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 PDF

Info

Publication number
CN110003503A
CN110003503A CN201910278854.9A CN201910278854A CN110003503A CN 110003503 A CN110003503 A CN 110003503A CN 201910278854 A CN201910278854 A CN 201910278854A CN 110003503 A CN110003503 A CN 110003503A
Authority
CN
China
Prior art keywords
rubber
carbon nanotube
weight
parts
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910278854.9A
Other languages
Chinese (zh)
Inventor
朱凉伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu General Science Technology Co Ltd
Original Assignee
Jiangsu General Science Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu General Science Technology Co Ltd filed Critical Jiangsu General Science Technology Co Ltd
Priority to CN201910278854.9A priority Critical patent/CN110003503A/en
Publication of CN110003503A publication Critical patent/CN110003503A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2307/00—Characterised by the use of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2311/00—Characterised by the use of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08J2323/22—Copolymers of isobutene; butyl rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2407/00—Characterised by the use of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2409/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2411/00—Characterised by the use of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2423/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08J2423/22—Copolymers of isobutene; butyl rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

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

The preparation method of high-dispersibility carbon nanotube base rubber composite material
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.
CN201910278854.9A 2019-04-09 2019-04-09 The preparation method of high-dispersibility carbon nanotube base rubber composite material Pending CN110003503A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910278854.9A CN110003503A (en) 2019-04-09 2019-04-09 The preparation method of high-dispersibility carbon nanotube base rubber composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910278854.9A CN110003503A (en) 2019-04-09 2019-04-09 The preparation method of high-dispersibility carbon nanotube base rubber composite material

Publications (1)

Publication Number Publication Date
CN110003503A true CN110003503A (en) 2019-07-12

Family

ID=67170400

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910278854.9A Pending CN110003503A (en) 2019-04-09 2019-04-09 The preparation method of high-dispersibility carbon nanotube base rubber composite material

Country Status (1)

Country Link
CN (1) CN110003503A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110606965A (en) * 2019-10-24 2019-12-24 苏州第一元素纳米技术有限公司 Carbon nanotube-natural rubber composite masterbatch and preparation method and preparation device thereof
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
CN111423641A (en) * 2019-12-31 2020-07-17 浙江工业大学 Method for preparing high-dispersion carbon black/rubber nano composite material
CN112210130A (en) * 2020-10-09 2021-01-12 山东玲珑轮胎股份有限公司 Semi-steel base rubber material using carbon nanotube composite masterbatch and preparation method thereof
CN115850819A (en) * 2023-02-06 2023-03-28 广东粤港澳大湾区黄埔材料研究院 Lower-layer tread rubber composition and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105482175A (en) * 2016-01-21 2016-04-13 中国民航大学 Preparation method for multiwalled carbon nanotube modified aircraft tire rubber material
CN105949536A (en) * 2016-07-14 2016-09-21 南京林业大学 {0><}0{>Preparation method of high-strength natural rubber (NR)/carbon nano tube (CNT) conductive composite film
CN108530697A (en) * 2018-05-03 2018-09-14 江苏通用科技股份有限公司 Carbon nanotube base rubber composite material and preparation method thereof
WO2019011006A1 (en) * 2017-07-12 2019-01-17 山东大展纳米材料有限公司 Method and apparatus for preparing mixed rubber by continuous spray mixing

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105482175A (en) * 2016-01-21 2016-04-13 中国民航大学 Preparation method for multiwalled carbon nanotube modified aircraft tire rubber material
CN105949536A (en) * 2016-07-14 2016-09-21 南京林业大学 {0><}0{>Preparation method of high-strength natural rubber (NR)/carbon nano tube (CNT) conductive composite film
WO2019011006A1 (en) * 2017-07-12 2019-01-17 山东大展纳米材料有限公司 Method and apparatus for preparing mixed rubber by continuous spray mixing
CN108530697A (en) * 2018-05-03 2018-09-14 江苏通用科技股份有限公司 Carbon nanotube base rubber composite material and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110606965A (en) * 2019-10-24 2019-12-24 苏州第一元素纳米技术有限公司 Carbon nanotube-natural rubber composite masterbatch and preparation method and preparation device thereof
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
CN111423641A (en) * 2019-12-31 2020-07-17 浙江工业大学 Method for preparing high-dispersion carbon black/rubber nano composite material
CN112210130A (en) * 2020-10-09 2021-01-12 山东玲珑轮胎股份有限公司 Semi-steel base rubber material using carbon nanotube composite masterbatch and preparation method thereof
WO2022073489A1 (en) * 2020-10-09 2022-04-14 山东玲珑轮胎股份有限公司 Semi-steel base rubber material using carbon nano tube composite masterbatch and preparation method therefor
CN115850819A (en) * 2023-02-06 2023-03-28 广东粤港澳大湾区黄埔材料研究院 Lower-layer tread rubber composition and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN110003503A (en) The preparation method of high-dispersibility carbon nanotube base rubber composite material
CN109942913A (en) The preparation method of polymolecularity graphite oxide alkenyl rubber composite material
CN101831090B (en) High-performance natural rubber vulcanized rubber of carbon-containing nano-tube, and preparation method thereof
CN107022119B (en) A kind of preparation method of graphene/silicon dioxide/rubber composite material
CN109671576A (en) Carbon nano tube-MXene composite three-dimensional porous carbon material and preparation method thereof
CN104627977B (en) Graphene oxide reinforced composite carbon nanopaper and production method thereof
CN105906854A (en) Graphene-modified natural latex polymer and modification method thereof
CN105754159B (en) Latex composite, preparation and the application of a kind of high intensity, antistatic
CN105131359A (en) Graphene/carbon nano tube hybridized filler network enhanced rubber material and preparation method thereof
KR101748142B1 (en) Latex composition, production method therefor, composite material and conductive compact
JP2007517760A5 (en)
CN102161785A (en) Preparation method of graphene/polymer nano composite material
CN106366418B (en) The method of nano-graphite load graphene nanobelt modified poly ethylene film
CN106496710A (en) A kind of expanded graphite/carbon nanotube conducting dual network structure rubber composite and preparation method thereof
CN105949536A (en) {0&gt;&lt;}0{&gt;Preparation method of high-strength natural rubber (NR)/carbon nano tube (CNT) conductive composite film
CN110467782A (en) A kind of carbon nanotube Plastic conductive composite material and its wet method preparation process
CN100436527C (en) Process for preparing organic modified clay and styrene butadiene rubber nano composite material
CN110564016B (en) High-reinforcement rubber latex wet mixing composite material and preparation process thereof
CN110387105B (en) High-filling graphene oxide/resin hybrid and preparation method and application thereof
CN108299579B (en) Graphene/nano silicon dioxide/polystyrene hybrid material and preparation method and application thereof
CN110003537A (en) The preparation method of the graphene-based rubber composite material of polymolecularity
CN108586836A (en) Carbon fiber-based rubber composite material and preparation method thereof
CN110577675B (en) Graphene/silicon dioxide/natural rubber composite material and preparation method and application thereof
CN110734593B (en) Method for preparing emulsion polymerized styrene butadiene rubber from modified graphene
CN108530697A (en) Carbon nanotube base rubber composite material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20190712

RJ01 Rejection of invention patent application after publication