CN110003503A - The preparation method of high-dispersibility carbon nanotube base rubber composite material - Google Patents
The preparation method of high-dispersibility carbon nanotube base rubber composite material Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of high-dispersibility carbon nanotube base rubber composite material, it first disperses carbon nanotube in water soluble polymer aqueous solution and prepares carbon nano tube dispersion liquid, then carbon nano tube dispersion liquid is added in rubber latex, the CaCl being added dropwise after mixing2It is demulsified as flocculant, carbon nanotube-rubber masterbatch is prepared after drying.High-dispersibility carbon nanotube base rubber composite material finally is prepared by mechanical mixing in rubber, carbon nanotube-rubber masterbatch, carbon black, rubber chemicals.Preparation method of the present invention is simple, step is easily operated, first disperse carbon nanotube in water soluble polymer aqueous solution, it is then added in rubber latex, prepare carbon nanotube-rubber masterbatch, it is agglomerating to avoid carbon nanotube aggregation, ensure that carbon nanotube is evenly dispersed in sizing material, the comprehensive performance of sizing material significantly improves.
Description
Technical field
The present invention relates to a kind of preparation methods of high-dispersibility carbon nanotube base rubber composite material, belong to rubber composite wood
Expect preparation technical field.
Background technique
Rubber is a kind of important strategic goods and materials, is widely used in aerospace, building because of its unique high resiliency
Its people's military project every field such as industry, auto industry.Rubber can generate change as a kind of elastomeric material in actual use
Shape, phenomena such as stress relaxation, aging, thermal cracking can be generated after heated.Therefore, the comprehensive performance of rubber is improved, is had very heavy
The practical significance wanted.
Research as nanodispersed granular materials are more and more deep in the application of high-end manufacturing field, to its performance
Cause the interest of numerous researchers.The mechanical property research of composite material becomes researchers' focus of attention.Carbon nanotube
Be crimped by single-layer or multi-layer graphite flake or inlaid-assembling at seamless hollow nanoscale coaxial cylindrical tubular material.Carbon is received
The carbon atom of mitron side wall is mainly with sp2Hydridization and adjacent carbon atom formed height it is delocalized pi-electron so that carbon nanometer
There are stronger Van der Waals force between pipe, easily gathers into bundles and be not easy to disperse.Carbon nanotube has in rubber as reinforcing filler
Important application.The comprehensive performance that carbon nanotube is introduced into raising rubber in rubber is had been a hot spot of research.
Carbon nanotube can not only improve the mechanical performance of rubber, while can assign its special functionality.Carbon is improved to receive
Dispersibility of the mitron in rubber is to play carbon nanotube performance, promotes the key of rubber comprehensive performance.However, improving carbon nanometer
The dispersibility of pipe is always the difficult point of scientific research technical field and industrial circle.
Summary of the invention
The purpose of the present invention is overcoming the deficiencies in the prior art, a kind of high-dispersibility carbon nanotube base rubber is provided
The preparation method of composite material.
According to technical solution provided by the invention, the preparation method of the high-dispersibility carbon nanotube base rubber composite material
The following steps are included:
A) water soluble polymer is dissolved in deionized water, configuration concentration is the water that weight percentage is 1%~20%
Soluble macromolecular aqueous solution;
B) carbon nanotube is added in water soluble polymer aqueous solution, in 20~100kHz frequency, 100~800W power
1~3h of lower ultrasonic disperse, obtains carbon nano tube dispersion liquid wherein, the mass ratio of carbon nanotube and water soluble polymer be 1:1~
60;
C) carbon nano tube dispersion liquid is added in rubber latex, mechanical stirring to dropwise addition weight percent after mixing contains
The CaCl that amount is 10%~20%2It is demulsified as flocculant, dries 0.5~36h after cohesion at 90~110 DEG C and carbon is prepared
Nanotube-rubber latex rubber master batch, in carbon nanotube-rubber latex rubber master batch, the mass ratio of carbon nanotube and rubber latex is 1:
10~100;
D) by the desired amount of 80~100 parts by weight of rubber material, carbon nanotube -10~50 parts of rubber latex rubber master batch, carbon black
30~60 parts by weight, 5~10 parts by weight of zinc oxide, 0.5~4 parts by weight of stearic acid, 1~5 parts by weight of anti-aging agent are added to mixing
In machine, dump temperature is set as 150-165 DEG C, obtains rubber master batch after mixing;
E) rubber master batch after mixing is kneaded on the double roll mill, 1~6 parts by weight of sulphur, accelerator NS is added after mixing
It is 0.1~0.2 parts by weight for 0.5~2 parts by weight, anti-scorching agent CTP, obtains polymolecularity carbon nanometer through conventional mechanical mixing
Pipe base rubber composite material.
The water soluble polymer is cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylamide
One of amine-b- polystyrene is a variety of.
The rubber latex is one of Heveatex, polybutadiene latex, styrene-butadiene latex, isoprene rubber latex or a variety of.
The rubber material is natural rubber, in butadiene rubber, butadiene-styrene rubber, butyl rubber, EP rubbers, neoprene
It is one or more.
The anti-aging agent is one of anti-aging agent RD, antioxidant 4020 or two kinds.
Preparation method of the present invention is simple, and step is easily operated, first disperses water soluble polymer aqueous solution for carbon nanotube
In, be then added in rubber latex, prepare carbon nanotube-rubber latex rubber master batch, avoid carbon nanotube aggregation it is agglomerating, ensure that
Carbon nanotube is evenly dispersed in sizing material, and it is evenly dispersed in sizing material to significantly improve carbon nanotube, improves sizing material
Comprehensive performance.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1
A kind of preparation method of high-dispersibility carbon nanotube base rubber composite material, the preparation method include carbon nanotube point
Preparation step, carbon nanotube-rubber latex rubber master batch preparation step and the high-dispersibility carbon nanotube base rubber composite wood of dispersion liquid
The preparation step of material, specifically:
1, the preparation of carbon nano tube dispersion liquid;
A) cellulose is dissolved in deionized water, is configured to the cellulose aqueous solution that weight percentage is 1%;
B) carbon nanotube is added in cellulose aqueous solution, ultrasonic disperse 2h is to carbon under 100W power, 20kHz frequency
Nanotube is evenly dispersed, obtains carbon nano tube dispersion liquid, wherein the mass ratio of carbon nanotube and cellulose is 1:20;
2, carbon nanotube-Heveatex rubber master batch preparation;
C) carbon nano tube dispersion liquid is added in Heveatex, mechanical stirring to dropwise addition weight percent after mixing contains
The CaCl that amount is 20%2It is demulsified as flocculant, dries 36h after cohesion at 90 DEG C and carbon nanotube-Heveatex is prepared
Rubber master batch, wherein in carbon nanotube-Heveatex rubber master batch, the mass ratio of carbon nanotube and Heveatex is 1:10;
3, the preparation of high-dispersibility carbon nanotube base rubber composite material;
D) by the desired amount of 100 parts by weight of natural rubber, carbon nanotube -10 parts by weight of Heveatex rubber master batch, 50 weight of carbon black
Amount part, 7 parts by weight of zinc oxide, 4 parts by weight of stearic acid, totally 1 parts by weight are added in mixer anti-aging agent RD, and dump temperature is
150-165 DEG C, obtain rubber master batch;
E) rubber master batch after mixing is kneaded on the double roll mill, 6 parts by weight of sulphur, accelerator NS 1 is added after mixing
Parts by weight, anti-scorching agent CTP are 0.2 parts by weight, and it is compound to obtain high-dispersibility carbon nanotube base rubber through conventional mechanical mixing
Material.
Embodiment 2
A kind of preparation method of high-dispersibility carbon nanotube base rubber composite material, the preparation method include carbon nanotube point
Preparation step, carbon nanotube-polybutadiene latex rubber master batch preparation step and the high-dispersibility carbon nanotube base rubber of dispersion liquid are multiple
The preparation step of condensation material, specifically:
1, the preparation of carbon nano tube dispersion liquid;
A) polyacrylamide-b- polystyrene is dissolved in deionized water, be configured to weight percentage be 10% it is poly-
Acrylamide-b- polystyrene aqueous solution;
B) carbon nanotube is added in polyacrylamide-b- polystyrene aqueous solution, in 800W power, 50kHz frequency
Lower ultrasonic disperse 1h is evenly dispersed to carbon nanotube, obtains carbon nano tube dispersion liquid.Wherein, carbon nanotube and polyacrylamide-
The mass ratio of b- polystyrene is 1:1.
2, carbon nanotube-polybutadiene latex rubber master batch preparation;
C) carbon nano tube dispersion liquid is added in polybutadiene latex, mechanical stirring to dropwise addition weight hundred after mixing
Dividing content is 10% CaCl2It is demulsified as flocculant, dries 0.5h drying after cohesion at 110 DEG C and carbon nanometer is prepared
Pipe-polybutadiene latex rubber master batch, wherein in carbon nanotube-polybutadiene latex rubber master batch, carbon nanotube and polybutadiene latex
Mass ratio is 1:100;
3, the preparation of high-dispersibility carbon nanotube base rubber composite material;
D) the desired amount of 40 parts by weight of butadiene rubber, 40 parts by weight of butadiene-styrene rubber, carbon nanotube-polybutadiene latex is female
50 parts by weight of glue, 30 parts by weight of carbon black, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, antioxidant 4020 are that 5 parts by weight are added to
In mixer, dump temperature is 150-165 DEG C, obtains rubber master batch;
E) rubber master batch after mixing is kneaded on the double roll mill, 4 parts by weight of sulphur, accelerator NS 2 is added after mixing
Parts by weight, anti-scorching agent CTP are 0.4 parts by weight, and it is compound to obtain high-dispersibility carbon nanotube base rubber through conventional mechanical mixing
Material.
Embodiment 3
A kind of preparation method of high-dispersibility carbon nanotube base rubber composite material, the preparation method include carbon nanotube point
Preparation step, carbon nanotube-styrene-butadiene latex rubber master batch preparation step and the high-dispersibility carbon nanotube base rubber composite wood of dispersion liquid
The preparation step of material, specifically:
1, the preparation of carbon nano tube dispersion liquid;
A) polyvinyl alcohol is dissolved in deionized water, is configured to the polyvinyl alcohol water solution that weight percentage is 20%;
B) carbon nanotube is added in polyvinyl alcohol water solution, the ultrasonic disperse 3h under 300W power, 100kHz frequency
It is evenly dispersed to carbon nanotube, obtain carbon nano tube dispersion liquid, wherein the mass ratio of carbon nanotube and polyvinyl alcohol is 1:50;
2, carbon nanotube-styrene-butadiene latex rubber master batch preparation;
C) carbon nano tube dispersion liquid is added in styrene-butadiene latex, mechanical stirring to dropwise addition weight percent after mixing contains
The CaCl that amount is 15%2It is demulsified as flocculant, dries 15h drying after cohesion at 100 DEG C and carbon nanotube-butylbenzene is prepared
Latex masterbatch;Wherein, in carbon nanotube-styrene-butadiene latex rubber master batch, the mass ratio of carbon nanotube and styrene-butadiene latex is 1:60;
3, the preparation of high-dispersibility carbon nanotube base rubber composite material;
D) by the desired amount of 30 parts by weight of butyl rubber, 30 parts by weight of EP rubbers, 30 parts by weight of neoprene, carbon nanometer
Pipe -30 parts by weight of styrene-butadiene latex rubber master batch, 60 parts by weight of carbon black, 10 parts of zinc oxide, 0.5 parts by weight of stearic acid, anti-aging agent RD are 1 weight
Amount part, antioxidant 4020 are that 2 parts by weight are added in mixer, and dump temperature is 150-165 DEG C, obtain rubber master batch;
E) rubber master batch after mixing is kneaded on the double roll mill, 1 parts by weight of sulphur is added after mixing, accelerator NS is
0.5 parts by weight, anti-scorching agent CTP are 0.1 parts by weight, and it is multiple to obtain high-dispersibility carbon nanotube base rubber through conventional mechanical mixing
Condensation material.
Comparative example 1
A kind of the step of preparation method of carbon nanotube base rubber composite material, preparation method are as follows:
1, the preparation of carbon nano tube dispersion liquid:
Carbon nano-tube aqueous solutions are configured, ultrasonic disperse 3h uniformly divides to carbon nanotube under 300W power, 100kHz frequency
It dissipates, obtains carbon nano tube dispersion liquid.
2, carbon nanotube-natural rubber rubber master batch preparation:
Carbon nano tube dispersion liquid is added in natural rubber latex, mechanical stirring to being added dropwise weight percent after mixing
The CaCl that content is 15%2It is demulsified as flocculant, carbon nanotube-natural rubber rubber master batch is prepared in drying after cohesion.Wherein,
In carbon nanotube-natural rubber rubber master batch, the mass ratio of carbon nanotube and natural rubber is 1:60.
3, the preparation of high-dispersibility carbon nanotube base rubber composite material:
A) by the desired amount of 90 parts by weight of natural rubber, carbon nanotube -30 parts by weight of natural rubber rubber master batch, 60 weight of carbon black
Part, 10 parts by weight of zinc oxide, 0.5 parts by weight of stearic acid, anti-aging agent RD are 1 parts by weight, antioxidant 4020 is that 2 parts by weight are added to
In mixer, dump temperature is 150-165 DEG C, obtains rubber master batch;
B) rubber master batch after mixing is kneaded on the double roll mill, 1 parts by weight of sulphur, accelerator NS is added after packet roller heap glue
It is 0.1 parts by weight for 0.5 parts by weight, anti-scorching agent CTP, obtains high-dispersibility carbon nanotube base rubber through conventional mechanical mixing
Composite material.
Comparative example 2
A kind of the step of preparation method of carbon nanotube base rubber composite material, preparation method are as follows:
1, the preparation of carbon nano tube dispersion liquid:
A) cellulose is dissolved in deionized water, is configured to the cellulose aqueous solution that weight percentage is 20%;
B) carbon nanotube is added in cellulose aqueous solution, ultrasonic disperse 3h is extremely under 300W power, 100kHz frequency
Carbon nanotube is evenly dispersed, obtains carbon nano tube dispersion liquid.Wherein, the mass ratio of carbon nanotube and cellulose is 1:50.Drying,
Obtain carbon nanotube-cellulose composite.
2, the preparation of high-dispersibility carbon nanotube base rubber composite material:
A) by the desired amount of 100 parts by weight of natural rubber, 30 parts by weight of carbon nanotube-cellulose composite, 60 weight of carbon black
Amount part, 10 parts by weight of zinc oxide, 0.5 parts by weight of stearic acid, anti-aging agent RD are 1 parts by weight, antioxidant 4020 is that 2 parts by weight are added
Into mixer, dump temperature is 150-165 DEG C, obtains rubber master batch;
B) rubber master batch after mixing is kneaded on the double roll mill, 1 parts by weight of sulphur, accelerator NS is added after packet roller heap glue
It is 0.1 parts by weight for 0.5 parts by weight, anti-scorching agent CTP, obtains high-dispersibility carbon nanotube base rubber through conventional mechanical mixing
Composite material.
The above embodiments 1, embodiment 2, embodiment 3 and comparative example 1, the test result data of comparative example 2 such as following table institute
Show:
As can be seen from the table, before and after aging, compared to the sizing material of comparative example 1 and comparative example 2, embodiment 1, embodiment 2
About 40% is promoted with the elongation rate of tensile failure before and after the sizing material aging of embodiment 3, tensile strength promotes about 50%, and tearing strength has not
With the promotion of degree.Its excellent comprehensive performance ensure that sizing material in the national military project such as aerospace, construction industry, auto industry
The application of every field.Wherein, comparative example 1 is not added with water soluble polymer, and comparative example 2 does not prepare Heveatex rubber master batch, shows
It first disperses carbon nanotube in water soluble polymer aqueous solution, is then added in Heveatex and prepares Heveatex rubber master batch, more
Be conducive to that carbon nanotube is evenly dispersed in sizing material, improve the comprehensive performance of sizing material.
Claims (5)
1. a kind of preparation method of high-dispersibility carbon nanotube base rubber composite material, it is characterized in that the preparation method includes following
Step:
A) water soluble polymer is dissolved in deionized water, configuration concentration is the high water solubility that weight percentage is 1% ~ 20%
Molecule aqueous solution;
B) carbon nanotube is added in water soluble polymer aqueous solution, is surpassed under 20 ~ 100 kHz frequencies, 100 ~ 800W power
Sound disperses 1 ~ 3h, obtains carbon nano tube dispersion liquid wherein, and the mass ratio of carbon nanotube and water soluble polymer is 1:1 ~ 60;
C) carbon nano tube dispersion liquid is added in rubber latex, mechanical stirring to dropwise addition weight percentage after mixing is
10% ~ 20% CaCl2It is demulsified as flocculant, dries 0.5 ~ 36h after cohesion at 90 ~ 110 DEG C and carbon nanotube-rubber is prepared
Glue latex masterbatch, in carbon nanotube-rubber latex rubber master batch, the mass ratio of carbon nanotube and rubber latex is 1:10 ~ 100;
D) by the desired amount of 80 ~ 100 parts by weight of rubber material, carbon nanotube -10 ~ 50 parts of rubber latex rubber master batch, carbon black 30 ~ 60
Parts by weight, 5 ~ 10 parts by weight of zinc oxide, 0.5 ~ 4 parts by weight of stearic acid, 1 ~ 5 parts by weight of anti-aging agent are added in mixer, dumping
Temperature setting is 150-165 DEG C, obtains rubber master batch after mixing;
E) rubber master batch after mixing is kneaded on the double roll mill, 1 ~ 6 parts by weight of sulphur, accelerator NS 0.5 is added after mixing
~ 2 parts by weight and anti-scorching agent CTP are 0.1 ~ 0.2 parts by weight, obtain high-dispersibility carbon nanotube base rubber through conventional mechanical mixing
Glue composite material.
2. the preparation method of high-dispersibility carbon nanotube base rubber composite material as described in claim 1, it is characterized in that: described
Water soluble polymer is cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylamide-bPolystyrene
One of or it is a variety of.
3. the preparation method of high-dispersibility carbon nanotube base rubber composite material as described in claim 1, it is characterized in that: described
Rubber latex is one of Heveatex, polybutadiene latex, styrene-butadiene latex, isoprene rubber latex or a variety of.
4. the preparation method of high-dispersibility carbon nanotube base rubber composite material as described in claim 1, it is characterized in that: described
Rubber material is one of natural rubber, butadiene rubber, butadiene-styrene rubber, butyl rubber, EP rubbers, neoprene or more
Kind.
5. the preparation method of high-dispersibility carbon nanotube base rubber composite material as described in claim 1, it is characterized in that: described
Anti-aging agent is one of anti-aging agent RD, antioxidant 4020 or two kinds.
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CN110655693A (en) * | 2019-10-24 | 2020-01-07 | 苏州第一元素纳米技术有限公司 | Rubber composite material and preparation method thereof |
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