CN111040433A - Low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material and preparation method thereof - Google Patents
Low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/08—Metals
- C08K2003/0806—Silver
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/02—Flame or fire retardant/resistant
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
The invention discloses a low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material and a preparation method thereof, belonging to the technical field of modification of high polymer materials. The low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material comprises the following components in parts by weight: PA 6: 500-640 parts, aromatic polyamide: 60-200 parts of flame retardant: 60-150 parts of graphite: 100-200 parts of nano conductive particles: 20-50 parts of coupling agent: 1-3 parts of a crystallization promoter: 5-10 parts of assistant and 5-20 parts of assistant. According to the invention, the nanometer conductive particles and graphite are adopted for filling, so that the conductivity and the wear resistance of the PA6 material are improved, and meanwhile, the hygroscopicity of the PA6 material is reduced by adding the aromatic polyamide and the crystallization promoter, so that higher performance retention rate and dimensional stability are obtained, and the PA6 material is particularly suitable for being applied to the field of load transportation with flame retardant and antistatic requirements.
Description
Technical Field
The invention relates to the field of modification of high polymer materials, and particularly relates to a low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material and a preparation method thereof.
Background
PA6, also known as nylon 6, is a translucent or opaque milky white crystalline polymer with excellent mechanical properties, chemical resistance and processability. The PA6 has the defects that the PA6 is easy to absorb water, the tensile strength and the bending strength of the PA6 are greatly reduced after the water is absorbed, and the performance is poor, so that the PA6 cannot be applied to a high-humidity environment; on the other hand, the water absorption of PA6 causes the product size to be difficult to control, the product is easy to warp and deform, and the requirement of high processing precision cannot be met.
In addition, PA6 has no conductivity, and under the action of long-term friction, the surface of the material is easy to generate static accumulation, so that the material cannot be used in an anti-static situation, and the material needs to be subjected to conductive modification. However, after the PA6 material is subjected to conductive modification, the wear resistance is reduced, and the abrasion is severe under the condition of load friction. Moreover, with the improvement of safety consciousness of people, the requirement on the flame retardant property of the material is further strengthened, and the flame retardant property of the PA6 material cannot meet the requirement of the flame retardant standard.
Therefore, how to provide a low moisture absorption, wear resistance, flame retardant, and conductive PA6 composite material is a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention aims to provide a low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material and a preparation method thereof, wherein the moisture absorption condition of the material is improved by introducing aromatic polyamide and a crystallization promoter; the wear resistance of the material is improved by introducing graphite with a special structure; the conductive requirement can be met by introducing the nano conductive particles to realize small amount of filling, and the physical properties of the material are not influenced; the mechanical property of the material is improved by introducing a coupling agent; by introducing the microencapsulated red phosphorus particles, a good flame retardant effect is achieved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material comprises the following components in parts by weight: PA 6: 500-640 parts, aromatic polyamide: 60-200 parts of flame retardant: 60-150 parts of graphite: 100-200 parts of nano conductive particles: 20-50 parts of coupling agent: 1-3 parts of a crystallization promoter: 5-10 parts of an auxiliary agent: 5-20 parts.
Further, the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material comprises the following components in parts by weight: PA 6: 520-600 parts of aromatic polyamide: 80-160 parts of flame retardant: 70-120 parts of graphite: 120-180 parts of nano conductive particles: 20-35 parts of a coupling agent: 1.5-3 parts of crystallization accelerator: 5-8 parts of an auxiliary agent: 5-15 parts.
Further, the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material comprises the following components in parts by weight:
PA 6: 520 parts, aromatic polyamide: 150 parts, flame retardant: 80 parts, graphite: 160 parts, nano conductive particles: 30 parts, coupling agent: 2.5 parts, crystallization promoter: 6 parts of an auxiliary agent: 12 parts.
By adopting the technical scheme, the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material is low in moisture absorption and friction coefficient, good in conductive performance, flame-retardant, stable in size and good in mechanical property.
Further, the viscosity of the PA6 is between 2.2 and 2.6.
By adopting the technical scheme, if the viscosity is less than 2.2, the obtained low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material is too brittle, and if the viscosity is more than 2.6, the preparation process is not favorable for filler dispersion; the viscosity of the PA6 is 2.2-2.6, so that the filler can be fully dispersed, and the obtained low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material has certain toughness.
Further, the aromatic polyamide is polyhexamethylene isophthalamide or a copolymer thereof.
By adopting the technical scheme, the aromatic polyamide and the PA6 are utilized to form the alloy, and the low hygroscopicity of the aromatic polyamide is utilized to improve the barrier property of the PA6 to water.
Further, the flame retardant is a resin-coated microencapsulated red phosphorus flame retardant.
By adopting the technical scheme, the smaller the grain diameter of the red phosphorus flame retardant is, the better the flame retardant effect is, but the red phosphorus flame retardant is easy to decompose by overheating, and the microencapsulated red phosphorus flame retardant coated by the resin can have the self-pyrolysis defect while the flame retardant effect is ensured.
Further, the graphite is high-purity graphite powder with a lamellar structure, and the particle size of the graphite powder is between 800 and 2000 meshes.
By adopting the technical scheme, the graphite has good self-lubricating property, the graphite effect of the flake structure is better, and meanwhile, the proper particle size has an auxiliary effect on the performance of the conductive network.
Further, the nano conductive particles are one or a mixture of carbon nano tubes, nano carbon black and nano metal.
By adopting the technical scheme, a plurality of conductive fillers with different structural characteristics (fibrous fillers with length-diameter ratio and granular fillers are matched to construct a conductive network) are utilized, and a better conductive effect can be realized by a small amount of filling.
Further, the coupling agent is one or a mixture of silane coupling agent, titanate coupling agent and bimetallic coupling agent.
By adopting the technical scheme, the coupling agent can improve the interaction force between the surface of the filler and the matrix resin, and form a chemical bond or a hydrogen bond, thereby improving the mechanical property of the material.
Further, the crystallization promoter is one or more of inorganic mineral nucleating agent (10000-20000 mesh) or organic metal salt nucleating agent; the auxiliary agent is an antioxidant and a lubricating dispersant.
By adopting the technical scheme, the crystallization nucleating agent (namely the crystallization promoter) can improve the crystallinity of PA, and the crystalline structure can effectively prevent moisture from entering, improve the moisture absorption performance of the material and simultaneously improve the dimensional stability of the material; the antioxidant plays a role in preventing the degradation of the material in the processing process, and the lubricating dispersant can improve the dispersion condition of the filler in the resin, improve the appearance of a finished piece and improve the mechanical property of the material.
The invention further provides a preparation method of the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material, which comprises the following steps:
s1, uniformly mixing PA6, aromatic polyamide, graphite, nano conductive particles, a coupling agent, a crystallization promoter and an auxiliary agent to obtain a mixture;
s2, adding the mixture from the main material port, adding the flame retardant from the side feed, and extruding and granulating through an extruder under the conditions that the rotating speed is 200-240 rpm and the temperature of each section is 200-240 ℃, so as to obtain the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material.
Further, in step S1, the temperature of mixing is 70-90 ℃, preferably 80 ℃.
Further, in step S1, the mixing speed is 300-800 rpm.
Further, in step S2, the rotation speed of the mixing is 220 rpm.
Further, the temperature of each section of the extruder comprises a first zone temperature of 200-220 ℃, a second zone temperature of 200-220 ℃, a third zone temperature of 220-240 ℃, a fourth zone temperature of 220-240 ℃, a fifth zone temperature of X220-X240 ℃, a sixth zone temperature of 200-220 ℃, a seventh zone temperature of 200-220 ℃, an eighth zone temperature of 200-220 ℃, a ninth zone temperature of 200-220 ℃ and a head temperature of 230-240 ℃.
According to the technical scheme, compared with the prior art, the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material and the preparation method thereof have the following technical effects:
(1) according to the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material, the crystallization condition of PA6 is improved by introducing the crystallization promoter, and the moisture absorption characteristic of the composite material is improved by matching with the aromatic polyamide; the good conductivity can be realized by adding a small amount of nano conductive particles, and the mechanical property of the material is not influenced; the graphite with a special structure can improve the wear resistance of the material and provide a synergistic effect on the conductivity of the material.
(2) In addition, the microencapsulated red phosphorus particles coated by the surface resin have better processing stability and dispersion effect, and have higher flame retardant effect than other flame retardants; the addition of the coupling agent improves the interface effect of the resin and the filler, and provides favorable guarantee for realizing various good performances of the composite material.
(3) The preparation method of the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material provided by the invention is simple in process, excellent in physical property, convenient to popularize and apply, and especially suitable for the field of load transportation with flame-retardant and antistatic requirements.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material provided by the embodiment of the invention, the moisture absorption condition of the material is improved by introducing the aromatic polyamide and the crystallization promoter; the wear resistance of the material is improved by introducing graphite with a special structure; the conductive requirement can be met by introducing the nano conductive particles to realize small amount of filling, and the physical properties of the material are not influenced; the mechanical property of the material is improved by introducing a coupling agent; by introducing the microencapsulated red phosphorus particles, a good flame retardant effect is achieved. On the other hand, the preparation method of the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material provided by the embodiment of the invention firstly adds PA6, aromatic polyamide, graphite, nano conductive particles, a coupling agent, a crystallization promoter and an auxiliary agent into a high-speed mixer in proportion to be mixed uniformly, and adds a flame retardant from a side feed, so that the high-efficiency flame-retardant conductive low-moisture-absorption wear-resistant PA6 composite material is particularly suitable for the field of load transportation with flame retardance and antistatic requirements.
It is to be noted that the raw materials used in the examples: the viscosity of PA6 is 2.5, the aromatic polyamide is PA6I/X, the used nano conductive particles are one or a mixture of more of Carbon Nano Tubes (CNT) and nano metal silver, the used graphite is CDP-4, the used coupling agent is KH792, the used crystallization promoter is one or a mixture of more of P22 (Malgemann) and 10000-mesh talcum powder, the assistant is a mixture of an antioxidant and a lubricating dispersant, the antioxidant is one or a mixture of more of 1010, 1098, 168, PEPQ and 9228, and the lubricating dispersant is one or a mixture of more of silicone powder, ethylene bis-oleamide lubricant EBO or ethylene bis-stearamide EBS.
Example 1
The embodiment provides a low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material, which comprises the following components in parts by weight: 2.5 viscosity PA 6: 530 parts, PA 6I/X: 150 parts, microencapsulated red phosphorus: 80 parts, CDP-4: 160 parts, CNT: 30 parts, KH 792: 3 parts, P22: 6 parts of an auxiliary agent: 10 parts of auxiliary agent, wherein the auxiliary agent comprises 2 parts of antioxidant 1098, 3 parts of antioxidant 9228 and 5 parts of ethylene bis-oleamide lubricant EBO.
The preparation method of the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material comprises the following steps: firstly, adding PA6, PA6I/X, CDP-4, CNT, KH792, P22 and an auxiliary agent into a high-speed mixer according to the proportion, uniformly mixing at 80 ℃, then extruding and granulating the uniformly mixed materials through a double-screw extruder, adding microencapsulated red phosphorus from a side feed, and setting the temperature of each section of the extruder to be: 200 ℃, 210 ℃, 220 ℃, 240 ℃, 230 ℃, 240 ℃, the screw speed is set as 220 rpm.
Example 2
The embodiment provides a low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material, which comprises the following components in parts by weight: 2.5 viscosity PA 6: 580 parts, PA 6I/X: 100 parts of microencapsulated red phosphorus: 90 parts, CDP-4: 170 parts, CNT: 25 parts, KH 792: 2.5 parts, P22: 5 parts of an auxiliary agent: 12 parts of an auxiliary agent, wherein the auxiliary agent comprises 3 parts of an antioxidant 1010, 3 parts of an antioxidant 168 and 6 parts of ethylene bis stearamide EBS.
The preparation method of the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material comprises the following steps: firstly, adding PA6, PA6I/X, CDP-4, CNT, KH792, P22 and an auxiliary agent into a high-speed mixer according to the proportion, uniformly mixing at 80 ℃, then extruding and granulating the uniformly mixed materials through a double-screw extruder, adding microencapsulated red phosphorus from a side feed, and setting the temperature of each section of the extruder to be: 200 ℃, 210 ℃, 220 ℃, 240 ℃, 230 ℃, 240 ℃, the screw speed is set as 220 rpm.
Example 3
The embodiment provides a low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material, which comprises the following components in parts by weight: 2.5 viscosity PA 6: 530 parts, PA 6I/X: 150 parts, microencapsulated red phosphorus: 85 parts, CDP-4: 150 parts, CNT: 20 parts, 10 parts of nano metal silver, KH 792: 2 parts, P22: 5 parts of an auxiliary agent: 11 parts of auxiliary agent, wherein the auxiliary agent comprises 2 parts of antioxidant 1098, 3 parts of antioxidant PEPQ and 6 parts of silicone powder.
The preparation method of the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material comprises the following steps: PA6, PA6I/X, CDP-4, CNT, nano metallic silver, KH792, P22 and an auxiliary agent are added into a high-speed mixer according to the proportion and are uniformly mixed at the temperature of 80 ℃, then the uniformly mixed materials are extruded and granulated by a double-screw extruder, microencapsulated red phosphorus is added from a side feed, and the set temperature of each section of the extruder is as follows: 200 ℃, 210 ℃, 220 ℃, 240 ℃, 230 ℃, 240 ℃, the screw speed is set as 220 rpm.
Example 4
The embodiment provides a low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material, which comprises the following components in parts by weight: 2.5 viscosity PA 6: 520 parts, PA 6I/X: 160 parts, microencapsulated red phosphorus: 80 parts, CDP-4: 140 parts, CNT: 25 parts, 10 parts of nano metal silver, KH 792: 3 parts, P22: 5 parts, 10000 meshes of talcum powder: 3 parts of auxiliary agent: 15 parts of an auxiliary agent, wherein the auxiliary agent comprises 3 parts of an antioxidant 1010, 5 parts of an antioxidant 168 and 7 parts of an ethylene bis-oleamide lubricant EBO.
The preparation method of the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material comprises the following steps: firstly, adding PA6, PA6I/X, CDP-4, CNT, nano metallic silver, KH792, P22, 10000 meshes of talcum powder and an auxiliary agent into a high-speed mixer according to the proportion, uniformly mixing at 80 ℃, then extruding and granulating the uniformly mixed materials through a double-screw extruder, adding microencapsulated red phosphorus from a side feed, and setting the temperature of each section of the extruder to be: 200 ℃, 210 ℃, 220 ℃, 240 ℃, 230 ℃, 240 ℃, the screw speed is set as 220 rpm.
Example 5
The embodiment provides a low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material, which comprises the following components in parts by weight: 2.2 viscosity PA 6: 500 parts, PA 6I/X: 60 parts, microencapsulated red phosphorus: 60 parts, CDP-4: 100 parts, CNT: 20 parts, KH 792: 1 part, P22: 6 parts of an auxiliary agent: 5 parts of an auxiliary agent, wherein the auxiliary agent comprises 1 part of an antioxidant 1098, 2 parts of an antioxidant 9228 and 2 parts of an ethylene bis-oleamide lubricant EBO.
The preparation method of the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material comprises the following steps: firstly, adding PA6, PA6I/X, CDP-4, CNT, KH792, P22 and an auxiliary agent into a high-speed mixer according to the proportion, uniformly mixing at 90 ℃, then extruding and granulating the uniformly mixed materials through a double-screw extruder, adding microencapsulated red phosphorus from a side feed, and setting the temperature of each section of the extruder to be: 200 ℃, 210 ℃, 220 ℃, 240 ℃, 230 ℃, 240 ℃, the screw speed is set as 240 rpm.
Example 6
The embodiment provides a low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material, which comprises the following components in parts by weight: 2.6 viscosity PA 6: 640 parts, PA 6I/X: 200 parts of microencapsulated red phosphorus: 150 parts, CDP-4: 200 parts, CNT: 50 parts, KH 792: 3 parts, P22: 10 parts of an auxiliary agent: 20 parts of an auxiliary agent, wherein the auxiliary agent comprises 4 parts of antioxidant 1010, 6 parts of antioxidant 168 and 10 parts of silicone powder.
The preparation method of the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material comprises the following steps: firstly, adding PA6, PA6I/X, CDP-4, CNT, KH792, P22 and an auxiliary agent into a high-speed mixer according to the proportion, uniformly mixing at 70 ℃, then extruding and granulating the uniformly mixed materials through a double-screw extruder, adding microencapsulated red phosphorus from a side feed, and setting the temperature of each section of the extruder to be: 200 ℃, 210 ℃, 220 ℃, 240 ℃, 230 ℃, 240 ℃, the screw speed is set to 200 rpm.
Comparative example 1
The comparative example provides a PA6 composite material, which comprises the following components in parts by weight: 2.5 viscosity PA 6: 530 parts, PA 6I/X: 150 parts, common red phosphorus master batch: 80 parts, CDP-4: 160 parts, CNT: 30 parts, KH 792: 3 parts, P22: 6 parts of an auxiliary agent: 10 parts of auxiliary agent, wherein the auxiliary agent comprises 2 parts of antioxidant 1098, 3 parts of antioxidant 9228 and 5 parts of ethylene bis-oleamide lubricant EBO.
The preparation method of the PA6 composite material comprises the following steps: firstly, adding PA6, PA6I/X, CDP-4, CNT, KH792, P22 and an auxiliary agent into a high-speed mixer according to the proportion, uniformly mixing at 80 ℃, then extruding and granulating the uniformly mixed materials through a double-screw extruder, adding common red phosphorus master batches from a side feed, and setting the temperature of each section of the extruder to be: 200 ℃, 210 ℃, 220 ℃, 240 ℃, 230 ℃, 240 ℃, the screw speed is set as 220 rpm.
Comparative example 2
The comparative example provides a PA6 composite material, which comprises the following components in parts by weight: 2.5 viscosity PA 6: 530 parts, PA 6I/X: 150 parts, microencapsulated red phosphorus: 80 parts of 1250-mesh common graphite powder: 160 parts, CNT: 30 parts, KH 792: 3 parts, P22: 6 parts of an auxiliary agent: 10 parts of auxiliary agent, wherein the auxiliary agent comprises 2 parts of antioxidant 1098, 3 parts of antioxidant 9228 and 5 parts of ethylene bis-oleamide lubricant EBO.
The preparation method of the PA6 composite material comprises the following steps: PA6, PA6I/X, 1250-mesh common graphite powder, CNT, KH792, P22 and an auxiliary agent are added into a high-speed mixer according to the proportion and are uniformly mixed at 80 ℃, then the uniformly mixed material is extruded and granulated by a double-screw extruder, microencapsulated red phosphorus is added from a side feed, and the set temperature of each section of the extruder is as follows: 200 ℃, 210 ℃, 220 ℃, 240 ℃, 230 ℃, 240 ℃, the screw speed is set as 220 rpm.
Comparative example 3
The comparative example provides a PA6 composite material, which comprises the following components in parts by weight: 2.5 viscosity PA 6: 530 parts, PA 6I/X: 150 parts, microencapsulated red phosphorus: 80 parts of CDP-4: 160 parts, conductive carbon black XC72 (cabot): 30 parts, KH 792: 3 parts, P22: 6 parts of an auxiliary agent: 10 parts of auxiliary agent, wherein the auxiliary agent comprises 2 parts of antioxidant 1098, 3 parts of antioxidant 9228 and 5 parts of ethylene bis-oleamide lubricant EBO.
The preparation method of the PA6 composite material comprises the following steps: PA6, PA6I/X, CDP-4, conductive carbon black XC72 (Kabot), KH792, P22 and an auxiliary agent are added into a high-speed mixer according to the proportion and are uniformly mixed at 80 ℃, then the uniformly mixed materials are extruded and granulated by a double-screw extruder, microencapsulated red phosphorus is added from a side feed, and the set temperature of each section of the extruder temperature is as follows: 200 ℃, 210 ℃, 220 ℃, 240 ℃, 230 ℃, 240 ℃, the screw speed is set as 220 rpm.
Comparative example 4
The comparative example provides a PA6 composite material, which comprises the following components in parts by weight: 2.5 viscosity PA 6: 530 parts, PA 6I/X: 150 parts, microencapsulated red phosphorus: 80 parts of CDP-4: 160 parts, CNT: 30 parts, KH 792: 3 parts of auxiliary agent: 10 parts of auxiliary agent, wherein the auxiliary agent comprises 2 parts of antioxidant 1098, 3 parts of antioxidant 9228 and 5 parts of ethylene bis-oleamide lubricant EBO.
The preparation method of the PA6 composite material comprises the following steps: firstly, adding PA6, PA6I/X, CDP-4, CNT, KH792 and an auxiliary agent into a high-speed mixer according to the proportion, uniformly mixing at 80 ℃, then extruding and granulating the uniformly mixed materials through a double-screw extruder, adding microencapsulated red phosphorus from a side feed, and setting the temperature of each section of the extruder to be: 200 ℃, 210 ℃, 220 ℃, 240 ℃, 230 ℃, 240 ℃, the screw speed is set as 220 rpm.
Comparative example 5
The comparative example provides a PA6 composite material, which comprises the following components in parts by weight: 2.5 viscosity PA 6: 530 parts of microencapsulated red phosphorus: 80 parts of CDP-4: 160 parts, CNT: 30 parts, KH 792: 3 parts of auxiliary agent: 10 parts of auxiliary agent, wherein the auxiliary agent comprises 2 parts of antioxidant 1098, 3 parts of antioxidant 9228 and 5 parts of ethylene bis-oleamide lubricant EBO.
The preparation method of the PA6 composite material comprises the following steps: the PA6, the CDP-4, the CNT, the KH792 and the auxiliary agent are added into a high-speed mixer according to the proportion and are uniformly mixed at the temperature of 80 ℃, then the uniformly mixed materials are extruded and granulated by a double-screw extruder, the microencapsulated red phosphorus is added from a side feed, and the set temperature of each section of the extruder temperature is as follows: 200 ℃, 210 ℃, 220 ℃, 240 ℃, 230 ℃, 240 ℃, the screw speed is set as 220 rpm.
Comparative example 6
The comparative example provides a PA6 composite material, which comprises the following components in parts by weight: 2.5 viscosity PA 6: 530 parts, PA 6I/X: 150 parts, microencapsulated red phosphorus: 80 parts, CDP-4: 160 parts, CNT: 30 parts, P22: 6 parts of an auxiliary agent: 10 parts of auxiliary agent, wherein the auxiliary agent comprises 2 parts of antioxidant 1098, 3 parts of antioxidant 9228 and 5 parts of ethylene bis-oleamide lubricant EBO.
The preparation method of the PA6 composite material comprises the following steps: firstly, adding PA6, PA6I/X, CDP-4, CNT, P22 and an auxiliary agent into a high-speed mixer according to the proportion, uniformly mixing at 80 ℃, then extruding and granulating the uniformly mixed materials through a double-screw extruder, adding microencapsulated red phosphorus from a side feed, and setting the temperature of each section of the extruder to be: 200 ℃, 210 ℃, 220 ℃, 240 ℃, 230 ℃, 240 ℃, the screw speed is set as 220 rpm.
Comparative example 7
The comparative example provides a PA6 composite material, which comprises the following components in parts by weight: 2.5 viscosity PA 6: 700 parts, PA 6I/X: 150 parts, microencapsulated red phosphorus: 80 parts of CDP-4: 160 parts, CNT: 30 parts, KH 792: 3 parts, P22: 6 parts of an auxiliary agent: 10 parts of auxiliary agent, wherein the auxiliary agent comprises 2 parts of antioxidant 1098, 3 parts of antioxidant 9228 and 5 parts of ethylene bis-oleamide lubricant EBO.
The preparation method of the PA6 composite material comprises the following steps: firstly, adding PA6, PA6I/X, CDP-4, CNT, KH792, P22 and an auxiliary agent into a high-speed mixer according to the proportion, uniformly mixing at 80 ℃, then extruding and granulating the uniformly mixed materials through a double-screw extruder, adding microencapsulated red phosphorus from a side feed, and setting the temperature of each section of the extruder to be: 200 ℃, 210 ℃, 220 ℃, 240 ℃, 230 ℃, 240 ℃, the screw speed is set as 220 rpm.
Comparative example 8
The comparative example provides a PA6 composite material, which comprises the following components in parts by weight: 2.5 viscosity PA 6: 530 parts, PA 6I/X: 150 parts, microencapsulated red phosphorus: 80 parts, CDP-4: 160 parts, CNT: 30 parts, KH 792: 3 parts, P22: 6 parts of an auxiliary agent: 10 parts of auxiliary agent, wherein the auxiliary agent comprises 2 parts of antioxidant 1098, 3 parts of antioxidant 9228 and 5 parts of ethylene bis-oleamide lubricant EBO.
The preparation method of the PA6 composite material comprises the following steps: firstly, adding PA6, PA6I/X, CDP-4, CNT, KH792, P22 and an auxiliary agent into a high-speed mixer according to the proportion, uniformly mixing at 80 ℃, then extruding and granulating the uniformly mixed materials through a double-screw extruder, adding microencapsulated red phosphorus from a side feed, and setting the temperature of each section of the extruder to be: 200 ℃, 240 ℃, 260 ℃, 250 ℃, and the screw speed is set to 380 rpm.
To further illustrate the technical effects of the present invention, the PA6 composite materials of examples 1 to 6 and comparative examples 1 to 8 were subjected to performance tests, and the test results are shown in tables 1.1 and 1.2.
The tensile strength test is carried out by adopting a plastic tensile property test method (ISO 527-2), the balance water absorption test is carried out by adopting a plastic water absorption test method (ISO 62), the surface resistance test is carried out by adopting a test method for measuring the insulation resistance of a solid insulating material (IEC 60167), the dynamic friction coefficient test is carried out by adopting a plastic sliding friction wear test method (GB/T3960), and the flame retardance evaluation is carried out by adopting a UL94 combustion rating in a UL standard.
Table 1.1 performance test results for low moisture absorption abrasion resistant flame retardant electrically conductive PA6 composites of examples 1-6
TABLE 1.2 PA6 composite Performance test results for comparative examples 1-8
As is apparent from the data in tables 1.1 and 1.2, it can be seen from the results of the performance tests of comparative examples 1 to 6 and comparative example 1 that the flame retardancy of examples 1 to 6 is superior to that of comparative example 1 because examples 1 to 6 provide a more efficient flame retardant effect than the flame retardant red phosphorus master batch by using the microencapsulated red phosphorus fine powder coated with the resin.
As can be seen from the data in tables 1.1 and 1.2, it can be seen from the results of the performance tests of comparative examples 1 to 6 and comparative example 2 that the coefficient of dynamic friction of examples 1 to 6 is significantly smaller than that of comparative example 2, because examples 1 to 6 use the graphite powder having a high purity and an intact lamellar structure, which provides a more efficient self-lubricating effect than the conventional graphite powder.
As can be seen from the data in tables 1.1 and 1.2, it can be seen from the results of the performance tests of comparative examples 1-6 and comparative example 3 that the surface resistance of examples 1-6 is significantly less than that of comparative example 3, because examples 1-6, using nano-sized conductive particles, can provide better conductive performance at a lower content than conventional size conductive fillers.
As can be seen from the data in tables 1.1 and 1.2, the performance test results of comparative examples 1-6 and comparative example 4 show that the equilibrium water absorption of examples 1-6 is significantly better than that of comparative example 4, because the crystallization promoters are selected for examples 1-6, the crystallinity of PA can be improved, and the crystalline structure can effectively prevent moisture from entering, improve the moisture absorption performance of the material, and simultaneously improve the dimensional stability of the material.
As can be seen from the data in tables 1.1 and 1.2, it can be seen from the results of the performance tests comparing examples 1-6 and comparative example 5 that the tensile strength and the equilibrium water absorption of examples 1-6 are significantly better than that of comparative example 5 because the addition of the aromatic polyamide and the crystallization promoter in examples 1-6 improves the crystalline structure and the barrier property of the material, effectively improves the mechanical properties of the material, and reduces the moisture absorption.
As can be seen from the data in tables 1.1 and 1.2, from the results of the performance tests of comparative examples 1-6 and comparative example 6, it can be seen that the tensile strength of examples 1-6 is significantly higher than that of comparative example 6, because comparative example 6 has no coupling agent added, and the filler and PA6 are not effectively compatible, resulting in a loss of mechanical properties.
As can be seen from the data in tables 1.1 and 1.2, through the performance test results of comparative examples 1-6 and comparative example 7, it can be seen that the performances, especially tensile strength and equilibrium water absorption rate, of examples 1-6 are better than those of comparative example 6, because the amount of PA6 in comparative example 7 is too large, the water absorption resistance of PA6 itself is poor, and the excessive amount of PA6 added affects the balance of the material system, and weakens the optimization effect of the crystallization promoter and the aromatic nylon on the crystallinity and the barrier performance of the material system.
As can be seen from the data in tables 1.1 and 1.2, it is apparent from the results of the performance tests of comparative examples 1-6 and comparative example 8 that the tensile strength, surface resistance and flame retardancy of examples 1-6 are all superior to those of comparative example 8 because excessive processing temperature and rotation speed cause decomposition of the flame retardant and destruction of the microstructure of the nano conductive particles during extrusion, thereby reducing the conductivity, mechanical properties and flame retardancy of the material.
According to the test results, the formula and the preparation method of the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material provided by the embodiment of the invention have the advantages that the PA6 composite material which is conductive, wear-resistant, flame-retardant and low-moisture-absorption can be obtained by adding the aromatic polyamide, the flame retardant, the graphite, the nano conductive particles, the coupling agent and the crystallization promoter for modification, and the mechanical property is kept good.
On the other hand, the preparation method of the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material provided by the embodiment of the invention effectively prevents the decomposition of the flame retardant and the damage of the microstructure of the nano conductive particles through the optimization of the processing technology, thereby ensuring that the material has excellent conductivity, mechanical property and flame retardant property.
It will be apparent to those skilled in the art that many modifications and variations can be made in the present invention without departing from the spirit and scope of the invention. It is therefore contemplated that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material is characterized by comprising the following components in parts by weight: PA 6: 500-640 parts, aromatic polyamide: 60-200 parts of flame retardant: 60-150 parts of graphite: 100-200 parts of nano conductive particles: 20-50 parts of coupling agent: 1-3 parts of a crystallization promoter: 5-10 parts of an auxiliary agent: 5-20 parts.
2. The low moisture absorption abrasion resistant flame retardant conductive PA6 composite material according to claim 1, characterized by comprising the following components in parts by weight: PA 6: 520-600 parts of aromatic polyamide: 80-160 parts of flame retardant: 70-120 parts of graphite: 120-180 parts of nano conductive particles: 20-35 parts of a coupling agent: 1.5-3 parts of crystallization accelerator: 5-8 parts of an auxiliary agent: 5-15 parts.
3. The low moisture absorption abrasion resistant flame retardant electrically conductive PA6 composite material according to claim 1 or 2, wherein the PA6 viscosity is between 2.2-2.6.
4. The low moisture absorption abrasion resistant flame retardant electrically conductive PA6 composite material of claim 1 or 2, wherein the aromatic polyamide is polyhexamethylene isophthalamide or a copolymer thereof.
5. The low moisture absorption abrasion resistant flame retardant electrically conductive PA6 composite material according to claim 1 or 2, wherein the flame retardant is a resin microcapsule coated red phosphorus flame retardant.
6. The low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material as claimed in claim 1 or 2, wherein the graphite is high-purity graphite powder with a lamellar structure, and the particle size of the high-purity graphite powder is between 800 and 2000 meshes.
7. The low moisture absorption abrasion resistant flame retardant conductive PA6 composite material of claim 1 or 2, wherein the nano conductive particles are one or more of carbon nanotubes, nano carbon black, and nano metals.
8. The low moisture absorption abrasion resistant flame retardant conductive PA6 composite material according to claim 1 or 2, wherein the coupling agent is one or more of silane coupling agent, titanate coupling agent and bimetallic coupling agent.
9. The low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material as claimed in claim 1 or 2, wherein the crystallization promoter is one or a mixture of inorganic mineral nucleating agent and organic metal salt nucleating agent; the auxiliary agent comprises an antioxidant and a lubricating dispersant.
10. The preparation method of the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material according to any one of claims 1-9, characterized by comprising the following steps:
s1, uniformly mixing PA6, aromatic polyamide, graphite, nano conductive particles, a coupling agent, a crystallization promoter and an auxiliary agent to obtain a mixture;
s2, adding the mixture from the main material port, adding the flame retardant from the side feed, and extruding and granulating through an extruder under the conditions that the rotating speed is 200-240 rpm and the temperature of each section is 200-240 ℃, so as to obtain the low-moisture-absorption wear-resistant flame-retardant conductive PA6 composite material.
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