CN113308104A - High-conductivity plastic master batch, preparation method thereof and conductive plastic particles - Google Patents
High-conductivity plastic master batch, preparation method thereof and conductive plastic particles Download PDFInfo
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Abstract
The application relates to the field of high polymer materials, in particular to a high-conductivity plastic master batch and a preparation method thereof, and conductive plastic particles and a preparation method thereof. The high-conductivity plastic master batch is formed by mixing conductive particles and plastic particles according to the mass ratio of 0.01-0.5:1, wherein the conductive particles are formed by mixing conductive fillers and lubricants according to the mass ratio of 1:0.01-0.5 and then compacting and granulating; the preparation method comprises the following steps: uniformly mixing the conductive filler and the lubricant, and then compacting and granulating to prepare conductive particles; and uniformly mixing the conductive particles and the plastic particles, and then performing melt extrusion and granulation to prepare the high-conductivity plastic master batch. The lubricant and the conductive filler are uniformly dispersed and combined with a compaction granulation means, so that the conductive filler is stably combined, the prepared high-conductivity plastic master batch has higher conductivity, conductive plastic particles and downstream products can be further prepared, and the performance is stable.
Description
Technical Field
The application relates to the field of high polymer materials, in particular to a high-conductivity plastic master batch, a preparation method thereof and conductive plastic particles.
Background
With the rapid development of electronic information technology, the conductive polymer composite material has wide application in the electronic and electrical industry and plays an important role in the development of the electronic and electrical industry. The conductive polymer composite material has the characteristics of excellent electrical property, light weight, stable physical and chemical properties, easiness in forming and processing, low cost and the like, is widely used as a shell material, a coating material, a matrix material and a dielectric insulating layer material of electronic and electrical equipment and components, and is also widely applied to the field of electronic packaging such as chip trays, conductive carrier tapes and the like.
For the conductive additive in the conductive polymer composite material, the conductive filler widely applied at present comprises conductive carbon fiber, a permanent antistatic agent, carbon nano tubes and conductive carbon black, wherein, researches show that the carbon fiber reinforced plastic is not suitable for extrusion and secondary forming of sheet materials; the price of the permanent antistatic agent is higher, and the surface resistivity can not reach 104Ω/m2Or less, the conductivity of the conductive polymer composite material is influenced; the carbon nano tube has higher price and poor dispersibility, and has dust problem when being copolymerized with engineering plastics, and the generated dust easily affects the operation of production equipment on one hand and affects the conductivity of the conductive polymer composite material on the other hand.
In view of the above-mentioned related technologies, the applicant believes that the problem of dispersibility of the conductive additive in the polymer material affects the application range of the conductive polymer composite material.
Disclosure of Invention
In order to solve the problem of dispersibility of the conductive additive in a high polymer material, the application provides a high-conductivity plastic master batch, a preparation method thereof and conductive plastic particles.
In a first aspect, the present application provides a highly conductive plastic masterbatch, which adopts the following technical scheme:
the high-conductivity plastic master batch comprises conductive particles and plastic particles which are mixed according to the mass ratio of 0.01-0.5:1, wherein the conductive particles comprise conductive fillers and lubricants which are mixed according to the mass ratio of 1:0.01-0.5, and the mixture is compacted and granulated.
The conductive filler has better conductivity, but the dispersibility of the conductive filler (such as the carbon nano tube) is poorer, so that the conductive master batch prepared by blending the conductive filler and the high polymer has dust phenomenon, the generated dust can influence the production environment and equipment, parts of the production equipment are easy to block, and the dust can also easily influence the health of production personnel and operators using the conductive master batch to produce downstream products.
In contrast, according to the preparation method, the conductive filler and the lubricant are blended, then the conductive particles are prepared by compacting and granulating, and then the conductive particles are mixed with the plastic particles, so that the problems of dust generation and the like after the conductive filler and the plastic particles are mixed are solved, the prepared high-conductivity plastic master batch is good in stability and high in conductivity, the dust phenomenon is not easy to generate, and the high-conductivity content and dust-free diffusion effect is realized.
Preferably, the conductive filler is one or more of single-walled carbon nanotube, double-walled carbon nanotube, multi-walled carbon nanotube, carbon black, graphite and graphene.
Preferably, the conductive filler is an oligowall carbon nanotube, and the oligowall carbon nanotube is at least two of a single-wall carbon nanotube, a double-wall carbon nanotube and a triple-wall carbon nanotube.
The conductive filler has high conductivity, so that the prepared high-conductivity plastic master batch has high conductivity; on the other hand, the carbon nano tube has low dispersibility, the prepared conductive particles and the high-conductivity plastic master batch are easy to generate dust, and the dust is more obvious if the content of the carbon nano tube is increased, so that the dust diffusion phenomenon can be effectively reduced by preparing the carbon nano tube conductive particles by mixing the lubricant with the carbon nano tube and compacting and granulating; the multi-wall carbon nano-tube is a carbon nano-tube with more than three layers of wall layers. Other conductive fillers, such as carbon black, graphite, graphene and the like, have better dispersibility than the carbon nano tube, and the prepared conductive particles and the high-conductivity plastic master batch have no dust diffusion phenomenon by adopting the means of blending, dispersing, compacting and granulating the lubricant.
Preferably, the lubricant is a combination of one or more of E wax, polyethylene wax, montan wax, oxidized polyethylene wax, amide wax, montan wax, paraffin wax, silicone, pentaerythritol stearate, sorbitol partial ester, ethylene bis-stearic acid amide.
By adopting the lubricant, the internal lubricity among the conductive fillers can be improved, the external lubricity of the blending granulation of the conductive particles and the plastic particles can be improved, the extrusion granulation is easy, and the prepared high-conductivity plastic master batch has a stable structure and a smooth surface; among them, more preferably, the lubricant is E wax and/or polyethylene wax.
Preferably, the plastic particles are one or more of polycarbonate, nylon 6, nylon 66, polyphenylene, polyethylene, polypropylene, acrylonitrile-butadiene-styrene plastic, PC/ASB alloy, ethylene-vinyl acetate copolymer, polyurethane elastomer, polyether ether ketone, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate-1, 4-cyclohexane dimethanol ester, and polylactic acid.
By adopting the plastic particles, the stability is high, the plastic particles can be uniformly blended and dispersed with the conductive particles prepared by compaction granulation, and the plastic master batch with high conductivity can be prepared after extrusion granulation.
The carrier tape formed by polystyrene and acrylonitrile-butadiene-styrene copolymer conductive sheets is widely applied to the field of electronic packaging such as chip packaging, chip trays and conductive carrier tapes at present, but has the defects of no high temperature resistance and limited application on the chip carrier tape packaging requiring high temperature resistance. In the high-temperature-resistant engineering plastic, the thermal deformation temperature of Polycarbonate (PC) is higher, the polycarbonate can be used for a long time at 120 ℃, can resist 140 ℃ in a short time, has the glass transition temperature of 140-150 ℃, is an amorphous material, has excellent dimensional stability and creep resistance, has performance superior to that of polyamide and polyformaldehyde, and does not have the problem of deformation caused by crystallization in secondary forming of an extruded sheet. Although the price of polycarbonate is higher, compared with other engineering plastics, the polycarbonate has higher tensile strength and impact strength, so that the polycarbonate sheet can be made thinner under the same mechanical strength requirement, so that the cost is not increased too much relatively, and the polycarbonate sheet can be used as one of high-temperature-resistant conductive polymer composite materials. Therefore, for the high-temperature-resistant conductive composite material, polycarbonate can be used as plastic particles, the application focuses on taking polycarbonate as an example, the performance of the high-conductivity plastic master batch prepared by mixing the plastic particles and the compacted and granulated conductive particles is analyzed, and in actual production application, the high-temperature-resistant conductive composite material can be prepared by adopting the corresponding plastic particles according to the performance requirement of the required plastic master batch.
In a second aspect, the present application provides a method for preparing a highly conductive plastic masterbatch, which adopts the following technical scheme:
a preparation method of high-conductivity plastic master batch comprises the following steps:
preparation of conductive particles: uniformly mixing the conductive filler and the lubricant according to the mass ratio, then compacting, granulating and drying to obtain conductive particles;
preparing the high-conductivity plastic master batch: and uniformly mixing the conductive particles and the plastic particles according to the mass ratio, and then carrying out melt extrusion and granulation to obtain the high-conductivity plastic master batch.
In order to solve the problem of poor dispersibility of the conductive filler, the carbon nano tube, a dispersing agent and a solvent are mixed according to the weight part ratio of (5-8): (3-5): (87-92) mixing to form a slurry state, ball-milling the slurry, drying the slurry after ball-milling to form a paste, and cutting and granulating to prepare the carbon nano tube conductive master batch. However, the solvent added in the scheme is large in amount which is 10-18 times of that of the carbon nano tube, the mixed material is a slurry-shaped material, and after the solvent is dried and removed, the solid content of the carbon nano tube in the conductive master batch is 50-70%, and the content is low, so that the conductivity of the conductive master batch is influenced.
In contrast, in the application, the conductive filler and the lubricant are mixed according to the weight ratio of 1:0.01-0.5, the lubricant is utilized to improve the internal lubricity among the conductive fillers and the external lubricity dispersed with plastic particles, the conductive filler with the internal lubrication is compacted and granulated to prepare the densified conductive particles, the conductive particles only contain the conductive filler and the lubricant, the relative content of the conductive filler in the conductive particles is high, and the conductive performance of the conductive plastic master batch can be improved. In addition, the prepared conductive particles are granular, flaky or capsule-shaped, and are easy to further blend with plastic particles to prepare the high-conductivity plastic master batch.
On the other hand, the conductive filler and the lubricant are mixed and then are subjected to dry compaction granulation, the lubricant has an internal lubricating effect on the conductive filler, the binding property between the conductive fillers in the compaction process can be improved, the prepared conductive particle has a compact structure, compared with the conductive particle prepared by blending and extruding the conductive filler and high polymer in the related technology, the compaction granulation reduces the dust diffusion of the conductive particles, the lubricant can improve the binding property when the conductive particles and plastic particles are blended and extruded, the dust diffusion of the conductive filler is reduced, the use condition of the conductive filler is reduced, and the application range of conductive plastic master batches and downstream products is widened. Meanwhile, drying treatment is not needed after compaction, so that the cost is reduced, and the productivity is improved. Specifically, the compacting granulation is to compact the conductive filler powder mixed with the lubricant by using a dry-method rolling granulator, and apply pressure by rolling a rotating pipe wall to densify the conductive filler, so as to prepare the conductive particles.
The technical difficulty of the application lies in that the higher content of the conductive filler can easily generate dust diffusion, the traditional wet compaction process is complex and high in cost, and the lubricant and the dry compaction granulation means are combined, so that the higher content of the conductive filler can be compacted tightly, the dust diffusion condition is reduced, and the high conductive content and dust diffusion-free effect are realized.
Preferably, in the preparation process of the conductive particles, the mixing temperature of the conductive filler and the lubricant is 50-150 ℃, and the mixing and stirring time is 10-30 min.
The lubricant can be melted and uniformly dispersed with the conductive filler by controlling the mixing temperature and mixing duration of the conductive filler and the lubricant, so that the internal lubricity and bonding property between the conductive fillers are improved by using the lubricant, and the conductive particles with higher density are prepared by compacting and granulating. Among them, it is preferable to uniformly disperse the lubricant and the conductive filler by using a high-speed mixer.
Preferably, the pressure for compacting and granulating in the preparation process of the conductive particles is 1-20 MPa.
By controlling the compaction pressure of compaction granulation, the conductive filler mixed with the lubricant can be compacted tightly, the binding property between the conductive fillers is high, the prepared conductive particles are free from dust diffusion, the surface of the prepared high-conductivity plastic master batch is further clean and free from powder falling, and the application range of the high-conductivity plastic master batch is widened. If the pressure for compacting and granulating is too low, the binding property between the conductive fillers is low, and the dust diffusion phenomenon is likely to occur.
Preferably, the conductive particles are compacted and granulated to have a bulk density of 0.05 to 0.40g/cm3。
By controlling the pressure of compaction granulation and the bulk density target of the conductive particles, the conductive filler in the conductive particles has high associativity and no dust diffusion phenomenon, and the application range of the conductive particles, the highly conductive plastic master batches and the conductive plastic particles is widened.
In a third aspect, the present application provides a conductive plastic particle, which adopts the following technical scheme:
the conductive plastic particles are formed by mixing high-conductivity plastic master batches and plastic particles according to the mass ratio of 0.1-2:1, wherein the high-conductivity plastic master batches are the high-conductivity plastic master batches.
The prepared high-conductivity plastic master batch is further blended with plastic particles for extrusion granulation, so that the conductive plastic particles capable of being directly injection molded can be further prepared, and the conductive plastic particles can be used for directly injection molding to prepare plastic products with conductive performance.
Preferably, the plastic particles are one or more of polycarbonate, nylon 6, nylon 66, polyphenylene, polyethylene, polypropylene, acrylonitrile-butadiene-styrene plastic, PC/ASB alloy, ethylene-vinyl acetate copolymer, polyurethane elastomer, polyether ether ketone, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate-1, 4-cyclohexane dimethanol ester, and polylactic acid.
The plastic particles are stable in performance, can be mixed with the high-conductivity plastic master batch to be extruded and granulated to prepare the conductive plastic particles capable of being directly injection-molded, the plastic particles with corresponding performance can be selected according to the performance required by the conductive plastic particles, the plastic particles with the same performance and the same type are required to be used for preparing the conductive plastic particles and the high-conductivity plastic master batch, if the plastic particles used for preparing the high-conductivity plastic master batch are polycarbonate, the plastic particles used for further preparing the conductive plastic particles are also polycarbonate, and the plastic particles of other materials are also the same.
Preferably, the preparation method of the conductive plastic particles adopts the following technical scheme:
and uniformly mixing the high-conductivity plastic master batch and the plastic particles according to the mass ratio, and performing melt extrusion and granulation to obtain the conductive plastic particles.
By adopting the high-conductivity plastic master batch to further blend with plastic particles for extrusion granulation, the prepared conductive plastic particles are not easy to generate dust phenomenon, and have high stability and wide application range.
In summary, the present application has the following beneficial effects:
1. this application adopts emollient and electrically conductive filler dispersion even, improves the interior lubrication action between the electrically conductive filler to combine compaction granulation means, make to combine stably between the electrically conductive filler, form the higher electrically conductive granule of bulk density.
2. According to the preparation method, the dosage ratio of the conductive filler to the lubricant and the dosage ratio of the conductive particles to the plastic particles are controlled, so that the high-conductivity plastic master batch has higher conductivity, and the conductive particles are prepared by compacting and granulating and then are blended with the plastic particles to be extruded and granulated, so that the mechanical property of a plastic particle base material can be maintained, the cost is low, the processability is better, a large amount of industrial production can be realized, and the preparation method is suitable for the electronic packaging field such as chip packaging, chip trays and conductive carrier tapes.
3. The high-conductivity plastic master batch and the plastic particles prepared by the method are further blended and extruded, and the prepared conductive plastic particles are high in stability and good in conductivity, can be applied to preparation of products such as chip trays and the like, and are wide in application range.
Drawings
FIG. 1 is a photograph of a PC conductive plastic particle with a multi-walled carbon nanotube content of 2% in application example 1 of the present application;
FIG. 2 is an SEM image of a brittle section of a plate sample prepared by injection molding of PC conductive plastic particles containing 2% of multi-wall carbon nanotubes in example 1;
FIG. 3 is a photograph of a sample plate of the present application example 1, which was injection molded from PC conductive plastic particles having a 2% multiwall carbon nanotube content.
Detailed Description
The present application will be described in further detail with reference to fig. 1 to 3, and examples and application examples.
Examples
Example 1
A preparation method of high-conductivity polycarbonate master batch comprises the following steps:
(1) preparation of conductive particles: adding 1000g of multi-wall carbon nanotube powder and 200g E wax into a high-speed mixer, mixing for 15min at 100 ℃ and 400rpm, and performing compaction granulation by using a dry-method granulator under the condition of 5Mpa to prepare carbon nanotube conductive particles;
(2) preparing the conductive master batch: and (2) uniformly mixing the carbon nano tube conductive particles prepared in the step (1) with 5466.7g of polycarbonate plastic particles, extruding and granulating in a double-screw extruder, wherein in an extrusion granulation section, the processing temperature of the first section is 260 ℃, the processing temperature of the second section is 270 ℃, the processing temperature of the third section is 280 ℃, the processing temperature of the fourth section is 280 ℃, the processing temperature of the fifth section is 280 ℃, the processing temperature of the sixth section is 280 ℃, the processing temperature of the seventh section is 280 ℃, the processing temperature of the eighth section is 280 ℃, the processing temperature of the ninth section is 280 ℃, the die head temperature is 290 ℃, the rotation speed of a main machine is 300r/min, and finally, the PC conductive master batch is prepared and dried for later use.
Example 2
A preparation method of high-conductivity polycarbonate master batch comprises the following steps:
(1) preparation of conductive particles: adding 1000g of multi-wall carbon nanotube powder and 200g of polyethylene wax into a high-speed mixer, mixing for 15min at 100 ℃ and 400rpm, and performing compaction granulation by using a dry-method granulator under the condition of 5Mpa to prepare carbon nanotube conductive particles;
(2) preparing the conductive master batch: and (2) uniformly mixing the carbon nano tube conductive particles prepared in the step (1) with 5466.7g of polycarbonate plastic particles, extruding and granulating in a double-screw extruder, wherein in an extrusion granulation section, the processing temperature of the first section is 260 ℃, the processing temperature of the second section is 270 ℃, the processing temperature of the third section is 280 ℃, the processing temperature of the fourth section is 280 ℃, the processing temperature of the fifth section is 280 ℃, the processing temperature of the sixth section is 280 ℃, the processing temperature of the seventh section is 280 ℃, the processing temperature of the eighth section is 280 ℃, the processing temperature of the ninth section is 280 ℃, the die head temperature is 290 ℃, the rotation speed of a main machine is 300r/min, and finally, the PC conductive master batch is prepared and dried for later use.
Example 3
A preparation method of high-conductivity nylon 66 master batch comprises the following steps:
(1) preparation of conductive particles: adding 1000g of multi-wall carbon nanotube powder and 200g E wax into a high-speed mixer, mixing for 15min at 100 ℃ and 400rpm, and performing compaction granulation by using a dry-method granulator under the condition of 5Mpa to prepare carbon nanotube conductive particles;
(2) preparing the conductive master batch: and (2) uniformly mixing the carbon nano tube conductive particles prepared in the step (1) with 5466.7g of nylon 66 plastic particles, extruding and granulating in a double-screw extruder, wherein in an extrusion and granulation section, the processing temperature of the first section is 265 ℃, the processing temperature of the second section is 280 ℃, the processing temperature of the third section is 290 ℃, the processing temperature of the fourth section is 290 ℃, the processing temperature of the fifth section is 290 ℃, the processing temperature of the sixth section is 290 ℃, the processing temperature of the seventh section is 290 ℃, the processing temperature of the eighth section is 290 ℃, the processing temperature of the ninth section is 290 ℃, the die head temperature is 300 ℃, the rotation speed of a main machine is 300r/min, and finally, the nylon 66 conductive master batch is prepared and dried for later use.
Example 4
A preparation method of high-conductivity polycarbonate master batch comprises the following steps:
(1) preparation of conductive particles: adding 1000g of multi-wall carbon nanotube powder and 500g E wax into a high-speed mixer, mixing for 15min at 100 ℃ and 400rpm, and performing compaction granulation by using a dry-method granulator under the condition of 5Mpa to prepare carbon nanotube conductive particles;
(2) preparing the conductive master batch: and (2) uniformly mixing the carbon nano tube conductive particles prepared in the step (1) with 5166.7g of polycarbonate plastic particles, extruding and granulating in a double-screw extruder, wherein in an extrusion granulation section, the processing temperature of the first section is 260 ℃, the processing temperature of the second section is 270 ℃, the processing temperature of the third section is 280 ℃, the processing temperature of the fourth section is 280 ℃, the processing temperature of the fifth section is 280 ℃, the processing temperature of the sixth section is 280 ℃, the processing temperature of the seventh section is 280 ℃, the processing temperature of the eighth section is 280 ℃, the processing temperature of the ninth section is 280 ℃, the die head temperature is 290 ℃, the rotation speed of a main machine is 300r/min, and finally, the PC conductive master batch is prepared and dried for later use.
Example 5
A preparation method of high-conductivity polycarbonate master batch comprises the following steps:
(1) preparation of conductive particles: adding 1000g of multi-wall carbon nanotube powder and 200g E wax into a high-speed mixer, mixing for 15min at 120 ℃ and 400rpm, and performing compaction granulation by using a dry granulator under the condition of 5Mpa to prepare carbon nanotube conductive particles;
(2) preparing the conductive master batch: and (2) uniformly mixing the carbon nano tube conductive particles prepared in the step (1) with 3800g of polycarbonate plastic particles, extruding and granulating in a double-screw extruder, wherein in an extrusion granulation section, the processing temperature of the first section is 260 ℃, the processing temperature of the second section is 270 ℃, the processing temperature of the third section is 280 ℃, the processing temperature of the fourth section is 280 ℃, the processing temperature of the fifth section is 280 ℃, the processing temperature of the sixth section is 280 ℃, the processing temperature of the seventh section is 280 ℃, the processing temperature of the eighth section is 280 ℃, the processing temperature of the ninth section is 280 ℃, the die head temperature is 290 ℃, the rotation speed of a main machine is 300r/min, and finally, the PC conductive master batch is prepared and dried for later use.
Example 6
A preparation method of high-conductivity polycarbonate master batch comprises the following steps:
(1) preparation of conductive particles: adding 1000g of multi-wall carbon nanotube powder and 200g E wax into a high-speed mixer, mixing for 15min at 100 ℃ and 400rpm, and performing compaction granulation by using a dry granulator under the condition of 20Mpa to prepare carbon nanotube conductive particles;
(2) preparing the conductive master batch: and (2) uniformly mixing the carbon nano tube conductive particles prepared in the step (1) with 5466.7g of polycarbonate plastic particles, extruding and granulating in a double-screw extruder, wherein in an extrusion granulation section, the processing temperature of the first section is 260 ℃, the processing temperature of the second section is 270 ℃, the processing temperature of the third section is 280 ℃, the processing temperature of the fourth section is 280 ℃, the processing temperature of the fifth section is 280 ℃, the processing temperature of the sixth section is 280 ℃, the processing temperature of the seventh section is 280 ℃, the processing temperature of the eighth section is 280 ℃, the processing temperature of the ninth section is 280 ℃, the die head temperature is 290 ℃, the rotation speed of a main machine is 300r/min, and finally, the PC conductive master batch is prepared and dried for later use.
Application example
Application example 1
666.7g of the PC conductive master batch containing 15 percent of carbon nano tubes prepared in the embodiment 1 and 4333.3g of pure PC plastic particles are mixed, and then a double-screw extruder is used for extrusion granulation to prepare the PC conductive plastic particles with the multi-wall carbon nano tube content of 2 percent; mixing 1000g of the PC conductive master batch containing 15% of carbon nanotubes prepared in the example 1 with 4000g of pure PC plastic particles, and then performing extrusion granulation by using a double-screw extruder to prepare the PC conductive plastic particles with the multi-wall carbon nanotube content of 3%; 1333.3g of the PC conductive master batch containing 15% of the carbon nanotubes prepared in the example 1 and 3666.7g of pure PC plastic particles are mixed and extruded and granulated by a double-screw extruder to prepare the PC conductive plastic particles with the multi-wall carbon nanotube content of 4%.
In the extrusion granulation section for preparing the PC conductive plastic particles, the processing temperature of the first section is 260 ℃, the processing temperature of the second section is 270 ℃, the processing temperature of the third section is 280 ℃, the processing temperature of the fourth section is 280 ℃, the processing temperature of the fifth section is 280 ℃, the processing temperature of the sixth section is 280 ℃, the processing temperature of the seventh section is 280 ℃, the processing temperature of the eighth section is 280 ℃, the processing temperature of the ninth section is 280 ℃, and the die head temperature is 290 ℃, and finally the PC conductive plastic particles are prepared.
The PC conductive plastic particles prepared in the application example 1 are subjected to injection molding and proofing, and the mechanical properties and the surface resistivity of a sample are detected according to an ASTM standard, wherein the test data are shown in the following table 1:
table 1 mechanical properties and surface resistivity data of PC conductive plastic particles of application example 1
As can be seen from the performance data in the above table 1, the increase of the content of the multi-walled carbon nanotube shows that the tensile strength, the elongation at break, the impact strength and the bending strength of the prepared PC conductive plastic particle are all in a descending trend, the surface resistivity is reduced, and the conductivity is improved, which indicates that the addition amount of the multi-walled carbon nanotube is increased, the mechanical property of the composite material is reduced, and when the addition amount of the multi-walled carbon nanotube is 2%, the mechanical property and the conductivity are both improved compared with pure polycarbonate.
As can be seen by combining the attached figure 1, the prepared PC conductive plastic particles have smooth surfaces without defects, uniform particle sizes and no broken particles; and referring to the SEM picture of the brittle cross-section of the plate made of the PC conductive plastic particles by injection molding in conjunction with fig. 2, it can be seen that the carbon nanotubes are uniformly dispersed, and there is no aggregation phenomenon of the carbon nanotubes inside the PC conductive plastic particles or other defect problems caused by the aggregation of the carbon nanotubes. As can be seen by combining the attached figure 3, the plate prepared by injection molding of the PC conductive plastic particles has a smooth mirror surface effect and does not have surface defects caused by carbon nanotube agglomeration.
Application example 2
The present application example differs from the above application example 1 in that: the PC conductive master batch prepared in the embodiment 2 and pure PC plastic particles are blended and granulated, other treatment means are the same as those in the application example 1, and the E wax is replaced by the same amount of polyethylene wax in the process of preparing the PC conductive particles in the embodiment 2.
The PC conductive plastic particles prepared in the application example 2 are subjected to injection molding and proofing, and the mechanical properties and the surface resistivity of a sample are detected according to an ASTM standard, wherein the test data are shown in the following table 2:
table 2 mechanical properties and surface resistivity data of PC conductive plastic particles of application example 2
As can be seen from the performance data in table 2 above, in the process of preparing the PC conductive master batch in example 2, the same amount of polyethylene wax is used to replace the E wax, and the PC conductive plastic particles are further prepared from the PC conductive master batch prepared in example 2, compared with the performance data in application example 1, the PC conductive plastic particles prepared in application example 2 have a tendency of decreasing tensile strength, elongation at break, impact strength, and bending strength, and increasing surface resistivity, decreasing conductivity, indicating that the kind of the lubricant also affects the dispersibility of the conductive filler, further affects the conductivity of the high polymer, and affects the mechanical properties of the high polymer material, while in application example 2, compared with application example 1, the polyethylene wax may not have the same blending dispersibility as the E wax to the multiwall carbon nanotubes, so that the dispersibility of the multiwall carbon nanotubes is decreased, and the conductivity of the PC conductive plastic particles is decreased, and may affect the mechanical properties of the PC conductive plastic particles.
Application example 3
The present application example differs from the above application example 1 in that: the nylon 66 conductive master batch prepared in the example 3 and pure nylon 66 plastic particles are blended and granulated, and other processing means are the same as the application example 1.
The method comprises the following specific steps:
666.7g of the nylon 66 conductive master batch containing 15 percent of carbon nano tubes prepared in the embodiment 3 and 4333.3g of pure nylon 66 plastic particles are mixed, and then a double-screw extruder is used for 500-extrusion granulation to prepare the nylon 66 conductive plastic particles with the multi-wall carbon nano tube content of 2 percent; mixing 1000g of the nylon 66 conductive master batch containing 15% of carbon nanotubes prepared in the embodiment 3 with 4000g of pure nylon 66 plastic particles, and then carrying out extrusion granulation by using a double-screw extruder to prepare the nylon 66 conductive plastic particles with the multi-wall carbon nanotube content of 3%; 1333.3g of the nylon 66 conductive masterbatch containing 15% of carbon nanotubes prepared in example 3 and 3666.7g of pure nylon 66 plastic particles were mixed, and then extruded and granulated by a twin-screw extruder to prepare nylon 66 conductive plastic particles containing 4% of multi-wall carbon nanotubes.
In the extrusion granulation section of the preparation of the nylon 66 conductive plastic particles, the processing temperature of the first section is 265 ℃, the processing temperature of the second section is 280 ℃, the processing temperature of the third section is 290 ℃, the processing temperature of the fourth section is 290 ℃, the processing temperature of the fifth section is 290 ℃, the processing temperature of the sixth section is 290 ℃, the processing temperature of the seventh section is 290 ℃, the processing temperature of the eighth section is 290 ℃, the processing temperature of the ninth section is 290 ℃, and the die temperature is 300 ℃ to finally prepare the nylon 66 conductive plastic particles.
The nylon 66 conductive plastic particles prepared in the application example 3 are subjected to injection molding and proofing, and the mechanical properties and the surface resistivity of a sample are detected according to the ASTM standard, wherein the test data are shown in the following table 3:
table 3 mechanical properties and surface resistivity property data of nylon 66 conductive plastic particles of application example 3
It can be seen from the performance data in table 3 above that, the increase of the content of the multi-walled carbon nanotube, the tensile strength, the elongation at break, the impact strength and the bending strength of the prepared nylon 66 conductive plastic particle all show a descending trend, the surface resistivity is reduced, the conductivity is improved, and when the addition amount of the multi-walled carbon nanotube is 2%, the mechanical property and the conductivity are both improved compared with those of pure nylon 66. In addition, by combining table 1 and application example 1, when the addition amount of the multi-walled carbon nanotube is increased, the mechanical property of the conductive composite material is reduced, and when the addition amount of the multi-walled carbon nanotube is 2%, both the mechanical property and the conductivity are improved compared with the properties of a pure polymer.
Application example 4
The present application example differs from the above application example 1 in that: the PC conductive master batch prepared in the embodiment 4 and pure PC plastic particles are blended and granulated, other processing means are the same as the application example 1, wherein the dosage of the E wax is 500g in the process of preparing the PC conductive particles in the embodiment 4.
The PC conductive plastic particles prepared in the application example 4 are subjected to injection molding and proofing, and the mechanical properties and the surface resistivity of a sample are detected according to an ASTM standard, wherein the test data are shown in the following table 4:
table 4 mechanical properties and surface resistivity data of PC conductive plastic particles of application example 4
As can be seen from the performance data in table 4 above, in the process of preparing the PC conductive master batch in example 4, 500g of E wax is used, and the PC conductive master batch prepared in this example 4 is used to further prepare PC conductive plastic particles, compared with the performance data in application example 1, the PC conductive plastic particles prepared in application example 4 all have a tendency of decreasing tensile strength, elongation at break, impact strength, and bending strength, and have a decrease in surface resistivity and a decrease in conductivity, which indicates that the amount of the lubricant used may affect the mechanical properties of the high polymer material and may affect the conductivity of the high polymer material to some extent. Compared with application example 1, 500gE wax has better conductivity to the carbon nanotube conductive particles and the polycarbonate plastic particles than 200gE wax, but the mechanical property of the PC conductive plastic particles is obviously reduced.
Application example 5
500g of the PC conductive master batch containing 20% of the carbon nano tubes prepared in the embodiment 5 is mixed with 4500g of pure PC plastic particles, and then a double-screw extruder is used for extrusion granulation to prepare the PC conductive plastic particles with the multi-wall carbon nano tube content of 2%; 750g of the PC conductive master batch containing 20% of the carbon nanotubes prepared in the example 5 and 4250g of pure PC plastic particles are mixed, and then a double-screw extruder is used for extrusion granulation to prepare the PC conductive plastic particles with the multi-wall carbon nanotube content of 3%; 1000g of the PC conductive master batch containing 20% of the carbon nanotubes prepared in the example 5 and 4000g of pure PC plastic particles are mixed and extruded and granulated by a double-screw extruder to prepare the PC conductive plastic particles with the multi-wall carbon nanotube content of 4%.
In the extrusion granulation section for preparing the PC conductive plastic particles, the processing temperature of the first section is 260 ℃, the processing temperature of the second section is 270 ℃, the processing temperature of the third section is 280 ℃, the processing temperature of the fourth section is 280 ℃, the processing temperature of the fifth section is 280 ℃, the processing temperature of the sixth section is 280 ℃, the processing temperature of the seventh section is 280 ℃, the processing temperature of the eighth section is 280 ℃, the processing temperature of the ninth section is 280 ℃, and the die head temperature is 290 ℃, and finally the PC conductive plastic particles are prepared.
The PC conductive plastic particles prepared in the application example 5 are subjected to injection molding and proofing, and the mechanical properties and the surface resistivity of a sample are detected according to an ASTM standard, wherein the test data are shown in the following table 5:
TABLE 5 data of mechanical Properties and surface resistivity Properties of PC conductive Plastic particles of application example 5
As can be seen from the performance data in table 5 above, in the process of preparing the PC conductive master batch in example 5, the content of the conductive filler (carbon nanotube) in the conductive master batch is 20%, and when the PC conductive master batch prepared in example 5 is used to further prepare the PC conductive plastic particles, compared with the performance data in application example 1, the tensile strength, the elongation at break and the bending strength of the PC conductive plastic particles prepared in application example 5 are slightly improved, while the impact strength is reduced, the surface resistivity is also increased, and the conductivity is reduced, which indicates that the content of the carbon nanotube affects the mechanical properties of the high polymer material and affects the conductivity of the high polymer material to a certain extent. Compared with the application example 1, in the application example 5, when the content of the conductive filler in the conductive master batch exceeds a certain critical value, the conductive master batch is adopted to further prepare the conductive plastic particles, the conductive master batch is more difficult to disperse in the preparation process, and the mechanical property and the conductive property of the high polymer material are further reduced.
Application example 6
The present application example differs from the above application example 1 in that: the PC conductive master batch prepared in the embodiment 6 and pure PC plastic particles are blended and granulated, other processing means are the same as those in the application example 1, and in the process of preparing the PC conductive particles in the embodiment 2, the pressure is changed from 5MPa to 20 MPa.
The PC conductive plastic particles prepared in the application example 6 are subjected to injection molding and proofing, and the mechanical properties and the surface resistivity of a sample are detected according to an ASTM standard, wherein the test data are shown in the following table 2:
table 6 mechanical properties and surface resistivity data of PC conductive plastic particles of application example 6
As can be seen from the performance data in table 6 above, in the process of preparing the PC conductive particles in example 6, the pressure is 20MPa, and the PC conductive plastic particles are further prepared from the PC conductive master batch prepared in example 6, compared with the performance data in application example 1, the PC conductive plastic particles prepared in application example 6 have slightly improved tensile strength, elongation at break, and bending strength, but reduced impact strength, increased surface resistivity, and reduced conductivity, which indicates that the pressure in the process of preparing the conductive particles can affect the mechanical properties of the high polymer material and can affect the conductivity of the high polymer material to a certain extent. Compared with the application example 1, in the application example 6, when the pressure exceeds a certain critical value in the preparation process of the conductive particles, the conductive particles are more compact, so that the conductive filler is difficult to disperse in the preparation process of the conductive master batch, and the conductivity of the conductive plastic particles prepared from the conductive master batch is influenced.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A high-conductivity plastic master batch is characterized in that: the conductive particle is prepared by mixing conductive particles and plastic particles according to the mass ratio of 0.01-0.5:1, and the conductive particles are prepared by mixing conductive filler and lubricant according to the mass ratio of 1:0.01-0.5, and then compacting and granulating.
2. The highly conductive plastic masterbatch according to claim 1, wherein: the conductive filler is one or a combination of more of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, carbon black, graphite and graphene.
3. The highly conductive plastic masterbatch according to claim 1 or 2, wherein: the conductive filler is an oligowall carbon nanotube, and the oligowall carbon nanotube is at least two of a single-wall carbon nanotube, a double-wall carbon nanotube and a triple-wall carbon nanotube.
4. The highly conductive plastic masterbatch according to claim 1, wherein: the lubricant is one or more of E wax, polyethylene wax, montan wax, oxidized polyethylene wax, amide wax, montan wax, paraffin wax, silicone, pentaerythritol stearate, sorbitol partial ester and ethylene bis-stearic acid amide.
5. The highly conductive plastic masterbatch according to claim 1, wherein: the plastic particles are one or a combination of a plurality of polycarbonate, nylon 6, nylon 66, polyphenylene, polyethylene, polypropylene, acrylonitrile-butadiene-styrene plastic, PC/ASB alloy, ethylene-vinyl acetate copolymer, polyurethane elastomer, polyether ether ketone, polyethylene glycol terephthalate, polybutylene terephthalate, polyethylene glycol terephthalate-1, 4-cyclohexane dimethanol ester and polylactic acid.
6. The method for preparing the highly conductive plastic master batch as claimed in any one of claims 1 to 5, wherein the method comprises the following steps: the method comprises the following steps:
preparation of conductive particles: uniformly mixing the conductive filler and the lubricant according to the mass ratio, and then compacting and granulating to obtain conductive particles;
preparing the high-conductivity plastic master batch: and uniformly mixing the conductive particles and the plastic particles according to the mass ratio, and then carrying out melt extrusion and granulation to obtain the high-conductivity plastic master batch.
7. The method for preparing the highly conductive plastic masterbatch according to claim 6, wherein the method comprises the following steps: in the preparation process of the conductive particles, the mixing temperature of the conductive filler and the lubricant is 50-150 ℃, and the mixing and stirring time is 10-30 min.
8. The method for preparing the highly conductive plastic masterbatch according to claim 6, wherein the method comprises the following steps: in the preparation process of the conductive particles, the pressure of the compaction granulation is 1-20MPa, and the compaction granulation is carried out until the bulk density of the conductive particles is 0.05-0.40g/cm3。
9. An electrically conductive plastic particle, characterized by: the high-conductivity plastic master batch is prepared by mixing high-conductivity plastic master batches and plastic particles according to the mass ratio of 0.1-2:1, wherein the high-conductivity plastic master batches are the high-conductivity plastic master batches in any one of claims 1-5 or the high-conductivity plastic master batches prepared by the preparation method in any one of claims 6-8.
10. The conductive plastic particle of claim 8, wherein: the plastic particles are one or a combination of more of polycarbonate, nylon 6, nylon 66, polyphenylene, polyethylene, polypropylene, acrylonitrile-butadiene-styrene plastic, PC/ASB alloy, ethylene-vinyl acetate copolymer, polyurethane elastomer, polyether ether ketone, polyethylene terephthalate (alcohol), polybutylene terephthalate, polyethylene terephthalate-1, 4-cyclohexane dimethanol ester and polylactic acid.
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