CN112646370B - Preparation method of recyclable wear-resistant high-thermal-conductivity nylon 66 composite material - Google Patents
Preparation method of recyclable wear-resistant high-thermal-conductivity nylon 66 composite material Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
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- C09K5/14—Solid materials, e.g. powdery or granular
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- C—CHEMISTRY; METALLURGY
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- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The application relates to the technical field of nylon 66 composite materials, and particularly discloses a preparation method of a recyclable wear-resistant high-thermal-conductivity nylon 66 composite material, wherein S1 comprises the following raw materials in percentage by weight: nylon 66 resin, graphene nanoplatelets, modified nano-silica, a compatilizer, an antioxidant, a silane coupling agent and carbon fibers; s2, mixing graphene, modified nano-silica and a silane coupling agent at the temperature of 60-80 ℃, stirring for 4-8min, cooling to 50-70 ℃, adding nylon 66 resin, an antioxidant and a compatilizer, and continuously stirring for 4-8min to obtain a mixture; and S3, adding carbon fibers into the mixture, mixing, and then melting, extruding, cooling and granulating to obtain the nylon 66 composite material. The nylon 66 composite material obtained by the application has excellent heat conductivity, wear resistance and mechanical properties through the synergistic effect of the raw materials.
Description
Technical Field
The application relates to the technical field of nylon 66 composite materials, in particular to a preparation method of a recyclable wear-resistant high-thermal-conductivity nylon 66 composite material.
Background
Nylon is a polyamide fiber and also an engineering plastic with wide application. Nylon 66 is polyhexamethylene adipamide, which is a polycondensation product of hexamethylene adipamide, has the advantages of high strength, good rigidity, easy processing and chemical resistance, and is widely used in the fields of electronics, communication, aerospace, machinery and the like. However, nylon 66 has a large hygroscopic property and poor dimensional stability due to the hydrophilic amide group. In the related art, in order to improve the performance of nylon 66, the disadvantages of the material itself are generally overcome by a reinforcing method, so that the performance is improved. However, with the development of the fields of electronics, communications and the like, higher requirements are also put forward on the performance of the material, and the common material cannot meet the market demand.
In the related art, in order to improve the strength of the nylon 66, glass fibers are generally added to raw materials, but the inventors believe that the addition of the glass fibers improves the strength of the nylon 66, but the abrasion resistance of the nylon 66 cannot be improved well, and the service life of the nylon 66 is affected.
Disclosure of Invention
In order to improve the wear resistance of the composite material and simultaneously improve the heat conductivity of the composite material, the application provides a preparation method of a recyclable wear-resistant high-heat-conductivity nylon 66 composite material.
The application provides a preparation method of a recyclable wear-resistant high-thermal-conductivity nylon 66 composite material, which adopts the following technical scheme:
a preparation method of a recyclable wear-resistant high-thermal-conductivity nylon 66 composite material comprises the following steps:
s1, weighing the following raw materials in percentage by weight:
30.3-52.2% of nylon 66 resin, 10-20% of graphene microchip, 5-10% of modified nano silicon dioxide, 2-5% of compatilizer, 0.2-0.6% of antioxidant, 0.1-0.5% of silane coupling agent and 30-40% of carbon fiber;
s2, mixing graphene, modified nano-silica and a silane coupling agent at the temperature of 60-80 ℃, stirring for 4-8min, cooling to 50-70 ℃, adding nylon 66 resin, an antioxidant and a compatilizer, and continuously stirring for 4-8min to obtain a mixture;
and S3, adding carbon fibers into the mixture, mixing, and then melting, extruding, cooling and granulating to obtain the nylon 66 composite material.
By adopting the technical scheme, the nylon 66 composite material obtained by the preparation method of the recyclable wear-resistant high-thermal-conductivity nylon 66 composite material has high tensile strength, impact strength and thermal conductivity value, wherein the tensile strength is 188-231MPa, and the impact strength is 16.5-22.4KJ/m2The heat conduction value is 2.53-3.48W/m.k, the wear rate is lower, the wear rate is 1.03-1.31%, and the nylon 66 composite material has good heat conductivity and wear resistance, excellent mechanical properties and the advantage of recoverability through the synergistic effect of the raw materials, can be applied to the fields of automobile accessories, industrial parts and the like, and meets the market demand.
The graphene microchip, the modified nano silicon dioxide and the carbon fiber are added into the raw materials of the nylon 66 composite material, and the synergistic effect of the graphene microchip, the modified nano silicon dioxide and the carbon fiber can effectively increase the heat conduction value of the nylon 66 composite material, improve the tensile strength and the impact strength of the nylon 66 composite material, and obviously reduce the wear rate of the nylon 66 composite material, so that the nylon 66 composite material has excellent heat conductivity, wear resistance and mechanical property. The silane coupling agent and the compatilizer are added into the raw materials, and the synergistic effect between the silane coupling agent and the compatilizer is utilized, so that the interface binding force between the raw materials is effectively improved, the stability of graphene micro-sheets, modified nano-silicon dioxide and carbon fibers in the raw materials is improved, the wear rate of the nylon 66 composite material is reduced, the mechanical property of the nylon 66 composite material is improved, and the service life of the nylon 66 composite material is prolonged.
Meanwhile, under the condition that the temperature is 60-80 ℃, the graphene, the modified nano-silica and the silane coupling agent are mixed, the processing performance of the mixture can be effectively improved, the silane coupling agent can be coated on the surfaces of the graphene and the modified nano-silica and can be mixed more uniformly, carbon fibers are added into the mixture, the mixing of the carbon fibers and the mixture is realized, the influence of the carbon fibers on equipment in the mixing process of the mixture is reduced, and the stability of the nylon 66 composite material is improved.
Optionally, the modified nano-silica is prepared by the following method:
under the protection of inert gas, adding sodium dodecyl sulfate into toluene, stirring for 4-8min, then adding nano silicon dioxide twice, after adding the nano silicon dioxide each time, performing ultrasonic dispersion for 30-40min, then adding a silane coupling agent, continuing to perform ultrasonic dispersion for 10-20min, then heating to 50-60 ℃ under the condition of continuous stirring, performing heat preservation reaction for 8-10h, filtering, washing and drying to obtain modified nano silicon dioxide;
the weight ratio of the silane coupling agent to the nano silicon dioxide is 1 (15-20);
and the silane coupling agent used in the preparation of the modified nano-silica is the same as the silane coupling agent in the raw material of the nylon 66 composite material.
By adopting the technical scheme, the sodium dodecyl sulfate is added into the toluene, then the nano silicon dioxide is added, the dispersibility of the nano silicon dioxide in the toluene can be effectively improved, the agglomeration of the nano silicon dioxide in the toluene is reduced, the nano silicon dioxide is added twice at the same time, the dispersion of the nano silicon dioxide is realized, the silane coupling agent is added, the modification of the silane coupling agent on the nano silicon dioxide is realized, the dispersibility and the bonding force of the nano silicon dioxide and the raw materials can be effectively increased, and meanwhile, the silane coupling agent used in the preparation of the modified nano silicon dioxide is the same as the silane coupling agent in the raw materials of the nylon 66 composite material, so that the dispersion of the modified silicon dioxide is facilitated.
Optionally, the graphene nanoplatelets are pretreated before use, and the pretreatment adopts the following method:
adding graphene nanoplatelets into a nitric acid solution, soaking for 4-6h, filtering and drying;
under the protection of inert gas, adding sodium dodecyl sulfate into toluene, stirring for 4-8min, then adding the graphene nanoplatelets subjected to nitric acid treatment, stirring for 8-10min, then adding a silane coupling agent, continuing stirring, heating to 50-60 ℃, carrying out heat preservation reaction for 5-7h, filtering, washing and drying to obtain pretreated graphene nanoplatelets;
the weight ratio of the silane coupling agent to the graphene nanoplatelets is 1 (55-65);
and the silane coupling agent used for pretreating the graphene microchip is the same as the silane coupling agent in the raw material of the nylon 66 composite material.
By adopting the technical scheme, the graphene is soaked in the nitric acid solution, the graphene is acidified, the active sites on the surface of the graphene are increased, then the graphene nanoplatelets are modified by using the silane coupling agent, the dispersibility and the bonding force of the graphene nanoplatelets and the raw materials can be effectively increased, and meanwhile, the silane coupling agent in the pretreatment of the graphene nanoplatelets is the same as the silane coupling agent in the raw materials of the nylon 66 composite material, so that the dispersion of the graphene nanoplatelets is facilitated.
Optionally, the carbon fibers are chopped carbon fibers, the average length of the carbon fibers is 3-5mm, the average diameter of the carbon fibers is 1-10 μm, the average particle size of the modified nano-silica is 1.3-5 μm, the average particle size of the graphene nanoplatelets is 10-20 μm, and the average thickness of the graphene nanoplatelets is 1-20 nm.
By adopting the technical scheme, the carbon fibers, the modified nano-silica and the graphene nanoplatelets are further limited, so that the carbon fibers, the modified nano-silica and the graphene nanoplatelets are stably dispersed in the raw materials, and the performance of the nylon 66 composite material is further improved.
Optionally, the compatilizer is an ethylene-acrylate-glycidyl methacrylate terpolymer, and the silane coupling agent is gamma-aminopropyltriethoxysilane.
By adopting the technical scheme, the ethylene-acrylate-glycidyl methacrylate terpolymer can increase the binding force between raw materials, the gamma-aminopropyltriethoxysilane can be adsorbed on the surface of the carbon fiber, the dispersibility of the carbon fiber and the raw materials is further increased, and the performance of the nylon 66 composite material is effectively improved through the synergistic effect of the ethylene-acrylate-glycidyl methacrylate terpolymer and the gamma-aminopropyltriethoxysilane.
Optionally, the antioxidant is a compound of a hindered phenol antioxidant and a phosphite antioxidant, and the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 2.
By adopting the technical scheme, the oxidation resistance of the nylon 66 composite material is improved by the synergistic effect of the hindered phenol antioxidant and the phosphite antioxidant.
Optionally, the average viscosity of the nylon 66 resin is 2.4-3.2 dl/g.
By adopting the technical scheme, the viscosity of the nylon 66 resin is limited, and the performance of the nylon 66 resin is further improved.
Optionally, the nylon 66 resin is subjected to drying pretreatment before use, wherein the drying pretreatment temperature is 100-120 ℃, and the drying pretreatment time is 4-6 h.
By adopting the technical scheme, because the amide group in the nylon 66 resin has hydrophilicity, when the nylon 66 resin is stored for a long time, the polyamide resin has larger moisture, and the nylon 66 resin is dried and pretreated, so that the moisture of the nylon 66 resin is reduced, and the influence of the moisture on the nylon 66 composite material is reduced.
Optionally, in step S3, a twin-screw extruder is used to mix the mixture and the carbon fiber, the mixture is fed from a main feeding hopper of the twin-screw extruder, the carbon fiber is fed from a side feeding hopper of the twin-screw extruder, and the processing temperature of the twin-screw extruder is 250-.
By adopting the technical scheme, the carbon fibers are fed from the side feeding hopper of the double-screw extruder, the influence of the carbon fibers on the equipment in the step S2 is reduced, and meanwhile, the processing temperature and the rotating speed are limited, so that the raw materials are convenient to melt and mix.
Optionally, the processing temperature of the twin-screw extruder is divided into ten zones, and the temperatures of the first zone to the ten zones are 250 ℃, 255 ℃, 260 ℃, 270 ℃, 275 ℃, 270 ℃ and 285 ℃.
By adopting the technical scheme, the processing temperature is divided into ten areas, so that the raw materials are convenient to melt and mix.
In summary, the present application has the following beneficial effects:
1. the application of nylon 66 composite adds modified nanometer silica in the raw materials, modifies nanometer silica, can make its more even distribution to nylon 66 resin, increases the interface bonding strength between nanometer silica and the nylon 66 resin, and modified nanometer silica cladding is on nylon 66 resin surface, effectual reduction nylon 66 composite's wearing and tearing volume.
2. The utility model provides a nylon 66 combined material, add the graphite alkene microchip in the raw materials, because the heat conductivity of graphite alkene microchip is far above the heat conductivity of general material, can form effectual heat conduction passageway, and improve nylon 66 combined material's heat conductivility, and because the graphite alkene microchip is the individual layer lamellar structure that the carbon atom constitutes, effort between each lamella is very little, lower coefficient of friction has, its synergistic action with modified nano silica, further reduce the wearing and tearing volume of nylon 66 resin, effectively reduce the loss of material promptly, the extension material service life.
3. According to the nylon 66 composite material, the carbon fibers are added into the raw materials, and have the characteristics of high strength, high modulus and high temperature resistance due to the carbon sheet layer structure, so that the heat conductivity, the wear resistance and the strength of the nylon 66 are greatly improved; and its fibrous network structure connects the graphite alkene microchip, forms the heat conduction network, and the heat that the material produced in the use can scatter rapidly like this, reduces the damage of friction to the material to a certain extent, combines nanometer silica itself to have fine wearability to through the synergistic effect between carbon fiber, graphite alkene microchip, the modified nanometer silica three, make nylon 66 combined material have excellent heat conductivity, wearability and mechanical properties.
Detailed Description
The present application will be described in further detail with reference to examples.
Raw materials
The average viscosity of the nylon 66 resin is 2.4-3.2dl/g, preferably the average viscosity of the nylon 66 resin is 2.8dl/g and is selected from Huafeng group EP-158; the average particle size of the graphene nanoplatelets is 10-20 μm and the average thickness is 1-20nm, preferably the average particle size of the graphene nanoplatelets is 15 μm and the average thickness is 13nm, and the graphene nanoplatelets are selected from KNG-C162 of Xiamen graphene technology Limited company; the compatibilizer is ethylene-acrylate-glycidyl methacrylate terpolymer selected from Achima (ARKEMA) AX 8900; the silane coupling agent is gamma-aminopropyltriethoxysilane and is selected from Japanese Beacon (Shin-Etsu) KBE-903; the carbon fiber is chopped carbon fiber, has an average length of 3-5mm and an average diameter of 1-10 μm, preferably has an average length of 4mm and an average diameter of 6 μm, and is selected from T700-12K of Toray corporation of Japan; the antioxidant is a compound of hindered phenol antioxidant and phosphite antioxidant, the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1:2, the hindered phenol antioxidant is 1010 and is selected from Switzerland Ciba, and the phosphite antioxidant is 168 and is selected from Switzerland Ciba; the nano silicon dioxide is selected from XF103, Nanjing Xiancheng nanometer material science and technology Limited.
Preparation example
Preparation example 1
A modified nano-silica is prepared by the following method:
under the protection of nitrogen, adding 0.3kg of sodium dodecyl sulfate into 50kg of toluene, stirring for 4min, then adding 2kg of nano-silica twice, adding 1kg of nano-silica each time, ultrasonically dispersing for 40min after adding the nano-silica each time, then adding 0.1kg of silane coupling agent which is gamma-aminopropyltriethoxysilane, continuing to ultrasonically disperse for 20min, then heating to 60 ℃ under the condition of continuous stirring, carrying out heat preservation reaction for 8h, filtering, washing and drying to obtain modified silicon dioxide, wherein the average particle size of the modified nano-silica is 3 mu m.
Wherein, the washing is carried out by pure ethanol and is carried out for three times.
Preparation example 2
A modified nano-silica is prepared by the following method:
under the protection of nitrogen, adding 0.3kg of sodium dodecyl sulfate into 50kg of toluene, stirring for 6min, then adding 1.5kg of nano-silica twice, adding 0.75kg of nano-silica each time, ultrasonically dispersing for 35min after adding the nano-silica each time, then adding 0.1kg of silane coupling agent which is gamma-aminopropyl triethoxysilane, continuing to ultrasonically disperse for 15min, then heating to 55 ℃ under the condition of continuous stirring, carrying out heat preservation reaction for 9h, filtering, washing and drying to obtain modified silica, wherein the average particle size of the modified nano-silica is 1.3 mu m.
Wherein, the washing is carried out by pure ethanol and is carried out for three times.
Preparation example 3
A modified nano-silica is prepared by the following method:
under the protection of nitrogen, adding 0.3kg of sodium dodecyl sulfate into 50kg of toluene, stirring for 4min, then adding 1.8kg of nano-silica twice, adding 0.9kg of nano-silica each time, ultrasonically dispersing for 30min after adding the nano-silica each time, then adding 0.1kg of silane coupling agent which is gamma-aminopropyl triethoxysilane, continuing to ultrasonically disperse for 10min, then heating to 50 ℃ under the condition of continuous stirring, carrying out heat preservation reaction for 10h, filtering, washing and drying to obtain modified silica, wherein the average particle size of the modified nano-silica is 5 mu m.
Wherein, the washing is carried out by pure ethanol and is carried out for three times.
Examples
Table 1 example the content (unit: wt%) of each raw material of the nylon 66 composite material
| Raw materials | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Nylon 66 resin | 44.7 | 33.3 | 47.7 | 48.1 | 52.2 | 30.3 |
| Graphene nanoplatelets | 14 | 16 | 12 | 10 | 10 | 20 |
| Modified nano silicon dioxide | 8 | 5 | 6 | 8 | 5 | 10 |
| Compatilizer | 3 | 5 | 4 | 3 | 2 | 4 |
| Antioxidant agent | 0.2 | 0.4 | 0.2 | 0.6 | 0.4 | 0.2 |
| Silane coupling agent | 0.1 | 0.3 | 0.1 | 0.3 | 0.4 | 0.5 |
| Carbon fiber | 30 | 40 | 30 | 30 | 30 | 35 |
| Total up to | 100 | 100 | 100 | 100 | 100 | 100 |
Example 1
The raw material proportion of the recyclable wear-resistant high-thermal-conductivity nylon 66 composite material is shown in table 1.
Wherein, the modified nano silicon dioxide is obtained by adopting preparation example 1.
A preparation method of a recyclable wear-resistant high-thermal-conductivity nylon 66 composite material comprises the following steps:
s1, weighing the following raw materials according to the following table 1:
nylon 66 resin, graphene micro-sheets, modified nano-silica, a compatilizer, an antioxidant, a silane coupling agent and carbon fibers.
S2, mixing the graphene, the modified nano-silica and the silane coupling agent at the temperature of 80 ℃, stirring for 6min, cooling to 70 ℃, adding the nylon 66 resin, the antioxidant and the compatilizer, and continuously stirring for 8min to obtain a mixture.
Wherein the nylon 66 resin is subjected to drying pretreatment before use, the temperature of the drying pretreatment is 120 ℃, and the time is 4 hours.
And S3, putting the mixture into a main feeding hopper of a double-screw extruder, putting carbon fibers into a side feeding hopper of the double-screw extruder, and then melting, extruding, cooling and granulating to obtain the nylon 66 composite material.
Wherein the processing temperature of the double-screw extruder is 250-285 ℃, and the processing temperature is divided into ten zones, and the temperatures of the one zone to the ten zones are 250 ℃, 255 ℃, 260 ℃, 270 ℃, 275 ℃, 270 ℃ and 285 ℃. The rotation speed of the double-screw extruder is 350 r/min.
Examples 2 to 6
The recyclable wear-resistant high-thermal-conductivity nylon 66 composite material is different from the nylon 66 composite material in the raw material ratio shown in the table 1 in the examples 2 to 6.
Example 7
A recyclable wear-resistant high-thermal-conductivity nylon 66 composite material, which is different from the nylon 66 composite material prepared in the example 1 in the preparation method.
A preparation method of a recyclable wear-resistant high-thermal-conductivity nylon 66 composite material comprises the following steps:
s1, weighing the following raw materials according to the following table 1:
nylon 66 resin, graphene micro-sheets, modified nano-silica, a compatilizer, an antioxidant, a silane coupling agent and carbon fibers.
S2, mixing the graphene, the modified nano-silica and the silane coupling agent at the temperature of 70 ℃, stirring for 4min, cooling to 60 ℃, adding the nylon 66 resin, the antioxidant and the compatilizer, and continuously stirring for 4min to obtain a mixture.
Wherein the nylon 66 resin is subjected to drying pretreatment before use, the temperature of the drying pretreatment is 110 ℃, and the time is 5 hours.
And S3, putting the mixture into a main feeding hopper of a double-screw extruder, putting carbon fibers into a side feeding hopper of the double-screw extruder, and then melting, extruding, cooling and granulating to obtain the nylon 66 composite material.
Wherein the processing temperature of the double-screw extruder is 250-285 ℃, and the processing temperature is divided into ten zones, and the temperatures of the one zone to the ten zones are 250 ℃, 255 ℃, 260 ℃, 270 ℃, 275 ℃, 270 ℃ and 285 ℃. The rotation speed of the twin-screw extruder is 400 r/min.
Example 8
A recyclable wear-resistant high-thermal-conductivity nylon 66 composite material, which is different from the nylon 66 composite material prepared in the example 1 in the preparation method.
A preparation method of a recyclable wear-resistant high-thermal-conductivity nylon 66 composite material comprises the following steps:
s1, weighing the following raw materials according to the following table 1:
nylon 66 resin, graphene micro-sheets, modified nano-silica, a compatilizer, an antioxidant, a silane coupling agent and carbon fibers.
S2, mixing the graphene, the modified nano-silica and the silane coupling agent at the temperature of 60 ℃, stirring for 8min, cooling to 50 ℃, adding the nylon 66 resin, the antioxidant and the compatilizer, and continuously stirring for 6min to obtain a mixture.
Wherein the nylon 66 resin is subjected to drying pretreatment before use, the temperature of the drying pretreatment is 100 ℃, and the time is 6 hours.
And S3, putting the mixture into a main feeding hopper of a double-screw extruder, putting carbon fibers into a side feeding hopper of the double-screw extruder, and then melting, extruding, cooling and granulating to obtain the nylon 66 composite material.
Wherein the processing temperature of the double-screw extruder is 250-285 ℃, and the processing temperature is divided into ten zones, and the temperatures of the one zone to the ten zones are 250 ℃, 255 ℃, 260 ℃, 270 ℃, 275 ℃, 270 ℃ and 285 ℃. The rotation speed of the twin-screw extruder is 300 r/min.
Example 9
The recyclable wear-resistant high-thermal-conductivity nylon 66 composite material is different from the nylon 66 composite material in the embodiment 1 in that modified nano-silica is different from the nylon 66 composite material in the embodiment 2.
Example 10
The recyclable wear-resistant high-thermal-conductivity nylon 66 composite material is different from the nylon 66 composite material in the embodiment 1 in that modified nano-silica is different from the nylon 66 composite material in raw materials, and the modified nano-silica is obtained by the preparation example 3.
Example 11
A recyclable wear-resistant high-thermal-conductivity nylon 66 composite material, which is different from the nylon 66 composite material in that graphene micro-sheets are pretreated before use in the preparation of the nylon 66 composite material.
The pretreatment of the graphene nanoplatelets adopts the following method:
adding the graphene nanoplatelets into a nitric acid solution with the concentration of 30%, soaking for 6 hours, filtering and drying.
Under the protection of nitrogen, adding 1.2kg of sodium dodecyl sulfate into 80kg of toluene, stirring for 4min, then adding 5.5kg of graphene nanoplatelets treated by nitric acid, stirring for 10min, then adding 0.1kg of silane coupling agent which is gamma-aminopropyltriethoxysilane, continuing stirring, heating to 50 ℃, carrying out heat preservation reaction for 7h, filtering, washing and drying to obtain the pretreated graphene nanoplatelets.
Wherein, the washing is carried out by pure ethanol and is carried out for three times.
Example 12
A recyclable wear-resistant high-thermal-conductivity nylon 66 composite material, which is different from the nylon 66 composite material in that graphene micro-sheets are pretreated before use in the preparation of the nylon 66 composite material.
The pretreatment of the graphene nanoplatelets adopts the following method:
adding the graphene nanoplatelets into a nitric acid solution with the concentration of 30%, soaking for 5 hours, filtering and drying.
Under the protection of nitrogen, adding 1.2kg of sodium dodecyl sulfate into 80kg of toluene, stirring for 6min, then adding 6kg of graphene nanoplatelets treated by nitric acid, stirring for 6min, then adding 0.1kg of silane coupling agent which is gamma-aminopropyltriethoxysilane, continuing stirring, heating to 55 ℃, carrying out heat preservation reaction for 6h, filtering, washing and drying to obtain the pretreated graphene nanoplatelets.
Wherein, the washing is carried out by pure ethanol and is carried out for three times.
Example 13
A recyclable wear-resistant high-thermal-conductivity nylon 66 composite material, which is different from the nylon 66 composite material in that graphene micro-sheets are pretreated before use in the preparation of the nylon 66 composite material.
The pretreatment of the graphene nanoplatelets adopts the following method:
adding the graphene nanoplatelets into a nitric acid solution with the concentration of 30%, soaking for 4 hours, filtering and drying.
Under the protection of nitrogen, adding 1.2kg of sodium dodecyl sulfate into 80kg of toluene, stirring for 8min, then adding 6.5kg of graphene nanoplatelets treated by nitric acid, stirring for 8min, then adding 0.1kg of silane coupling agent which is gamma-aminopropyltriethoxysilane, continuing stirring, heating to 60 ℃, carrying out heat preservation reaction for 5h, filtering, washing and drying to obtain the pretreated graphene nanoplatelets.
Wherein, the washing is carried out by pure ethanol and is carried out for three times.
Comparative example
Comparative example 1
A recyclable wear-resistant high-thermal-conductivity nylon 66 composite material, which is different from the embodiment 1 in that carbon fibers are replaced by the same amount of nylon 66 resin in the raw material of the nylon 66 composite material.
Comparative example 2
The recyclable wear-resistant high-thermal-conductivity nylon 66 composite material is different from the embodiment 1 in that the raw material of the nylon 66 composite material is modified nano silicon dioxide replaced by the same amount of nylon 66 resin.
Comparative example 3
The recyclable wear-resistant high-thermal-conductivity nylon 66 composite material is different from the embodiment 1 in that the raw material of the nylon 66 composite material is provided with the same amount of nylon 66 resin instead of graphene micro-sheets.
Comparative example 4
The recyclable wear-resistant high-thermal-conductivity nylon 66 composite material is different from the embodiment 1 in that the raw materials of the nylon 66 composite material are prepared by replacing graphene micro-sheets and modified nano-silica with the same amount of nylon 66 resin.
Comparative example 5
The recyclable wear-resistant high-thermal-conductivity nylon 66 composite material is different from the embodiment 1 in that carbon fibers, modified nano-silica and graphene micro-sheets are replaced by the same amount of nylon 66 resin in raw materials of the nylon 66 composite material.
Comparative example 6
A recyclable wear-resistant high-thermal-conductivity nylon 66 composite material, which is different from the nylon 66 composite material in example 1 in that the silane coupling agent is replaced by an equal amount of nylon 66 resin in the raw material of the nylon 66 composite material.
Comparative example 7
A recyclable wear-resistant high-thermal-conductivity nylon 66 composite material, which is different from the composite material in example 1 in that the raw material of the nylon 66 composite material is replaced by an equal amount of nylon 66 resin for a compatilizer.
Comparative example 8
The recyclable wear-resistant high-thermal-conductivity nylon 66 composite material is different from the embodiment 1 in that the silane coupling agent and the compatilizer are replaced by the same amount of nylon 66 resin in the raw materials of the nylon 66 composite material.
Comparative example 9
A recyclable wear-resistant high-thermal-conductivity nylon 66 composite material, which is different from the embodiment 1 in that carbon fibers are replaced by equal amounts of glass fibers in the raw material of the nylon 66 composite material.
Performance test
Test pieces were prepared from the nylon 66 composite materials obtained in examples 1 to 13 and comparative examples 1 to 9, and the following property tests were carried out, and the test results are shown in Table 2.
Wherein the tensile strength is detected according to ISO 527 standard; detecting the notch impact strength according to ISO 180 standard; the heat conduction value is detected according to the ISO 22007 standard; the wear resistance of a material is characterized by the wear rate, and the wear rate of the material is (mass before material wear-mass after material wear)/mass before material wear x 100%.
TABLE 2 test results
| Detecting items | Tensile Strength/(MPa) | Impact Strength/(KJ/m)2) | Heat conductivity value/(W/m.k) | Wear Rate/(%) |
| Example 1 | 223 | 21.2 | 3.27 | 1.09 |
| Example 2 | 226 | 17.7 | 3.31 | 1.28 |
| Example 3 | 198 | 19.1 | 2.9 | 1.22 |
| Example 4 | 207 | 18.3 | 2.72 | 1.19 |
| Example 5 | 188 | 16.5 | 2.78 | 1.31 |
| Example 6 | 192 | 16.7 | 3.30 | 1.06 |
| Example 7 | 221 | 21.3 | 3.14 | 1.09 |
| Example 8 | 222 | 20.8 | 3.16 | 1.10 |
| Example 9 | 214 | 20.2 | 2.78 | 1.23 |
| Example 10 | 208 | 19.3 | 2.53 | 1.22 |
| Example 11 | 231 | 21.7 | 3.32 | 1.03 |
| Example 12 | 218 | 22.4 | 3.35 | 1.06 |
| Example 13 | 224 | 21.5 | 3.48 | 1.05 |
| Comparative example 1 | 87 | 17.8 | 2.17 | 1.43 |
| Comparative example 2 | 189 | 20.1 | 2.53 | 1.69 |
| Comparative example 3 | 171 | 19.4 | 1.19 | 1.57 |
| Comparative example 4 | 193 | 19.7 | 1.08 | 1.87 |
| Comparative example 5 | 72 | 15.8 | 0.60 | 2.13 |
| Comparative example 6 | 197 | 20.3 | 2.61 | 1.21 |
| Comparative example 7 | 233 | 14.8 | 3.10 | 1.13 |
| Comparative example 8 | 224 | 14.5 | 2.56 | 1.28 |
| Comparative example 9 | 156 | 17.6 | 2.14 | 1.58 |
As can be seen from Table 2, the nylon 66 composite material obtained by the preparation method of the recyclable wear-resistant high-thermal-conductivity nylon 66 composite material has high tensile strength, impact strength and thermal conductivity value, wherein the tensile strength is 188-231MPa, and the impact strength is 16.5-22.4KJ/m2The heat conduction value is 2.53-3.48W/m.k, the wear rate is lower, the wear rate is 1.03-1.31%, and the nylon 66 composite material has good heat conductivity and wear resistance, excellent mechanical property and the advantage of recoverability through the synergistic effect of the raw materials, so that the market demand is met.
Comparing example 1 with comparative example 1, it can be seen that the tensile strength, impact strength and thermal conductivity of the nylon 66 composite material can be obviously improved and the wear rate of the nylon 66 composite material can be obviously reduced by adding carbon fiber into the raw materials. In addition, comparing with comparative example 9, it can be seen that the addition of glass fiber to the raw materials can improve the tensile strength and impact strength of the nylon 66 composite, but cannot improve the thermal conductivity of the nylon 66 composite or reduce the wear rate of the nylon 66 composite, and the addition of carbon fiber to the raw materials can improve the tensile strength and impact strength of the nylon 66 composite.
Comparing the example 1 with the comparative example 2, it can be seen that the tensile strength and the impact strength of the nylon 66 composite material can be obviously improved by adding the modified nano-silica into the raw materials, the heat conductivity value can also be improved, the wear rate of the nylon 66 composite material is obviously reduced, and the service life of the nylon 66 composite material is prolonged.
Comparing the example 1 with the comparative example 3, it can be seen that the tensile strength and the heat conductivity value of the nylon 66 composite material can be obviously improved and the wear rate of the nylon 66 composite material can be obviously reduced by adding the graphene nanoplatelets into the raw materials. In addition, when comparing with examples 11 to 13, it can be seen that the pretreatment of the graphene nanoplatelets can further improve the thermal conductivity value of the nylon 66 composite material.
Comparing the example 1 with the comparative examples 1 to 5, it can be seen that the carbon fiber, the graphene and the modified nano-silica are added into the raw materials, and the synergistic effect therebetween can effectively improve the tensile strength, the impact strength and the heat conductivity value of the nylon 66 composite material, reduce the wear rate of the nylon 66 composite material, and enable the nylon 66 composite material to have good mechanical properties.
Comparing example 1 with comparative examples 6 to 8, it can be seen that the addition of the silane coupling agent to the raw materials can effectively improve the tensile strength and the thermal conductivity of the nylon 66 composite material, and reduce the wear rate of the nylon 66 composite material. The compatilizer is added into the raw materials, has a toughening effect, reduces the tensile strength of the nylon 66 composite material, can effectively improve the impact strength and the heat conduction value of the nylon 66 composite material, and can reduce the wear rate of the nylon 66 composite material. And the mechanical property of the nylon 66 composite material can be effectively improved through the synergistic effect of the silane coupling agent and the compatilizer.
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 (7)
1. A preparation method of a recyclable wear-resistant high-thermal-conductivity nylon 66 composite material is characterized by comprising the following steps: the method comprises the following steps:
s1, weighing the following raw materials in percentage by weight:
30.3-52.2% of nylon 66 resin, 10-20% of graphene microchip, 5-10% of modified nano silicon dioxide, 2-5% of compatilizer, 0.2-0.6% of antioxidant, 0.1-0.5% of silane coupling agent and 30-40% of carbon fiber;
s2, mixing graphene, modified nano-silica and a silane coupling agent at the temperature of 60-80 ℃, stirring for 4-8min, cooling to 50-70 ℃, adding nylon 66 resin, an antioxidant and a compatilizer, and continuously stirring for 4-8min to obtain a mixture;
s3, adding carbon fibers into the mixture, mixing, and then melting, extruding, cooling and granulating to obtain the nylon 66 composite material;
the modified nano silicon dioxide is prepared by the following method:
under the protection of inert gas, adding sodium dodecyl sulfate into toluene, stirring for 4-8min, then adding nano silicon dioxide twice, after adding the nano silicon dioxide each time, performing ultrasonic dispersion for 30-40min, then adding a silane coupling agent, continuing to perform ultrasonic dispersion for 10-20min, then heating to 50-60 ℃ under the condition of continuous stirring, performing heat preservation reaction for 8-10h, filtering, washing and drying to obtain modified nano silicon dioxide;
the weight ratio of the silane coupling agent to the nano silicon dioxide is 1 (15-20);
the silane coupling agent used in the preparation of the modified nano-silica is the same as the silane coupling agent in the raw material of the nylon 66 composite material;
the graphene nanoplatelets are pretreated before use, and the pretreatment adopts the following method:
adding graphene nanoplatelets into a nitric acid solution, soaking for 4-6h, filtering and drying;
under the protection of inert gas, adding sodium dodecyl sulfate into toluene, stirring for 4-8min, then adding the graphene nanoplatelets subjected to nitric acid treatment, stirring for 8-10min, then adding a silane coupling agent, continuing stirring, heating to 50-60 ℃, carrying out heat preservation reaction for 5-7h, filtering, washing and drying to obtain pretreated graphene nanoplatelets;
the weight ratio of the silane coupling agent to the graphene nanoplatelets is 1 (55-65);
moreover, a silane coupling agent used for preprocessing the graphene microchip is the same as the silane coupling agent in the raw material of the nylon 66 composite material;
the compatilizer is an ethylene-acrylate-glycidyl methacrylate terpolymer, and the silane coupling agent is gamma-aminopropyltriethoxysilane.
2. The preparation method of the recyclable wear-resistant high thermal conductivity nylon 66 composite material as claimed in claim 1, wherein the preparation method comprises the following steps: the carbon fibers are chopped carbon fibers, the average length of the carbon fibers is 3-5mm, the average diameter of the carbon fibers is 1-10 mu m, the average particle size of the modified nano silicon dioxide is 1.3-5 mu m, the average particle size of the graphene micro-sheet is 10-20 mu m, and the average thickness of the graphene micro-sheet is 1-20 nm.
3. The preparation method of the recyclable wear-resistant high thermal conductivity nylon 66 composite material as claimed in claim 1, wherein the preparation method comprises the following steps: the antioxidant is a compound of hindered phenol antioxidant and phosphite antioxidant, and the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 2.
4. The preparation method of the recyclable wear-resistant high thermal conductivity nylon 66 composite material as claimed in claim 1, wherein the preparation method comprises the following steps: the average viscosity of the nylon 66 resin is 2.4-3.2 dl/g.
5. The preparation method of the recyclable wear-resistant high thermal conductivity nylon 66 composite material as claimed in claim 1, wherein the preparation method comprises the following steps: the nylon 66 resin is subjected to drying pretreatment before use, wherein the temperature of the drying pretreatment is 100-120 ℃, and the time is 4-6 h.
6. The preparation method of the recyclable wear-resistant high thermal conductivity nylon 66 composite material as claimed in claim 1, wherein the preparation method comprises the following steps: in step S3, a double-screw extruder is used for mixing the mixture and the carbon fiber, the mixture is fed from a main feeding hopper of the double-screw extruder, the carbon fiber is fed from a side feeding hopper of the double-screw extruder, the processing temperature of the double-screw extruder is 250-class 285 ℃, and the rotating speed of the double-screw extruder is 300-class 400 r/min.
7. The preparation method of the recyclable wear-resistant high thermal conductivity nylon 66 composite material as claimed in claim 6, wherein the preparation method comprises the following steps: the processing temperature of the double screw extruder is divided into ten zones, and the temperatures of one zone to ten zones are 250 ℃, 255 ℃, 260 ℃, 270 ℃, 275 ℃, 270 ℃ and 285 ℃.
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