighs 26 parts of carbon blacks, processing aids, 12min after cure is blended in mixer, rubber is made Glue composite material.
Embodiment 6
1)It weighs 3g carbon nanotubes and is added in the sodium hydrate aqueous solution of a concentration of 2.3mol/L of 50mL and stirs and divide It dissipates;The carbon nano tube dispersion liquid is poured into 175 DEG C of reaction 2.5h after autoclave seals;It is cooled to room temperature after reaction, It is neutrality to be filtered, washed to filter liquor, and again with methanol is washed 2 times;Much filtrate is dried in vacuo to obtain hydroxyl modification carbon nanotube powders End;Carbon nanotube is added to the water and prepares the carbon nano-tube aqueous solutions of mass concentration 4%;
2)Prepare the butadiene-styrene rubber of carbon nanotubes.The control of deionized water temperature is added in condensing field at 60 DEG C, by 21% sulphur Sour aluminum solutions 150ml is added in condensing field, starts stirring, and speed of agitator 350r/min adds in 15 parts of steps 1)Hydroxyl modification Carbon nano-tube aqueous solutions stir 5min;99 parts of SBR-1502 latex are slowly added to, and the butadiene-styrene rubber particle after the completion of cohesion is taken off Water is dried;
3)Weigh carbon containing nanometer made from 20 parts of molybdenum system high vinyl polybutadiene (HVPBR) rubber and 80 parts of steps 1) The butadiene-styrene rubber of pipe, 42 parts of carbon blacks, a certain amount of processing aid, co-vulcanization is made rubber and answers after 10min is blended in mixer Condensation material.
Comparative example 1
90 parts of styrene butadiene rubber sbr -1502,10 part molybdenum system high vinyl polybutadiene (HVPBR) rubber are weighed in mixing Blending is plasticated after five minutes in machine, weighs 50 parts of carbon blacks, processing aid, rubber is made in co-vulcanization after 20min is blended in mixer Composite material.
Comparative example 2
85 parts are weighed containing styrene butadiene rubber sbr -1502 that mass fraction is 0.3% carbon nanotube, carbon nanometer in butadiene-styrene rubber The addition of pipe and modification mode are common in mixer with 1,15 parts of molybdenum system high vinyl polybutadiene (HVPBR) rubber of embodiment Mixed to plasticate after five minutes, processing aid, rubber composite material is made in co-vulcanization after 20min is blended in mixer.
Comparative example 3
80 parts of styrene butadiene rubber sbr -1502,20 part molybdenum system high vinyl polybutadiene (HVPBR) rubber are weighed, close Blending is plasticated after five minutes in mill, weighs 50 parts of carbon blacks, processing aid, rubber is made in co-vulcanization after 20min is blended in mixer Glue composite material.
The performance test results of each embodiment and comparative example composite material are shown in Table 1.
The performance test results of 1 embodiment and comparative example composite material of table
Upper table is the project testing situation of embodiment and comparative example.As can be seen from the table, carbon nanometer is contained in embodiment The tensile strength and stress at definite elongation of pipe rubber composite material are substantially better than comparative example, and resistivity is compared with resistance in comparative example in embodiment Rate reduces an order of magnitude, shows that carbon nanotube can significantly improve the electric conductivity of rubber composite material, thermal conductivity in embodiment Rise with the increase of content of carbon nanotubes, show that the heat conductivility of carbon nanotubes rubber composite material is better than in comparative example not The rubber composite material of carbon nanotubes.From comparative example 2 it can be seen that when content of carbon nanotubes is too low, effect is not to manage very much Think, but have certain modified effect.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc. Imitate embodiment.But it is every without departing from technical solution of the present invention content, technical spirit according to the present invention is to above example institute Any simple modification, equivalent variations and the remodeling made still fall within the protection domain of technical solution of the present invention.

Claims (8)

1. a kind of SBR/HVPBR rubber composite materials, which is characterized in that parts by weight composition includes:High vinyl polybutadiene rubber 80 ~ 90 parts of the butadiene-styrene rubber of 10 ~ 20 parts of glue, carbon nanotubes;
Mass fraction in the butadiene-styrene rubber of the carbon nanotubes shared by carbon nanotube is 0.75% ~ 1.2%;
Preparation process is:
1)Carbon nanotube is added to the water and prepares the carbon nano-tube aqueous solutions of mass concentration 4% ~ 7%;
2)It prepares the salting liquid that mass concentration is 17 ~ 23% and is used as flocculation mother liquor;
3)By step 2)Obtained flocculation mother liquor is added in condensing field, is added in 15 ~ 20 parts of carbon nano-tube aqueous solutions, is stirred evenly 80 ~ 99 parts of SBR emulsion is added dropwise again afterwards, is coagulated under conditions of 60 ~ 70 DEG C of temperature, 300 ~ 400r/min of speed of agitator Poly- reaction obtains the butadiene-styrene rubber of carbon nanotubes after the completion of cohesion;
4)The butadiene-styrene rubber of 10 ~ 20 parts of high vinyl polybutadiene rubbers and 80 ~ 90 parts of carbon nanotubes is weighed, close In mill be blended 10 ~ 15min after co-vulcanization to obtain the final product.
2. a kind of SBR/HVPBR rubber composite materials according to claim 1, it is characterised in that:The high-vinyl Polybutadiene rubber is more than 60%, Mooney viscosity ML for contents of ethylene1+4100 DEG C be 55 ~ 95 unformed elastomer.
3. a kind of SBR/HVPBR rubber composite materials according to claim 1, it is characterised in that:Step 1)Described in Carbon nanotube is the carbon nanotube using hydroxyl modification or utilizes carboxy-modified carbon nanotube.
4. a kind of SBR/HVPBR rubber composite materials according to claim 3, it is characterised in that:Described utilizes hydroxyl Modified carbon nanotube is to carry out the carbon of hydroxyl modification that hydroxyl modification obtains to carbon nanotube using sodium hydrate aqueous solution to receive Mitron.
5. a kind of SBR/HVPBR rubber composite materials according to claim 3, it is characterised in that:Described utilizes hydroxyl The specific preparation process of modified carbon nanotube is:It weighs 2 ~ 3g carbon nanotubes and is added to a concentration of 1.7 ~ 2.3mol/L of 50mL Sodium hydrate aqueous solution in and be dispersed with stirring;After the carbon nano tube dispersion liquid is poured into autoclave sealing, 175 ~ 185 DEG C React 1.5 ~ 2.5h;It is cooled to room temperature after reaction, it is neutrality to be filtered, washed to filter liquor, and again with methanol is washed 2 ~ 3 times; Much filtrate is dried in vacuo to obtain hydroxyl modification carbon nanotube powder.
6. a kind of SBR/HVPBR rubber composite materials according to claim 3, it is characterised in that:Described utilizes carboxyl Modified carbon nanotube is to carry out carboxy-modified carboxyl obtained to carbon nanotube using the toluene solution of azodiisobutyronitrile to change Property carbon nanotube.
7. a kind of SBR/HVPBR rubber composite materials according to claim 3, it is characterised in that:Described utilizes carboxyl The specific preparation process of modified carbon nanotube is,
1)Under continual stirring conditions, carbon nanotube and azodiisobutyronitrile in mass ratio 1:(1.5~2.3)It is added separately to first In benzene;After logical nitrogen deoxygenation, 3 ~ 5h is reacted at 70 DEG C ~ 78 DEG C;Reaction product is dried in vacuo after washing 4 ~ 5 times with toluene and obtains AIBN modified carbon nano tube pipe powders;
2)AIBN modified carbon nano-tubes are scattered in the methanol solution of sodium hydroxide, 60 DEG C ~ 65 DEG C 40 ~ 50h of reflux;Reaction knot PH value is adjusted to acidity by Shu Hou with hydrochloric acid;Product is washed with deionized 4 ~ 5 times, and vacuum drying obtains carboxy-modified carbon and receives Mitron powder.
8. a kind of SBR/HVPBR rubber composite materials according to claim 1, it is characterised in that:Step 2)Described in Salting liquid is sodium-chloride water solution, one kind in calcium chloride water, aluminum sulfate aqueous solution.
CN201510336420.1A 2015-06-17 2015-06-17 A kind of SBR/HVPBR rubber composite materials CN106317517B (en)

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