CN111518388A - High-strength high-temperature-resistant conductive nylon composite material and preparation method thereof - Google Patents
High-strength high-temperature-resistant conductive nylon composite material and preparation method thereof Download PDFInfo
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Abstract
A high-strength high-temperature-resistant conductive nylon composite material and a preparation method thereof are disclosed, wherein the nylon composite material comprises the following components: nylon resin, a reinforcing material, a conductive agent, a coupling agent, an antioxidant, a dispersing agent and a lubricating agent. The method comprises the following steps: (1) heating the conductive agent, adding the coupling agent, and stirring to obtain a coupled conductive agent; (2) mixing and stirring the coupled conductive agent, the antioxidant, the dispersant and the lubricant to obtain a conductive mixture; when the conductive agent contains a conductive polymer, adding the conductive polymer in the step (2); (3) stirring and mixing the conductive mixture with a part of nylon resin, heating and banburying, and slicing to obtain conductive master batches; (4) preheating the double screws, adding the conductive master batch, the reinforcing material and the rest part of nylon resin, blending, extruding and granulating to obtain the composite material. The nylon composite material has the advantages of high strength, high temperature resistance, excellent conductivity, aging resistance and the like; the method is simple, low in cost and suitable for industrial production.
Description
Technical Field
The invention relates to a nylon composite material and a preparation method thereof, in particular to a high-strength high-temperature-resistant conductive nylon composite material and a preparation method thereof.
Background
With the development of communication and electronic industries, the demand of conductive composite materials is increasing, especially the miniaturization and high performance of electronic communication equipment and the development of welding technologies, such as the application of high-frequency ultrasonic welding and infrared welding technologies, have high requirements on the high temperature resistance and mechanical properties of conductive composite materials. The common conductive PA6 and PA66 composite materials have temperature resistance and mechanical properties which can not meet the market demand, and particularly the traditional conductive carbon black or graphite composite nylon has poor mechanical properties due to large addition amount, so that the use requirements can not be met. In recent years, some people adopt graphene to prepare the conductive composite nylon, but the size of the graphene preparation technology still is in a test stage, the size of the graphene cannot reach the size of a single layer or below 5 layers, the used graphene with at least micron-scale size is not graphene in the true sense, the conductive characteristic of the graphene cannot be realized, the price is high, particularly, the graphene is difficult to disperse, and the industrialization is difficult to realize.
CN106398205A discloses a preparation method of a conductive nylon material, which adopts N-butyl bromide and N-vinylimidazole to treat a carbon nanotube as a conductive agent of nylon. Although the obtained nylon material has good conductive effect, the process is very complex, and a large amount of organic wastewater generated in the treatment process pollutes the environment.
CN106280421A discloses an antistatic/conductive nylon 6 composite material and a preparation method thereof, which adopts carbon nano tubes, graphite, polyether amide, polyethylene glycol and the like as conductive agents. However, in practice, neither polyetheramide nor polyethylene glycol has conductivity, and the carbon nanotubes and graphite used are uniformly dispersed in nylon resin to generate the conductive effect, and meanwhile, the patent proposes that the interpenetrating network can be formed by adopting the reaction between POE and PA6 to improve the conductive effect, firstly, the reaction between POE and PA6 only enhances the compatibility between POE and PA6, and secondly, the reaction between POE and the terminal group of PA6 only can not form the interpenetrating network structure.
CN101407632A discloses a conductive and antistatic nylon, which is prepared by adopting 1-15 parts of inorganic nano-filler and 5-30 parts of carbon black. However, the impact strength of the composite material is poor due to the addition of too much conductive agent.
CN10274663A discloses a polycarbonate/ABS resin plastic alloy with low temperature impact resistance, which is prepared by adopting 17-28 parts of inorganic filler and 8-16 parts of conductive agent to prepare conductive PA610 and PA 66. However, there is also a disadvantage of low impact strength.
CN107163397A discloses a conductive polypropylene/nylon composite material and a preparation method thereof, which adopts silicon carbide, potassium titanate, aluminum borate whisker and conductive carbon black to compound with polypropylene and PA6 to prepare PP/PA6 conductive composite material. However, in fact, since the molecular chain of PP does not contain polar groups, in order to make PP/PA6 have higher conductivity, a large amount of conductive agent needs to be added, and the mechanical property of the composite material is inevitably greatly reduced.
In conclusion, the nylon composite material has low impact strength due to the large amount of the selected conductive agent. At present, no high-strength high-temperature-resistant conductive nylon composite material is reported. Therefore, it is of great significance to develop a high-strength and high-temperature-resistant conductive nylon composite material to meet the requirements of the electronic communication industry.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a high-strength high-temperature-resistant conductive nylon composite material with the surface resistance reaching the conductive level, high tensile strength, high bending modulus, high notch impact strength and high thermal deformation temperature.
The invention further aims to solve the technical problem of overcoming the defects in the prior art and provide a preparation method of the high-strength high-temperature-resistant conductive nylon composite material, which is simple in process, low in cost and suitable for industrial production.
The technical scheme adopted by the invention for solving the technical problems is as follows: a high-strength high-temperature-resistant conductive nylon composite material comprises the following components: nylon resin, a reinforcing material, a conductive agent, a coupling agent, an antioxidant, a dispersing agent and a lubricating agent.
Preferably, the high-strength high-temperature-resistant conductive nylon composite material comprises the following components in parts by weight: 100 parts of nylon resin, 30-60 parts of reinforcing material, 1-15 parts (preferably 1.5-10 parts) of conductive agent, 0.2-0.5 part of coupling agent, 0.1-0.7 part of antioxidant, 0.2-0.8 part (preferably 0.3-0.6 part) of dispersant and 0.2-0.7 part (preferably 0.3-0.6 part) of lubricant. If the dosage of the reinforcing material is too much, the processing fluidity of the composite material is poor, and the conductivity is reduced; if the dosage of the reinforcing material is too small, the reinforcing effect of the composite material is low. When the consumption of the conductive agent is too small, the conductive effect is poor, and when the consumption is too large, the compatibility of the conductive agent and nylon is reduced, so that the mechanical property of the composite material is reduced. The coupling agent can be bonded with the surface of the conductive agent, and epoxy groups in molecules can react with amino groups of the nylon resin to play a role of a bridge for connecting the conductive agent and the nylon resin; meanwhile, the coupling agent has a coating effect on the conductive agent, so that the agglomeration effect of the conductive agent is reduced, and the conductive effect of the conductive agent is improved. Amino or epoxy in the dispersant molecule can react with the terminal group of the nylon resin macromolecular chain in the melt blending extrusion process to form chemical combination, and the chemical combination has better compatibility with the nylon resin and better cohesiveness with the surface group of the reinforced fiber, thereby promoting the dispersion of the reinforced fiber in the nylon resin.
Preferably, the conductive agent is one or more of graphene, metal powder, metal oxide whisker or conductive polymer. Graphene is a novel material with electric and heat conduction characteristics discovered in recent years, and when nano-scale graphene is peeled into a single-layer to 5-layer laminated structure, the nano-scale graphene can be dispersed in matrix resin to form network channels, the network channels endow the material with good heat and electricity conduction performance, the usage amount is small, and the electric conduction effect can be exerted by generally using 1-2%.
Preferably, the particle size of the graphene is 20-100 nm.
Preferably, the metal powder is one or more of copper powder, silver powder or aluminum powder. The metal powder has good electric conduction property, particularly, the aluminum powder has good electric conduction property and good heat conduction property, is relatively cheap, and has great cost advantage.
Preferably, the particle size of the metal powder is 10 to 50 μm. More preferably, the aluminum powder is metal powder, and the particle size of the metal powder is 10-40 μm.
Preferably, the metal oxide whiskers are zinc oxide whiskers and/or zirconium oxide whiskers and the like. The metal oxide whisker has good conductive property, particularly the zinc oxide whisker has a three-dimensional network structure which endows the zinc oxide whisker with higher electron conduction stability and smaller linear expansion coefficient.
Preferably, the metal oxide whisker has a root length of 10 to 100 μm and a diameter of 0.1 to 3.0 μm. More preferably, the zinc oxide whisker is a metal oxide whisker, the root length of which is 50 to 100 μm and the diameter of which is 0.1 to 1.0 μm. The crystal whisker of zinc oxide crystal whisker with large length-diameter ratio also has the similar reinforcing effect of fiber, and has lower price than crystal whiskers such as zirconia and the like, thereby having cost advantage.
Preferably, the conductive polymer is one or more of polyaniline, polyacetylene or polypyrrole. The polymer has good conductive property and good compatibility with nylon resin, so that the polymer can be uniformly dispersed in the nylon resin and has excellent conductivity and temperature resistance. The compatibility order of the several conductive polymers and the nylon resin is polyaniline (PP)n) Polypyrrole (PPY) > polyacetylene (PPV), more preferably polyaniline is a conductive polymer.
Preferably, the mass ratio of the graphene to the metal powder, the metal oxide whisker and the conductive polymer is 0-1: 0-5: 0-4: 3-8, and the mass ratio of the graphene to the metal powder, the metal oxide whisker and the conductive polymer is not 0 at the same time.
More preferably, in the conductive agent, the mass ratio of the graphene to the conductive polymer is 1: 3-8.
More preferably, in the conductive agent, the mass ratio of the metal powder to the conductive polymer is 3: 3-8.
More preferably, in the conductive agent, the mass ratio of the metal oxide whiskers to the conductive polymer is 2: 3-8.
More preferably, in the conductive agent, the mass ratio of the graphene to the metal powder to the conductive polymer is 1: 2-5: 3-6.
More preferably, in the conductive agent, the mass ratio of the graphene to the metal oxide whisker to the conductive polymer is 1: 2-4: 3-6.
Because the particle size of the graphene is too small, the dispersion is difficult and not good, the graphene fine particles are easy to agglomerate, the usage amount required for forming a network structure is large, and if the usage amount of the graphene is too large, the impact resistance of the composite material is too poor, and the graphene is expensive; if the using amount of the metal oxide whiskers is too large, the whiskers are agglomerated, and the performance of the composite material is reduced; if the amount of the conductive polymer is too large, the compatibility of the conductive polymer and nylon is reduced, a two-phase structure is formed, and the mechanical property of the composite material is reduced. When graphene is used in the conductive agent, the use amount of the graphene is minimum, and the influence on the performance of the composite material is small; when the metal powder is used in the conductive agent, the metal powder is used in a larger amount, and the proper amount can reduce the influence of poor compatibility with nylon resin; when the metal oxide whiskers are used in the conductive agent, the metal oxide whiskers have a good conductive effect and have small influence on the performance of the composite material, but the price of the metal oxide whiskers is higher than that of metal powder, and the addition amount of the metal oxide whiskers is smaller than that of the metal powder; when the conductive polymer is used in the conductive agent, the conductive polymer has good compatibility with nylon resin, good conductivity and high price. Therefore, considering the dispersibility and price of the conductive agent and the influence on the mechanical property of the material, the composite mode of the conductive agents is obtained, and the conductive agent has higher conductivity, lower influence on the mechanical property and high cost performance.
Preferably, the viscosity of the nylon resin is 2.0-2.5. If the viscosity of the resin is too low, the reinforcing effect of the composite material is poor, and if the viscosity of the resin is too high, the fluidity of the resin is poor, the coating effect on the fibers is poor, and the conductivity and the mechanical property of the composite material are influenced.
Preferably, the nylon resin is one or more of PA4T, PA6T, PA9T, PA10, PA12T or PA 46. PA4T, PA6T, PA9T, PA10 and PA12T are semi-aromatic nylon resins, and have excellent high-temperature resistance due to the benzene ring structure contained in the main chain of the macromolecule, and the water absorption of the resin is small, so the resin has good dimensional stability and is particularly suitable for electronic and electrical communication equipment parts and automobile structural parts. PA46 is a high crystalline nylon with crystallinity greater than 51%, has excellent high temperature resistance and processing fluidity, and is suitable for manufacturing electronic equipment parts with complex structures.
Preferably, the reinforcing material is one or more of glass fiber, carbon fiber or basalt fiber and the like. In particular, the carbon fiber not only has a reinforcing effect, but also has a good conductive effect. Different fibers can be selected as reinforcing materials according to different purposes, and the reinforcing materials can be used independently or compositely.
Preferably, the coupling agent is a silane compound.
Preferably, the silane compound is one or more of KH550, KH560 or KH 570. Considering the higher resin processing temperature, a coupling agent with better temperature resistance needs to be selected, and the temperature resistance sequence of the coupling agent is as follows: KH570 > KH560 > KH550, more preferably KH570 is the coupling agent.
Preferably, the antioxidant is a high-temperature resistant hindered phenol antioxidant and/or a phosphate antioxidant and the like. The hindered phenol antioxidant and the phosphate antioxidant have higher thermal decomposition temperature, the decomposition temperature is above 360 ℃, the hindered phenol antioxidant and the phosphate antioxidant are not decomposed in the blending, extrusion and processing processes of the composite material, and the mechanical property of the composite material is not reduced when the composite material is used at higher temperature (such as 120 ℃).
Preferably, the mass ratio of the high-temperature-resistant hindered phenol antioxidant to the phosphate antioxidant is 3: 1-2.
Preferably, the high-temperature resistant hindered phenol antioxidant is one or more of H10, SC02X or H330.
Preferably, the phosphate antioxidant is 626 and/or S9228 and the like.
More preferably, the antioxidant is H10 or SC02X and S9228 which are compounded and used according to the mass ratio of 1.5-2.5: 1.
Preferably, the dispersant is an aliphatic amide compound.
Preferably, the aliphatic amide compound is one or more of erucamide, ethylene bis-oleamide, ethylene bis-stearamide or polymethacrylate glycidyl ester-methyl methacrylate-butyl acrylate terpolymer and the like. The dispersing agent has the following reaction activity sequence on enhancing the dispersibility of the fibers and the nylon resin: polymethacrylate glycidyl ester-methyl methacrylate-butyl acrylate terpolymer (GMA) > Ethylene Bisstearamide (EBS) > Ethylene Bisoleamide (EBO) > erucamide (ER-CH). GMA is a high molecular polymer and is more resistant to high temperature than other dispersing agents, and GMA is more preferably a dispersing agent.
Preferably, the lubricant is a pentaerythritol ester and/or a polysiloxane, and the like. The Pentaerythritol Ester (PETS) has good internal and external lubrication, and the polysiloxane (SI) is high molecular weight silicone, has excellent lubricity, demolding property and temperature resistance, is particularly suitable for preparing high-temperature-resistant composite materials, and is more preferably a lubricant.
The technical scheme adopted for further solving the technical problems is as follows: a preparation method of a high-strength high-temperature-resistant conductive nylon composite material comprises the following steps:
(1) heating the conductive agent, adding the coupling agent, and stirring to obtain a coupled conductive agent;
(2) mixing and stirring the coupled conductive agent obtained in the step (1) with an antioxidant, a dispersant and a lubricant to obtain a conductive mixture;
when the conductive agent contains a conductive polymer, adding the conductive polymer in the step (2);
(3) stirring and mixing the conductive mixture obtained in the step (2) with a part of nylon resin, heating and banburying, and slicing to obtain conductive master batches;
(4) and (4) preheating the double screws, adding the conductive master batch obtained in the step (3), the reinforcing material and the rest of the nylon resin, blending, extruding and granulating to obtain the high-strength high-temperature-resistant conductive nylon composite material.
Preferably, in the step (1), the heating temperature is 60-90 ℃. In the heating process, the coupling agent is bonded with the surface of the conductive agent, and plays a role in coating the conductive agent, so that the agglomeration effect of the conductive agent is reduced, and the conductive effect of the conductive agent is improved; the conductive polymer is a soluble polymer, can be mutually fused with resin through melt blending extrusion, and does not need to be coupled. If the temperature is too high, the coupling agent is easily volatilized, and if the temperature is too low, the coupling effect is reduced.
Preferably, in the step (1), the stirring speed is 100-300 rpm, and the time is 3-10 min.
Preferably, in the step (2), the mixing and stirring speed is 150-300 rpm, and the time is 3-8 min.
Preferably, in the step (3), the amount of the nylon resin is 10-30% of the total mass of the nylon resin.
Preferably, in the step (3), the stirring and mixing speed is 150-250 rpm, and the time is 2-6 min.
The method of the invention is that the conductive agent, the auxiliary agent, the conductive polymer and the nylon resin are mixed to prepare the conductive master batch: firstly, the conductive agent nano material cannot be directly added into the double screw for blending and extrusion, secondly, the nano powder such as the conductive agent can be added at one time by adopting a mixing process, and the internal mixer has extremely strong mixing effect and can uniformly disperse the conductive agent in the nylon resin; thirdly, the conductive master batch prepared by mixing and the nylon resin are added into a double-screw extruder to be blended again, so that the conductive agent can be further dispersed, and the composite material with excellent conductivity is prepared.
Preferably, in the step (3), the temperature for heating and banburying is 280-340 ℃ and the time is 30-60 min. Heating and banburying effects: firstly, solve the difficult problem that nanometer material can't directly add the twin-screw, secondly, utilize banbury mixer high shear effect, improve the dispersibility of conducting agent nanometer material. The temperature can ensure that the coupling agent is not decomposed in the blending extrusion processing process on the premise of ensuring that the nylon resin is not degraded, otherwise, the performance of the composite material and the appearance of the product are influenced.
Preferably, in the step (4), the temperature of the blending extrusion is 250-330 ℃, the vacuum degree is-0.6-0.9 MPa, and the rotating speed of the screw is 450-600 rpm.
The invention has the following beneficial effects:
(1) the nylon composite material has the advantages of high strength, high temperature resistance, excellent conductivity, aging resistance and the like, the surface resistance is as low as 1.1 × 10 omega, the tensile strength can be as high as 305MPa, the bending strength can be as high as 365MPa, the bending modulus can be as high as 1.65GPa, and the notch impact strength can be as high as 19.3kJ/m2The heat distortion temperature exceeds 280 ℃;
(2) the method has simple process, particularly adopts the process of treating the coated conductive agent by using the high-temperature-resistant coupling agent and preparing the conductive master batch by adopting the banburying process, greatly improves the dispersibility of the conductive agent, improves the conductive effect, has low cost and is suitable for industrial production.
Detailed Description
The present invention will be further described with reference to the following examples.
The PA6T (relative viscosity is 2.1), PA9T (relative viscosity is 2.3) and PA10T (relative viscosity is 2.1) nylon resins used in the examples of the invention are respectively purchased from Qingdao Sanli, Japan Coly and Guangzhou Jinfa; the used glass fiber 301HP is purchased from Chongqing International composite materials GmbH; the carbon fibers used were purchased from east japan; graphene (particle size 100 nm) used was purchased from the university of Hunan; the antioxidant used was purchased from Rohm and Haas; the polysiloxane used was purchased from Sichuan morning light; the grain diameter of the used aluminum powder is 40 μm, the root length of the zinc oxide whisker is 50 μm, the diameter is 0.8 μm, and the aluminum powder and the zinc oxide whisker are all purchased from the market; the starting materials or chemical reagents used in the present invention are, unless otherwise specified, commercially available in a conventional manner.
Examples 1 to 9 of a high-strength, high-temperature-resistant, conductive nylon composite material
The components and parts by weight of the high-strength high-temperature-resistant conductive nylon composite materials of examples 1 to 9 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1A high-strength, high-temperature-resistant, electrically conductive nylon composite, examples 1 to 9 and comparative examples 1 to 3, the components and parts by weight of which are shown in Table
Note: in the table, "-" indicates no addition; the numerical values before and after "/" in the nylon resin respectively represent the parts by weight of the nylon resin added in the steps (3) and (4) of the production methods of examples 1 to 9 and comparative example 1, and the steps (1) and (2) of the production methods of comparative examples 2 and 3.
Preparation method of high-strength high-temperature-resistant conductive nylon composite material, examples 1 to 4
(1) Heating the conductive agent to 80 ℃ according to the weight parts of the components in the examples 1-4 in the table 1, adding the coupling agent, and stirring for 4min at 200rpm to obtain a coupled conductive agent;
(2) respectively mixing and stirring the coupled conductive agent obtained in the step (1), an antioxidant, a dispersant and a lubricant for 6min at 250rpm according to the parts by weight of the components in the examples 1-4 in the table 1 to obtain a conductive mixture;
when the conductive agent contains a conductive polymer, adding the conductive polymer in the step (2);
(3) respectively stirring and mixing the conductive mixture obtained in the step (2) with a part of nylon resin at 150rpm according to the weight parts of the components in the examples 1-4 in the table 1 for 5min, heating and banburying at 300 ℃ for 50min, and slicing to obtain conductive master batches;
(4) and (3) preheating the double screws according to the weight parts of the components in the embodiments 1-4 in the table 1, adding the conductive master batch obtained in the step (3), the reinforcing material and the rest of nylon resin, blending, extruding and granulating at the blending, extruding and zoning temperatures of 250, 280, 310, 320, 280, 290 and 300 ℃ in sequence, the vacuum degree of-0.8 MPa and the screw rotation speed of 550rpm to respectively obtain the high-strength high-temperature-resistant conductive nylon composite materials 1-4.
Preparation method of high-strength high-temperature-resistant conductive nylon composite material, examples 5 to 9
(1) Heating the conductive agent to 70 ℃ according to the weight parts of the components in the examples 5-9 in the table 1, adding the coupling agent, and stirring for 6min at 100rpm to obtain a coupled conductive agent;
(2) respectively mixing and stirring the coupled conductive agent obtained in the step (1), an antioxidant, a dispersant and a lubricant for 4min at 200rpm according to the parts by weight of the components in the examples 5-9 in the table 1 to obtain a conductive mixture;
when the conductive agent contains a conductive polymer, adding the conductive polymer in the step (2);
(3) respectively stirring and mixing the conductive mixture obtained in the step (2) with a part of nylon resin at 200rpm according to the weight parts of the components in the examples 5-9 in the table 1 for 3min, heating and banburying at 320 ℃ for 40min, and slicing to obtain conductive master batches;
(4) and (2) preheating the double screws according to the weight parts of the components in the examples 5-9 in the table 1, adding the conductive master batch obtained in the step (3), the reinforcing material and the rest of nylon resin, blending, extruding and granulating at the blending, extruding and zoning temperatures of 250, 280, 310, 320, 280, 290 and 300 ℃ in sequence, the vacuum degree of-0.6 MPa and the screw rotation speed of 500rpm to respectively obtain 5-9 high-strength high-temperature-resistant conductive nylon composite materials.
Comparative example 1
According to the weight parts of the components in comparative example 1 in the table 1, the nylon composite material 1 is prepared by the preparation methods of examples 5 to 9. The same as in examples 5 to 9.
Comparative example 2
(1) Mixing and stirring an antioxidant, a dispersant and a lubricant for 4min at 200rpm according to the weight parts of the components in comparative example 2 shown in Table 1, adding 20 weight parts of PA66, continuously stirring to obtain a mixture, and adding the mixture into a hopper 2;
(2) according to the weight parts of the components of comparative example 2 in table 1, after preheating the twin screws, adding 80 parts by weight of PA66 into a hopper 1, adding carbon fibers into a side feeding hopper of the screws, starting the metering extruders 1 and 2 and side feeding at one time to enter the twin screw extruder, heating, melting, blending and extruding, and blending, extruding and granulating to obtain the nylon composite material 2, wherein the blending and extruding zone temperature is 250, 280, 290, 250 and 260 ℃ in sequence, the vacuum degree is-0.6 MPa, and the screw rotation speed is 500 rpm.
Comparative example 3
(1) Mixing and stirring an antioxidant, a dispersant, a lubricant and a coupling agent for 4min at 200rpm according to the weight parts of the components in comparative example 3 shown in Table 1, adding 20 weight parts of PA10T, continuously stirring to obtain a mixture, and adding the mixture into a hopper 2;
(2) according to the weight parts of the components of comparative example 3 in table 1, after preheating the twin screws, adding 80 parts by weight of PA10T into a hopper 1, adding glass fibers into a screw side feeding hopper, starting the metering extruders 1 and 2 once and feeding the side feeding materials into the twin screw extruder, heating, melting, blending and extruding at the temperature of blending and extruding subareas of 280, 300, 310, 320, 280, 290, 300 ℃, the vacuum degree of-0.6 MPa and the screw rotation speed of 500rpm, and granulating to obtain the nylon composite material 3.
The high-strength high-temperature-resistant conductive nylon composite materials 1-9 and the nylon composite materials 1-3 were respectively sampled and injection-molded into standard sample bars, and the tensile strength (ASTM D638), the flexural strength (ASTM D790), the flexural modulus (ASTM D790), the notched impact strength (ASTM D756), the heat distortion temperature (ASTM D648) and the surface resistance (GB/T2018-06-29) were measured, and the results are shown in Table 2.
TABLE 2 Performance parameter tables for high-strength, high-temperature resistant, electrically conductive nylon composites 1-9 and nylon composites 1-3
As can be seen from table 2, in example 6, the surface resistance is small and the conductive effect is good only by adding graphene into the conductive agent; examples 5, 7 to 9 use graphene/Zinc oxide whisker/PPnThe nylon composite material ternary used as the conductive agent has low surface resistance and good conductive effect; example 9 use of graphene/Zinc oxide whisker/PPnThe nylon composite material which is used as the conductive agent and compounded with the carbon fiber has the lowest surface resistance and the best conductive effect; the surface resistance of the high-strength high-temperature-resistant conductive nylon composite materials 1, 4-9 reaches the conductive level; the tensile strength of the high-strength high-temperature-resistant conductive nylon composite material 1-9 can be up to 305MPa, the bending strength can be up to 365MPa, the bending modulus can be up to 1.65GPa, and the notch impact strength can be up to 19.3kJ/m2The heat distortion temperature exceeds 280 ℃. Although the comparative example 1 is superior in electrical conductivity, the heat distortion temperature is low; comparative example 2, which is an insulator with high surface resistance, was not added with a conductive agent; although comparative example 3 has high mechanical properties and high heat distortion temperature, it has no conductivity. Therefore, the high-strength high-temperature-resistant conductive nylon composite material has high strength, high temperature resistance and high conductivity, and can be widely applied to electronic communication equipment parts.
Claims (10)
1. The high-strength high-temperature-resistant conductive nylon composite material is characterized by comprising the following components: nylon resin, a reinforcing material, a conductive agent, a coupling agent, an antioxidant, a dispersing agent and a lubricating agent.
2. The high-strength high-temperature-resistant conductive nylon composite material as claimed in claim 1, wherein the weight parts of the components are as follows: 100 parts of nylon resin, 30-60 parts of reinforcing material, 1-15 parts of conductive agent, 0.2-0.5 part of coupling agent, 0.1-0.7 part of antioxidant, 0.2-0.8 part of dispersant and 0.2-0.7 part of lubricant.
3. The high-strength high-temperature-resistant conductive nylon composite material as claimed in claim 1 or 2, wherein: the conductive agent is one or more of graphene, metal powder, metal oxide whiskers or conductive polymers; the particle size of the graphene is 20-100 nm; the metal powder is one or more of copper powder, silver powder or aluminum powder; the particle size of the metal powder is 10-50 mu m; the metal oxide whisker is a zinc oxide whisker and/or a zirconium oxide whisker; the root length of the metal oxide whisker is 10-100 mu m, and the diameter of the metal oxide whisker is 0.1-3.0 mu m; the conductive polymer is one or more of polyaniline, polyacetylene or polypyrrole; the mass ratio of the graphene to the metal powder, the metal oxide whisker and the conductive polymer is 0-1: 0-5: 0-4: 3-8, and the mass ratio of the graphene to the metal powder, the metal oxide whisker and the conductive polymer is not 0 at the same time.
4. The high-strength high-temperature-resistant conductive nylon composite material as claimed in claim 3, wherein: in the conductive agent, the mass ratio of the graphene to the conductive polymer is 1: 3-8; the mass ratio of the metal powder to the conductive polymer is 3: 3-8; the mass ratio of the metal oxide whiskers to the conductive polymer is 2: 3-8; the mass ratio of the graphene to the metal powder to the conductive polymer is 1: 2-5: 3-6; the mass ratio of the graphene to the metal oxide whisker to the conductive polymer is 1: 2-4: 3-6.
5. The high-strength high-temperature-resistant conductive nylon composite material as claimed in any one of claims 1 to 4, wherein: the viscosity of the nylon resin is 2.0-2.5; the nylon resin is one or more of PA4T, PA6T, PA9T, PA10, PA12T or PA 46;
the reinforced material is one or more of glass fiber, carbon fiber or basalt fiber;
the coupling agent is a silane compound; the silane compound is one or more of KH550, KH560 or KH 570;
the antioxidant is a high-temperature resistant hindered phenol antioxidant and/or a phosphate antioxidant; the mass ratio of the high-temperature-resistant hindered phenol antioxidant to the phosphate antioxidant is 3: 1-2; the high-temperature resistant hindered phenol antioxidant is one or more of H10, SC02X or H330; the phosphate antioxidant is 626 and/or S9228;
the dispersing agent is an aliphatic amide compound; the aliphatic amide compound is one or more of erucamide, ethylene bisoleamide, ethylene bisstearamide or polymethacrylate glycidyl ester-methyl methacrylate-butyl acrylate terpolymer;
the lubricant is pentaerythritol ester and/or polysiloxane.
6. A preparation method of the high-strength high-temperature-resistant conductive nylon composite material as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
(1) heating the conductive agent, adding the coupling agent, and stirring to obtain a coupled conductive agent;
(2) mixing and stirring the coupled conductive agent obtained in the step (1) with an antioxidant, a dispersant and a lubricant to obtain a conductive mixture;
when the conductive agent contains a conductive polymer, adding the conductive polymer in the step (2);
(3) stirring and mixing the conductive mixture obtained in the step (2) with a part of nylon resin, heating and banburying, and slicing to obtain conductive master batches;
(4) and (4) preheating the double screws, adding the conductive master batch obtained in the step (3), the reinforcing material and the rest of the nylon resin, blending, extruding and granulating to obtain the high-strength high-temperature-resistant conductive nylon composite material.
7. The preparation method of the high-strength high-temperature-resistant conductive nylon composite material according to claim 6, characterized in that: in the step (1), the heating temperature is 60-90 ℃; the stirring speed is 100-300 rpm, and the time is 3-10 min.
8. The preparation method of the high-strength high-temperature-resistant conductive nylon composite material according to claim 6 or 7, characterized in that: in the step (2), the mixing and stirring speed is 150-300 rpm, and the time is 3-8 min.
9. The preparation method of the high-strength high-temperature-resistant conductive nylon composite material according to any one of claims 6 to 8, characterized in that: in the step (3), the using amount of the nylon resin is 10-30% of the total mass of the nylon resin; the stirring and mixing speed is 150-250 rpm, and the time is 2-6 min; the heating and banburying temperature is 280-340 ℃, and the time is 30-60 min.
10. The preparation method of the high-strength high-temperature-resistant conductive nylon composite material according to any one of claims 6 to 9, characterized by comprising the following steps: in the step (4), the temperature of the blending extrusion is 250-330 ℃, the vacuum degree is-0.6-0.9 MPa, and the rotating speed of a screw is 450-600 rpm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112223577A (en) * | 2020-09-24 | 2021-01-15 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | Mixing method for anti-static plastic granulation for injection molding |
| CN112898767A (en) * | 2021-01-25 | 2021-06-04 | 江阴市宏丰塑业有限公司 | High-temperature-resistant antistatic modified polyamide and preparation method thereof |
| CN113308104A (en) * | 2021-06-01 | 2021-08-27 | 江苏天奈科技股份有限公司 | High-conductivity plastic master batch, preparation method thereof and conductive plastic particles |
| CN113755007A (en) * | 2021-09-03 | 2021-12-07 | 惠州市良化新材料有限公司 | Nylon 6 composite material with electromagnetic shielding effect |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407632A (en) * | 2008-11-14 | 2009-04-15 | 佛山市顺德区高怡新塑料有限公司 | Conductive and antistatic nylon |
| CN101870812A (en) * | 2009-04-24 | 2010-10-27 | 上海金发科技发展有限公司 | Conductive nylon 66 material and preparation method thereof |
| CN101955653A (en) * | 2010-10-29 | 2011-01-26 | 南京鸿瑞塑料制品有限公司 | Enhanced conductive nylon material and preparation method thereof |
| CN102731994A (en) * | 2012-07-03 | 2012-10-17 | 金发科技股份有限公司 | Nylon composite, preparation method, application thereof and plastic product of nylon composite |
| CN102863787A (en) * | 2012-09-14 | 2013-01-09 | 毛澄宇 | Conductive-antistatic composite material and preparation method thereof |
| CN103740102A (en) * | 2013-12-27 | 2014-04-23 | 安徽科聚新材料有限公司 | Conductive nylon composite material and preparation method thereof |
| CN105131588A (en) * | 2015-08-28 | 2015-12-09 | 古道尔工程塑胶（深圳）有限公司 | Low-warpage high-heat-resistance conductive inflaming-retarding composite material and preparing method thereof |
| CN105219077A (en) * | 2015-11-14 | 2016-01-06 | 华文蔚 | A kind of enhancing conductive nylon material and preparation method thereof |
| CN106867243A (en) * | 2015-12-11 | 2017-06-20 | 上海杰事杰新材料(集团)股份有限公司 | A kind of antistatic high temperature resistant nylon composite material of high heat conduction and preparation method thereof |
| CN107189428A (en) * | 2017-07-12 | 2017-09-22 | 长沙五犇新材料科技有限公司 | Graphene/carbon fiber reinforced nylon composite abrasion resistance material and preparation method and application |
| CN110358294A (en) * | 2019-08-21 | 2019-10-22 | 长沙五犇新材料科技有限公司 | A kind of high intensity Heat conduction nylon composite material and its preparation method and application |
-
2020
- 2020-05-21 CN CN202010434931.8A patent/CN111518388B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407632A (en) * | 2008-11-14 | 2009-04-15 | 佛山市顺德区高怡新塑料有限公司 | Conductive and antistatic nylon |
| CN101870812A (en) * | 2009-04-24 | 2010-10-27 | 上海金发科技发展有限公司 | Conductive nylon 66 material and preparation method thereof |
| CN101955653A (en) * | 2010-10-29 | 2011-01-26 | 南京鸿瑞塑料制品有限公司 | Enhanced conductive nylon material and preparation method thereof |
| CN102731994A (en) * | 2012-07-03 | 2012-10-17 | 金发科技股份有限公司 | Nylon composite, preparation method, application thereof and plastic product of nylon composite |
| CN102863787A (en) * | 2012-09-14 | 2013-01-09 | 毛澄宇 | Conductive-antistatic composite material and preparation method thereof |
| CN103740102A (en) * | 2013-12-27 | 2014-04-23 | 安徽科聚新材料有限公司 | Conductive nylon composite material and preparation method thereof |
| CN105131588A (en) * | 2015-08-28 | 2015-12-09 | 古道尔工程塑胶（深圳）有限公司 | Low-warpage high-heat-resistance conductive inflaming-retarding composite material and preparing method thereof |
| CN105219077A (en) * | 2015-11-14 | 2016-01-06 | 华文蔚 | A kind of enhancing conductive nylon material and preparation method thereof |
| CN106867243A (en) * | 2015-12-11 | 2017-06-20 | 上海杰事杰新材料(集团)股份有限公司 | A kind of antistatic high temperature resistant nylon composite material of high heat conduction and preparation method thereof |
| CN107189428A (en) * | 2017-07-12 | 2017-09-22 | 长沙五犇新材料科技有限公司 | Graphene/carbon fiber reinforced nylon composite abrasion resistance material and preparation method and application |
| CN110358294A (en) * | 2019-08-21 | 2019-10-22 | 长沙五犇新材料科技有限公司 | A kind of high intensity Heat conduction nylon composite material and its preparation method and application |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112223577A (en) * | 2020-09-24 | 2021-01-15 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | Mixing method for anti-static plastic granulation for injection molding |
| CN112898767A (en) * | 2021-01-25 | 2021-06-04 | 江阴市宏丰塑业有限公司 | High-temperature-resistant antistatic modified polyamide and preparation method thereof |
| CN113308104A (en) * | 2021-06-01 | 2021-08-27 | 江苏天奈科技股份有限公司 | High-conductivity plastic master batch, preparation method thereof and conductive plastic particles |
| CN113755007A (en) * | 2021-09-03 | 2021-12-07 | 惠州市良化新材料有限公司 | Nylon 6 composite material with electromagnetic shielding effect |
| CN113755007B (en) * | 2021-09-03 | 2023-12-19 | 惠州市良化新材料有限公司 | Nylon 6 composite material with electromagnetic shielding effect |
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