CN113150541A - High-strength high-thermal-conductivity nylon composite material and preparation method thereof - Google Patents
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Abstract
The invention provides a high-strength high-thermal-conductivity nylon composite material and a preparation method thereof, wherein the nylon composite material is prepared from the following raw materials in parts by weight: 100 parts of nylon resin, 5-30 parts of carbon fiber, 10-30 parts of heat-conducting filler, 0.1-5 parts of dispersant and 0.1-5 parts of antioxidant; the nylon resin is composed of 5-30% of graphene nylon master batch and 70-95% of pure nylon resin; the surface of the carbon fiber is grafted with a carbon nanotube; according to the invention, the high-thermal-conductivity filler such as graphene and carbon nano tubes is pretreated and then is subjected to melt blending, so that the filler is well dispersed, and a thermal conduction passage can be constructed at a low content, thereby the thermal conductivity of the composite material is obviously improved, and the overall mechanical property of the material is improved, the dimensional stability is improved, and the water absorption of nylon is reduced.
Description
Technical Field
The invention belongs to the technical field of heat conduction materials, and particularly relates to a high-strength high-heat-conductivity nylon composite material and a preparation method thereof.
Background
The heat-conducting polymer composite material is a polymer composite material system with a heat-conducting function, which is prepared by taking a polymer material as a matrix and adding a heat-conducting filler. It is of great interest because of its low cost, simple processing technology and suitability for mass production.
Most of the heat-conducting nylon on the market is directly melted and blended with nylon by using heat-conducting fillers, but the heat-conducting nylon usually needs to be added with more heat-conducting fillers to have remarkable effect. However, the melt viscosity is increased due to the excessively high content of the filler, which is not favorable for industrial production and limits the application of the heat-conducting nylon. For example, CN110218442A discloses a high-flow heat-conducting nylon composite material, and a preparation method and application thereof, the authors add 40-55 parts of hydroxide as a heat-conducting filler, and increase the fluidity by adding melamine urate and other lubricants, because the fluidity is insufficient due to the excessively high content (more than 50 wt%) of the filler, and the injection molding is difficult.
Carbon materials such as graphene and carbon nanotubes have excellent heat conducting property and electric conductivity, but the graphene and the carbon nanotubes have small particle size and are easy to agglomerate, and good dispersion is difficult to achieve by simple melt blending. For example, CN104844795A discloses a high-strength heat-conducting nylon 6 and a preparation method thereof, and an author adds a modified graphene dispersion liquid into a caprolactam polymerization system, and successfully improves the dispersion of graphene in a nylon 6 matrix by matching with a magnetic field and ultrasonic treatment.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-strength high-heat-conductivity nylon composite material and a preparation method thereof. According to the invention, the high-thermal-conductivity filler such as graphene and carbon nano tubes is pretreated and then is subjected to melt blending, so that the filler is well dispersed, and a thermal-conductivity passage can be constructed under low content, thereby remarkably improving the thermal conductivity of the composite material. And the carbon fiber is added into the matrix, so that the overall mechanical property of the material is improved, the dimensional stability is improved, and the water absorption of the nylon is reduced. The invention forms a perfect heat conduction path through the synergistic effect of the fillers with various sizes, and has higher heat conduction performance and excellent mechanical property.
The technical scheme of the invention is as follows:
a high-strength high-thermal-conductivity nylon composite material is composed of the following raw materials in parts by weight:
100 parts of nylon resin, 5-30 parts of carbon fiber, 10-30 parts of heat-conducting filler, 0.1-5 parts of dispersant and 0.1-5 parts of antioxidant.
The nylon resin is composed of 5-30% of graphene nylon master batch and 70-95% of pure nylon resin; the graphene nylon master batch is prepared from caprolactam through a monomer casting nylon polymerization method, the content of graphene is 1-5%, the graphene is uniformly dispersed and fixed in a matrix through in-situ polymerization of monomers and a mechanical stirring effect, and the heat conductivity of the material is remarkably improved under low content; the pure nylon resin is selected from one or more of PA6, PA66, PA46 and PA 1010; the graphene includes single-layer graphene or multi-layer graphene, and the number of the multi-layer graphene is generally less than 10.
Specifically, the graphene nylon master batch is prepared by the following method:
(1) dissolving graphene in a caprolactam monomer melt, and mechanically stirring at 80-100 ℃ for 30-60 min to prepare a caprolactam/graphene suspension with graphene concentration of 1-5%;
(2) vacuum dewatering caprolactam/graphene suspension at 130-150 ℃ for 1h, then adding initiator sodium hydroxide and activator toluene diisocyanate, uniformly mixing, pouring into a mold at 160-180 ℃ for polymerization for 30min, and obtaining graphene/MCPA 6 resin;
(3) and crushing the obtained graphene/MCPA 6 resin to obtain the graphene nylon master batch.
The graphene heat-conducting master batch obtained by the method has the advantages of low viscosity of caprolactam monomer, short molecular chain, good dispersibility of graphene in a matrix and the like. Graphene is a novel two-dimensional carbon nanomaterial and has excellent mechanical properties and heat conductivity. Theoretical research shows that the room-temperature thermal conductivity coefficient of the single-layer graphene is as high as 5300W/m.K, and the graphene is an ideal thermal conductive filler with the highest thermal conductivity coefficient. Graphene is of a nanosheet structure, the particle size is very small, the graphene can be well filled in irregular gaps formed among conventional heat-conducting fillers, the graphene is uniformly dispersed in master batches in advance under the action of monomer in-situ polymerization and mechanical stirring, the graphene cannot agglomerate during melt blending, a bridge frame and a communication effect can be achieved, all components are connected, more stable heat-conducting passages are formed, and due to the fact that the graphene is high in heat-conducting coefficient, the heat-conducting performance of the nylon composite material can be remarkably improved when the graphene is used in a very small amount.
The carbon nano tubes are grafted on the surfaces of the carbon fibers, and are coated on the surfaces of the carbon fibers by a chemical grafting method, so that the compatibility of the carbon fibers and a matrix is improved, the carbon nano tubes are prevented from agglomerating, the radial heat conduction capacity of the carbon fibers is also improved, and meanwhile, the carbon fibers have extremely high modulus and strength and can remarkably improve the mechanical property of the composite material.
Specifically, the method for grafting the carbon nanotubes on the surface of the carbon fiber comprises the following steps:
(1) cleaning carbon fibers with acetone to remove surface impurities, mixing the carbon fibers with concentrated nitric acid (60-70%), oxidizing for 4 hours at 80 ℃, washing with deionized water to be neutral, and drying to obtain carbon fibers with carboxyl on the surfaces;
(2) adding carbon fibers with carboxyl on the surface into an ethanol solution containing 3 percent of KH550, reacting for 5 hours at 60 ℃, then washing with ethanol, and drying to obtain the carbon fibers grafted with KH 550;
(3) hydrolyzing KH560 in ethanol to obtain KH560 hydrolysate, dripping the obtained KH560 hydrolysate into a hydroxylated carbon nanotube aqueous solution at 50 ℃, reacting for 5h, and drying to obtain the carbon nanotube grafted with KH 560;
wherein the weight ratio of the carbon nano tube to the KH560 is 10: 1;
(4) adding the carbon fiber grafted with the KH550 into a toluene solution containing 5 percent of the grafted KH560 carbon nano tubes, stirring for 5h at 90 ℃, then washing with ethanol and drying to obtain the carbon fiber with the surface grafted with the carbon nano tubes.
The carbon fiber with the surface grafted with the carbon nano tube obtained by the method improves the surface roughness of the fiber, improves the interface bonding force between the carbon fiber and a nylon matrix, improves the compatibility between the fiber and the matrix and promotes the formation of a heat conduction path. Compared with the traditional glass fiber, the carbon fiber has the advantages of high axial strength and modulus, low density, small thermal expansion coefficient and good axial heat conductivity, but the radial heat conductivity is not ideal. Therefore, the carbon nano tubes are grafted to the surface of the carbon fibers, so that the radial heat conduction capability is further improved. The carbon nanotubes are fixed on the carbon fibers by a chemical grafting method, thereby avoiding agglomeration and promoting the formation of a heat conduction path.
The heat-conducting filler is selected from one or a mixture of more than two of nano aluminum oxide, aluminum nitride, boron nitride, silicon carbide, crystalline flake graphite, graphite powder, scale-shaped high-heat-conductivity carbon powder, fibrous high-heat-conductivity carbon powder, graphene and carbon nano tubes in any proportion; the heat conductivity coefficient of the heat-conducting filler is 30-1000W/mK.
The dispersing agent is selected from one or a mixture of more than two of silicone powder, TAF-A, EBS and zinc stearate in any proportion.
The antioxidant is one or a mixture of two of 1098[ N, N '-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine ], 626[ bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite ], preferably 1098[ N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine ], 626[ bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite ] in a weight ratio of 1: 1-2.
The preparation method of the high-strength high-thermal conductivity nylon composite material comprises the following steps:
the nylon resin, the carbon fiber, the heat-conducting filler, the dispersant and the antioxidant are dried in vacuum at 85 ℃ for 12 hours, then added into a double-screw extruder according to the formula, and subjected to extrusion blending, grain cutting and injection molding to obtain the high-strength high-heat-conducting nylon composite material;
the temperature range of the double-screw extruder is 260-280 ℃.
The high-strength high-thermal-conductivity nylon composite material can be applied to the fields of LED lamp shell heat dissipation materials, low-voltage electrical appliances and electronic heat dissipation elements.
Compared with the prior art, the invention has the beneficial effects that:
1. the graphene has excellent heat-conducting property, but the graphene is easy to agglomerate due to small granularity, so that the graphene is uniformly dispersed by utilizing the action of mechanical stirring when nylon master batches are polymerized in situ, and is fixed in situ along with the increase of molecular chains, and then is uniformly dispersed in a matrix through melt blending, and the overall heat conductivity of the matrix is improved under low content. According to the invention, the graphene nylon 6 master batch and nylon are compounded to serve as a matrix material, so that the dispersibility of graphene in the matrix is improved, a good heat conduction path is constructed by the graphene and the high-heat-conductivity nano-grade material and other conventional heat conduction fillers, and the heat conductivity of the composite material can be obviously improved at a lower content.
2. The carbon nano tube is loaded on the carbon fiber to form a three-dimensional heat conduction network, and meanwhile, agglomeration is avoided, and interface thermal resistance is reduced. The composite material obtained by the invention has the advantages that the multiple carbon materials have synergistic effect and are well dispersed, the heat-conducting property of the material can be further improved under the condition of low filler content, and the mechanical property is improved. The carbon fiber is subjected to surface modification, and the carbon nanotube is used for coating the carbon fiber, so that the carbon nanotube is uniformly dispersed in the matrix material, the interface interaction force between the carbon fiber and the carbon nanotube and the nylon matrix is strong, the conduction of heat at the interface is facilitated, the interface thermal resistance is reduced, the transmission of stress at the interface is facilitated, and the mechanical property and the thermal stability of the composite material are improved.
3. According to the invention, carbon materials with various sizes and conventional heat-conducting fillers are compounded, so that a perfect heat-conducting path is constructed, the content of the fillers is reduced, good mechanical property and heat-conducting property are ensured, the production cost is greatly reduced, and the large-scale industrial production can be realized.
Drawings
Fig. 1 is a schematic structural diagram of the composite material of the present invention.
Detailed Description
The invention is further described below by means of specific examples, without the scope of protection of the invention being limited thereto.
Unless otherwise specified, the percentages in the present invention are all by mass.
The carbon fiber grafted carbon nanotube comprises the following specific steps:
(1) cleaning carbon fibers with acetone to remove surface impurities, placing 200g of the carbon fibers in a flask, adding 200mL of concentrated nitric acid (60-70%) to oxidize at 80 ℃ for 4h, washing with deionized water to be neutral, and drying to obtain the carbon fibers with carboxyl on the surfaces.
(2) Adding 200g of carbon fiber with carboxyl on the surface into 500mL of ethanol solution containing 3% KH550, reacting for 5 hours at 60 ℃, then washing with ethanol, and drying to obtain the KH550 grafted carbon fiber.
(3) Hydrolyzing 15mg KH560 in 100mL ethanol, adding 300mL of 0.5mg/mL hydroxylated carbon nanotube aqueous solution into a 50 ℃ three-necked flask, dropwise adding KH560 hydrolysate for 30 minutes, reacting for 5 hours, and drying to obtain the KH560 grafted carbon nanotube. Wherein the weight ratio of the carbon nano tube to the KH560 is 10: 1.
(4) adding 200g of the carbon fiber grafted with the KH550 into 3000mL of toluene solution containing 5% of the grafted KH560 carbon nanotubes, stirring for 5h at 90 ℃, washing the carbon fiber with ethanol, and drying to obtain the carbon fiber with the surface grafted with the carbon nanotubes.
The MCPA6 resin containing 5% of graphene is prepared by an in-situ polymerization method, and the method comprises the following specific steps:
(1) dissolving 5g of graphene in 100g of caprolactam monomer melt, mechanically stirring the graphene in water bath at 90 ℃ for 45 minutes to prepare caprolactam/graphene suspension with 5% of graphene concentration;
(2) the suspension was placed in a heating mantle at 140 ℃ for 1 hour with vacuum dewatering, 0.5g of initiator sodium hydroxide and 0.5g of activator toluene diisocyanate were added, shaken rapidly and vigorously and poured into a mold at 170 ℃ for polymerization for 30 min.
(3) And crushing the obtained graphene/MCPA 6 resin in a high-speed crusher to obtain the heat-conducting master batch with the graphene content of 5%.
Example 1
1.5kg of nylon 66, 450g of spherical alumina, 7.5g of silicone powder, 3g of antioxidant 1098 and 3g of antioxidant 626 are dried in vacuum at 85 ℃ for 12h, extruded and granulated by a double screw, and then injection molded into mechanical sample strips and wafers.
Temperature of each zone of the extruder: a first area: 260 ℃ and a second zone: 265 ℃ and three zones: 270 ℃ and four zones: 275 ℃ and five zones: 280 ℃ and six regions: 280 ℃ and seven regions: 275 ℃ and eight regions: 270 ℃ and nine zones: 270 ℃ and ten regions: 275 ℃. The specific properties are shown in Table II.
Example 2
1.35kg of nylon 66, 150g of graphene nylon 6 master batch, 450g of spherical alumina, 7.5g of silicone powder, 3g of antioxidant 1098 and 3g of antioxidant 626 are dried in vacuum at 85 ℃ for 12h, extruded by a double screw and granulated, and then mechanical sample strips and wafers are injection molded.
Temperature of each zone of the extruder: a first area: 260 ℃ and a second zone: 265 ℃ and three zones: 270 ℃ and four zones: 275 ℃ and five zones: 280 ℃ and six regions: 280 ℃ and seven regions: 275 ℃ and eight regions: 270 ℃ and nine zones: 270 ℃ and ten regions: 275 ℃. The specific properties are shown in Table II.
Example 3
1.35kg of nylon 66, 150g of graphene nylon 6 master batch, 450g of spherical alumina, 150g of carbon fiber, 7.5g of silicone powder, 3g of antioxidant 1098 and 3g of antioxidant 626 are dried in vacuum at 85 ℃ for 12h, extruded and granulated by a double screw, and then mechanical sample strips and wafers are injection molded.
Temperature of each zone of the extruder: a first area: 260 ℃ and a second zone: 265 ℃ and three zones: 270 ℃ and four zones: 275 ℃ and five zones: 280 ℃ and six regions: 280 ℃ and seven regions: 275 ℃ and eight regions: 270 ℃ and nine zones: 270 ℃ and ten regions: 275 ℃. The specific properties are shown in Table II.
Example 4
1.35kg of nylon 66, 150g of graphene nylon 6 master batch, 450g of spherical alumina, 150g of carbon nanotube-coated carbon fiber, 7.5g of silicone powder, 3g of antioxidant 1098 and 3g of antioxidant 626 are dried in vacuum at 85 ℃ for 12 hours, extruded and granulated by a double screw, and then injection molded into mechanical splines and wafers.
Temperature of each zone of the extruder: a first area: 260 ℃ and a second zone: 265 ℃ and three zones: 270 ℃ and four zones: 275 ℃ and five zones: 280 ℃ and six regions: 280 ℃ and seven regions: 275 ℃ and eight regions: 270 ℃ and nine zones: 270 ℃ and ten regions: 275 ℃. The specific properties are shown in Table II.
Example 5
1.2kg of nylon 66, 300g of graphene nylon 6 master batch, 450g of spherical alumina, 300g of carbon nanotube-coated carbon fiber, 7.5g of silicone powder, 3g of antioxidant 1098 and 3g of antioxidant 626 are dried in vacuum at 85 ℃ for 12 hours, extruded and granulated by a double screw, and then a mechanical spline and a wafer are injection molded.
Temperature of each zone of the extruder: a first area: 260 ℃ and a second zone: 265 ℃ and three zones: 270 ℃ and four zones: 275 ℃ and five zones: 280 ℃ and six regions: 280 ℃ and seven regions: 275 ℃ and eight regions: 270 ℃ and nine zones: 270 ℃ and ten regions: 275 ℃. The specific properties are shown in Table II.
The formula (converted into parts) of the different heat-conducting nylon materials in the embodiment of the invention is shown in the following table one:
watch 1
The mechanical and thermal conductivity of the heat-conducting nylon composite material prepared by the embodiment of the invention is shown in the following table two:
watch two
The mechanical properties of the composite material were tested using a universal tester ((Instron-5966, USA.) according to ISO 527-2, tensile tests were carried out at a speed of 50mm/min at 23 ℃ and 50% relative humidity using type A test specimens, for bending tests, test specimens were prepared according to ISO 178 standard, testing being carried out at a span of 64mm and at a speed of 2mm/min, respectively.
Based on the Hot plate transient planar source method, the thermal conductivity of the composite material was quantitatively analyzed using a thermal constant analyzer (Hot Disk TPS2500S, Sweden). The thermal conductivity was measured at room temperature in an air atmosphere using a disc having a radius of 25 mm and a thickness of 2 mm.
Claims (7)
1. The high-strength high-thermal-conductivity nylon composite material is characterized by comprising the following raw materials in parts by weight:
100 parts of nylon resin, 5-30 parts of carbon fiber, 10-30 parts of heat-conducting filler, 0.1-5 parts of dispersant and 0.1-5 parts of antioxidant;
the nylon resin is composed of 5-30% of graphene nylon master batch and 70-95% of pure nylon resin; the graphene nylon master batch is prepared from caprolactam through a monomer casting nylon polymerization method, and the graphene content is 1-5%; the pure nylon resin is selected from one or more of PA6, PA66, PA46 and PA 1010; the graphene comprises single-layer graphene or multi-layer graphene, and the number of the multi-layer graphene is less than 10;
the surface of the carbon fiber is grafted with carbon nanotubes.
2. The nylon composite material of claim 1, wherein the heat conductive filler is selected from one or a mixture of two or more of nano alumina, aluminum nitride, boron nitride, silicon carbide, flake graphite, graphite powder, scale-shaped high heat conductive carbon powder, fibrous high heat conductive carbon powder, graphene and carbon nanotubes in any proportion.
3. The nylon composite material with high strength and high thermal conductivity as claimed in claim 1, wherein the dispersant is one or a mixture of more than two of silicone powder, TAF-A, EBS and zinc stearate in any proportion.
4. The nylon composite material of claim 1, wherein the antioxidant is 1098[ N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine ], 626[ bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite ], or a mixture thereof.
5. The high-strength high-thermal-conductivity nylon composite material as claimed in claim 1, wherein the graphene nylon masterbatch is prepared by the following method:
(1) dissolving graphene in a caprolactam monomer melt, and mechanically stirring at 80-100 ℃ for 30-60 min to prepare a caprolactam/graphene suspension with graphene concentration of 1-5%;
(2) vacuum dewatering caprolactam/graphene suspension at 130-150 ℃ for 1h, then adding initiator sodium hydroxide and activator toluene diisocyanate, uniformly mixing, pouring into a mold at 160-180 ℃ for polymerization for 30min, and obtaining graphene/MCPA 6 resin;
(3) and crushing the obtained graphene/MCPA 6 resin to obtain the graphene nylon master batch.
6. The nylon composite material with high strength and high thermal conductivity as claimed in claim 1, wherein the carbon nanotubes are grafted on the surface of the carbon fibers by a method comprising:
(1) cleaning carbon fibers with acetone to remove surface impurities, mixing the carbon fibers with concentrated nitric acid, oxidizing at 80 ℃ for 4 hours, washing with deionized water to be neutral, and drying to obtain carbon fibers with carboxyl on the surfaces;
(2) adding carbon fibers with carboxyl on the surface into an ethanol solution containing 3 percent of KH550, reacting for 5 hours at 60 ℃, then washing with ethanol, and drying to obtain the carbon fibers grafted with KH 550;
(3) hydrolyzing KH560 in ethanol to obtain KH560 hydrolysate, dripping the obtained KH560 hydrolysate into a hydroxylated carbon nanotube aqueous solution at 50 ℃, reacting for 5h, and drying to obtain the carbon nanotube grafted with KH 560; wherein the weight ratio of the carbon nano tube to the KH560 is 10: 1;
(4) adding the carbon fiber grafted with the KH550 into a toluene solution containing 5 percent of the grafted KH560 carbon nano tubes, stirring for 5h at 90 ℃, then washing with ethanol and drying to obtain the carbon fiber with the surface grafted with the carbon nano tubes.
7. The preparation method of the high-strength high-thermal-conductivity nylon composite material as claimed in claim 1, wherein the preparation method comprises the following steps:
the nylon resin, the carbon fiber, the heat-conducting filler, the dispersant and the antioxidant are dried in vacuum at 85 ℃ for 12 hours, then added into a double-screw extruder according to the formula, and subjected to extrusion blending, grain cutting and injection molding to obtain the high-strength high-heat-conducting nylon composite material;
the temperature range of the double-screw extruder is 260-280 ℃.
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