CN114989640B - Carbon nano tube modification method, conductive PA material and preparation method thereof - Google Patents

Carbon nano tube modification method, conductive PA material and preparation method thereof Download PDF

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CN114989640B
CN114989640B CN202210716315.0A CN202210716315A CN114989640B CN 114989640 B CN114989640 B CN 114989640B CN 202210716315 A CN202210716315 A CN 202210716315A CN 114989640 B CN114989640 B CN 114989640B
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carbon nano
conductive
nano tube
dispersion liquid
resin
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CN114989640A (en
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李子轩
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Shenzhen Feimo Technology Co ltd
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Shenzhen Feimo Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
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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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    • C08K7/00—Use of ingredients characterised by shape
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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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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    • C08K2201/001—Conductive additives
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    • C08L2201/00—Properties
    • C08L2201/04—Antistatic

Abstract

The application belongs to the technical field of high polymer materials, and particularly relates to a carbon nano tube modification method, a conductive PA material and a preparation method thereof. The carbon nano tube modification method comprises the following preparation steps: step one, mixing polyurethane solution with carbon nano tubes, and grinding uniformly to obtain pre-dispersion liquid; dispersing the pre-dispersion liquid by adopting a micro-jet dispersion technology to obtain dispersion liquid; and thirdly, freeze-drying the dispersion liquid to obtain the modified carbon nano tube. The carbon nanotube modification method can effectively improve the dispersion performance of the carbon nanotubes in the PA resin and the compatibility of the carbon nanotubes with the PA resin.

Description

Carbon nano tube modification method, conductive PA material and preparation method thereof
Technical Field
The application belongs to the technical field of high polymer materials, and particularly relates to a carbon nano tube modification method, a conductive PA material and a preparation method thereof.
Background
The conductive plastic is a functional polymer material obtained by mixing a resin and a conductive substance and processing the mixture by a plastic processing method. The method is mainly applied to the fields of electronics, integrated circuit packaging, electromagnetic wave shielding and the like. It is the most important class of conductive polymer materials. Since plastics are used as insulating materials in the electrical field, conductive plastics are often treated as special functional materials.
Polyamide is commonly called Nylon (Nylon), and the English name Polyamide (PA) is a thermoplastic resin general term containing repeated amide groups- (NHCO) on a molecular main chain, and the PA has good comprehensive properties including mechanical properties, heat resistance, abrasion resistance, chemical resistance and self-lubricity, is low in friction coefficient, has certain flame retardance, is easy to process, is suitable for filling and reinforcing modification by glass fibers and other fillers, and improves the performance and expands the application range.
The carbon nanotube, also called bucky tube, is a one-dimensional quantum material with a special structure (the radial dimension is in the order of nanometers, the axial dimension is in the order of micrometers, and both ends of the tube are basically sealed). Carbon nanotubes mainly consist of layers to tens of layers of coaxial round tubes of carbon atoms arranged in a hexagonal manner. The layer-to-layer distance is kept constant, about 0.34nm, and the diameter is typically 2-20 nm. Carbon nanotubes have many unusual mechanical, electrical and chemical properties, and have been applied in the field of conductive plastics in recent years, and the conductivity of plastics can be effectively improved by using a small amount of carbon nanotubes.
In the prior art, carbon nano tubes, a coupling agent, a dispersing agent and plastic particles are added into a double-screw machine to prepare carbon nano tube conductive plastic master batch, and then banburying or injection molding is carried out. However, due to poor compatibility of the carbon nanotubes and the PA, the carbon nanotubes cannot be uniformly dispersed in the PA, so that the prepared composite material has poor conductivity and mechanical properties, and the application of the conductive PA material is affected.
Disclosure of Invention
The first object of the present application is to provide a carbon nanotube modification method which can effectively improve the dispersion performance of carbon nanotubes in PA resin and the compatibility of carbon nanotubes with PA resin.
A second object of the present application is to provide a conductive PA material having high electrical conductivity and mechanical properties.
The third purpose of the application is to provide a preparation method of the conductive PA material, and the PA material prepared by the method has uniformly dispersed carbon nanotubes and high conductivity and mechanical properties.
In order to achieve the above object, the present application adopts the following technical scheme:
in one aspect, the application provides a method for modifying a carbon nanotube, comprising the following steps:
step one, mixing polyurethane solution with carbon nano tubes, and grinding uniformly to obtain pre-dispersion liquid;
dispersing the pre-dispersion liquid by adopting a micro-jet dispersion technology to obtain dispersion liquid;
and thirdly, freeze-drying the dispersion liquid to obtain the modified carbon nano tube.
The weight ratio of the polyurethane solution to the carbon nano tube is 15-23:1, and the polyurethane solution comprises 8-12 parts by weight of polyurethane and 900-950 parts by weight of organic solvent.
Wherein the organic solvent comprises at least one of ethanol, ethylene glycol, n-propanol, isopropanol, propylene glycol, butanol, toluene and xylene.
Wherein the polyurethane solution also comprises 8-12 parts by weight of coupling agent.
Wherein the coupling agent comprises at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent.
In the first step, a colloid mill is used for grinding for 0.5-1h at the frequency of 20-40 Hz.
In the second step, the micro-jet pressure is 110-130MPa, and the treatment is carried out for 1-2 times.
In the third step, freeze drying is carried out for 24-36h under the condition that the vacuum degree is 50-300 mTorr and the cold trap temperature is minus 40-minus 10 ℃.
The application also provides a conductive PA material, which comprises the following raw materials in percentage by mass: 4-6% of the modified carbon nano tube, 14-16% of carbon fiber, 0-2% of auxiliary agent and the balance of PA resin.
According to the preparation method, 4-6% of the modified carbon nano tube, 14-16% of carbon fiber, 0-1% of auxiliary agent and the balance of PA resin are stirred in a high-speed stirrer for 5-15min according to mass percent, and then the stirred mixture is granulated by a double-screw machine and injection molded to prepare the conductive PA material.
The application has the beneficial effects that:
according to the embodiment of the application, polyurethane and carbon nano tubes are mixed, the mixed solution is sequentially subjected to grinding and microjet dispersion treatment, so that the carbon nano tubes are uniformly dispersed in the polyurethane solution, and finally, the dispersion solution is subjected to freeze drying, so that the modification treatment of the carbon nano tubes is realized, the modified carbon nano tubes are coated with polyurethane resin, and the polyurethane coating on the surfaces of the carbon nano tubes can effectively improve the compatibility between the carbon nano tubes and the PA resin due to good compatibility between the polyurethane resin and the PA resin, so that the carbon nano tubes can be uniformly dispersed in the PA resin, and the conductivity and mechanical property of the PA material are improved.
According to the carbon nanotube modification method, the solution is pre-dispersed in a grinding mode, and then the solution is secondarily dispersed in a microjet mode, so that the dispersion effect of the carbon nanotubes and polyurethane can be effectively improved, the polyurethane is fully wrapped on the surfaces of the carbon nanotubes, the compatibility of the carbon nanotubes and the PA material is improved, the uniform dispersion of the carbon nanotubes in the PA material is facilitated, and the conductivity and mechanical property of the PA material are improved.
Detailed Description
For the purpose of making the objects, technical solutions and technical effects of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application are clearly and completely described, and the embodiments described below are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art without the benefit of the teachings of this application, are intended to be within the scope of the application. The specific conditions are not noted in the examples, and are carried out according to conventional conditions or conditions suggested by the manufacturer; the reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the description of the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the description of the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that the weights of the relevant components mentioned in the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components are scaled up or down according to the embodiments of the present application, which are within the scope of the present disclosure. Specifically, the weight in the embodiment of the application can be mass units well known in the chemical industry field such as mu g, mg, g, kg.
In addition, the expression of a word in the singular should be understood to include the plural of the word unless the context clearly indicates otherwise. The terms "comprises" or "comprising" are intended to specify the presence of stated features, integers, steps, operations, elements, components, or groups thereof, but are not intended to preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or groups thereof.
The embodiment of the application provides a carbon nano tube modification method, which comprises the following preparation steps:
step one, mixing polyurethane solution with carbon nano tubes, and grinding uniformly to obtain pre-dispersion liquid;
dispersing the pre-dispersion liquid by adopting a micro-jet dispersion technology to obtain dispersion liquid;
and thirdly, freeze-drying the dispersion liquid to obtain the modified carbon nano tube.
According to the embodiment of the application, polyurethane and carbon nano tubes are mixed, the mixed solution is sequentially subjected to grinding and microjet dispersion treatment, so that the carbon nano tubes are uniformly dispersed in the polyurethane solution, and finally, the dispersion solution is subjected to freeze drying, so that the modification treatment of the carbon nano tubes is realized, the modified carbon nano tubes are coated with polyurethane resin, and the polyurethane coating on the surfaces of the carbon nano tubes can effectively improve the compatibility between the carbon nano tubes and the PA resin due to good compatibility between the polyurethane resin and the PA resin, so that the carbon nano tubes can be uniformly dispersed in the PA resin, and the conductivity and mechanical property of the PA material are improved.
According to the carbon nanotube modification method, the solution is pre-dispersed in a grinding mode, and then the solution is secondarily dispersed in a microjet mode, so that the dispersion effect of the carbon nanotubes and polyurethane can be effectively improved, the polyurethane is fully wrapped on the surfaces of the carbon nanotubes, the compatibility of the carbon nanotubes and the PA material is improved, the uniform dispersion of the carbon nanotubes in the PA material is facilitated, and the conductivity and mechanical property of the PA material are improved.
In an embodiment of the present application, the carbon nanotubes are at least one of single-walled carbon nanotubes, double-walled carbon nanotubes, or multi-walled carbon nanotubes.
The weight ratio of the polyurethane solution to the carbon nano tube is 15-23:1, and the polyurethane solution comprises 8-12 parts by weight of polyurethane and 900-950 parts by weight of organic solvent.
The polyurethane solution and the carbon nano tubes in the proportion are mixed, enough polyurethane can be wrapped on the surfaces of the carbon nano tubes, when the addition amount of the polyurethane is too large, the excessive polyurethane can influence the connection between the carbon nano tubes, so that the carbon nano tubes are difficult to form a conductive network in a PA system, the final conductive performance and mechanical performance of the PA material are further influenced, when the addition amount of the polyurethane is too small, the compatibility of the modified carbon nano tubes and the PA resin can be influenced, the dispersion performance of the modified carbon nano tubes in the PA resin is reduced, and the conductivity and mechanical performance of the prepared PA composite material are influenced.
In the embodiment of the application, the weight ratio of the polyurethane solution to the carbon nanotubes may be, but not limited to, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1 or 23:1, the weight part of the polyurethane in the polyurethane solution may be, but not limited to, 8, 9, 10, 11, 12, and the weight part of the organic solvent in the polyurethane solution may be, but not limited to, 900, 905, 910, 913, 915, 920, 925, 930, 935, 940 or 950.
Wherein the organic solvent comprises at least one of ethanol, ethylene glycol, n-propanol, isopropanol, propylene glycol, butanol, toluene and xylene.
Wherein the polyurethane solution also comprises 8-12 parts by weight of coupling agent. The addition of the coupling agent can enable the carbon nano tube to be grafted with the oxygen-containing functional group, improve the affinity of the carbon nano tube and the high polymer material, further improve the compatibility of the carbon nano tube and the PA material, enable the carbon nano tube to be more uniformly dispersed in the PA material, and improve the conductivity and mechanical property of the PA composite material. In the embodiment of the application, the coupling agent is added in parts by weight, which is not limited to 8, 9, 10, 11 or 12, and if the coupling agent is added in excessive amount, the connection between the carbon nanotubes is affected, so that the carbon nanotubes are difficult to form a conductive network in the PA material, and the conductivity of the PA composite material is further affected.
Wherein the coupling agent comprises at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent. In an embodiment of the present application, the preferred coupling agent is a silane coupling agent, which may be specifically but not limited to at least one of KH550, KH560, KH 570. The silane coupling agent of the above kind is more advantageous for improving the compatibility between the carbon nanotubes and the PA resin.
In an embodiment of the application, the preparation method of the polyurethane solution comprises the following steps: the polyurethane resin and the coupling agent are added into the organic solvent according to the weight portions, and are stirred for 5-15min at the stirring speed of 700-900rpm/min, so as to prepare the polyurethane solution.
In the first step, a colloid mill is used for grinding for 0.5-1h at the frequency of 20-40 Hz. The application is beneficial to improving the surface defect of the carbon nano tube by controlling the grinding frequency and the grinding time of the colloid mill, is convenient for the reaction of the carbon nano tube and other components, is beneficial to improving the compatibility of the modified carbon nano tube and the PA material, ensures that the modified carbon nano tube is more uniformly dispersed in the PA resin, and is more beneficial to improving the conductivity and the mechanical property of the PA composite material. When the grinding frequency is too high or the grinding time is too long, the pipe diameter of the carbon nano tube is too short, so that the carbon nano tube is difficult to form a continuous conductive network in the PA system, and further the conductivity and mechanical property of the PA composite material are deteriorated. When the grinding frequency is too small or the grinding time is too short, the carbon nanotubes are unevenly dispersed and cannot be fully contacted with components in the polyurethane solution, so that the compatibility between the modified carbon nanotubes and the PA resin can be influenced, the carbon nanotubes cannot be evenly distributed in the PA material, and the PA composite material is weak in conductivity and mechanical property. In embodiments of the present application, the colloid milling frequency may be, but is not limited to, specifically 20Hz, 22Hz, 25Hz, 30Hz, 35Hz, 38Hz, or 40Hz, and the milling time may be, but is not limited to, specifically 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, or 1h.
In the second step, the micro-jet pressure is 110-130MPa, and the treatment is carried out for 1-2 times. The application is beneficial to improving the dispersion effect of the carbon nano tube in the polyurethane solution by controlling the pressure, so that the carbon nano tube is fully contacted with the components in the polyurethane solution, the compatibility of the modified carbon nano tube and the PA resin is beneficial to improving, the modified carbon nano tube can be better dispersed in the PA material, and the electric conduction and mechanical properties of the PA composite material are improved. In embodiments of the present application, the microfluidic pressure may be, in particular but not limited to, 110MPa, 115MPa, 120MPa, 125MPa or 130MPa.
In the third step, freeze drying is carried out for 24-36h under the condition that the vacuum degree is 50-300 mTorr and the cold trap temperature is minus 40-minus 10 ℃.
The application also provides a conductive PA material, which comprises the following raw materials in percentage by mass: 4-6% of the modified carbon nano tube, 14-16% of carbon fiber, 0-2% of auxiliary agent and the balance of PA resin.
According to the conductive PA material, as the polyurethane molecules with good compatibility with the PA resin are wrapped on the surface of the modified carbon nano tube, the modified carbon nano tube is uniformly dispersed in the PA system and acts together with the carbon fiber to form a continuous conductive network, so that the conductive performance and mechanical performance of the PA composite material are effectively improved.
Specifically, in the embodiment of the application, the auxiliary agent is formed by combining a lubricant and an antioxidant according to the weight ratio of 1:1, wherein the lubricant is at least one of E wax, polyethylene wax, paraffin, silicone, pentaerythritol stearate, sorbitol partial ester and ethylene bis-stearamide, and the antioxidant is at least one of 1010, 1076, 264, B225 and TPP.
According to the preparation method, 4-6% of the modified carbon nano tube, 14-16% of carbon fiber, 0-1% of auxiliary agent and the balance of PA resin are stirred in a high-speed stirrer for 5-15min according to mass percent, and then the stirred mixture is granulated by a double-screw machine and injection molded to prepare the conductive PA material.
The preparation method of the conductive PA material is simple, the prepared PA material has high conductivity and high mechanical property, and the modified carbon nano tube has good compatibility with PA resin because the surface of the modified carbon nano tube is wrapped with polyurethane, can be uniformly dispersed in a PA system, and is not easy to agglomerate during injection molding, so that the prepared PA composite material has better conductivity and mechanical property.
In order that the details of the above-described implementations and operations of the present application may be clearly understood by those skilled in the art, and that the present application may be embodied with significant improvements in the embodiments of the present application, the above-described technical solutions will be exemplified by a plurality of embodiments. Specifically, the carbon nanotubes used in the following specific examples and comparative examples were multiwall carbon nanotubes produced in the same batch.
Example 1
The conductive PA material comprises the following raw materials in percentage by mass: 5% of modified carbon nano tube, 15% of carbon fiber, 0.5% of polyethylene wax lubricant, 0.5% of 1010 antioxidant and the balance of PA6 resin.
The preparation method of the conductive PA material comprises the following preparation steps:
s1, adding 10 parts by weight of polyurethane resin into 940 parts by weight of isopropanol organic solvent, and stirring at a stirring speed of 800rpm/min for 10min to prepare a polyurethane solution;
s2, mixing the polyurethane solution and the carbon nano tube according to the weight ratio of 19:1, and grinding for 0.8h in a colloid mill at the frequency of 30Hz to obtain pre-dispersion liquid;
s3, adopting a micro-jet dispersion technology, controlling the pressure of the micro-jet to be 120MPa, and treating the pre-dispersion liquid for 2 times to obtain a dispersion liquid;
s4, performing freeze drying treatment on the dispersion liquid for 30 hours under the condition that the vacuum degree is 100mTorr and the cold trap temperature is minus 40 ℃ to obtain the modified carbon nano tube.
S5, stirring 5% of the modified carbon nano tube, 15% of carbon fiber, 0.5% of lubricant, 0.5% of antioxidant and the balance of PA6 resin in a high-speed stirrer for 10min according to mass percentage, granulating the stirred mixture by a double-screw extruder at 250 ℃, and performing injection molding to obtain the conductive PA material.
Example 2
The conductive PA material comprises the following raw materials in percentage by mass: 5% of modified carbon nano tube, 15% of carbon fiber, 0.5% of polyethylene wax lubricant, 0.5% of 1010 antioxidant and the balance of PA6 resin.
The preparation method of the conductive PA material comprises the following preparation steps:
s1, adding 10 parts by weight of polyurethane resin and 10 parts by weight of KH550 coupling agent into 930 parts by weight of isopropanol organic solvent, and stirring at a stirring speed of 800rpm/min for 10min to obtain polyurethane solution;
s2, mixing the polyurethane solution and the carbon nano tube according to the weight ratio of 19:1, and grinding for 0.8h in a colloid mill at the frequency of 30Hz to obtain pre-dispersion liquid;
s3, adopting a micro-jet dispersion technology, controlling the pressure of the micro-jet to be 120MPa, and treating the pre-dispersion liquid for 2 times to obtain a dispersion liquid;
s4, freeze-drying the dispersion liquid for 30 hours under the condition that the vacuum degree is 100mTorr and the cold trap temperature is minus 40 ℃ to obtain the modified carbon nano tube.
S5, stirring 5% of the modified carbon nano tube, 15% of carbon fiber, 0.5% of lubricant, 0.5% of antioxidant and the balance of PA6 resin in a high-speed stirrer for 10min according to mass percentage, granulating the stirred mixture by a double-screw extruder at 250 ℃, and performing injection molding to obtain the conductive PA material.
Example 3
The conductive PA material comprises the following raw materials in percentage by mass: 6% of modified carbon nano tube, 16% of carbon fiber, 1% of polyethylene wax lubricant, 1% of 1010 antioxidant and the balance of PA6 resin.
The preparation method of the conductive PA material comprises the following preparation steps:
s1, adding 12 parts by weight of polyurethane resin into 938 parts by weight of propylene glycol organic solvent, and stirring for 15min at a stirring speed of 900rpm/min to obtain polyurethane solution;
s2, mixing the polyurethane solution and the carbon nano tube according to the weight ratio of 23:1, and grinding for 1h in a colloid mill at the frequency of 40Hz to obtain pre-dispersion liquid;
s3, adopting a micro-jet dispersion technology, controlling the pressure of the micro-jet to be 130MPa, and treating the pre-dispersion liquid for 2 times to obtain a dispersion liquid;
s4, freeze-drying the dispersion liquid for 36 hours under the condition that the vacuum degree is 300mTorr and the cold trap temperature is minus 10 ℃ to obtain the modified carbon nano tube.
S5, according to the mass percentage, 6% of modified carbon nano tube, 16% of carbon fiber, 1% of polyethylene wax lubricant and 1% of 1010 antioxidant, and the balance of PA6 resin are stirred in a high-speed stirrer for 15min, and then the stirred mixture is granulated by a double-screw machine at the temperature of 280 ℃ and injection molded to obtain the conductive PA material.
Example 4
The conductive PA material comprises the following raw materials in percentage by mass: 4% of modified carbon nano tube, 14% of carbon fiber and the balance of PA6 resin.
The preparation method of the conductive PA material comprises the following preparation steps:
s1, adding 8 parts by weight of polyurethane resin into 942 parts by weight of ethanol organic solvent, and stirring for 5min at a stirring speed of 700rpm/min to obtain polyurethane solution;
s2, mixing the polyurethane solution and the carbon nano tube according to the weight ratio of 15:1, and grinding for 0.5h in a colloid mill at the frequency of 20Hz to obtain pre-dispersion liquid;
s3, adopting a micro-jet dispersion technology, controlling the pressure of the micro-jet to be 110MPa, and treating the pre-dispersion liquid for 1 time to obtain a dispersion liquid;
s4, freeze-drying the dispersion liquid for 24 hours under the condition that the vacuum degree is 50mTorr and the cold trap temperature is minus 10 ℃ to obtain the modified carbon nano tube.
S5, stirring 4% of the modified carbon nano tube, 14% of carbon fiber and the balance of PA6 resin in a high-speed stirrer for 5min according to mass percent, granulating the stirred mixture by a double-screw extruder at 220 ℃, and performing injection molding to obtain the conductive PA material.
Comparative example 1
The preparation method of the conductive PA material comprises the following preparation steps:
s1, adding 10 parts by weight of KH550 coupling agent into 940 parts by weight of isopropanol organic solvent, and stirring at a stirring speed of 800rpm/min for 10min to obtain a modified solution;
s2, mixing the modified solution and the carbon nano tube according to the weight ratio of 19:1, and grinding for 0.8h in a colloid mill at the frequency of 30Hz to obtain pre-dispersion liquid;
s3, adopting a micro-jet dispersion technology, controlling the pressure of the micro-jet to be 120MPa, and treating the pre-dispersion liquid for 2 times to obtain a dispersion liquid;
s4, performing freeze drying treatment on the dispersion liquid for 30 hours under the condition that the vacuum degree is 100mTorr and the cold trap temperature is minus 40 ℃ to obtain the modified carbon nano tube.
S5, stirring 5% of the modified carbon nano tube, 15% of carbon fiber, 0.5% of lubricant, 0.5% of antioxidant and the balance of PA6 resin in a high-speed stirrer for 10min according to mass percentage, granulating the stirred mixture by a double-screw extruder at 250 ℃, and performing injection molding to obtain the conductive PA material.
Comparative example 2
The preparation method of the conductive PA material comprises the following preparation steps:
s1, adding 15 parts by weight of polyurethane resin into 935 parts by weight of isopropanol organic solvent, and stirring at a stirring speed of 800rpm/min for 10min to prepare polyurethane solution;
s2, mixing the polyurethane solution and the carbon nano tube according to the weight ratio of 19:1, and grinding for 0.8h in a colloid mill at the frequency of 30Hz to obtain pre-dispersion liquid;
s3, adopting a micro-jet dispersion technology, controlling the pressure of the micro-jet to be 120MPa, and treating the pre-dispersion liquid for 2 times to obtain a dispersion liquid;
s4, performing freeze drying treatment on the dispersion liquid for 30 hours under the condition that the vacuum degree is 100mTorr and the cold trap temperature is minus 40 ℃ to obtain the modified carbon nano tube.
S5, stirring 5% of the modified carbon nano tube, 15% of carbon fiber, 0.5% of lubricant, 0.5% of antioxidant and the balance of PA6 resin in a high-speed stirrer for 10min according to mass percentage, granulating the stirred mixture by a double-screw extruder at 250 ℃, and performing injection molding to obtain the conductive PA material.
Comparative example 3
The preparation method of the conductive PA material comprises the following preparation steps:
according to the mass percentage, 5% of unmodified carbon nano tube, 15% of carbon fiber, 0.5% of lubricant, 0.5% of antioxidant and the balance of PA6 resin are stirred in a high-speed stirrer for 10min, and then the stirred mixture is granulated by a double-screw machine at the temperature of 250 ℃ and injection molded to obtain the conductive PA material.
Performance test:
the conductive PA materials prepared in examples 1-4 and comparative examples 1-3 were tested for surface resistance, tensile strength, and notched strength, and the test results are shown in table 1.
Table 1 test results table
Test sample Surface resistance (omega cm) Tensile Strength (MPa) Notch strength (kJ/m) 2 )
Example 1 30 96.2 5.3
Example 2 28 97.0 5.5
Example 3 35 94.1 4.6
Example 4 36 94.2 4.8
Comparative example 1 45 90.4 4.6
Comparative example 2 103 90.5 5.3
Comparative example 3 170 80.5 4.0
As shown by the test results of the table, the method is used for modifying the carbon nano tube, which is beneficial to improving the compatibility between the carbon nano tube and the PA resin material, so that the carbon nano tube can be uniformly dispersed in the PA material, and the conductivity and the mechanical property of the PA composite material are improved. As can be seen from comparison of the results of example 1 and example 2, the addition of the coupling agent is beneficial to further improving the compatibility and dispersibility between the carbon nanotubes and the polymer resin material, thereby improving the conductivity and mechanical properties of the PA composite material. As is apparent from the results of comparative examples 1 and 1, the preparation method of comparative example 1 is different from that of example 1 in that the carbon nanotubes in comparative example 1 are modified by the coupling agent, are not modified by the polyurethane resin, and a proper amount of polyurethane is used to modify the carbon nanotubes, so that the dispersion and compatibility of the carbon nanotubes in the PA resin are improved, and the conductivity and mechanical properties of the PA material are improved. In contrast, comparative example 2 is different from example 1 in that comparative example 2 modifies the carbon nanotubes with an excessive amount of polyurethane resin, and the excessive amount of polyurethane resin completely encapsulates the surfaces of the carbon nanotubes, so that the carbon nanotubes are difficult to form a conductive network in the PA material, resulting in a decrease in the conductive properties of the PA material prepared in comparative example 2. The carbon nanotubes in comparative example 3 were not modified, and were easily agglomerated in PA resin, and were difficult to uniformly disperse, so that the prepared PA composite material was poor in conductivity and mechanical properties.
The foregoing examples illustrate only a few embodiments of the application and are described in detail herein without thereby limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.

Claims (7)

1. The carbon nanotube modifying process includes the following steps:
step one, mixing polyurethane solution with carbon nano tubes, and grinding uniformly to obtain pre-dispersion liquid;
dispersing the pre-dispersion liquid by adopting a micro-jet dispersion technology to obtain dispersion liquid;
step three, freeze-drying the dispersion liquid to obtain modified carbon nanotubes;
the weight ratio of the polyurethane solution to the carbon nano tube is 15-23:1, and the polyurethane solution comprises 8-12 parts by weight of polyurethane and 900-950 parts by weight of organic solvent;
grinding for 0.5-1h at the frequency of 20-40Hz by using a colloid mill;
in the second step, the microjet pressure is 110-130MPa, and the treatment is carried out for 1-2 times.
2. The method for modifying a carbon nanotube according to claim 1, wherein the organic solvent comprises at least one of ethanol, ethylene glycol, n-propanol, isopropanol, propylene glycol, butanol, toluene, and xylene.
3. The method for modifying a carbon nanotube as set forth in claim 1, wherein the polyurethane solution further comprises 8 to 12 parts by weight of a coupling agent.
4. The method of claim 3, wherein the coupling agent comprises at least one of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent.
5. The method for modifying a carbon nanotube according to claim 1, wherein in the third step, the carbon nanotube is freeze-dried at a cold trap temperature of-40 to-10 ℃ for 24 to 36 hours under a vacuum of 50 to 300 mTorr.
6. The conductive PA material is characterized by comprising the following raw materials in percentage by mass: 4-6% of modified carbon nano-tubes, 14-16% of carbon fibers, 0-2% of auxiliary agent and the balance of PA resin, wherein the modified carbon nano-tubes are prepared by the method of any one of claims 1-5.
7. A preparation method of a conductive PA material is characterized in that, according to mass percentage, 4-6% of modified carbon nano tubes, 14-16% of carbon fibers, 0-1% of auxiliary agent and the balance of PA resin are stirred in a high-speed stirrer for 5-15min, and then the stirred mixture is granulated by a double-screw machine and injection molded to prepare the conductive PA material, wherein the modified carbon nano tubes are prepared by the method of any one of claims 1-5.
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