CN110835465A - Preparation and application of nylon/carbon nanotube master batch for improving material conductivity - Google Patents
Preparation and application of nylon/carbon nanotube master batch for improving material conductivity Download PDFInfo
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Abstract
A preparation and application of nylon/carbon nanotube master batch for improving material conductivity relate to the field of applying a carbon nanotube surface modification technology and a nylon solution convection coagulation technology in combination to the preparation of polymer conductive master batch, so that the aim of obviously improving the conductivity of a polymer composite material by mechanical mixing in a short time can be fulfilled. The modification method is characterized in that 25-35 wt% of polyether surfactant and aminosilane coupling agent complex is added into ethanol-water solution, the mixture is modified in liquid phase with 0.01-20 wt% of acidified carbon nanotube liquid content by utilizing a surface grafting and coating modification method, then the suspension with 0.1-10 wt% of carbon nanotube content is prepared again, and finally the suspension is subjected to convection intersection with nylon formic acid solution to complete co-coagulation, so that master batch with 0.1-60 wt% of carbon nanotube load is continuously prepared. The master batch can be blended with various polymers, so that the carbon nano tubes in the prepared composite material are uniformly distributed, and the conductivity is obviously improved. The preparation method is simple and feasible, and the raw materials are easily available.
Description
The technical field is as follows:
the application relates to the field of functional plastic composite materials, in particular to a method for preparing carbon nanotube master batches and compounding the carbon nanotube master batches with plastic.
Background art:
the carbon nano tube is a seamless nano-scale tubular shell structure formed by curling single-layer or multi-layer graphite flakes, the diameter of the carbon nano tube is within 100nm, and the length-diameter ratio of the carbon nano tube is very high; the carbon nanotube surface has many topological defects, which are represented by a large number of pairs of five-membered rings and seven-membered rings. The carbon nano tube has special surface effect, small size effect, quantum size effect and macroscopic quantum tunneling effect due to the structural characteristics, and the material compounded by the carbon nano tube can also show unique mechanical, thermal, magnetic, electrical and optical properties. The use of carbon nanotubes to improve the electrical properties of polymer materials is one of the hot spots in polymer composite research in recent years. At present, polymers can be changed into semiconductors or even conductors from insulators by utilizing the addition of carbon nanotubes, so that the application prospect of the traditional polymer material is changed, and the carbon nanotube filled polymer material has successful application cases in the fields of conductive adhesives, antistatic coatings and packaging, electromagnetic shielding materials and the like.
The conductivity of the polymer/carbon nanotube composite material generally conforms to the percolation threshold theory, namely: when the addition amount of the carbon nano tube is less, the whole conductivity of the polymer material is not obviously changed, and when the carbon nano tube is added with a certain amount, the carbon nano tube is added with a very small amount, the conductivity of the composite material can be improved by several orders of magnitude, and an exponential relationship is presented. The percolation threshold phenomenon is related to the formation of a conductive network in the composite material, the conductive network is not formed before the percolation threshold is approached, conductive channels are few, the material does not show conductivity, and the formation of the conductive network can be greatly promoted by only adding a small amount of carbon nano tubes on the basis, so that the conductivity of the material is exponentially improved.
From the viewpoint of industrial application, the price of the carbon nanotube is high, and the addition of a large amount inevitably leads to an increase in material cost. While according to percolation threshold theory, the key to improving the conductivity of a polymer material is to build a conductive network inside the polymer. Theoretically, the dispersibility of the carbon nano tube in the polymer is improved, the efficient construction of the conductive network can be ensured, and the consumption of the carbon nano tube required by the construction of the conductive network is reduced, so that the raw material cost of the high-conductivity polymer/carbon nano tube composite material is reduced.
In the process of preparing the conductive composite material, the carbon nano tube is mixed with the polymer for a long time, so that the dispersibility of the carbon nano tube in the polymer can be effectively improved; however, mixing for a long time also leads to degradation of the polymer and destruction of the carbon nanotube structure, thereby degrading the overall performance of the composite. The carbon nanotube master batch can be prepared by pre-dispersing the carbon nanotubes and adding a large amount of carbon nanotubes into the polymer. The master batch is used for replacing the unprocessed carbon nano tube to be compounded with the polymer, so that the high-conductivity polymer composite material can be prepared under the condition of short-time mixing. Therefore, the preparation and the use of the carbon nano tube master batch have great significance for expanding the application range of the conductive polymer composite material.
However, most of the carbon nanotube master batches are prepared by adopting long-time melt blending, so that the carbon nanotubes are dispersed in the polymer by utilizing the shearing action of polymer delivery equipment, and the method cannot avoid the damage of the carbon nanotube structure. In addition, carbon nanotubes are difficult to modify effectively in a polymer matrix, and their properties of being susceptible to self-aggregation remain. When the carbon nanotube master batch and the polymer are blended to prepare the composite material with conductivity, the carbon nanotube in the master batch still has poor dispersion after entering the polymer.
In order to realize ideal dispersion of the carbon nano tube in the polymer after short-time mixing, the invention designs a method for realizing continuous preparation of the carbon nano tube nylon master batch by finishing the surface modification treatment of the carbon nano tube in a solution and carrying out convection flocculation on modified carbon nano tube ethanol slurry and a nylon formic acid solution. The nylon/carbon nano tube master batch prepared by the invention is used as a raw material, and the plastic composite material with antistatic and even conductive properties can be obtained by mixing in a short time, and the mechanical properties of the material can be improved to a certain extent.
The invention content is as follows:
the invention designs a method for preparing nylon/carbon nano tube master batch, which is mainly realized by two main steps of modification treatment of carbon nano tubes in a liquid phase, convection flocculation of carbon nano tube suspension and nylon solution and the like. The preparation of the master batch can ensure that the carbon nano tube can be uniformly dispersed in the polymer material in a short time, the damage to the structure and the performance of the material in the mixing processing process is reduced, and meanwhile, the convection flocculation method is very favorable for realizing the industrial continuous production of the nylon/carbon nano tube master batch. Experiments show that the use of the master batch is helpful for reducing the carbon nano tube dosage in the polymer composite material with specific conductive grade and improving the overall mechanical property of the material.
The invention is realized by the following technical scheme:
1. preparing the surface modified carbon nano tube:
(1) acidizing the carbon nano tube slurry: preparing mixed concentrated acid with the ratio of nitric acid to sulfuric acid being 1: 3, placing a container filled with the mixed concentrated acid into an ultrasonic water tank, adding the carbon nano tube into the container, and performing ultrasonic oscillation at the frequency of 15-40KHz for 2-8 hours at the temperature of 50-70 ℃ to obtain acidified carbon nano tube slurry.
(2) Drying the acidified carbon nano tube: and centrifuging the carbon nanotube slurry after the acidification treatment for 10 minutes by using a centrifuge under the condition of 4000 r/min to separate the mixed solution into layers, repeatedly washing the carbon nanotube suspension with black carbon nanotube at the bottom layer by using clean water, adjusting the pH value of the suspension to be more than 6, drying the suspension to constant weight at the temperature of 60-80 ℃ by using a vacuum oven to obtain the acidified carbon nanotube, and refining the supernatant after the separation to remove impurities for repeated use. Through acidification treatment, hydroxyl (-OH) and carboxyl (-COOH) groups appear on the surface of the carbon nano tube, and a structural basis is provided for surface grafting modification treatment of the carbon nano tube.
(3) Preparation of Mixed modifier
Adding 20-50 wt% of polyether surfactant with the structure of formula (I) and 80-50 wt% of aminosilane coupling agent with the structure of formula (II) into the same container, stirring at 30-45 ℃ and 2000rpm for 0.2-2 hours, wherein the mixture is ensured to be in a flowing state, and the final product is a uniform mixed solution. Wherein m has a value of between 1 and 20, n has a value of between 3 and 20, p has a value of between 2 and 8 and X represents an alkoxy group.
CH3(CH2)m(OCH2CH2)nO
(I)
NH-(CH3)p-Si-X3
(II)
The amino silane coupling agent can react with hydroxyl or carboxyl on the surface of the acidified carbon nano tube by utilizing a hydroxyl group at the tail end of the amino silane coupling agent to form chemical grafting, and meanwhile, the amino can be chemically combined with a nylon carboxyl end, so that the carbon nano tube and a nylon carrier form chemical combination, and the carbon nano tube is uniformly dispersed in the nylon carrier and is not easy to be aggregated again. Meanwhile, the polyether surfactant can form hydrogen bond action with hydroxyl on the surface of the carbon nano tube by utilizing the polyether structure of the polyether surfactant, so that the carbon nano tube is coated and modified, and the carbon nano tube is easy to disperse in a nylon carrier quickly. In addition, the polyether surfactant can form a coating structure with the amino silane coupling agent, so that the hydrolysis degree of the amino silane coupling agent in the next hydrolysis process is controlled, and the amino silane coupling agent is prevented from being obviously self-polymerized after being hydrolyzed.
(4) Preparation of carbon nano tube modified solution
Preparing ethanol and water into a solution with the ethanol content of 80-95 wt%, dropwise adding formic acid to adjust the pH value of the solution to 4-6, then adding a mixed modifier with the total amount of 15-45 wt% of the modified solution into the solution, moving a container filled with the solution into an ultrasonic wave tank with a heating function, heating the solution to 50-80 ℃, stirring at the speed of 500-2000rpm and simultaneously matching with 10-30KHz ultrasonic oscillation to hydrolyze the aminosilane coupling agent for 2-20 hours, thus obtaining mixed hydrolysate, wherein the hydrolysate is used as the modified solution of the carbon nano tube. The preferred amount of the mixed modifier added is 25 to 35 wt% of the total amount of the modifying solution.
(5) Modification treatment of carbon nanotubes
Setting the ultrasonic frequency of the ultrasonic water tank to be 20-50KHz and the temperature to be 50-80 ℃, adding the prepared dried acidified carbon nano tubes into the container at one time, wherein the adding amount of the carbon nano tubes is 0.01-20 wt% of the solution, stirring at the speed of 500-2000rpm to ensure that the carbon nano tube mixed solution is in a flowing state, and modifying for 1-10 hours under the condition of keeping the temperature and the stirring speed stable.
(6) Modified carbon nanotube-ethanol suspension preparation
Transferring the modified carbon nanotube slurry into a centrifuge, setting the rotation speed of the centrifuge to 4000 r/min, performing centrifugal separation for 10 min to layer the mixed solution, separating out the carbon nanotube suspension at the bottom layer, washing for 3 times by using ethanol, adding ethanol to prepare the modified carbon nanotube-ethanol suspension with the carbon nanotube content of 0.1-10%, and replenishing the mixed modifier in the supernatant for reuse.
2. Preparation of nylon solution:
the formic acid is heated to 50-80 ℃, 5-15 wt% of nylon 6 or nylon 66 particles are put in, the temperature is kept constant, and the stirring is carried out at the speed of 500-2500rpm until the nylon particles completely disappear and the liquid is completely transparent, so as to prepare the nylon solution with the concentration of 5-15 wt%.
3. Preparing nylon/carbon nano tube master batch:
(1) and (3) respectively putting the carbon nanotube ethanol suspension obtained in the step (1) and the nylon formic acid solution obtained in the step (2) into two containers with stirring devices, wherein the lower end of each container is provided with a discharge hole, and the outflow speed of the liquid can be stably controlled.
(2) The stirring devices in the two containers are respectively started, the carbon nanotube suspension is stirred at the speed of 500-.
(3) Preparing a container for containing a product, placing the container between the two containers, enabling the discharge ports of the two containers to be close to each other, ensuring that liquid in the two containers can intersect before entering the containing container in the falling process of the liquid, simultaneously opening the discharge ports of the two containers, and respectively adjusting the flow rate of the liquid outlet of the two containers according to the loading capacity of the designed carbon nano tube in the master batch and the proportion.
In the process, the modified carbon nano tubes suspended in the ethanol are uniformly mixed into the nylon formic acid solution under the flowing action of the liquid flow, the nylon formic acid solution can be separated out after encountering the ethanol, and the carbon nano tubes dispersed in the nylon can be wrapped and taken out while the nylon is separated out, so that the nylon/carbon nano tube master batch is formed. When the two flows of liquid fall into the product container at the lower end after confluence, a certain liquid flow impact effect can be achieved, the nylon solution can be more fully contacted with ethanol, and the precipitation of nylon is further accelerated. Because the modified carbon nano tube is coated with and grafted with a certain amount of organic modifier on the surface, and the suspension liquid flow of the carbon nano tube and the liquid flow of the nylon solution are uniformly and stably mixed in the mixing process, the carbon nano tube can be effectively and uniformly dispersed in nylon, and the ethanol can quickly separate out the carbon nano tube wrapped by the nylon, so that the uniformly dispersed state of the carbon nano tube in the nylon carrier is kept until master batches are formed, and finally the carbon nano tube in the nylon/carbon nano tube master batches can be uniformly dispersed. In addition, the preparation process of the master batch is realized through continuous flow, so that the stable and continuous production of the nylon/carbon nano tube master batch can be realized without introducing a huge reaction container.
(4) After preparing enough nylon/carbon nano tube master batch, simultaneously closing discharge ports of the two containers, putting a product in the container at the lower end into a centrifuge, centrifugally separating for 5 minutes under the condition of 2000 r/min, collecting a lower precipitate, and drying to constant weight at 80-120 ℃ by using a vacuum oven to obtain the nylon/carbon nano tube master batch. The upper solution mainly contains formic acid, ethanol and a small amount of mixed modifier, and ethanol and formic acid are recovered by distillation for reuse.
4. The application of the nylon/carbon nano tube master batch comprises the following steps:
one or more plastic raw materials including polyolefin plastics, polyester plastics, polyamide plastics, polyolefin derivative plastics and polyolefin block structure-containing plastics are taken, other components including a reinforcing functional component, a flame-retardant functional component and a toughening functional component are selectively added, then 0.1-100 wt% of the nylon/carbon nanotube master batch is added, after primary simple mechanical mixing, the nylon/carbon nanotube master batch is added into plastic processing equipment which can provide a shearing action, such as an open mill, an internal mixer or a screw extruder, and the plastic composite material with the conductive or antistatic characteristic is prepared by melt blending.
In addition to the above components, various other auxiliary additives commonly used in the field of plastic composite processing are used in the preparation process of the present invention.
The principle of the invention is as follows:
(1) the surface of the carbon nano tube after the acidification treatment has a large amount of hydroxyl and carboxyl, the surface chemical grafting modification of the carbon nano tube can be realized by using a silane coupling agent, and the physical coating modification of the carbon nano tube can be realized by using a polyether surfactant, so that the characteristic that the carbon nano tube is easy to self-aggregate can be effectively changed by using two modifying agents together by means of grafting and coating; meanwhile, the silane coupling agent can form a chemical combination effect with the nylon carrier through the amino group, the carbon nano tube and the nylon carrier can be more easily compatible by being coated by the surfactant, the two modification combinations can help the carbon nano tube to be uniformly dispersed in the nylon carrier, and the self-aggregation is not easy to occur again when the carrier is mixed with plastic.
(2) The formic acid solution of nylon can be separated out after encountering ethanol, which is the basic principle for preparing nylon/carbon nano tube master batch by a convection method. The compatibility of the carbon nano tube fully modified by the method of the invention and the nylon carrier is greatly improved, therefore, the carbon nano tube can be rapidly blended with nylon and uniformly dispersed in a nylon matrix. On the basis of the above conditions, after the formic acid solution of nylon and the ethanol suspension of the carbon nano tubes are mixed, the nylon can wrap the carbon nano tubes mixed therein and precipitate together. Therefore, the state that the carbon nano tubes are uniformly mixed into the nylon can be kept, and the problem that the structure of the carbon nano tubes is deteriorated due to long-time mixing in high-concentration formic acid is also avoided. The invention relates to a carbon nano tube modification method and a method for preparing nylon/carbon nano tube master batch by convection, which are integrated technologies.
Experiments prove that the loading capacity of the carbon nano tube in the nylon/carbon nano tube master batch prepared by the invention is accurate and controllable, and the carbon nano tube is uniformly dispersed. The nylon/carbon nanotube master batch is used for preparing the plastic composite material, so that the conductivity of the plastic composite material is obviously improved, and meanwhile, the mechanical property of the composite material can be improved to a certain extent.
Description of the drawings:
FIG. 1 is a Transmission Electron Microscope (TEM) photograph of the nylon/carbon nanotube master batch prepared according to the preparation method described in example 1.
The specific implementation mode is as follows:
for further understanding of the present invention, the following description of preferred embodiments of the preparation and use of a nylon/carbon nanotube master batch for improving the conductivity of a material according to the present invention is provided in conjunction with the examples, but it should be understood that these descriptions are only for the purpose of illustrating the features and advantages of the present invention in more detail, and are not intended to limit the claims of the present invention in any way.
Example 1:
500g of mixed concentrated acid of nitric acid and sulfuric acid in a ratio of 1: 3 is prepared in a 1000ml beaker, 10 g of commercially available carbon nanotubes (6 nanometers) are added into the beaker, the beaker is placed into an ultrasonic water tank, the temperature of the ultrasonic water tank is adjusted to be 60 ℃, the ultrasonic oscillation is carried out for 3 hours at the frequency of 20KHz, the obtained mixed slurry is centrifugally separated for 10 minutes by a centrifuge under the condition of 4000 r/min, and the mixed slurry is layered, so that the carbon nanotube suspension liquid at the bottom layer is separated. And repeatedly washing the suspension with clear water to enable the pH value of the suspension to be more than 6, and drying the suspension to constant weight at 70 ℃ by using a vacuum oven to obtain 9.8 g of the acidified carbon nano tube.
And adding 45 g of aliphatic vinyl ether (A) and 105 g of aminopropyltriethoxysilane (B) into a 500ml beaker, and stirring at the speed of 500rpm at the temperature of 45 ℃ for 0.5 hour to obtain the mixed modifier with the content of the aliphatic vinyl ether of 30 percent. And adding 720 g of ethanol and 80 g of water into a 2000ml beaker, dropwise adding formic acid into the beaker to adjust the pH value of the solution to 4, adding 200 g of the mixed modifier into the beaker, then putting the beaker into an ultrasonic water tank, adjusting the temperature of the water tank to 60 ℃, setting the frequency of ultrasonic oscillation to be 20Hz, simultaneously stirring the mixed solution in the beaker by using a stirring paddle at the speed of 500rpm, keeping the temperature in the beaker stable, and obtaining mixed hydrolysate after 3 hours, wherein the hydrolysate is used as the modified solution of the carbon nano tube.
CH3(CH2)8(OCH2CH2
(A)
NH-(CH3)3-Si-(OC2H5)3
(B)
Adjusting the frequency of ultrasonic oscillation to 30Hz, keeping the temperature at 60 ℃, adding 9.8 g of the obtained acidified carbon nano tube into a beaker at one time, adjusting the stirring speed to 800rpm, ensuring that the mixed solution of the carbon nano tube is in a flowing state, and modifying for 2 hours under the condition of keeping the temperature and the stirring speed stable. And then, transferring the modified carbon nanotube slurry into a centrifuge, setting the rotation speed of the centrifuge to be 4000 r/min, performing centrifugal separation for 10 min, layering the mixed solution, separating out 100 g of carbon nanotube suspension at the bottom layer, washing for 3 times by using ethanol, and adding ethanol to prepare modified carbon nanotube-ethanol suspension with the total weight of 1000g and the carbon nanotube content of about 0.98%.
900 g of formic acid was taken in a 2000ml beaker, the formic acid temperature was adjusted to 60 ℃ using a water bath, 100 g of nylon 6 particles were placed, the temperature was kept constant, and stirring was carried out at 1000rpm until the nylon particles completely disappeared and the liquid was completely transparent, whereby a 10 wt% nylon solution was prepared.
And respectively putting the obtained carbon nano tube-ethanol suspension and the nylon formic acid solution into a glass kettle with a discharge hole at the bottom. The stirring devices equipped in the two kettles were respectively started, the carbon nanotube suspension was stirred at a speed of 600rpm, and the nylon formic acid solution was stirred at a speed of 400 rpm. The discharge hole positions of the two kettles are adjusted to be close to each other, so that the liquid in the two containers can flow out and can be converged as soon as possible in the falling process, and a 5000ml beaker is taken and placed under the discharge hole positions of the two kettles. And simultaneously opening the discharge ports of the two containers, and adjusting to ensure that the quality of the liquid flowing out of the two containers in unit time is the same. Keeping the outflow liquid flow of the two kettles stable, and closing the discharge holes of the two kettles simultaneously after finishing the outflow of the materials in the two kettles. And putting a product in a beaker with the lower end of 5000ml into a centrifuge, centrifuging for 5 minutes under the condition of 2000 r/min, collecting the precipitate at the lower part, and drying to constant weight at 80 ℃ by using a vacuum oven to obtain the nylon 6/carbon nanotube master batch with about 108 g and the carbon nanotube loading of about 9%. By observing the master batch with a Transmission Electron Microscope (TEM), it can be seen that the carbon nanotubes are dispersed in the master batch very uniformly, which is directly related to the modification treatment of the carbon nanotubes and the convection preparation of the nylon/carbon nanotube master batch, as shown in figure 1.
Example 2:
2000g of mixed concentrated acid with nitric acid and sulfuric acid being 1: 3 is prepared in a 5000ml beaker, 100 g of commercially available carbon nano tube (6 nano scale) is added into the beaker, the beaker is placed into an ultrasonic water tank, the temperature of the water tank is adjusted to be 70 ℃, the water tank is subjected to ultrasonic oscillation for 8 hours at the frequency of 40KHz, the obtained mixed slurry is subjected to centrifugal separation for 10 minutes by using a centrifugal machine under the condition of 4000 r/min, and the mixed slurry is layered, so that the black carbon nano tube suspension at the bottom layer is separated. And repeatedly washing the suspension with clear water to enable the pH value of the suspension to be more than 6, and drying the suspension to constant weight at 80 ℃ by using a vacuum oven to obtain 97.5 g of the acidified carbon nano tube.
And adding 200 g of aliphatic vinyl ether (A) and 600g of aminopropyltrimethoxysilane (B) into a 3000ml beaker, and stirring at the speed of 1500rpm for 2 hours at the temperature of 35 ℃ to obtain the mixed modifier with the content of the aliphatic vinyl ether of 25 percent. And adding 3600 g of ethanol and 400 g of water into a 10000ml beaker, dropwise adding formic acid to adjust the pH value of the solution to 5, adding 1000g of a mixed modifier into the beaker, then putting the beaker into an ultrasonic water tank, adjusting the temperature of the water tank to 80 ℃, setting the frequency of ultrasonic oscillation to 30Hz, simultaneously stirring the mixed solution in the beaker by using a stirring paddle at the speed of 2000rpm, keeping the temperature in the beaker stable, and obtaining a mixed hydrolysate after 18 hours, wherein the hydrolysate is used as a modified solution of the carbon nano tube.
CH3(CH2)10(OCH2CH2)
(A)
NH-(CH3)3-Si-(OCH3)3
(B)
Adjusting the frequency of ultrasonic oscillation to 40Hz, keeping the temperature at 80 ℃, adding 97.5 g of the obtained acidified carbon nano tube into a beaker at one time, adjusting the stirring speed to 2000rpm to ensure that the mixed solution of the carbon nano tube is in a flowing state, and modifying for 10 hours under the condition of keeping the temperature and the stirring speed stable. And then, transferring the modified carbon nanotube slurry into a centrifuge, setting the rotation speed of the centrifuge to be 4000 r/min, performing centrifugal separation for 10 min, layering the mixed solution, separating out 1000g of carbon nanotube suspension at the bottom layer, washing for 3 times by using ethanol, and adding ethanol to prepare the modified carbon nanotube-ethanol suspension with the total weight of 1000g and the carbon nanotube content of about 9.75%.
3400 g of formic acid was taken and added to a 10000ml beaker, the formic acid temperature was adjusted to 80 ℃ using a water bath, 600g of nylon 66 particles were put in, the temperature was kept constant, and stirring was carried out at 2500rpm until the nylon particles completely disappeared and the liquid was completely transparent, whereby a 15 wt% nylon solution was prepared.
And respectively putting the obtained carbon nano tube-ethanol suspension and the nylon formic acid solution into a glass kettle with a discharge hole at the bottom. The stirring devices in the two tanks were opened, respectively, and the carbon nanotube suspension was stirred at 3500rpm and the nylon formic acid solution was stirred at 1000 rpm. The discharge hole positions of the two kettles are adjusted to be close to each other, so that the liquid in the two containers can flow out and can be converged as soon as possible in the falling process, and a 5000ml beaker is taken and placed under the discharge hole positions of the two kettles. And simultaneously opening the discharge ports of the two containers, and adjusting the outflow speed of the nylon solution to be 3.70 times of that of the carbon nanotube suspension. Keeping the outflow liquid flow of the two kettles stable, and closing the discharge holes of the two kettles simultaneously after the nylon solution flows out 300 g. And replacing a 5000ml beaker, placing the beaker under the discharge ports of the two kettles, simultaneously opening the discharge ports of the two containers, and adjusting the outflow speed of the nylon solution to be 1.95 times of the carbon nanotube turbid liquid. Keeping the outflow liquid flow of the two kettles stable, and closing the discharge holes of the two kettles simultaneously after the nylon solution flows out 300 g. And replacing a 5000ml beaker again and placing the beaker under the discharge ports of the two kettles, simultaneously opening the discharge ports of the two containers, and adjusting the outflow speed of the nylon solution to be 1.21 times of the carbon nanotube turbid liquid. Keeping the outflow liquid flow of the two kettles stable, and closing the discharge holes of the two kettles simultaneously after the nylon solution flows out 300 g. And finally, replacing a 5000ml beaker for the first time and placing the beaker under the discharge ports of the two kettles, simultaneously opening the discharge ports of the two containers, and adjusting the outflow speed of the nylon solution to be 0.79 time of the carbon nanotube suspension. Keeping the outflow liquid flow of the two kettles stable, and closing the discharge holes of the two kettles simultaneously after the nylon solution flows out 300 g. Putting the products in four 5000ml beakers into a centrifuge once, performing centrifugal separation for 5 minutes under the condition of 2000 r/min, collecting the lower precipitate, and drying to constant weight at 100 ℃ by using a vacuum oven to obtain four nylon 66/carbon nanotube master batches with the theoretical loading capacity of the carbon nanotubes of 15%, 25%, 35% and 45% in sequence. The four master batches are sequentially tested by using a Thermal Gravimetric Analyzer (TGA), and the obtained firing allowance at 800 ℃ is 16.3%, 26.7%, 36.1% and 46.2% in sequence, which is almost equivalent to the theoretical loading capacity of the carbon nano tube, and thus, the loading capacity of the carbon nano tube in the master batch prepared by the method is controllable.
Example 3:
a2000 ml beaker is taken, 1000g of mixed concentrated acid with nitric acid and sulfuric acid being 1: 3 is prepared in the beaker, 30 g of commercially available carbon nano tubes (6 nanometer scale) are added into the beaker, the beaker is placed into an ultrasonic water tank, the temperature of the water tank is adjusted to be 50 ℃, the water tank is ultrasonically oscillated for 5 hours at the frequency of 30KHz, the obtained mixed slurry is centrifugally separated for 10 minutes by a centrifuge under the condition of 4000 r/min, and the mixed slurry is layered, so that the carbon nano tube suspension liquid at the bottom layer is separated. And repeatedly washing the suspension with clear water to enable the pH value of the suspension to be more than 6, and drying the suspension to constant weight at 80 ℃ by using a vacuum oven to obtain 29.3 g of acidified carbon nano tubes.
And adding 150 g of aliphatic vinyl ether (A) and 150 g of aminopropyltriethoxysilane (B) into a 1000ml beaker, and stirring at the temperature of 40 ℃ and the speed of 1000rpm for 1 hour to obtain the mixed modifier with the aliphatic vinyl ether content of 50%. And adding 1120 g of ethanol and 180 g of water into a 5000ml beaker, dropwise adding formic acid into the beaker to adjust the pH value of the solution to 6, adding 700 g of the mixed modifier into the beaker, then putting the beaker into an ultrasonic water tank, adjusting the temperature of the water tank to 80 ℃, setting the frequency of ultrasonic oscillation to be 30Hz, simultaneously stirring the mixed solution in the beaker by using a stirring paddle at the speed of 1000rpm, keeping the temperature in the beaker stable, and obtaining a mixed hydrolysate after 5 hours, wherein the hydrolysate is used as a modified solution of the carbon nano tube.
CH3(CH2)12(OCH2CH2)7O
(A)
NH-(CH3)3-Si-(OC2H5)3
(B)
Adjusting the frequency of ultrasonic oscillation to 40Hz, keeping the temperature at 70 ℃, adding 29.3 g of the obtained acidified carbon nano tube into a beaker at one time, adjusting the stirring speed to 1200rpm to ensure that the mixed solution of the carbon nano tube is in a flowing state, and modifying for 4 hours under the condition of keeping the temperature and the stirring speed stable. And then, transferring the modified carbon nanotube slurry into a centrifuge, setting the rotation speed of the centrifuge to be 4000 r/min, performing centrifugal separation for 10 min, layering the mixed solution, separating out 300 g of carbon nanotube suspension at the bottom layer, washing for 3 times by using ethanol, and adding ethanol to prepare the modified carbon nanotube-ethanol suspension with the total weight of 1000g and the carbon nanotube content of about 2.93%.
1900 g of formic acid was taken in a 3000ml beaker, the formic acid temperature was adjusted to 60 ℃ using a water bath, 100 g of nylon 6 particles were put in, the temperature was kept constant, and stirring was carried out at 2000rpm until the nylon particles completely disappeared and the liquid was completely transparent, whereby a 5 wt% nylon solution was prepared.
And respectively putting the obtained carbon nano tube-ethanol suspension and the nylon formic acid solution into a glass kettle with a discharge hole at the bottom. The stirring devices equipped in the two kettles were respectively started, the carbon nanotube suspension was stirred at 1000rpm, and the nylon formic acid solution was stirred at 1000 rpm. The discharge hole positions of the two kettles are adjusted to be close to each other, so that the liquid in the two containers can flow out and can be converged as soon as possible in the falling process, and a 5000ml beaker is taken and placed under the discharge hole positions of the two kettles. And simultaneously opening the discharge ports of the two containers, adjusting the outflow speed of the nylon solution to be 2.34 times of that of the carbon nanotube suspension, keeping the outflow liquid flow of the two kettles stable, and simultaneously closing the discharge ports of the two kettles after the material in one of the kettles flows out. And putting a product in a beaker with the lower end of 5000ml into a centrifuge, centrifuging for 5 minutes under the condition of 2000 r/min, collecting the precipitate at the lower part, and drying to constant weight at 120 ℃ by using a vacuum oven to obtain the nylon 6/carbon nanotube master batch with the carbon nanotube load of about 20%.
According to the formulation shown in Table 1, the raw materials were thoroughly mixed and then extruded at a screw speed of 35rpm at 230 ℃ and 260 ℃ using a twin-screw extruder to pelletize. And then adopting an injection molding method to prepare nylon composite materials containing different carbon nano tube filling parts, and testing the volume resistivity and the flame retardant property of the materials, wherein the results are shown in table 2. The result shows that the nylon 6/carbon nano tube master batch can be used together with the flame-retardant master batch, and the functions of the nylon 6/carbon nano tube master batch and the flame-retardant master batch cannot be influenced mutually, so that the conductivity and the flame retardance of the material can be improved simultaneously. In addition, the test result also shows that the nylon/carbon nanotube master batch has very obvious improvement on the conductivity of the material, and the use of 10 percent of the nylon/carbon nanotube master batch can improve the conductivity of nylon 6 by more than 6 orders of magnitude, which accords with the assumption that the preparation of the carbon nanotube master batch improves the conductivity of the material.
TABLE 1
| Sample 0 | Sample 1 | Sample 2 | Sample 3 | Sample No. 4 | |
| Nylon 6 | 80 | 70 | 60 | 50 | 40 |
| Nylon 6/carbon nanotube master batch | 0 | 10 | 20 | 30 | 40 |
| Halogen-free flame-retardant master batch | 20 | 20 | 20 | 20 | 20 |
| Antioxidant 1010 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Antioxidant 168 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Lubricant EBS | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
TABLE 2
| Sample 0 | Sample 1 | Sample 2 | Sample 3 | Sample No. 4 | |
| Volume resistivity/Ω · cm | ＞1×1014 | 6×108 | 2×106 | 3×105 | 8×104 |
| Conductivity grade/UL 94 | V-0 | V-0 | V-0 | V-0 | V-0 |
Example 4:
1500g of mixed concentrated acid of nitric acid and sulfuric acid in a ratio of 1: 3 is prepared in a 2000ml beaker, 40 g of commercially available carbon nano tubes (6 nanometer scale) are added into the beaker, the beaker is placed into an ultrasonic water tank, the temperature of the water tank is adjusted to be 60 ℃, ultrasonic oscillation is carried out for 4 hours at the frequency of 25KHz, the obtained mixed slurry is centrifugally separated for 10 minutes by a centrifuge under the condition of 4000 r/min, and the mixed slurry is layered, so that the carbon nano tube suspension liquid at the bottom layer is separated. And repeatedly washing the suspension with clear water to enable the pH value of the suspension to be more than 6, and drying the suspension to constant weight at 80 ℃ by using a vacuum oven to obtain 39.2 g of acidified carbon nano tubes.
And adding 200 g of aliphatic vinyl ether (A) and 400 g of aminoethyl trimethoxysilane (B) into a 1000ml beaker, and stirring at the speed of 1200rpm for 1 hour at the temperature of 45 ℃ to obtain the mixed modifier with the aliphatic vinyl ether content of 33%. And adding 1620 g of ethanol and 180 g of water into a 4000ml beaker, dropwise adding formic acid to adjust the pH value of the solution to 5, adding 600g of a mixed modifier into the beaker, then putting the beaker into an ultrasonic water tank, adjusting the temperature of the water tank to 70 ℃, setting the frequency of ultrasonic oscillation to 25Hz, simultaneously stirring the mixed solution in the beaker at the speed of 1200rpm by using a stirring paddle, keeping the temperature in the beaker stable, and obtaining a mixed hydrolysate after 4 hours, wherein the hydrolysate is used as a modified solution of the carbon nano tube.
CH3(CH2)13(OCH2CH2)5
(A)
NH-(CH2)2-Si-(OCH3)3
(B)
Adjusting the frequency of ultrasonic oscillation to 30Hz, keeping the temperature at 70 ℃, adding 39.2 g of the obtained acidified carbon nano tube into a beaker at one time, adjusting the stirring speed to 1500rpm to ensure that the mixed solution of the carbon nano tube is in a flowing state, and modifying for 6 hours under the condition of keeping the temperature and the stirring speed stable. And then, transferring the modified carbon nanotube slurry into a centrifuge, setting the rotation speed of the centrifuge to be 4000 r/min, performing centrifugal separation for 10 min, layering the mixed solution, separating 500g of carbon nanotube suspension at the bottom layer, washing for 3 times by using ethanol, and adding ethanol to prepare the modified carbon nanotube-ethanol suspension with the total weight of 1000g and the carbon nanotube content of about 3.92%.
1800 g of formic acid were taken and added to a 3000ml beaker, the formic acid temperature was adjusted to 60 ℃ using a water bath, 200 g of nylon 6 pellets were placed, the temperature was kept constant, and stirring was carried out at 1500rpm until the nylon pellets completely disappeared and the liquid was completely transparent, whereby a 10 wt% nylon solution was prepared.
And respectively putting the obtained carbon nano tube-ethanol suspension and the nylon formic acid solution into a glass kettle with a discharge hole at the bottom. The stirring devices equipped in the two kettles were respectively started, the carbon nanotube suspension was stirred at 800rpm, and the nylon formic acid solution was stirred at 800 rpm. The discharge hole positions of the two kettles are adjusted to be close to each other, so that the liquid in the two containers can flow out and can be converged as soon as possible in the falling process, and a 5000ml beaker is taken and placed under the discharge hole positions of the two kettles. And simultaneously opening the discharge ports of the two containers, adjusting the outflow speed of the nylon solution to be 0.92 times of that of the carbon nanotube suspension, keeping the outflow liquid flow of the two kettles stable, and simultaneously closing the discharge ports of the two kettles after the material in one of the kettles flows out. And putting a product in a beaker with the lower end of 5000ml into a centrifuge, centrifuging for 5 minutes under the condition of 2000 r/min, collecting the precipitate at the lower part, and drying to constant weight at 100 ℃ by using a vacuum oven to obtain the nylon 6/carbon nanotube master batch with the carbon nanotube load of about 30%.
According to the formulation shown in Table 3, the raw materials were thoroughly mixed and extruded at a screw speed of 35rpm at 230 ℃ and 260 ℃ using a twin-screw extruder to pelletize. Further, the nylon composite material containing the same masterbatch and different glass fiber portions was prepared by injection molding, and the mechanical properties and conductivity of the material were measured, the results of which are shown in table 4. The result shows that the nylon 6/carbon nano tube master batch can be used together with the reinforced fiber, so that the conductivity of the material is obviously improved, and the mechanical property of the material can be improved to a certain extent.
TABLE 3
| Sample No. 5 | Sample No. 6 | Sample 7 | Sample 8 | |
| Nylon 6 | 80 | 60 | 70 | 50 |
| Nylon 6/carbon nanotube master batch | 0 | 20 | 0 | 20 |
| Glass fiber | 20 | 20 | 30 | 30 |
| Antioxidant 1010 | 0.1 | 0.1 | 0.1 | 0.1 |
| Antioxidant 168 | 0.2 | 0.2 | 0.2 | 0.2 |
| Lubricant EBS | 0.3 | 0.3 | 0.3 | 0.3 |
TABLE 4
| Sample No. 5 | Sample No. 6 | Sample 7 | Sample 8 | |
| Volume resistivity/Ω · cm | ＞1×1014 | 1×106 | ＞1×1014 | 8×105 |
| Tensile strength/MPa | 116 | 120 | 141 | 144 |
| Flexural Strength/MPa | 149 | 157 | 205 | 211 |
| Flexural modulus/MPa | 4711 | 4786 | 6892 | 7103 |
| Impact Strength/kJ.m2 | 11 | 12 | 12 | 13 |
Example 5:
a1000 ml beaker is taken, 600g of mixed concentrated acid with nitric acid and sulfuric acid being 1: 3 is prepared in the beaker, 50 g of commercially available carbon nano tubes (6 nanometer scale) are added into the beaker, the beaker is placed into an ultrasonic water tank, the temperature of the water tank is adjusted to be 50 ℃, after ultrasonic oscillation is carried out for 6 hours at the frequency of 30KHz, the obtained mixed slurry is centrifugally separated for 10 minutes by a centrifuge under the condition of 4000 r/min, and the mixed slurry is layered, so that the carbon nano tube suspension liquid at the bottom layer is separated. And repeatedly washing the suspension with clear water to enable the pH value of the suspension to be more than 6, and drying the suspension to constant weight at 80 ℃ by using a vacuum oven to obtain 49.5 g of acidified carbon nano tubes.
And adding 200 g of aliphatic vinyl ether (A) and 600g of aminopropyltrimethoxysilane (B) into a 2000ml beaker, and stirring at the temperature of 40 ℃ and the speed of 1500rpm for 1.5 hours to obtain the mixed modifier with the content of the aliphatic vinyl ether of 25 percent. And adding 1080 g of ethanol and 120 g of water into a 4000ml beaker, dropwise adding formic acid into the beaker to adjust the pH value of the solution to 5, adding 600g of a mixed modifier into the beaker, then putting the beaker into an ultrasonic water tank, adjusting the temperature of the water tank to 80 ℃, setting the frequency of ultrasonic oscillation to 15Hz, simultaneously stirring the mixed solution in the beaker at 1400rpm by using a stirring paddle, keeping the temperature in the beaker stable, and obtaining a mixed hydrolysate after 7 hours, wherein the hydrolysate is used as a modified solution of the carbon nano tube.
CH3(CH2)10(OCH2CH2)6
(A)
NH-(CH2)3-Si-(OCH3)3
(B)
Adjusting the frequency of ultrasonic oscillation to 25Hz, keeping the temperature at 80 ℃, adding 49.5 g of the obtained acidified carbon nano tube into a beaker at one time, adjusting the stirring speed to 1200rpm to ensure that the mixed solution of the carbon nano tube is in a flowing state, and modifying for 5 hours under the condition of keeping the temperature and the stirring speed stable. And then, transferring the modified carbon nanotube slurry into a centrifuge, setting the rotation speed of the centrifuge to be 4000 r/min, performing centrifugal separation for 10 min, layering the mixed solution, separating out 600g of carbon nanotube suspension at the bottom layer, washing for 3 times by using ethanol, and adding ethanol to prepare modified carbon nanotube-ethanol suspension with the total weight of 2000g and the carbon nanotube content of about 2.47%.
1800 g of formic acid were taken and put into a 3000ml beaker, the formic acid temperature was adjusted to 70 ℃ using a water bath, 200 g of nylon 6 pellets were put into the beaker, the temperature was kept constant, and the beaker was stirred at 1300rpm until the nylon pellets completely disappeared and the liquid was completely transparent, whereby a 10 wt% nylon solution was prepared.
And respectively putting the obtained carbon nano tube-ethanol suspension and the nylon formic acid solution into a glass kettle with a discharge hole at the bottom. The stirring devices equipped in the two kettles were respectively started, the carbon nanotube suspension was stirred at 1000rpm, and the nylon formic acid solution was stirred at 700 rpm. The discharge hole positions of the two kettles are adjusted to be close to each other, so that the liquid in the two containers can flow out and can be converged as soon as possible in the falling process, and a 5000ml beaker is taken and placed under the discharge hole positions of the two kettles. And simultaneously opening the discharge ports of the two containers, adjusting the outflow speed of the nylon solution to be 4.48 times of that of the carbon nanotube turbid liquid, keeping the outflow liquid flows of the two kettles stable, and simultaneously closing the discharge ports of the two kettles after the material in one of the kettles flows out. And putting a product in a beaker with the lower end of 5000ml into a centrifuge, centrifuging for 5 minutes under the condition of 2000 r/min, collecting the precipitate at the lower part, and drying to constant weight at 100 ℃ by using a vacuum oven to obtain the nylon 6/carbon nanotube master batch with the carbon nanotube load of about 5%.
The master batch is directly put into an internal mixer and mixed for 5 minutes at the rotating speed of 35rpm, and the mixing temperature is kept at 240 ℃ and 260 ℃. Further, a nylon material was prepared by compression molding, and mechanical properties and conductivity of the material were measured and compared with those of pure nylon 6, and the results are shown in table 5. The result shows that the nylon 6/carbon nano tube master batch can improve the mechanical property of the material to a certain extent while obviously improving the conductivity of the material.
TABLE 5
| Nylon 6/carbon nanotube master batch | Nylon 6 | |
| Volume resistivity/Ω · cm | 5×105 | ＞1×1014 |
| Tensile strength/MPa | 63 | 61 |
| Flexural Strength/MPa | 91 | 86 |
| Flexural modulus/MPa | 2193 | 2077 |
| Impact Strength/kJ.m2 | 22 | 20 |
Claims (10)
1. The preparation and application of nylon/carbon nanotube master batch for improving the conductivity of the material are characterized in that 0.1-60 wt% of carbon nanotubes are loaded in the product master batch, and the preparation steps are as follows:
1) preparing the surface modified carbon nano tube:
1.1) acidizing treatment of carbon nano tube slurry: adding carbon nano tubes into mixed concentrated acid with the ratio of nitric acid to sulfuric acid being 1: 3, and carrying out ultrasonic oscillation at the frequency of 15-40KHz for 2-8 hours at the temperature of 50-70 ℃ to obtain carbon nano tube slurry after acidification treatment;
1.2) drying of acidified carbon nanotubes: centrifuging the carbon nanotube slurry subjected to acidification treatment for 10 minutes by using a centrifuge under the condition of 4000 r/min to layer the mixed solution, recovering the supernatant for reuse, repeatedly washing the separated black carbon nanotube suspension at the bottom layer by using clear water, adjusting the pH value of the suspension to be more than 6, and drying the suspension to constant weight at the temperature of 60-80 ℃ by using a vacuum oven to obtain the acidified carbon nanotube;
1.3) preparation of carbon nano tube modified solution: preparing a solution by using ethanol and water, wherein the amount of the ethanol is 80-95 wt%, heating the solution to 50-80 ℃, then adjusting the pH value of the solution to 4-6 by using formic acid, then adding a mixed modifier of an aminosilane coupling agent and a polyether surfactant into the solution, stirring at the speed of 500-2000rpm and simultaneously matching with 10-30KHz ultrasonic oscillation to hydrolyze the aminosilane coupling agent for 2-20 hours, thus obtaining a mixed hydrolysate, and using the hydrolysate as a modified solution of the carbon nano tube;
1.4) modification treatment of carbon nanotubes: adding the acidified carbon nano tube into the carbon nano tube modified solution prepared in the step 1.3), wherein the adding amount of the carbon nano tube is 0.01-20 wt% of the solution, adjusting the temperature of the solution to 50-80 ℃, matching with ultrasonic treatment, and fully modifying the carbon nano tube, wherein the modification time is 1-10 hours, and stirring at the speed of 500-2000rpm during the modification time to ensure that the carbon nano tube mixed solution is in a flowing state;
1.5) preparing a modified carbon nanotube-ethanol suspension: and centrifuging the modified carbon nanotube slurry for 10 minutes by using a centrifuge at 4000 r/min to separate the mixed solution into layers, separating out the carbon nanotube suspension at the bottom layer, washing for 3 times by using ethanol, and adding ethanol to prepare the modified carbon nanotube-ethanol suspension with the carbon nanotube content of 0.1-10 wt%.
2) Preparation of nylon solution:
the formic acid is heated to 50-80 ℃, 5-15 wt% of nylon particles are put into the formic acid, the temperature is kept constant, and the formic acid is stirred at the speed of 500-2500rpm until the nylon particles completely disappear and the liquid is completely transparent, so as to prepare the nylon solution.
3) Preparing nylon/carbon nano tube master batch:
3.1) respectively putting the carbon nanotube ethanol suspension obtained in the step 1) and the nylon formic acid solution obtained in the step 2) into two containers with stirring devices, wherein the containers are provided with discharge ports and can stably control the outflow speed of the liquid;
3.2) stirring the carbon nanotube slurry at the speed of 500-4000rpm by using a stirring device in the container, and stirring the nylon solution at the speed of 300-1000 rpm;
3.3) enabling the discharge ports of the two containers to be close, placing the containers to contain products below the discharge ports, opening the discharge ports, and respectively setting outlet flow rates of the two containers according to the designed loading capacity of the carbon nanotubes in the master batches in proportion to ensure that liquid flows discharged by the two containers can be converged before falling to the containing containers;
and 3.4) simultaneously closing the discharge ports of the two containers, centrifugally separating the product in the container at the lower end for 5 minutes by using a centrifugal machine under the condition of 2000 r/min, collecting the precipitate at the lower part, and drying to constant weight by using a vacuum oven at the temperature of 80-120 ℃ to obtain the nylon/carbon nano tube master batch.
4) Application of nylon/carbon nano tube master batch
The nylon/carbon nano tube master batch is taken as a conductive auxiliary agent and is compounded with one or more plastics and one or more functional components with reinforcing or flame retarding properties in a melt blending mode to prepare the plastic composite material with antistatic or conductive properties.
2. The method for preparing nylon/carbon nanotube master batch with improved material conductivity according to claim 1, wherein the structural formula of the polyether surfactant in the step 1.3) is as follows:
wherein m has a value between 1 and 20 and n has a value between 3 and 20.
3. The method for preparing nylon/carbon nanotube master batch for improving the conductivity of the material according to claim 1, wherein the structural formula of the aminosilane coupling agent in the step 1.3) is as follows:
NH-(CH3)p-Si-X3
wherein X represents an alkoxy group and p has a value of between 2 and 8.
4. The method for preparing nylon/carbon nanotube master batch for improving the conductivity of the material according to claim 1, wherein the mixture of the aminosilane coupling agent and the polyether surfactant in the 1.3) is prepared according to the following method:
adding 20-50% of polyether surfactant and 80-50% of aminosilane coupling agent into the same container, stirring at 30-45 ℃ and 2000rpm for 0.2-2 hours, wherein the mixture is ensured to be in a flowing state.
5. The method for preparing nylon/carbon nanotube master batch with improved material conductivity according to claim 1, wherein the mixed modifier of the aminosilane coupling agent and the polyether surfactant in 1.3) is added in an amount of 15-45 wt%, preferably 25-35 wt%, based on the total amount of the modified solution.
6. The method for preparing the nylon/carbon nanotube master batch for improving the conductivity of the material according to claim 1, wherein the modification treatment of the carbon nanotubes in the 1.3) and the 1.4) is performed in an ultrasonic tank with a heating function, and the ultrasonic frequency is 20 to 50KHz, preferably 30 to 40 Hz.
7. The method of claim 1, wherein the nylon used in the preparation of the nylon solution in the step 2) is polycaprolactam (nylon 6) or polyhexamethylene adipamide (nylon 66).
8. The method of claim 1, wherein in the step 4), when the plastic composite material with antistatic or conductive properties is prepared, the plastic used includes one or more plastic materials including but not limited to polyolefin plastics, polyester plastics, polyamide plastics, polyolefin derivative plastics, and polyolefin block structure-containing plastics.
9. The method according to claim 1, wherein in the step 4), when the plastic composite material with antistatic or conductive properties is prepared, the nylon/carbon nanotube masterbatch, one or more plastic materials, and other components including but not limited to the reinforcing functional component, the flame retardant functional component, and the toughening functional component are melt-blended with the plastic processing equipment capable of providing a shearing action, such as an open mill, an internal mixer, or a screw extruder, to prepare the composite material with conductive or antistatic properties.
10. The method of claim 1, wherein in the step 4), the nylon/carbon nanotube master batch is added in an amount of 0.1-100 wt% when the plastic composite material with antistatic or conductive properties is prepared.
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Application publication date: 20200225 |