CN111253656A - Carbon nano tube/antistatic agent composite modified polyethylene material and preparation method thereof - Google Patents

Carbon nano tube/antistatic agent composite modified polyethylene material and preparation method thereof Download PDF

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CN111253656A
CN111253656A CN201911347494.XA CN201911347494A CN111253656A CN 111253656 A CN111253656 A CN 111253656A CN 201911347494 A CN201911347494 A CN 201911347494A CN 111253656 A CN111253656 A CN 111253656A
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antistatic agent
nano tube
carbon nano
polyethylene
carbon nanotube
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唐宇航
温原
施海锋
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Zhejiang Rotoun Plastic Technology Co ltd
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Zhejiang Rotoun Plastic Technology Co ltd
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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/017—Additives being an antistatic agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

Abstract

The invention relates to the technical field of modified polyethylene materials, and provides a carbon nanotube/antistatic agent composite modified polyethylene material and a preparation method thereof, aiming at solving the problems that the surface resistivity of the material cannot be reduced by adding an antistatic agent alone and the material performance is greatly reduced and the cost is increased by adding a large number of carbon nanotubes for reducing the surface resistivity in the traditional polyethylene modification process, wherein the preparation method comprises the following components in percentage by mass: 40-99% of polyethylene, 0.01-0.4% of carbon nano tube, 0.3-5% of antistatic agent and the balance of auxiliary agent. The invention utilizes the synergistic effect of the carbon nano tube and the antistatic agent as the composite antistatic agent, and the antistatic agent is added into the carbon nano tube with extremely low content, so that the surface resistivity of the polyethylene composite material is obviously reduced, and the cost is reduced; the invention has low surface resistivity, good mechanical property, easy molding and good appearance of products. Can be used in amusement facilities, military industry boxes and the like which simultaneously need antistatic and good mechanical performance.

Description

Carbon nano tube/antistatic agent composite modified polyethylene material and preparation method thereof
Technical Field
The invention relates to the technical field of modified polyethylene materials, in particular to a carbon nano tube/antistatic agent composite modified polyethylene material and a preparation method thereof.
Background
Polyethylene (PE) is a thermoplastic resin obtained by polymerizing ethylene, and industrially, it also includes a copolymer of ethylene and a small amount of α -olefin, and it is odorless, non-toxic, has a wax-like hand feeling, has excellent low-temperature resistance (the lowest using temperature can be-70 deg.C), good chemical stability, and can resist most of acid and alkali corrosion (it cannot resist acid with oxidation property), and it is insoluble in general solvent at normal temperature, and its water absorption is small, and its electric insulating property is good17About 10 in surface resistivity17On the left and right sides, the surface of the material is easy to generate static charges in the processes of friction, peeling, induction and the like, the generated static charges are difficult to transfer due to high volume resistivity and surface resistivity, and when the surface static charges are accumulated to a certain degree, serious dangers such as dust absorption, discharge, breakdown, even combustion or explosion are easy to cause, so that the polyethylene can only be applied to the field of insulation in industry or life, the application range of the polyethylene is greatly limited, and people pay more and more attention to the antistatic problem of the polyethylene.
Chinese patent literature discloses 'a flame-retardant antistatic polyethylene composition special for rotational molding and a preparation method thereof', and the application publication number is CN 106867080A; chinese patent literature discloses 'antistatic flame-retardant modified polyethylene powder and a preparation method thereof', and the application publication number of the polyethylene powder is CN 103849024A; both the two inventions adopt a screw granulation method to fully disperse the antistatic component into the base material, so as to form the composite material with uniform material quality and uniform antistatic effect. However, the antistatic grade is difficult to reach 108And below, the application is limited.
In the prior art, there is also modified polyethylene using carbon nanotubes alone as antistatic agent, and chinese patent document discloses "an antistatic polyethylene film", with an authorization publication number of CN205997472U, in order to achieve antistatic or conductive properties on the surface of a product, the utility model coats, laminates or compounds a material having antistatic or conductive properties on a base material, although the surface resistivity can reach 104However, the cost is high because single-layer carbon nanotubes are used. Chinese patent literature discloses a preparation method of antistatic modified plastic, the application publication number of which is CN 107325520A, and the surface resistivity of the modified plastic can reach 106However, the addition amount of the carbon nanotubes is as high as 3 wt%, which is very costly.
Disclosure of Invention
The invention provides a carbon nanotube/antistatic agent composite modified polyethylene material which has low surface resistivity, good mechanical property and processing fluidity and is suitable for a rotational molding production process, and aims to solve the problems that the surface resistivity of the material cannot be reduced by adding an antistatic agent alone and the material performance is greatly reduced and the cost is increased by adding a large amount of carbon nanotubes for reducing the surface resistivity in the traditional polyethylene modification process.
The invention also provides a preparation method of the carbon nano tube/antistatic agent composite modified polyethylene material, which is simple, does not need complex equipment and is easy to realize industrial operation.
In order to achieve the purpose, the invention adopts the following technical scheme:
a carbon nanotube/antistatic agent composite modified polyethylene material comprises the following components in percentage by mass: 40-99% of polyethylene, 0.01-0.4% of carbon nano tube, 0.3-5% of antistatic agent and the balance of auxiliary agent.
According to the invention, after polyethylene, carbon nano tubes, an antistatic agent and the like are mixed and granulated according to the proportion, the composite modified polyethylene material with low surface resistivity, good mechanical property and processing fluidity is obtained at low cost on the premise of low addition of the carbon nano tubes, various products such as boxes, amusement facilities, ornaments and the like can be manufactured by a rotational molding processing technology, and the problem that the existing polyethylene cannot have low surface resistivity and good mechanical property at the same time is effectively solved.
Preferably, the density of the polyethylene is 0.910-0.965g/cm3The melt flow rate (190 ℃ C., 2.16Kg) is 1.0 to 20.0g/10 min.
Preferably, the carbon nano tube has the tube diameter of 1-25nm, the length of 0.5-30 mu m, the purity of 60-99% and the conductivity of more than 150 s/cm.
Preferably, the antistatic agent is a surfactant-based internal mixing type antistatic agent or a polymer permanent type antistatic agent.
Preferably, the auxiliary agent is selected from one or more of an antioxidant, a flame retardant, a light stabilizer, a lubricant and a pigment.
Preferably, the surface resistivity of the carbon nano tube/antistatic agent composite modified polyethylene material is 107～1011Ω。
A preparation method of a carbon nano tube/antistatic agent composite modified polyethylene material comprises the following steps:
(1) fully mixing polyethylene, the carbon nano tube and the antistatic agent according to the proportion to obtain a mixed material;
(2) melting and blending the mixed material obtained in the step (1) by using a double-screw extruder, and extruding and granulating to obtain a granular material;
(3) and (3) grinding the granules obtained in the step (2) by using a plastic grinding mill to obtain the carbon nano tube/antistatic agent composite modified polyethylene material.
Preferably, in the step (2), the extrusion process parameters are as follows: the melt temperature is 150-210 ℃, and the screw rotation speed is 100-500 rpm;
preferably, in the step (3), the milling process parameters are as follows: the temperature of the grinding disc is less than or equal to 75 ℃, and the rotating speed of the grinding disc is 2500-3200 rpm.
A preparation method of a carbon nano tube/antistatic agent composite modified polyethylene material comprises the following steps:
(1) the raw materials are weighed according to the mixture ratio,adding carbon nanotubes to 98 wt% H2SO4-68wt％HNO3Carrying out ultrasonic treatment in mixed acid at 35-40 ℃, cooling to room temperature, filtering with a microporous filter membrane, washing with deionized water to be neutral, and drying to obtain a modified carbon nano tube; the carbon nano tube is subjected to acid treatment, and the surface of the obtained modified carbon nano tube is provided with a large amount of oxygen-containing functional groups, namely carboxyl;
(2) dispersing the modified carbon nano tube obtained in the step (1) in water to obtain a modified carbon nano tube suspension, adding polyethylene, uniformly stirring, centrifuging, and drying to obtain a modified carbon nano tube/polyethylene composite material; in the step, a large number of oxygen-containing functional group-carboxyl modified carbon nanotubes are dispersed in water, the surfaces of the modified carbon nanotubes have a large number of negative charges, although the water solubility of polyethylene is poor, the surfaces of the polyethylene are easy to generate static charges, and the static charges are positive charges; when polyethylene is added into the modified carbon nanotube suspension, under the stirring condition, the polyethylene with positive charges and the modified carbon nanotubes with negative charges are rapidly combined through electrostatic adsorption, so that the modified carbon nanotubes are uniformly distributed on the surface of the polyethylene, and the dispersibility of the carbon nanotubes in a polyethylene system is improved;
(3) and (3) fully mixing the modified carbon nanotube/polyethylene composite material obtained in the step (2) with an antistatic agent, carrying out melt blending by using a double-screw extruder, and carrying out extrusion granulation and grinding to obtain the carbon nanotube/antistatic agent composite modified polyethylene material.
Preferably, in the step (1), the ultrasonic power is 120-140W, the ultrasonic frequency is 25-30 Hz, and the ultrasonic time is 1-2 h. Under the ultrasonic process condition, the appearance of the carbon nano tube can not be damaged, and the original performance is kept.
Preferably, in the step (1), the liquid-solid ratio (4-8) of the mixed acid to the carbon nano tube is controlled: 1.
preferably, the 98 wt% H2SO4-68wt％HNO3The volume ratio of sulfuric acid to nitric acid in the mixed acid is (1-2): 1.
therefore, the invention has the following beneficial effects:
(1) the invention utilizes the synergistic effect of the carbon nano tube and the antistatic agent as the composite antistatic agent, and the antistatic agent is added into the carbon nano tube with extremely low content, so that the surface resistivity of the polyethylene composite material is obviously reduced, and the cost is reduced;
(2) the material of the invention has low surface resistivity, good mechanical property, easy molding and good appearance of products. Can be used in amusement facilities, military industry boxes and the like which need antistatic and good mechanical properties at the same time;
(3) the invention has excellent processing fluidity, simple preparation method, no need of complex equipment and easy realization of industrial operation;
(4) the polyethylene with positive charges and the modified carbon nano tube with negative charges are utilized to improve the dispersibility of the carbon nano tube in a polyethylene system through electrostatic adsorption, the preparation process is simple, complex equipment is not needed, and the industrial operation is easy to realize.
Drawings
FIG. 1 is a graph showing the relationship between the amount of carbon nanotubes added and the surface resistivity of the product in examples 1 to 7 and comparative examples 1 to 8.
Detailed Description
The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
The polyethylene satisfies: the density is 0.910-0.965g/cm3The melt flow rate (190 ℃ C., 2.16Kg) is 1.0 to 20.0g/10 min. The raw materials are commercially available products and are directly used after being purchased from manufacturers. Preferred grades of polyethylene are Exxon Mobil 'S LLDPE LL8446.2.1, Siamese' S LLDPE 735RU, Tristar Korea 'S LLDPER901U, medium petrochemical refined LLDPE R546U, medium petrochemical refined DNDA-8320, medium petroleum company' S HDPE 5000S, and medium petrochemical Yanshan 1C 7A.
The carbon nano tube satisfies the following conditions: the pipe diameter is 1-25nm, the length is 0.5-30 μm, the purity is 60% -99%, and the conductivity is more than 150 s/cm. Is a commercially available product, purchased from a manufacturerCan be directly used after being obtained. The preferred grades for dispersing carbon nanotubes are CNT100 from Ching de Ke island technologies, Inc. of Beijing, and TUBALL from OCSIAL IncTMMATRIX beat 801. SWCNTs of Chengdu organic chemistry Co., Ltd, XFS14 of Nanjing Xiancheng nanomaterial science and technology Co., Ltd. Flotube 9100/9101 from Kaempferia corporation.
The antistatic agent is a commercial product and is directly used after being purchased from a manufacturer. The preferred brands of the antistatic agent are Japan Huawang TS-5, Hangzhou chemical research institute HKD-100, Jiahuajing EST-200, and Lingan Yongsheng HBS-302.
The modified polyethylene material of the invention can include any conventional additives such as antioxidants, flame retardants, light stabilizers, lubricants, pigments or the like.
Example 1
(1) According to the raw material ratio of Table 1, 97.98% polyethylene (density 0.950 g/cm)3The melt flow rate is 10.0g/10min), 0.002% carbon nano tube (tube diameter is 15nm, length is 20 μm, purity is 80%, conductivity is 200s/cm) and 2% antistatic agent (Lianan Yongsheng HBS-302) are fully mixed to obtain a mixed material;
(2) melting and blending the mixed material obtained in the step (1) by using a double-screw extruder, and extruding and granulating to obtain a granular material; the extrusion process parameters are as follows: the melt temperature is 200 ℃, and the screw rotation speed is 300 rpm;
(3) and (3) grinding the granules obtained in the step (2) by using a plastic grinding mill to obtain the carbon nano tube/antistatic agent composite modified polyethylene material. The milling process parameters are as follows: the temperature of the grinding disc is 50 ℃, and the rotating speed of the grinding disc is 3000 rpm.
Example 2
(1) According to the raw material ratio of Table 1, 97.96% polyethylene (density 0.910 g/cm)3The melt flow rate is 1.0g/10min), 0.004% of carbon nano tubes (the tube diameter is 25nm, the length is 0.5 mu m, the purity is 99%, and the conductivity is 500s/cm) and 2% of antistatic agent (HKD-100) are fully mixed to obtain a mixed material;
(2) melting and blending the mixed material obtained in the step (1) by using a double-screw extruder, and extruding and granulating to obtain a granular material; the extrusion process parameters are as follows: the melt temperature was 150 ℃ and the screw speed was 500 rpm;
(3) and (3) grinding the granules obtained in the step (2) by using a plastic grinding mill to obtain the carbon nano tube/antistatic agent composite modified polyethylene material. The milling process parameters are as follows: the temperature of the grinding disc is 75 ℃, and the rotating speed of the grinding disc is 3200 rpm.
Example 3
(1) According to the raw material ratio of Table 1, 97.92% polyethylene (density 0.965 g/cm)3The melt flow rate is 20.0g/10min), 0.008% carbon nano tube (tube diameter is 1nm, length is 30 μm, purity is 60%, conductivity is 400s/cm) and 2% antistatic agent (Japan Huawang TS-5) are fully mixed to obtain a mixed material;
(2) melting and blending the mixed material obtained in the step (1) by using a double-screw extruder, and extruding and granulating to obtain a granular material; the extrusion process parameters are as follows: the melt temperature was 210 ℃ and the screw speed was 100 rpm;
(3) and (3) grinding the granules obtained in the step (2) by using a plastic grinding mill to obtain the carbon nano tube/antistatic agent composite modified polyethylene material. The milling process parameters are as follows: the temperature of the grinding disc is 55 ℃, and the rotating speed of the grinding disc is 2500 rpm.
Example 4
(1) According to the raw material ratio of Table 1, 97.90% polyethylene (density 0.950 g/cm)3The melt flow rate is 15g/10min), 0.01 percent of carbon nano tube (the tube diameter is 20nm, the length is 15 mu m, the purity is 80 percent, and the conductivity is more than 150s/cm) and 2 percent of antistatic agent (Jiahuajing EST-200) are fully mixed to obtain a mixed material;
(2) melting and blending the mixed material obtained in the step (1) by using a double-screw extruder, and extruding and granulating to obtain a granular material; the extrusion process parameters are as follows: the melt temperature is 180 ℃, and the screw rotation speed is 200 rpm;
(3) and (3) grinding the granules obtained in the step (2) by using a plastic grinding mill to obtain the carbon nano tube/antistatic agent composite modified polyethylene material. The milling process parameters are as follows: the temperature of the grinding disc is less than or equal to 75 ℃, and the rotation speed of the grinding disc is 3100 rpm.
Example 5
(1) According to the raw material ratio of table 1, 97.8% of polyethylene, 0.02% of carbon nano tube and 2% of antistatic agent are fully mixed to obtain a mixed material;
(2) melting and blending the mixed material obtained in the step (1) by using a double-screw extruder, and extruding and granulating to obtain a granular material; the extrusion process parameters are as follows: the melt temperature is 160 ℃, and the screw rotation speed is 300 rpm;
(3) and (3) grinding the granules obtained in the step (2) by using a plastic grinding mill to obtain the carbon nano tube/antistatic agent composite modified polyethylene material. The milling process parameters are as follows: the temperature of the grinding disc is less than or equal to 75 ℃, and the rotating speed of the grinding disc is 28000 rpm.
Example 6
(1) According to the raw material ratio of table 1, 97.6% of polyethylene, 0.04% of carbon nano tube and 2% of antistatic agent are fully mixed to obtain a mixed material;
(2) melting and blending the mixed material obtained in the step (1) by using a double-screw extruder, and extruding and granulating to obtain a granular material; the extrusion process parameters are as follows: the melt temperature is 160 ℃, and the screw rotation speed is 300 rpm;
(3) and (3) grinding the granules obtained in the step (2) by using a plastic grinding mill to obtain the carbon nano tube/antistatic agent composite modified polyethylene material. The milling process parameters are as follows: the temperature of the grinding disc is less than or equal to 75 ℃, and the rotating speed of the grinding disc is 2700 rpm.
Example 7
(1) According to the raw material ratio of table 1, 97.5% of polyethylene, 0.05% of carbon nano tube and 2% of antistatic agent are fully mixed to obtain a mixed material;
(2) melting and blending the mixed material obtained in the step (1) by using a double-screw extruder, and extruding and granulating to obtain a granular material; the extrusion process parameters are as follows: the melt temperature was 200 ℃ and the screw rotation speed was 400 rpm;
(3) grinding the granules obtained in the step (2) by using a plastic grinding machine to obtain a carbon nano tube/antistatic agent composite modified polyethylene material; the milling process parameters are as follows: the temperature of the grinding disc is less than or equal to 75 ℃, and the rotating speed of the grinding disc is 2700 rpm.
Example 8
(1) Weighing the raw materials according to the proportion, adding 0.002% of carbon nano tube (the tube diameter is 15nm, the length is 20 mu m, the purity is 80%, and the conductivity is 200s/cm) into 98 wt% of H2SO4-68wt％HNO3Ultrasonic treatment is carried out in mixed acid at 38 ℃, and the volume ratio of sulfuric acid to nitric acid is 2:1, ultrasonic power 130W, ultrasonic frequency 28Hz, ultrasonic time 1.5h, controlling the liquid-solid ratio of mixed acid to carbon nano tube 6: 1, cooling to room temperature, filtering with a microporous filter membrane, washing with deionized water to be neutral, and drying to obtain a modified carbon nanotube;
(2) dispersing the modified carbon nano tube obtained in the step (1) in water to obtain a modified carbon nano tube suspension, adding 97.98% of polyethylene, uniformly stirring, centrifuging, and drying to obtain a modified carbon nano tube/polyethylene composite material;
(3) fully mixing the modified carbon nanotube/polyethylene composite material obtained in the step (2) with 2% of antistatic agent, melting and blending by using a double-screw extruder, and extruding and granulating to obtain a granular material; the extrusion process parameters are as follows: the melt temperature is 200 ℃, and the screw rotation speed is 300 rpm;
(4) and (4) grinding the granules obtained in the step (3) by using a plastic grinding mill to obtain the carbon nano tube/antistatic agent composite modified polyethylene material. The milling process parameters are as follows: the temperature of the grinding disc is 50 ℃, the rotating speed of the grinding disc is 3000rpm, and the carbon nano tube/antistatic agent composite modified polyethylene material is obtained.
Example 9
(1) Weighing the raw materials according to the proportion, adding 0.4 percent of carbon nano tube (the tube diameter is 15nm, the length is 20 mu m, the purity is 80 percent, and the conductivity is 200s/cm) into 98 percent by weight of H2SO4-68wt％HNO3Carrying out ultrasonic treatment at 35 ℃ in mixed acid, wherein the volume ratio of sulfuric acid to nitric acid is 1: 1, ultrasonic power of 120W, ultrasonic frequency of 30Hz and ultrasonic time of 2h, and controlling the liquid-solid ratio of mixed acid to carbon nano tube to be 4: 1, cooling to room temperature, filtering with a microporous filter membrane, washing with deionized water to be neutral, and drying to obtain a modified carbon nanotube;
(2) dispersing the modified carbon nano tube obtained in the step (1) in water to obtain a modified carbon nano tube suspension, adding 1% of polyethylene, uniformly stirring, centrifuging, and drying to obtain a modified carbon nano tube/polyethylene composite material;
(3) fully mixing the modified carbon nanotube/polyethylene composite material obtained in the step (2) with 5% of antistatic agent, 10% of antioxidant, 15% of flame retardant, 12% of light stabilizer, 10% of lubricant and 7.6% of pigment, carrying out melt blending by using a double-screw extruder, and carrying out extrusion granulation to obtain a granular material; the extrusion process parameters are as follows: the melt temperature was 150 ℃ and the screw speed was 500 rpm;
(4) and (4) grinding the granules obtained in the step (3) by using a plastic grinding mill to obtain the carbon nano tube/antistatic agent composite modified polyethylene material. The milling process parameters are as follows: the temperature of the grinding disc is less than or equal to 75 ℃, the rotating speed of the grinding disc is 2500rpm, and the carbon nano tube/antistatic agent composite modified polyethylene material is obtained.
Example 10
(1) Weighing the raw materials according to the proportion, adding 0.01 percent of carbon nano tube into 98 percent of H by weight2SO4-68wt％HNO3Carrying out ultrasonic treatment at 35-40 ℃ in mixed acid, wherein the volume ratio of sulfuric acid to nitric acid is 1.5: 1, ultrasonic power 140W, ultrasonic frequency 25Hz and ultrasonic time 1h, and controlling the liquid-solid ratio of mixed acid to carbon nano tube to be 8: 1, cooling to room temperature, filtering with a microporous filter membrane, washing with deionized water to be neutral, and drying to obtain a modified carbon nanotube;
(2) dispersing the modified carbon nano tube obtained in the step (1) in water to obtain a modified carbon nano tube suspension, adding 99% polyethylene, uniformly stirring, centrifuging, and drying to obtain a modified carbon nano tube/polyethylene composite material;
(3) fully mixing the modified carbon nanotube/polyethylene composite material obtained in the step (2) with 0.3% of antistatic agent and 0.69% of flame retardant, carrying out melt blending by using a double-screw extruder, and carrying out extrusion granulation to obtain a granular material; the extrusion process parameters are as follows: the melt temperature was 150 ℃ and the screw speed was 500 rpm;
(4) and (4) grinding the granules obtained in the step (3) by using a plastic grinding mill to obtain the carbon nano tube/antistatic agent composite modified polyethylene material. The milling process parameters are as follows: the temperature of the grinding disc is less than or equal to 75 ℃, the rotating speed of the grinding disc is 3200rpm, and the carbon nano tube/antistatic agent composite modified polyethylene material is obtained.
Comparative example 1 (without addition of carbon nanotubes)
Comparative example 1 differs from example 1 in the formulation, see table 1: 95% of polyethylene and 5% of antistatic agent, and the rest processes are completely the same.
Comparative examples 2 to 8 (without addition of antistatic agent)
Comparative examples 2 to 8 differ from example 1 in that no antistatic agent was added, the formulation is shown in Table 1, and the rest of the process was exactly the same.
For the product performance tests of examples 1-10 and comparative examples 1-8, the cantilever beam impact test is performed according to GB/T1843-:
TABLE 1 formulation and product Performance test results for examples 1-10 and comparative examples 1-8
Figure BDA0002333797540000081
FIG. 1 is a graph showing the relationship between the amount of carbon nanotubes added and the surface resistivity of the product in examples 1 to 7 and comparative examples 1 to 8. As can be seen from fig. 1 and table 1, the surface resistivity of the material of the present invention is significantly reduced after the antistatic agent is added to the carbon nanotube composite material in the same content in examples 1 to 7 as compared to comparative examples 2 to 8, and the surface resistivity of the material of the present invention is also greatly reduced in examples 1 to 8 as compared to the surface resistivity of comparative example 1 to which only the antistatic agent is added, which indicates that there is a good synergistic effect between the carbon nanotubes and the antistatic agent. Compared with the comparative example 7, the product with the same mechanical property and the same addition amount of the carbon nano tube in the example 6 has lower surface resistivity, and due to the characteristics, the material disclosed by the invention is beneficial to the expansion and optimization of product categories and is suitable for the production of processes such as rotational molding, injection molding, blow molding and the like. Compared with the embodiment 8, the embodiment 1 has the same formula and different mixing processes, the dispersibility of the carbon nano tube in a polyethylene system is improved by utilizing the polyethylene with positive charges and the modified carbon nano tube with negative charges through the electrostatic adsorption effect, the surface resistivity of the obtained product is obviously reduced, and the mechanical property is better.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.

Claims (10)

1. The carbon nanotube/antistatic agent composite modified polyethylene material is characterized by comprising the following components in percentage by mass: 40-99% of polyethylene, 0.01-0.4% of carbon nano tube, 0.3-5% of antistatic agent and the balance of auxiliary agent.
2. The carbon nanotube/antistatic agent composite modified polyethylene material as claimed in claim 1, wherein the density of the polyethylene is 0.910-0.965g/cm3The melt flow rate is 1.0-20.0 g/10 min.
3. The carbon nanotube/antistatic agent composite modified polyethylene material according to claim 1, wherein the carbon nanotube has a tube diameter of 1-25nm, a length of 0.5-30 μm, a purity of 60-99%, and an electrical conductivity of > 150 s/cm.
4. The carbon nanotube/antistatic agent composite modified polyethylene material of claim 1, wherein the antistatic agent is a surfactant-based internal mixing type antistatic agent or a polymer permanent type antistatic agent.
5. The carbon nanotube/antistatic agent composite modified polyethylene material as claimed in claim 1, wherein the auxiliary agent is one or more selected from antioxidant, flame retardant, light stabilizer, lubricant and pigment.
6. The carbon nanotube/antistatic agent composite modified polyethylene material as claimed in claim 1, wherein the surface resistivity of the carbon nanotube/antistatic agent composite modified polyethylene material is 107～1011Ω。
7. A preparation method of the carbon nanotube/antistatic agent composite modified polyethylene material as claimed in any one of claims 1 to 6, characterized by comprising the following steps:
(1) fully mixing polyethylene, the carbon nano tube and the antistatic agent according to the proportion to obtain a mixed material;
(2) melting and blending the mixed material obtained in the step (1) by using a double-screw extruder, and extruding and granulating to obtain a granular material;
(3) and (3) grinding the granules obtained in the step (2) by using a plastic grinding mill to obtain the carbon nano tube/antistatic agent composite modified polyethylene material.
8. The method for preparing the carbon nanotube/antistatic agent composite modified polyethylene material according to claim 7, wherein in the step (2), the extrusion process parameters are as follows: the melt temperature is 150-210 ℃, and the screw rotation speed is 100-500 rpm; in the step (3), the milling process parameters are as follows: the temperature of the grinding disc is less than or equal to 75 ℃, and the rotating speed of the grinding disc is 2500-3200 rpm.
9. A method for preparing the carbon nanotube/antistatic agent composite modified polyethylene material as claimed in any one of claims 1 to 8, which comprises the following steps:
(1) weighing the raw materials according to the proportion, adding the carbon nano tube into 98 wt% of H2SO4-68wt％HNO3Carrying out ultrasonic treatment in mixed acid at 35-40 ℃, cooling to room temperature, filtering with a microporous filter membrane, washing with deionized water to be neutral, and drying to obtain a modified carbon nano tube;
(2) dispersing the modified carbon nano tube obtained in the step (1) in water to obtain a modified carbon nano tube suspension, adding polyethylene, uniformly stirring, centrifuging, and drying to obtain a modified carbon nano tube/polyethylene composite material;
(3) and (3) fully mixing the modified carbon nanotube/polyethylene composite material obtained in the step (2) with an antistatic agent, carrying out melt blending by using a double-screw extruder, and carrying out extrusion granulation and grinding to obtain the carbon nanotube/antistatic agent composite modified polyethylene material.
10. The preparation method of the carbon nanotube/antistatic agent composite modified polyethylene material according to claim 9, wherein in the step (1), the ultrasonic power is 120-140W, the ultrasonic frequency is 25-30 Hz, and the ultrasonic time is 1-2 h; controlling the liquid-solid ratio (4-8) of the mixed acid to the carbon nano tube: 1; the 98 wt% of H2SO4-68wt％HNO3Sulfuric acid and sulfuric acid in mixed acidThe volume ratio of the nitric acid is (1-2): 1.
CN201911347494.XA 2019-12-24 2019-12-24 Carbon nano tube/antistatic agent composite modified polyethylene material and preparation method thereof Pending CN111253656A (en)

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