CN110305375A - A kind of carbon nano-tube modification natural rubber material and preparation method thereof - Google Patents
A kind of carbon nano-tube modification natural rubber material and preparation method thereof Download PDFInfo
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- CN110305375A CN110305375A CN201910623720.6A CN201910623720A CN110305375A CN 110305375 A CN110305375 A CN 110305375A CN 201910623720 A CN201910623720 A CN 201910623720A CN 110305375 A CN110305375 A CN 110305375A
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
- C08L7/02—Latex
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
The present invention discloses a kind of carbon nano-tube modification natural rubber material, raw material including following parts by weight: 100-110 parts of Heveatex, 3-6 parts of multi-walled carbon nanotube dispersion liquid, 40-65 parts of carbon black, 3-4 parts of zinc oxide, 1-5 parts of stearic acid, 1-5 parts of dispersing agent, 0.1-0.5 parts of promotor, 2-3 parts of sulphur, 65-80 parts of deionized water, wherein, the multi-walled carbon nanotube dispersion liquid is the suspension that multi-walled carbon nanotube is dissolved in dimethylformamide formation, the mass concentration 7%-10% of multi-walled carbon nanotube in the suspension；Meanwhile invention additionally discloses the preparation methods of the carbon nano-tube modification natural rubber material.The carbon nano-tube modification natural rubber material being prepared, carbon nanotube are uniformly dispersed wherein, and conductive, thermally conductive and wear hardness is excellent.
Description
Technical field
The invention belongs to technique for modifying rubbers fields, and in particular to a kind of carbon nano-tube modification natural rubber material and its system
Preparation Method.
Background technique
Carbon nanotube be widely used in polymer due to its unique structure and excellent physical and chemical performance to
Improve thermally conductive, the conductive and physical property etc. of polymer.But carbon nanotube itself has very high surface free energy, and group easily occurs
It is poly-, it is not easy to disperse in a polymer matrix, limit its application.The surface modification treatment of carbon nanotube is to improve it in polymer
In dispersibility so that excellent one of the important channel of carbon nano-tube/polymer composite material of processability.
Simple rubber material lacks good performance, without use value.In order to improve the performance of natural rubber,
It should be subject to some supporting materials in natural rubber products.And carbon nanotube has excellent physical and chemical performance, but carbon nanometer
Pipe is directly added into, and since the hydrophilicity of itself is poor, is occurred dispersion uneven phenomenon in later period demulsification, is led to the rubber material of preparation
The electrical and thermal conductivity performance of material is bad.So there is the native rubber composite material of superior electrical conductivity energy, heating conduction to have for preparation
Significance.
Summary of the invention
In view of the drawbacks of the prior art, the present invention provides a kind of carbon nano-tube modification natural rubber material and its preparation side
Method, obtained carbon nano-tube modification natural rubber material are had excellent performance, and have good thermally conductive, electric conductivity and rub resistance
Energy.
A kind of carbon nano-tube modification natural rubber material, the raw material including following parts by weight:
100-110 parts of Heveatex, 3-6 parts of multi-walled carbon nanotube dispersion liquid, 40-65 parts of carbon black, 3-4 parts of zinc oxide, stearic acid
1-5 parts, 1-5 parts of dispersing agent, 0.1-0.5 parts of promotor, 2-3 parts of sulphur, 65-80 parts of deionized water,
Wherein, the multi-walled carbon nanotube dispersion liquid is the suspension that multi-walled carbon nanotube is dissolved in dimethylformamide formation, institute
The mass concentration for stating multi-walled carbon nanotube in suspension is 7%-10%.
Preferably, the solid content of the natural emulsion is 60-70%.
Preferably, the dispersing agent be gum arabic, in SDS, PVP any one or it is two kinds any.When described
When dispersing agent is gum arabic, any two kinds in SDS, PVP, the ratio of the two is arbitrary proportion.
Preferably, the promotor is captax or accelerator NS.
The preparation method of the carbon nano-tube modification natural rubber material, comprising the following steps:
(1) carbon nano tube dispersion liquid, carbon black, zinc oxide, stearic acid, dispersing agent, promotor, sulphur are mixed, then grinding exists
Deionized water is added under stirring；
(2) product of step (1) is stirred by ultrasonic 30-60min in ultrasonic stirrer, temperature is 60 DEG C when stirring；
(3) under stirring, natural emulsion will be added in the product of step (2), then proceedes to ultrasonic agitation 10-15min；
(4) by the mixture progress of step (3), drying to constant weight, obtains solid product；
(5) solid product for obtaining step (4) vulcanizes, and vulcanizes 20min at 10MPa, 160 DEG C.
Preferably, the supersonic frequency of the ultrasonic agitation is 20-35KHz.
Preferably, the temperature of the drying is 100-110 DEG C.
In the present invention, the captax is 2-mercaptobenzothiazole, abbreviation MBT；The accelerator NS is N- tert-butyl-
2-[4-morpholinodithio sulfenamide；The SDS is lauryl sodium sulfate；The PVP is polyvinylpyrrolidone；The stearic acid
For octadecanoid acid.
Advantages of the present invention:
Carbon nano-tube modification natural rubber material provided by the invention, carbon nanotube are uniformly dispersed wherein, it is conductive, thermally conductive and
Wear hardness is excellent.
Specific embodiment
Embodiment 1
A kind of carbon nano-tube modification natural rubber material, the raw material including following parts by weight:
100 parts of Heveatex, 3 parts of multi-walled carbon nanotube dispersion liquid, 40 parts of carbon black, 3 parts of zinc oxide, 1 part of stearic acid, dispersing agent 1
Part, 0.1 part of promotor, 2 parts of sulphur, 65 parts of deionized water,
Wherein, the multi-walled carbon nanotube dispersion liquid is the suspension that multi-walled carbon nanotube is dissolved in dimethylformamide formation, institute
The mass concentration for stating multi-walled carbon nanotube in suspension is 7%；
The solid content of the natural emulsion is 60%；
The dispersing agent is gum arabic；
The promotor is captax；
The preparation method of the carbon nano-tube modification natural rubber material, comprising the following steps:
(1) carbon nano tube dispersion liquid, carbon black, zinc oxide, stearic acid, dispersing agent, promotor, sulphur are mixed, then grinding exists
Deionized water is added under stirring；
(2) product of step (1) is stirred by ultrasonic 30min in ultrasonic stirrer, temperature is 60 DEG C when stirring；Wherein, institute
The supersonic frequency for stating ultrasonic agitation is 20KHz.
(3) under stirring, natural emulsion will be added in the product of step (2), then proceedes to ultrasonic agitation 10min；
(4) by the mixture of step (3), at 100 DEG C, drying to constant weight, obtains solid product；
(5) solid product for obtaining step (4) vulcanizes, and vulcanizes 20min at 10MPa, 160 DEG C.
Embodiment 2
A kind of carbon nano-tube modification natural rubber material, the raw material including following parts by weight:
110 parts of Heveatex, 6 parts of multi-walled carbon nanotube dispersion liquid, 65 parts of carbon black, 4 parts of zinc oxide, 5 parts of stearic acid, dispersing agent 5
Part, 0.5 part of promotor, 3 parts of sulphur, 80 parts of deionized water,
Wherein, the multi-walled carbon nanotube dispersion liquid is the suspension that multi-walled carbon nanotube is dissolved in dimethylformamide formation, institute
The mass concentration for stating multi-walled carbon nanotube in suspension is 10%；
The solid content of the natural emulsion is 70%；
The dispersing agent is SDS；
The promotor is accelerator NS；
The preparation method of the carbon nano-tube modification natural rubber material, comprising the following steps:
(1) carbon nano tube dispersion liquid, carbon black, zinc oxide, stearic acid, dispersing agent, promotor, sulphur are mixed, then grinding exists
Deionized water is added under stirring；
(2) product of step (1) is stirred by ultrasonic 60min in ultrasonic stirrer, temperature is 60 DEG C when stirring；Wherein, institute
The supersonic frequency for stating ultrasonic agitation is 35KHz；
(3) under stirring, natural emulsion will be added in the product of step (2), then proceedes to ultrasonic agitation 15min；
(4) by the mixture of step (3), at 110 DEG C, drying to constant weight, obtains solid product；
(5) solid product for obtaining step (4) vulcanizes, and vulcanizes 20min at 10MPa, 160 DEG C.
Embodiment 3
A kind of carbon nano-tube modification natural rubber material, the raw material including following parts by weight:
105 parts of Heveatex, 5 parts of multi-walled carbon nanotube dispersion liquid, 55 parts of carbon black, 3.8 parts of zinc oxide, 2 parts of stearic acid, dispersing agent
3 parts, 0.4 part of promotor, 2.6 parts of sulphur, 75 parts of deionized water,
Wherein, the multi-walled carbon nanotube dispersion liquid is the suspension that multi-walled carbon nanotube is dissolved in dimethylformamide formation, institute
The mass concentration for stating multi-walled carbon nanotube in suspension is 8%；
The solid content of the natural emulsion is 65%；
The dispersing agent is PVP；
The promotor is captax or accelerator NS；
The preparation method of the carbon nano-tube modification natural rubber material, comprising the following steps:
(1) carbon nano tube dispersion liquid, carbon black, zinc oxide, stearic acid, dispersing agent, promotor, sulphur are mixed, then grinding exists
Deionized water is added under stirring；
(2) product of step (1) is stirred by ultrasonic 45min in ultrasonic stirrer, temperature is 60 DEG C when stirring；Wherein, institute
The supersonic frequency for stating ultrasonic agitation is 30KHz.
(3) under stirring, natural emulsion will be added in the product of step (2), then proceedes to ultrasonic agitation 12min；
(4) by the mixture of step (3), at 105 DEG C, drying to constant weight, obtains solid product；
(5) solid product for obtaining step (4) vulcanizes, and vulcanizes 20min at 10MPa, 160 DEG C.
Embodiment 4
A kind of carbon nano-tube modification natural rubber material, the raw material including following parts by weight:
100 parts of Heveatex, 4.3 parts of multi-walled carbon nanotube dispersion liquid, 50 parts of carbon black, 3.6 parts of zinc oxide, 2 parts of stearic acid, dispersion
3 parts of agent, 0.3 part of promotor, 2.1 parts of sulphur, 72 parts of deionized water,
Wherein, the multi-walled carbon nanotube dispersion liquid is the suspension that multi-walled carbon nanotube is dissolved in dimethylformamide formation, institute
The mass concentration for stating multi-walled carbon nanotube in suspension is 9%；
The solid content of the natural emulsion is 65%；
The dispersing agent is the mixture of gum arabic and SDS；
The promotor is captax；
The preparation method of the carbon nano-tube modification natural rubber material, with embodiment 3.
Embodiment 5
A kind of carbon nano-tube modification natural rubber material, the raw material including following parts by weight:
100 parts of Heveatex, 4.3 parts of multi-walled carbon nanotube dispersion liquid, 50 parts of carbon black, 3.6 parts of zinc oxide, 2 parts of stearic acid, dispersion
3 parts of agent, 0.3 part of promotor, 2.1 parts of sulphur, 72 parts of deionized water,
Wherein, the multi-walled carbon nanotube dispersion liquid is the suspension that multi-walled carbon nanotube is dissolved in dimethylformamide formation, institute
The mass concentration for stating multi-walled carbon nanotube in suspension is 9%；
The solid content of the natural emulsion is 65%；
The dispersing agent is the mixture of SDS and PVP；
The promotor is accelerator NS；
The preparation method of the carbon nano-tube modification natural rubber material, with embodiment 3.
One, performance detection
Using the volume resistance of high resistant instrument measurement composite material, using the thermally conductive system of thermal conductivity measuring apparatus measurement composite material
Number, using the wearability of Akron abrasion machine measurement carbon nano-tube modification natural rubber material, as a result such as table 1.
The performance of 1 carbon nano-tube modification natural rubber material of table
。
Claims (7)
1. a kind of carbon nano-tube modification natural rubber material, it is characterised in that: the raw material including following parts by weight:
100-110 parts of Heveatex, 3-6 parts of multi-walled carbon nanotube dispersion liquid, 40-65 parts of carbon black, 3-4 parts of zinc oxide, stearic acid
1-5 parts, 1-5 parts of dispersing agent, 0.1-0.5 parts of promotor, 2-3 parts of sulphur, 65-80 parts of deionized water,
Wherein, the multi-walled carbon nanotube dispersion liquid is the suspension that multi-walled carbon nanotube is dissolved in dimethylformamide formation, institute
State the mass concentration 7%-10% of multi-walled carbon nanotube in suspension.
2. a kind of carbon nano-tube modification natural rubber material according to claim 1, it is characterised in that: the natural emulsion
Solid content is 60-70%.
3. a kind of carbon nano-tube modification natural rubber material according to claim 1, it is characterised in that: the dispersing agent be Ah
Draw uncle's natural gum, in SDS, PVP any one or it is two kinds any.
4. a kind of carbon nano-tube modification natural rubber material according to claim 1, it is characterised in that: the promotor is to promote
Into agent M or accelerator NS.
5. the preparation method of any one of the claim 1-4 carbon nano-tube modification natural rubber material, it is characterised in that: including
Following steps:
(1) carbon nano tube dispersion liquid, carbon black, zinc oxide, stearic acid, dispersing agent, promotor, sulphur are mixed, then grinding exists
Deionized water is added under stirring；
(2) product of step (1) is stirred by ultrasonic 30-60min in ultrasonic stirrer, temperature is 60 DEG C when stirring；
(3) under stirring, natural emulsion will be added in the product of step (2), then proceedes to ultrasonic agitation 10-15min；
(4) by the mixture progress of step (3), drying to constant weight, obtains solid product；
(5) solid product for obtaining step (4) vulcanizes, and vulcanizes 20min at 10MPa, 160 DEG C.
6. the preparation method of carbon nano-tube modification natural rubber material according to claim 1, it is characterised in that: the ultrasound
The supersonic frequency of stirring is 20-35KHz.
7. the preparation method of carbon nano-tube modification natural rubber material according to claim 1, it is characterised in that: the drying
Temperature be 100-110 DEG C.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112831097A (en) * | 2020-05-08 | 2021-05-25 | 宁波中乌新材料产业技术研究院有限公司 | Preparation method of modified rubber composition containing carbon black and carbon nano tubes |
| CN112961413A (en) * | 2021-03-11 | 2021-06-15 | 江西耐普矿机股份有限公司 | Rubber lining for rubber hose, preparation method of rubber lining and mining machinery rubber hose |
| CN112961412A (en) * | 2021-01-25 | 2021-06-15 | 昆明理工大学 | Method and device for preparing ultrahigh-sensitivity natural rubber nano composite sensing material |
| CN113698708A (en) * | 2021-09-07 | 2021-11-26 | 宁波工程学院 | Ethylene propylene diene monomer composition and preparation method thereof |
| CN113881115A (en) * | 2021-10-21 | 2022-01-04 | 青岛科技大学 | Preparation method of modified carbon nanotube/carbon black/natural rubber composite material |
| CN114075352A (en) * | 2020-08-12 | 2022-02-22 | 苏州怒鲨智能科技有限公司 | Conductive rubber for flexible sensor and preparation method thereof |
| CN114075353A (en) * | 2020-08-12 | 2022-02-22 | 苏州怒鲨智能科技有限公司 | Graphene dielectric material for flexible sensor and preparation method thereof |
| WO2023077631A1 (en) * | 2021-11-02 | 2023-05-11 | 浙江大学台州研究院 | Method for treating heavy metal leaching wastewater by using multi-walled carbon nanotube cross-linked natural latex adsorbent |
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Application publication date: 20191008 |