WO2022121547A1 - 一种高导热的增强聚苯硫醚复合材料及其制备方法 - Google Patents

一种高导热的增强聚苯硫醚复合材料及其制备方法 Download PDF

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WO2022121547A1
WO2022121547A1 PCT/CN2021/127323 CN2021127323W WO2022121547A1 WO 2022121547 A1 WO2022121547 A1 WO 2022121547A1 CN 2021127323 W CN2021127323 W CN 2021127323W WO 2022121547 A1 WO2022121547 A1 WO 2022121547A1
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polyphenylene sulfide
composite material
thermal conductivity
reinforcement
thermally conductive
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PCT/CN2021/127323
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French (fr)
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周贵阳
尹红
陈志荣
韩雨晴
沈金涛
邓杭军
周有桂
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浙江大学
浙江新和成特种材料有限公司
浙江新和成股份有限公司
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Publication of WO2022121547A1 publication Critical patent/WO2022121547A1/zh

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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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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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    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/02—Polythioethers; Polythioether-ethers
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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
    • C08K3/38—Boron-containing compounds
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    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/34—Silicon-containing compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K7/00—Use of ingredients characterised by shape
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
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    • C08K7/14—Glass
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    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances

Definitions

  • the invention relates to the technical field of thermally conductive polyphenylene sulfide, in particular to a reinforced polyphenylene sulfide composite material with high thermal conductivity and a preparation method thereof.
  • Polyphenylene sulfide is a thermoplastic resin with a phenyl sulfide group in the main chain of the molecule. It is one of the most stable resins in thermoplastic polymer materials. Its chemical resistance is considered to be second only to polytetrafluoroethylene. Excellent heat resistance, chemical corrosion resistance, radiation resistance, flame retardancy, balanced physical and mechanical properties and good processing performance, are widely used in electronic appliances, chemical engineering, aerospace, automobile transportation and other fields, available For the preparation of thermally conductive plastic pipes. However, the thermal conductivity of polyphenylene sulfide itself is poor, so improving the thermal conductivity of polyphenylene sulfide is the key technology.
  • the main method is to add a variety of thermally conductive fillers to the base material, and prepare a high thermal conductivity polyphenylene sulfide composite material by blending and extrusion.
  • the Chinese patent document with the application publication number CN 109233279 A discloses a thermally conductive and insulating polyphenylene sulfide composite material, which is composed of 80-90 parts by weight of polyphenylene sulfide, 2-5 parts by weight of silicon carbide, 1-3 parts by weight of Carbolic acid, 0.5-1.5 parts by weight of boron nitride, etc., and the thermal conductivity of the PPS composite material is improved by adding a composite thermal conductivity aid.
  • Another example is the Chinese patent document whose application publication number is CN 111269551 A, which discloses a polyphenylene ether composition and its application in the battery protective shell of a new energy vehicle.
  • the polyphenylene ether composition comprises: polyphenylene ether resin 80 ⁇ 100 parts, 30-50 parts of polyamide resin, 10-20 parts of polyphenylene sulfide resin, 30-50 parts of composite thermal conductive filler, 10-20 parts of dispersant; boron composition.
  • the polyphenylene ether composition is obtained by mixing the raw materials uniformly and then putting them into a twin-screw extruder for melt extrusion and granulation.
  • the thermally conductive fillers due to the small amount of thermally conductive filler added, the thermally conductive fillers are isolated from each other and cannot form an effective thermal conduction path, so the degree of improvement in thermal conductivity is limited.
  • thermal conductivity In order to further improve the thermal conductivity, the most direct way is to increase the amount of thermally conductive fillers added.
  • thermally conductive fillers it is known that the addition of a large amount of thermally conductive fillers not only leads to poor fluidity and causes processing difficulties, but also leads to a significant decrease in the mechanical properties of composite materials. Therefore, simply by The improvement of thermal conductivity by increasing the amount of thermally conductive fillers is still limited.
  • the present invention discloses a reinforced polyphenylene sulfide composite material with high thermal conductivity and a preparation method thereof, which not only significantly improves the thermal conductivity of the polyphenylene sulfide composite material, but also ensures its excellent thermal conductivity. processability and mechanical properties.
  • a reinforced polyphenylene sulfide composite material with high thermal conductivity, by weight percentage, the raw material composition comprises:
  • Polyphenylene sulfide base material 30 ⁇ 50%
  • the surface carbonization reinforcement is a reinforcement whose outer surface is covered with a carbon layer.
  • the term "reinforcing body” mentioned in the claims especially refers to the reinforcing body that has not been surface-treated.
  • the invention discloses a reinforced polyphenylene sulfide composite material with high thermal conductivity.
  • the polyphenylene sulfide is used as a base material, the thermal conductivity of the composite material is improved by adding a thermally conductive filler, and the mechanical property of the composite material is improved by adding a reinforcing body.
  • the reinforcing body is subjected to surface modification treatment. By immersing the polymer monomer raw material liquid on the surface of the reinforcing body, after in-situ polymerization and carbonization treatment, the carbonized body is attached to the surface of the reinforcing body. Floor.
  • the surface carbonization reinforcement is mixed and extruded with other raw materials to prepare a composite material. It is found by comparative experiments that the use of surface carbonized reinforcements instead of ordinary reinforcements can further improve the thermal conductivity of the composites while ensuring the mechanical properties of the reinforcements.
  • the melt flow rate of the polyphenylene sulfide base material is 800-1200 g/10min. Selecting the polyphenylene sulfide at this melt flow rate is beneficial to reduce the difficulty of granulation and molding of the composite material.
  • the surface carbonization reinforcement is obtained by the following methods:
  • the monomer raw material, the reinforcement and the optional two-dimensional sheet-shaped thermally conductive filler are blended, and the surface carbonization reinforcement is obtained after in-situ polymerization and carbonization.
  • the reinforcement is selected from alkali-free glass fiber and/or carbon fiber; further preferably, the reinforcement has a length of 2-8 mm. If the length of the reinforcement is too short, the mechanical properties will be poor; if the length is too long, the dispersion will be poor and the thermal conductivity will be poor. Further preferably, the length of the reinforcing body is 4 mm. It is found through experiments that the thermal conductivity and mechanical properties of the prepared composite material are better when the reinforcing body with this length is used.
  • the thermally conductive filler is selected from graphite and/or silicon carbide; more preferably, graphite is used. It is found through experiments that in this system, the thermal conductivity effect after adding graphite is better than that of silicon carbide.
  • the mesh number of the graphite is selected from 200 to 800 mesh. It is found through experiments that in this system, the graphite particle size is too large, and the mechanical properties are poor; Low density and uneven mixing during extrusion. Still further preferably, the mesh number of the graphite is selected from 500 meshes, and it is found through experiments that using the graphite of this mesh number, the thermal conductivity and mechanical properties of the prepared composite material are better.
  • the carbon layer further contains a two-dimensional sheet-like thermally conductive filler; by doping the two-dimensional sheet-like thermally conductive filler in the polymer monomer raw material solution, after in-situ polymerization and carbonization, the two-dimensional sheet Shaped thermally conductive fillers are doped into the carbonized layer on the surface of the reinforcement. It has been found through experiments that the thermal conductivity of the composite material can be further significantly improved by doping the surface carbonized reinforcement with two-dimensional sheet-like thermally conductive fillers. And through comparative experiments, it is found that if the same amount of two-dimensional sheet-like thermally conductive fillers is directly added to the substrate by blending, the thermal conductivity of the final composite material is hardly affected due to the extremely low addition amount.
  • the precursor of the carbon layer is selected from polyimide (PI) or polyetherimide
  • the two-dimensional sheet-like thermally conductive filler is selected from graphene and/or boron nitride.
  • the precursor of the carbon layer is selected from PI
  • the two-dimensional sheet-like thermally conductive filler is selected from graphene.
  • the raw material composition of the high thermal conductivity reinforced polyphenylene sulfide composite material includes:
  • Polyphenylene sulfide base material 30 ⁇ 50%
  • the raw material composition includes:
  • Polyphenylene sulfide base material 30 ⁇ 50%
  • the raw material composition includes:
  • Polyphenylene sulfide base material 40 ⁇ 50%
  • the reinforcement is selected from 4mm carbon fiber;
  • the thermally conductive filler is selected from graphite with a mesh number of 500;
  • the precursor of the carbon layer is selected from PI;
  • the two-dimensional sheet-like thermally conductive filler is selected from graphene.
  • the thermal conductivity and mechanical properties of the prepared PPS composite material are the best.
  • the reinforced polyphenylene sulfide composite material with high thermal conductivity disclosed in the present invention can also be added with various functional additives according to the requirements of different application occasions.
  • functional additives such as coupling agent, compatibilizer, toughening agent and so on.
  • the invention also discloses a preparation method of the high thermal conductivity reinforced polyphenylene sulfide composite material, comprising the following steps:
  • step (2) Using a mixture comprising a polyphenylene sulfide base material, a thermally conductive filler and the surface carbonized reinforcement prepared in step (1) as a raw material, and after extrusion granulation, a reinforced polyphenylene sulfide composite material with high thermal conductivity is prepared.
  • step (1) a polymer monomer is used as a raw material, and a polymer layer is coated on the surface of the reinforcement by in-situ polymerization, and after carbonization, a reinforcement with a surface coated with a carbon layer is obtained.
  • the in-situ polymerization method adopts conventional technical means in the art, and according to the difference of the coated polymer layer, a suitable polymer monomer is selected. Because the method of immersion is adopted, solution polymerization is adopted, and the specific polymerization temperature, the type of solvent used, and the subsequent carbonization temperature are also adapted to the type of polymer layer, and are all selected conventionally in the field.
  • the monomer raw material is selected from p-phenylenediamine and biphenyltetracarboxylic dianhydride, and N,N'-dimethylacetamide is used as a solvent,
  • the polymerization temperature is normal temperature, and the carbonization temperature is 650 to 800°C.
  • a two-dimensional sheet-shaped thermally conductive filler is added to prepare a reinforcement whose surface is coated with a carbon layer doped with a two-dimensional sheet-shaped thermally conductive filler.
  • the mass ratio of the two-dimensional sheet-like thermally conductive filler to the reinforcement is 0.1-0.5:100; more preferably, 0.27:100.
  • step (2)
  • the polyphenylene sulfide base material and the thermally conductive filler are fed into the extruder from the main feeding port;
  • the surface carbonization reinforcement is fed into the extruder from the side feeding port;
  • the temperature of the extrusion granulation is 310-340°C.
  • the present invention has the following advantages:
  • the invention discloses a reinforced polyphenylene sulfide composite material with high thermal conductivity.
  • a polyphenylene sulfide base material, a thermally conductive filler and a surface-modified reinforcement are used as raw materials, and a polymer monomer raw material liquid is dipped on the surface of the reinforcement to obtain a high thermal conductivity. After in-situ polymerization and carbonization treatment, a carbonized layer is attached to the surface of the reinforcement.
  • the thermal conductivity of the polyphenylene sulfide composite was further improved by this design.
  • the present invention is by doping two-dimensional sheet-like thermally conductive fillers in the polymer monomer raw material liquid, and after in-situ polymerization and carbonization treatment, the surface of the reinforcement is attached and doped.
  • There is a carbonized layer of two-dimensional sheet-like thermally conductive filler and the synergistic effect of the carbonized layer and the two-dimensional sheet-like thermally conductive filler not only further greatly improves the thermal conductivity of the polyphenylene sulfide composite, but also ensures its excellent processing performance and mechanical properties. performance.
  • the polyphenylene sulfide composite material prepared by the invention has excellent thermal conductivity and mechanical properties, is a new type of thermal conductivity material with the prospect of large-scale industrial production, and can be used for heat exchangers, radiators, heat dissipation shells, LED plastic packaging, electronic devices, electronic devices, etc. Equipment and large-scale equipment fields with high requirements for heat dissipation.
  • Step (1) p-phenylenediamine (PDA, 8.9kg) are dissolved in 300L N,N'-dimethylacetamide, add 2kg graphene ( C-THERM TM ) ultrasonically dispersed for 10 h, then added biphenyltetracarboxylic dianhydride (BPDA, 24.4 kg), and mechanically stirred for 4 h under ice-water cooling. Add 750kg of alkali-free glass fiber (length: 4mm) to the mixed mucus, and continue to stir for 1h.
  • PDA p-phenylenediamine
  • the glass fiber dispersed polyimide mucilage was placed in a tube furnace, heated to 400 °C at a heating rate of 5 °C/min under N2 atmosphere, and then heated to 780 °C at a heating rate of 2 °C/min , and kept for 2h to obtain surface carbonized glass fiber.
  • step (2) the polyphenylene sulfide and graphite were dried at 120° C. for 4 h.
  • step (3) proportioning is carried out according to the following mass percentages: polyphenylene sulfide (NHU-PPS3490) 40%, graphite (500 mesh) 40%, surface carbonized glass fiber obtained in step (1) 20%, polyphenylene
  • the sulfide and graphite are mixed evenly, and then added to the main feeding hopper of the twin-screw extruder (18mm twin-screw extruder), and the surface carbonized glass fiber is added to the side feeding hopper, and the twin-screw extruder is set from
  • the temperature of each section from the hopper to the die head is: 285°C, 320°C, 340°C, 340°C, 325°C, 315°C, 325°C, the screw speed of the main machine is 350rpm, and the side feeding speed is 250rpm.
  • Melt extrusion pelletizing is carried out according to the following mass percentages: polyphenylene sulfide (NHU-PPS3490) 40%, graphite (500 mesh
  • step (4) sample preparation is performed for performance test, and the test results are shown in Table 2 below.
  • Step (1) p-phenylenediamine (PDA, 8.9kg) are dissolved in 300L N,N'-dimethylacetamide, add 2kg graphene ( C-THERMTM) ultrasonically dispersed for 10 h, then added biphenyltetracarboxylic dianhydride (BPDA, 24.4 kg), and mechanically stirred for 4 h under ice-water cooling. Add 750kg of alkali-free glass fiber (length: 2mm) to the mixed mucus, and continue to stir for 1h.
  • PDA p-phenylenediamine
  • the glass fiber dispersed polyimide mucilage was placed in a tube furnace, heated to 400 °C at a heating rate of 5 °C/min under N2 atmosphere, and then heated to 780 °C at a heating rate of 2 °C/min , and kept for 2h to obtain carbonized glass fibers on the surface.
  • step (2) the polyphenylene sulfide and graphite were dried at 120° C. for 4 h.
  • Step (3) carry out the proportioning according to the following mass percentages: 40% of polyphenylene sulfide (NHU-PPS3490), 40% of graphite (500 mesh), 20% of the surface carbonized glass fiber obtained in step (1), and then according to Extrusion granulation was carried out in the same steps in Example 1.
  • step (4) sample preparation is performed for performance test, and the test results are shown in Table 2 below.
  • Step (1) p-phenylenediamine (PDA, 8.9kg) are dissolved in 300L N,N'-dimethylacetamide, add 2kg graphene ( C-THERMTM) ultrasonically dispersed for 10 h, then added biphenyltetracarboxylic dianhydride (BPDA, 24.4 kg), and mechanically stirred for 4 h under ice-water cooling. Add 750kg of alkali-free glass fiber (length: 8mm) to the mixed mucus, and continue to stir for 1h.
  • PDA p-phenylenediamine
  • the glass fiber dispersed polyimide mucilage was placed in a tube furnace, heated to 400 °C at a heating rate of 5 °C/min under N2 atmosphere, and then heated to 780 °C at a heating rate of 2 °C/min , and kept for 2h to obtain carbonized glass fibers on the surface.
  • step (2) the polyphenylene sulfide and graphite were dried at 120° C. for 4 h.
  • Step (3) carry out the proportioning according to the following mass percentages: 40% of polyphenylene sulfide (NHU-PPS3490), 40% of graphite (500 mesh), 20% of the surface carbonized glass fiber obtained in step (1), and then according to Extrusion granulation was carried out in the same steps in Example 1.
  • step (4) sample preparation is performed for performance test, and the test results are shown in Table 2 below.
  • step (1) the surface carbonized glass fiber is prepared according to the method of Example 1.
  • step (2) the polyphenylene sulfide and graphite were dried at 120° C. for 4 h.
  • Step (3) carry out the proportioning according to the following mass percentages: 40% of polyphenylene sulfide (NHU-PPS3490), 40% of graphite (200 mesh), 20% of the surface carbonized glass fiber obtained in step (1), and then according to Extrusion granulation was carried out in the same steps in Example 1.
  • step (4) sample preparation is performed for performance test, and the test results are shown in Table 2 below.
  • step (1) the surface carbonized glass fiber is prepared according to the method of Example 1.
  • step (2) the polyphenylene sulfide and graphite were dried at 120° C. for 4 h.
  • Step (3) carry out the proportioning according to the following mass percentages: 40% of polyphenylene sulfide (NHU-PPS3490), 40% of graphite (800 mesh), 20% of the surface carbonized glass fiber obtained in step (1), and then according to Extrusion granulation was carried out in the same steps in Example 1.
  • step (4) sample preparation is performed for performance test, and the test results are shown in Table 2 below.
  • Step (1) p-phenylenediamine (PDA, 8.9kg) are dissolved in 300L N,N'-dimethylacetamide, add 2kg graphene ( C-THERMTM) ultrasonically dispersed for 10h, then added biphenyltetracarboxylic dianhydride (BPDA, 24.4kg), mechanically stirred under ice-water cooling for 4
  • PDA p-phenylenediamine
  • C-THERMTM graphene
  • BPDA biphenyltetracarboxylic dianhydride
  • step (2) the polyphenylene sulfide and graphite were dried at 120° C. for 4 h.
  • Step (3) carry out the proportioning according to the following mass percentages: 50% of polyphenylene sulfide (NHU-PPS3490), 40% of graphite (500 mesh), 10% of the surface carbonized carbon fibers obtained in step (1), and then implemented according to Example 1 Extrusion granulation was carried out in the same procedure.
  • step (4) sample preparation is performed for performance test, and the test results are shown in Table 2 below.
  • step (1) the surface carbonized glass fiber is prepared according to the method of Example 1.
  • step (2) the polyphenylene sulfide was dried at 120° C. for 4 h.
  • Step (3) proportion according to the following mass percentages: polyphenylene sulfide (NHU-PPS3490) 30%, silicon carbide 50%, surface carbonized glass fiber obtained in step (1) 20%, and then according to the same as Example 1 Extrusion granulation in the same procedure.
  • step (4) sample preparation is performed for performance test, and the test results are shown in Table 2 below.
  • Step (1) p-phenylenediamine (PDA, 8.9kg) was dissolved in 300L N,N'-dimethylacetamide, 2kg boron nitride was added for ultrasonic dispersion for 10h, then biphenyltetracarboxylic dianhydride (BPDA, 24.4kg), mechanically stirred for 4h under ice-water cooling. Add 750kg of alkali-free glass fiber (length: 4mm) to the mixed mucus, and continue to stir for 1h.
  • PDA p-phenylenediamine
  • the glass fiber dispersed polyimide mucilage was placed in a tube furnace, heated to 400 °C at a heating rate of 5 °C/min under N2 atmosphere, and then heated to 780 °C at a heating rate of 2 °C/min , and kept for 2h to obtain carbonized glass fibers on the surface.
  • step (2) the polyphenylene sulfide and graphite were dried at 120° C. for 4 h.
  • Step (3) carry out the proportioning according to the following mass percentages: 40% of polyphenylene sulfide (NHU-PPS3490), 40% of graphite (500 mesh), 20% of the surface carbonized glass fiber obtained in step (1), and then according to Extrusion granulation was carried out in the same steps in Example 1.
  • step (4) sample preparation is performed for performance test, and the test results are shown in Table 2 below.
  • Step (1) p-phenylenediamine (PDA, 8.9kg) was dissolved in 300L N,N'-dimethylacetamide, then added biphenyltetracarboxylic dianhydride (BPDA, 24.4kg), under ice-water cooling Mechanical stirring for 4h. Add 750kg of alkali-free glass fiber (length: 4mm) to the mixed mucus, and continue to stir for 1h.
  • PDA p-phenylenediamine
  • BPDA biphenyltetracarboxylic dianhydride
  • the glass fiber dispersed polyimide mucilage was placed in a tube furnace, heated to 400 °C at a heating rate of 5 °C/min under N2 atmosphere, and then heated to 780 °C at a heating rate of 2 °C/min , and kept for 2 h to obtain a carbonized glass fiber without graphene and coated with a polyimide carbon layer.
  • step (2) the polyphenylene sulfide and graphite were dried at 120° C. for 4 h.
  • step (3) proportioning is carried out according to the following mass percentages: 40% of polyphenylene sulfide, 40% of graphite, 20% of the surface carbonized glass fiber without graphene obtained in step (1), and the mixture of polyphenylene sulfide and graphite.
  • step (4) sample preparation is performed for performance test, and the test results are shown in Table 2 below.
  • step (1) bisphenol A diether dianhydride (BPADA, 5.2 kg) was dissolved in 100 L of N,N'-dimethylacetamide, and 0.4 kg of graphene was added for ultrasonic dispersion for 10 h.
  • p-phenylenediamine (PDA, 1.2 kg) was dissolved in 20 L of N,N'-dimethylacetamide, then added dropwise to the reaction solution, and mechanically stirred at 40° C. for 6 h. Add 150 kg of alkali-free glass fibers (length: 4 mm) to the mixed mucus, and continue to stir for 1 h.
  • the glass fiber dispersed polyetherimide mucilage was placed in a tube furnace, heated to 400 °C at a heating rate of 5 °C/min under N2 atmosphere, and then heated to 780 °C at a heating rate of 2 °C/min. °C, and kept for 2 h to obtain carbonized glass fibers on the surface.
  • step (2) the polyphenylene sulfide and graphite were dried at 120° C. for 4 h.
  • Step (3) carry out the proportioning according to the following mass percentages: 40% of polyphenylene sulfide (NHU-PPS3490), 40% of graphite (500 mesh), 20% of the surface carbonized glass fiber obtained in step (1), and then according to Extrusion granulation was carried out in the same steps in Example 1.
  • step (4) sample preparation is performed for performance test, and the test results are shown in Table 2 below.
  • Step (1) p-phenylenediamine (PDA, 8.9kg) was dissolved in 300L N,N'-dimethylacetamide, then added biphenyltetracarboxylic dianhydride (BPDA, 24.4kg), under ice-water cooling Mechanical stirring for 4h. Add 750kg of alkali-free glass fiber to the mixed mucus, and continue to stir for 1 hour. Finally, the glass fiber dispersed polyimide mucilage was placed in a tube furnace, heated to 400 °C at a heating rate of 5 °C/min under N2 atmosphere, and then heated to 780 °C at a heating rate of 2 °C/min , and kept for 2 h to obtain surface carbonized glass fibers without graphene.
  • PDA p-phenylenediamine
  • BPDA biphenyltetracarboxylic dianhydride
  • step (2) the polyphenylene sulfide and graphite were dried at 120° C. for 4 h.
  • step (3) proportioning is carried out according to the following mass percentages: 40% of polyphenylene sulfide, 40% of graphite, 19.95% of graphene-free surface carbonized glass fiber obtained in step (1), and 0.05% of graphene, the poly Phenyl sulfide, graphite and graphene are stirred evenly, then added to the main feeding hopper of a twin-screw extruder (18mm twin-screw extruder), glass fiber is added to the side feeding hopper, and twin-screw extrusion is set
  • the temperature of each section from the hopper to the die head is: 285°C, 320°C, 340°C, 340°C, 325°C, 315°C, 325°C, the screw speed of the main machine is 350rpm, and the side feeding speed is 250rpm. Blending, melt extrusion and pelletizing.
  • step (4) sample preparation is performed for performance test, and the test results are shown in Table 2 below.
  • Step (1) p-phenylenediamine (PDA, 8.9kg) was dissolved in 300L N,N'-dimethylacetamide, then added biphenyltetracarboxylic dianhydride (BPDA, 24.4kg), under ice-water cooling Mechanical stirring for 4h. Add 750kg of alkali-free glass fiber to the mixed mucus, and continue to stir for 1 hour.
  • PDA p-phenylenediamine
  • BPDA biphenyltetracarboxylic dianhydride
  • the glass fiber dispersed polyimide mucilage was placed in a tube furnace, heated to 400 °C at a heating rate of 5 °C/min under N2 atmosphere, and then heated to 780 °C at a heating rate of 2 °C/min , and kept for 2 h to obtain a carbonized glass fiber without graphene and coated with a polyimide carbon layer.
  • step (2) the polyphenylene sulfide and graphite were dried at 120° C. for 4 h.
  • step (3) proportioning is carried out according to the following mass percentages: 20% of polyphenylene sulfide, 40% of graphite, 20% of graphene-free surface carbonized glass fibers obtained in step (1), and 20% of graphene, and the poly Phenyl sulfide, graphite and graphene are stirred evenly, and then added to the main feeding hopper of a twin-screw extruder (50mm twin-screw extruder), glass fiber is added to the side feeding hopper, and the materials are blended and melted and extruded. Cut out.
  • a twin-screw extruder 50mm twin-screw extruder
  • step (4) sample preparation is performed for performance test, and the test results are shown in Table 2 below.
  • step (1) the polyphenylene sulfide and graphite were dried at 120° C. for 4 h.
  • Step (2) proportioning according to the following mass percentages: 40% of polyphenylene sulfide, 40% of graphite, 20% of alkali-free glass fibers without surface treatment (length: 4mm), and the polyphenylene sulfide and graphite are stirred uniform, and then added to the main feeding hopper of the twin-screw extruder, glass fiber was added to the side feeding hopper, and the temperature of each section of the twin-screw extruder from the hopper to the die was set as: 285°C, 320°C °C, 340°C, 340°C, 325°C, 315°C, 325°C, the screw speed of the main machine is 350rpm, the side feeding speed is 250rpm, and the materials are blended, melted, extruded and cut into pellets.
  • Step (3) sample preparation to carry out performance test, the test results are shown in Table 2 below.
  • Hot wire method GB/T 10297-2015 Determination of thermal conductivity of non-metallic solid materials.
  • the thermal conductivity of the PPS composite can be improved by carbonizing the surface of the reinforcement; and the thermal conductivity can be further significantly improved by adding a small amount of two-dimensional flake filler in the carbonized layer;
  • the added two-dimensional flake filler is directly added to the raw materials in the form of blending, and the improvement of thermal conductivity can be ignored; and if one wants to achieve thermal conductivity equivalent to the technical solution of the present invention, it is necessary to use the existing technology in the prior art.
  • Example 1 Comparing Example 1 with Examples 7, 8 and 10, it can be seen that the system composed of graphene as the two-dimensional flake filler, polyimide PI as the carbonization precursor, and graphite as the thermally conductive filler, finally
  • the prepared PPS composite material has better thermal conductivity.
  • Example 1 has comparable mechanical properties, but better thermal conductivity.

Abstract

本发明方法公开了一种高导热的增强聚苯硫醚复合材料及其制备方法，该高导热的增强聚苯硫醚复合材料，按重量百分比计，原料组成包括：聚苯硫醚基材30～50％；表面碳化增强体5～30％；导热填料20～60％；表面碳化增强体为外表面包覆有碳层的增强体。制备方法包括将单体原料、增强体与可选择加入的二维片状的导热填料共混，经原位聚合及碳化后得到表面碳化增强体；再以包括聚苯硫醚基材、导热填料与上述制备的表面碳化增强体为原料，经挤出造粒后制备得到高导热的增强聚苯硫醚复合材料。本发明公开的高导热的增强聚苯硫醚复合材料，在显著提高聚苯硫醚复合材料导热性能的同时，还保证了其优异的加工性能与力学性能。

Description

一种高导热的增强聚苯硫醚复合材料及其制备方法 技术领域
本发明涉及导热聚苯硫醚的技术领域，尤其涉及一种高导热的增强聚苯硫醚复合材料及其制备方法。
背景技术
近年来随着工业发展对导热材料耐腐蚀性、力学性能和加工性能等要求的提高，传统金属类导热材料在某些化工领域已满足不了应用的需求。金属型材在长期的使用过程中会出现腐蚀严重、结垢、不耐酸碱等严重的问题，降低使用寿命，影响设备安全，从而导致维修和更换成本升高；同时本身质量较重，不利于轻量化发展方向。高分子材料具有耐化学腐蚀、成型加工性能优良、电绝缘性能优异、力学性能优良等特点，用做型材时光滑不粘垢、重量轻、耐磨损、价廉，且使用寿命比金属型材长，在产品中逐步得到应用。但大部分高分子材料是热的不良导体，所以需要进行改性以提升材料的导热性能。
聚苯硫醚简称PPS，是分子主链中带有苯硫基的热塑性树脂，是热塑性高分子材料中稳定性最高的树脂之一，耐化学腐蚀性被认为仅次于聚四氟乙烯，具有优良的耐热性、耐化学腐蚀性、耐辐射性、阻燃性、均衡的物理机械性能和较好的加工性能，被广泛应用于电子电器、化学工程、航空航天、汽车运输等领域，可用于制备导热塑料管。然而，聚苯硫醚自身导热性能较差，所以改进聚苯硫醚的导热性能是技术关键。
目前，为了提高聚苯硫醚的导热性能，主要方法是在基材中加入多种导热填料，通过共混挤出制备高导热的聚苯硫醚复合材料。如申请公布号为CN 109233279 A的中国专利文献中公开了一种导热绝缘聚苯硫醚 复合材料，由80～90重量份聚苯硫醚、2～5重量份碳化硅、1～3重量份石碳酸、0.5～1.5重量份氮化硼等组成，通过加入复合的导热助剂来提高PPS复合材料的导热性。又如申请公布号为CN 111269551 A的中国专利文献中公开了一种聚苯醚组合物及其在新能源汽车电池防护壳中的应用，该聚苯醚组合物包括：聚苯醚树脂80～100份，聚酰胺树脂30～50份，聚苯硫醚树脂10～20份，复合导热填料30～50份，分散剂10～20份；复合导热填料由石墨烯微片、碳化硅以及氮化硼组成。通过将各原料混合均匀后放入双螺杆挤出机中进行熔融挤出造粒即得聚苯醚组合物。以上两篇技术方案中，由于导热填料的添加量较少，导热填料间彼此孤立，不能形成有效的导热通路，因此对导热性能的提高程度有限。
为进一步提高导热性能，最直接的方式是增加导热填料的添加量，但公知大量导热填料的加入不仅导致流动性太差造成加工困难，更会导致复合材料力学性能的显著下降，因此，简单通过增加导热填料的添加量对导热性能的提高程度仍然有限。
发明内容
针对现有技术中存在的上述问题，本发明公开了一种高导热的增强聚苯硫醚复合材料及其制备方法，在显著提高聚苯硫醚复合材料导热性能的同时，还保证了其优异的加工性能与力学性能。
具体技术方案如下：
一种高导热的增强聚苯硫醚复合材料，按重量百分比计，原料组成包括：
聚苯硫醚基材              30～50％；
表面碳化增强体            5～30％；
导热填料                  20～60％；
所述表面碳化增强体为外表面包覆有碳层的增强体。本发明中，尤其是权利要求中所提到的名词“增强体”特指还没有经过表面处理的增 强体，若需要表明是经过处理以后的，都用“表面碳化增强体”进行表示。
本发明公开了一种高导热的增强聚苯硫醚复合材料，以聚苯硫醚为基材，通过加入导热填料来提高复合材料的导热性能，通过加入增强体来提高复合材料的力学性能。为了进一步增强材料的导热性能，本发明中对增强体进行了表面改性处理，通过在增强体表面浸渍聚合物单体原料液，经原位聚合及碳化处理后，在增强体表面附着了碳化层。最后，再将该表面碳化增强体与其他原料共混挤出，制备得到复合材料。经对比试验发现，采用表面碳化增强体代替普通的增强体，在保证了增强体的增强复合材料的力学性能效果外，还可以进一步提高复合材料的导热性能。
优选的，所述聚苯硫醚基材的熔体流动速率为800～1200g/10min。选择该熔体流动速率下的聚苯硫醚有利于减小复合材料的造粒与成型难度。
所述的表面碳化增强体采用以下方法得到：
将单体原料、增强体与可选择加入的二维片状的导热填料共混，经原位聚合及碳化后得到表面碳化增强体。
优选的，所述增强体选自无碱玻璃纤维和/或碳纤维；进一步优选，所述增强体的长度为2～8mm。若增强体长度过短，则力学性能不佳；若长度过长，则分散性较差，导热性能不佳。再优选，所述增强体的长度为4mm。经试验发现，采用该长度下的增强体，制备得到的复合材料的导热性能与力学性能均达到更佳。
优选的，所述导热填料选自石墨和/或碳化硅；进一步优选为石墨，经试验发现，在本体系中，添加石墨后的导热效果优于碳化硅。
再优选，所述石墨的目数选自200～800目，经试验发现，在本体系中，石墨粒径过大，力学性能差；石墨粒径过小则易团聚，导热性低，且堆密度小，挤出时混合不均匀。再进一步优选，所述石墨的目数选自 500目，经试验发现，采用该目数的石墨，制备得到的复合材料的导热性能与力学性能均达到更佳。
优选的，所述碳层中还含有二维片状的导热填料；通过在聚合物单体原料液中掺杂二维片状的导热填料，经原位聚合及碳化处理后，将二维片状的导热填料掺杂进增强体表面的碳化层中。经试验发现，通过在表面碳化增强体中再掺杂二维片状的导热填料，可以再进一步显著提高复合材料的导热性能。并经过对比试验发现，若将同样量的二维片状的导热填料通过共混的方式直接加入基材中，由于添加量极低，对最终制备的复合材料的导热性能几乎没有影响。
优选的，所述碳层的前驱体选自聚酰亚胺(PI)或聚醚酰亚胺
(PEI)。
优选的，所述二维片状的导热填料选自石墨烯和/或氮化硼。
进一步优选，所述碳层的前驱体选自PI，所述二维片状的导热填料选自石墨烯。经试验发现，在本体系中，将石墨烯添加到聚酰亚胺的原料单体中发生原位聚合，石墨烯与聚酰亚胺产生协同效应，碳化后得到的碳层能大幅提高复合材料导热性能。
在上述优选的原料基础上，按重量百分比计，所述高导热的增强聚苯硫醚复合材料的原料组成包括：
聚苯硫醚基材               30～50％；
表面碳化增强体             10～20％；
导热填料                   40～60％。
进一步优选，原料组成包括：
聚苯硫醚基材               30～50％；
表面碳化增强体             10～20％；
导热填料                   40～50％。
再优选，原料组成包括：
聚苯硫醚基材               40～50％；
表面碳化增强体              10～20％；
导热填料                      40％。
再进一步优选：
所述增强体选自4mm的碳纤维；
所述导热填料选自目数为500目的石墨；
所述碳层的前驱体选自PI；
所述二维片状的导热填料选自石墨烯。
采用上述进一步优选的原料种类与原料组成，制备得到的PPS复合材料的导热性能与力学性能均达到最佳。
除上述原料外，本发明公开的高导热的增强聚苯硫醚复合材料还可根据不同的应用场合要求，加入各种功能性助剂。如偶联剂、相容剂、增韧剂等等。
本发明还公开了所述高导热的增强聚苯硫醚复合材料的制备方法，包括如下步骤：
(1)将单体原料、增强体与可选择加入的二维片状的导热填料共混，经原位聚合及碳化后得到表面碳化增强体；
(2)以包括聚苯硫醚基材、导热填料与步骤(1)制备的表面碳化增强体的混合物为原料，经挤出造粒后制备得到高导热的增强聚苯硫醚复合材料。
步骤(1)中，首先以聚合物单体为原料，通过原位聚合的方式，在增强体表面包覆聚合物层，再经过碳化后，获得表面包覆碳层的增强体。
所述原位聚合的方式采用本领域的常规技术手段，根据包覆的聚合物层的不同，选择与其相适应的聚合物单体。因为采用浸渍的方式，所以采用溶液聚合，具体的聚合温度，采用的溶剂种类，以及后续的碳化温度也均与聚合物层的种类相适应，均采用本领域的常规选择。
以所述碳层的前驱体选自聚酰亚胺为例，所述单体原料选自对苯二 胺和联苯四甲酸二酐，以N,N’-二甲基乙酰胺为溶剂，聚合温度为常温，碳化温度为650～800℃。
优选加入二维片状的导热填料，制备得到表面包覆掺杂有二维片状导热填料的碳层的增强体。
进一步优选，所述二维片状的导热填料与增强体的质量比为0.1～0.5：100；更优选为0.27:100。
步骤(2)中：
所述聚苯硫醚基材与导热填料从主喂料口加入挤出机；
所述表面碳化增强体从侧喂料口加入挤出机；
所述挤出造粒的温度为310～340℃。
与现有技术相比，本发明具有如下优点：
本发明公开了一种高导热的增强聚苯硫醚复合材料，采用聚苯硫醚基材、导热填料与表面改性的增强体为原料，通过在增强体表面浸渍聚合物单体原料液，经原位聚合及碳化处理后，在增强体表面附着碳化层。通过该设计进一步提高聚苯硫醚复合材料导热性能。而针对一些对导热性能有更高要求的领域，本发明通过在聚合物单体原料液中掺杂二维片状的导热填料，经原位聚合及碳化处理后，在增强体表面附着掺杂有二维片状的导热填料的碳化层，利用碳化层与二维片状的导热填料的协同作用，不仅进一步大幅提高聚苯硫醚复合材料导热性能，还保证了其优异的加工性能与力学性能。
本发明制备的聚苯硫醚复合材料导热及机械性能优异，是一种具有大规模工业化生产前景的新型导热材料，可用于热交换器，散热器，散热外壳，LED塑料包装，电子器件，电子设备以及对散热要求较高的大型装备领域。
具体实施方式
下面通过具体实施例对本发明作进一步说明，但本发明的保护范围不局限于以下实施例。
实施例1
步骤(1)、对苯二胺(PDA，8.9kg)溶于300L N,N′-二甲基乙酰胺中，加入2kg石墨烯(
Figure PCTCN2021127323-appb-000001
C-THERM TM)超声分散10h，然后加入联苯四甲酸二酐(BPDA，24.4kg)，在冰水冷却下机械搅拌4h。混合粘液中加750kg无碱玻璃纤维(长度：4mm)，继续搅拌1h。最后将分散了玻纤的聚酰亚胺粘液置于管式炉中，于N 2气氛下以5℃/min的升温速率加热至400℃，再以2℃/min的升温速率加热至780℃，保温2h，得到表面碳化玻纤。
步骤(2)、将聚苯硫醚及石墨在120℃下干燥4h。
步骤(3)、按以下质量百分比组成进行配比：聚苯硫醚(NHU-PPS3490)40％、石墨(500目)40％、步骤(1)得到的表面碳化玻纤20％，将聚苯硫醚与石墨搅拌均匀，然后加入到双螺杆挤出机(18mm双螺杆挤出机)的主喂料料斗中，表面碳化玻纤加入到侧喂料料斗中，设定双螺杆挤出机从料斗到模头的各段温度分别为：285℃、320℃、340℃、340℃、325℃、315℃、325℃，主机的螺杆转速为350rpm，侧喂料转速为250rpm，将物料共混熔融挤出切粒。
步骤(4)、制样进行性能测试，测试结果见下表2。
实施例2
步骤(1)、对苯二胺(PDA，8.9kg)溶于300L N,N′-二甲基乙酰胺中，加入2kg石墨烯(
Figure PCTCN2021127323-appb-000002
C-THERMTM)超声分散10h，然后加入联苯四甲酸二酐(BPDA，24.4kg)，在冰水冷却下机械搅拌4h。混合粘液中加750kg无碱玻璃纤维(长度：2mm)，继续搅拌1h。最后将分散了玻纤的聚酰亚胺粘液置于管式炉中，于N 2气氛下以 5℃/min的升温速率加热至400℃，再以2℃/min的升温速率加热至780℃，保温2h，得到表面碳化的玻纤。
步骤(2)、将聚苯硫醚及石墨在120℃下干燥4h。
步骤(3)、按以下质量百分比组成进行配比：聚苯硫醚(NHU-PPS3490)40％、石墨(500目)40％、步骤(1)得到的表面碳化玻纤20％，然后按照与实施例1相同步骤挤出造粒。
步骤(4)、制样进行性能测试，测试结果见下表2。
实施例3
步骤(1)、对苯二胺(PDA，8.9kg)溶于300L N,N′-二甲基乙酰胺中，加入2kg石墨烯(
Figure PCTCN2021127323-appb-000003
C-THERMTM)超声分散10h，然后加入联苯四甲酸二酐(BPDA，24.4kg)，在冰水冷却下机械搅拌4h。混合粘液中加750kg无碱玻璃纤维(长度：8mm)，继续搅拌1h。最后将分散了玻纤的聚酰亚胺粘液置于管式炉中，于N 2气氛下以5℃/min的升温速率加热至400℃，再以2℃/min的升温速率加热至780℃，保温2h，得到表面碳化的玻纤。
步骤(2)、将聚苯硫醚及石墨在120℃下干燥4h。
步骤(3)、按以下质量百分比组成进行配比：聚苯硫醚(NHU-PPS3490)40％、石墨(500目)40％、步骤(1)得到的表面碳化玻纤20％，然后按照与实施例1相同步骤挤出造粒。
步骤(4)、制样进行性能测试，测试结果见下表2。
实施例4
步骤(1)、按照实施例1的方法制备表面碳化的玻纤。
步骤(2)、将聚苯硫醚及石墨在120℃下干燥4h。
步骤(3)、按以下质量百分比组成进行配比：聚苯硫醚(NHU-PPS3490)40％、石墨(200目)40％、步骤(1)得到的表面碳化玻纤20％，然后按照与实施例1相同步骤挤出造粒。
步骤(4)、制样进行性能测试，测试结果见下表2。
实施例5
步骤(1)、按照实施例1的方法制备表面碳化的玻纤。
步骤(2)、将聚苯硫醚及石墨在120℃下干燥4h。
步骤(3)、按以下质量百分比组成进行配比：聚苯硫醚(NHU-PPS3490)40％、石墨(800目)40％、步骤(1)得到的表面碳化玻纤20％，然后按照与实施例1相同步骤挤出造粒。
步骤(4)、制样进行性能测试，测试结果见下表2。
实施例6
步骤(1)、对苯二胺(PDA，8.9kg)溶于300L N,N′-二甲基乙酰胺中，加入2kg石墨烯(
Figure PCTCN2021127323-appb-000004
C-THERMTM)超声分散10h，然后加入联苯四甲酸二酐(BPDA，24.4kg)，在冰水冷却下机械搅拌4
h。混合粘液中加750kg碳纤维(长度：4mm)，继续搅拌1h。最后将分散了碳纤维的聚酰亚胺粘液置于管式炉中，于N 2气氛下以5℃/min的升温速率加热至400℃，再以2℃/min的升温速率加热至780℃，保温2h，得到表面碳化碳纤。
步骤(2)、将聚苯硫醚及石墨在120℃下干燥4h。
步骤(3)、按以下质量百分比组成进行配比：聚苯硫醚(NHU-PPS3490)50％、石墨(500目)40％、步骤(1)得到的表面碳化碳纤10％，然后按照与实施例1相同步骤挤出造粒。
步骤(4)、制样进行性能测试，测试结果见下表2。
实施例7
步骤(1)、按照实施例1的方法制备表面碳化的玻纤。
步骤(2)、将聚苯硫醚在120℃下干燥4h。
步骤(3)、按以下质量百分比组成进行配比：聚苯硫醚(NHU-PPS3490)30％、碳化硅50％、步骤(1)得到的表面碳化玻纤20％，然后按照与实施例1相同步骤挤出造粒。
步骤(4)、制样进行性能测试，测试结果见下表2。
实施例8
步骤(1)、对苯二胺(PDA，8.9kg)溶于300L N,N′-二甲基乙酰胺中，加入2kg氮化硼超声分散10h，然后加入联苯四甲酸二酐(BPDA，24.4kg)，在冰水冷却下机械搅拌4h。混合粘液中加750kg无碱玻璃纤维(长度：4mm)，继续搅拌1h。最后将分散了玻纤的聚酰亚胺粘液置于管式炉中，于N 2气氛下以5℃/min的升温速率加热至400℃，再以2℃/min的升温速率加热至780℃，保温2h，得到表面碳化的玻纤。
步骤(2)、将聚苯硫醚及石墨在120℃下干燥4h。
步骤(3)、按以下质量百分比组成进行配比：聚苯硫醚(NHU-PPS3490)40％、石墨(500目)40％、步骤(1)得到的表面碳化玻纤20％，然后按照与实施例1相同步骤挤出造粒。
步骤(4)、制样进行性能测试，测试结果见下表2。
实施例9
步骤(1)、对苯二胺(PDA，8.9kg)溶于300L N,N′-二甲基乙酰胺中，然后加入联苯四甲酸二酐(BPDA，24.4kg)，在冰水冷却下机械搅拌4h。混合粘液中加750kg无碱玻璃纤维(长度：4mm)，继续搅拌1h。最后将分散了玻纤的聚酰亚胺粘液置于管式炉中，于N 2气氛下以5℃/min的升温速率加热至400℃，再以2℃/min的升温速率加热至780℃，保温2h，得到不含石墨烯的表面包覆聚酰亚胺碳层的碳化玻纤。
步骤(2)、将聚苯硫醚及石墨在120℃下干燥4h。
步骤(3)、按以下质量百分比组成进行配比：聚苯硫醚40％、石墨40％、步骤(1)得到的不含石墨烯的表面碳化玻纤20％，将聚苯硫醚与石墨搅拌均匀，然后加入到双螺杆挤出机的主喂料料斗中，玻纤加入到侧喂料料斗中，设定双螺杆挤出机从料斗到模头的各段温度分别为： 285℃、320℃、340℃、340℃、325℃、315℃、325℃，主机的螺杆转速为350rpm，侧喂料转速为250rpm，将物料共混熔融挤出切粒。
步骤(4)、制样进行性能测试，测试结果见下表2。
实施例10
步骤(1)、双酚A型二醚二酐(BPADA，5.2kg)溶于100L N,N′-二甲基乙酰胺中，加入0.4kg石墨烯超声分散10h。对苯二胺(PDA，1.2kg)溶于20L N,N′-二甲基乙酰胺中，然后逐滴加入到反应液中，在40℃下机械搅拌6h。混合粘液中加150kg无碱玻璃纤维(长度：4mm)，继续搅拌1h。最后将分散了玻纤的聚醚酰亚胺粘液置于管式炉中，于N 2气氛下以5℃/min的升温速率加热至400℃，再以2℃/min的升温速率加热至780℃，保温2h，得到表面碳化的玻纤。
步骤(2)、将聚苯硫醚及石墨在120℃下干燥4h。
步骤(3)、按以下质量百分比组成进行配比：聚苯硫醚(NHU-PPS3490)40％、石墨(500目)40％、步骤(1)得到的表面碳化玻纤20％，然后按照与实施例1相同步骤挤出造粒。
步骤(4)、制样进行性能测试，测试结果见下表2。
实施例11
步骤(1)、对苯二胺(PDA，8.9kg)溶于300L N,N’-二甲基乙酰胺中，然后加入联苯四甲酸二酐(BPDA，24.4kg)，在冰水冷却下机械搅拌4h。混合粘液中加750kg无碱玻璃纤维，继续搅拌1h。最后将分散了玻纤的聚酰亚胺粘液置于管式炉中，于N 2气氛下以5℃/min的升温速率加热至400℃，再以2℃/min的升温速率加热至780℃，保温2h，得到不含石墨烯的表面碳化玻纤。
步骤(2)、将聚苯硫醚及石墨在120℃下干燥4h。
步骤(3)、按以下质量百分比组成进行配比：聚苯硫醚40％、石墨40％、步骤(1)得到的不含石墨烯的表面碳化玻纤19.95％、石墨烯0.05％，将聚苯硫醚与石墨、石墨烯搅拌均匀，然后加入到双螺杆挤出机 (18mm双螺杆挤出机)的主喂料料斗中，玻纤加入到侧喂料料斗中，设定双螺杆挤出机从料斗到模头的各段温度分别为：285℃、320℃、340℃、340℃、325℃、315℃、325℃，主机的螺杆转速为350rpm，侧喂料转速为250rpm，将物料共混熔融挤出切粒。
步骤(4)、制样进行性能测试，测试结果见下表2。
实施例12
步骤(1)、对苯二胺(PDA，8.9kg)溶于300L N,N’-二甲基乙酰胺中，然后加入联苯四甲酸二酐(BPDA，24.4kg)，在冰水冷却下机械搅拌4h。混合粘液中加750kg无碱玻璃纤维，继续搅拌1h。最后将分散了玻纤的聚酰亚胺粘液置于管式炉中，于N 2气氛下以5℃/min的升温速率加热至400℃，再以2℃/min的升温速率加热至780℃，保温2h，得到不含石墨烯的表面包覆聚酰亚胺碳层的碳化玻纤。
步骤(2)、将聚苯硫醚及石墨在120℃下干燥4h。
步骤(3)、按以下质量百分比组成进行配比：聚苯硫醚20％、石墨40％、步骤(1)得到的不含石墨烯的表面碳化玻纤20％、石墨烯20％，将聚苯硫醚与石墨、石墨烯搅拌均匀，然后加入到双螺杆挤出机(50mm双螺杆挤出机)的主喂料料斗中，玻纤加入到侧喂料料斗中，将物料共混熔融挤出切粒。
步骤(4)、制样进行性能测试，测试结果见下表2。
本对比例中，由于加入的导热填料的含量高达60％，导致加工困难，无法采用常规设备(18mm双螺杆挤出机)进行挤出，因此更换为50mm双螺杆挤出机。
对比例1
步骤(1)、将聚苯硫醚及石墨在120℃下干燥4h。
步骤(2)、按以下质量百分比组成进行配比：聚苯硫醚40％、石墨40％、未经表面处理的无碱玻璃纤维20％(长度：4mm)，将聚苯硫醚与石墨搅拌均匀，然后加入到双螺杆挤出机的主喂料料斗中，玻纤加入 到侧喂料料斗中，设定双螺杆挤出机从料斗到模头的各段温度分别为：285℃、320℃、340℃、340℃、325℃、315℃、325℃，主机的螺杆转速为350rpm，侧喂料转速为250rpm，将物料共混熔融挤出切粒。
步骤(3)、制样进行性能测试，测试结果见下表2。
以上各实施例与对比例的配方组成见表1。
表2中各性能参数的测试：
ISO527-1-2012塑料拉伸性能的测定；
ISO527-2塑料拉伸性能的测定；
ISO178-2010塑料弯曲性能的测定；
ISO179-1-2000塑料简支梁冲击性能的测定；
ISO180-2000塑料伊兆特(Izod)冲击强度的测定；
热线法，GB/T 10297-2015非金属固体材料导热系数的测定。
表1
Figure PCTCN2021127323-appb-000005
Figure PCTCN2021127323-appb-000006
表2
Figure PCTCN2021127323-appb-000007
观察表2中数据，可知，通过在增强体表面进行碳化处理可以提高PPS复合材料的导热性能；而通过在碳化层中添加少量二维片状填料又 可以进一步地显著提高导热性能；但若将该增加的二维片状填料直接以共混的形式加入原料中，对于导热性能的提高基本可以忽略；而如果想要达到与本发明中的技术方案相当的导热性能，需要在现有技术的基础上加入高达60％的导热填料，但同时会导致加工困难，采用常规的挤出设备无法挤出；即使更换挤出设备实现顺利挤出，但制备的PPS复合材料的力学性能也出现了显著下降。
对比实施例1与实施例7、8与10，可知，以石墨烯为二维片状填料，以聚酰亚胺PI为碳化前驱体，以石墨为导热填料，三者复合组成的体系，最终制备的PPS复合材料具有更佳的导热性能。
进一步对比实施例1～3，可知，无碱玻璃纤维增强体的长度为4mm时，制备的PPS复合材料的力学性能与导热性能更佳；对比实施例1、4～5，可知，石墨的目数为500目时，制备的PPS复合材料的力学性能与导热性能更佳；对比实施例1与实施例6，可知，当增强体选自碳纤维时，在10％的添加量下即可获得与实施例1相当的力学性能，但导热性能更佳。

Claims (12)

  1. 一种高导热的增强聚苯硫醚复合材料，其特征在于，按重量百分比计，原料组成包括：
    聚苯硫醚基材              30～50％；
    表面碳化增强体             5～30％；
    导热填料                  20～60％；
    所述表面碳化增强体为外表面包覆有碳层的增强体。
  2. 根据权利要求1所述的高导热的增强聚苯硫醚复合材料，其特征在于，所述的增强聚苯硫醚复合材料由所述原料经过挤出造粒制备得到。
  3. 根据权利要求1所述的高导热的增强聚苯硫醚复合材料，其特征在于，所述聚苯硫醚基材的熔体流动速率为800～1200g/10min。
  4. 根据权利要求1所述的高导热的增强聚苯硫醚复合材料，其特征在于，所述的表面碳化增强体采用以下方法得到：
    将单体原料、增强体与可选择加入的二维片状的导热填料共混，经原位聚合及碳化后得到表面碳化增强体。
  5. 根据权利要求4所述的高导热的增强聚苯硫醚复合材料，其特征在于：
    所述增强体选自无碱玻璃纤维和/或碳纤维；
    所述导热填料选自石墨和/或碳化硅。
  6. 根据权利要求1所述的高导热的增强聚苯硫醚复合材料，其特征在于，所述碳层的前驱体选自聚酰亚胺或聚醚酰亚胺。
  7. 根据权利要求4所述的高导热的增强聚苯硫醚复合材料，其特征在于，所述碳层中还含有二维片状的导热填料；
    所述二维片状的导热填料选自石墨烯和/或氮化硼。
  8. 根据权利要求7所述的高导热的增强聚苯硫醚复合材料，其特征 在于，所述二维片状的导热填料与增强体的质量比为0.1～0.5:100。
  9. 根据权利要求1～8任一权利要求所述的高导热的增强聚苯硫醚复合材料，其特征在于，按重量百分比计，原料组成包括：
    聚苯硫醚基材               30～50％；
    表面碳化增强体             10～20％；
    导热填料                   40～60％。
  10. 根据权利要求9所述的高导热的增强聚苯硫醚复合材料，其特征在于：
    所述增强体的长度为2～8mm；
    所述增强体选自碳纤维；
    所述碳层的前驱体选自聚酰亚胺；
    所述导热填料选自石墨，目数选自200～800目；
    所述二维片状的导热填料选自石墨烯。
  11. 一种根据权利要求1～10任一权利要求所述的高导热的增强聚苯硫醚复合材料的制备方法，其特征在于，包括如下步骤：
    (1)将单体原料、增强体与可选择加入的二维片状的导热填料共混，经原位聚合及碳化后得到表面碳化增强体；
    (2)以包括聚苯硫醚基材、导热填料与步骤(1)制备的表面碳化增强体的混合物为原料，经挤出造粒后制备得到高导热的增强聚苯硫醚复合材料。
  12. 根据权利要求11所述的高导热的增强聚苯硫醚复合材料的制备方法，其特征在于，步骤(2)中：
    所述聚苯硫醚基材与导热填料从主喂料口加入挤出机；
    所述表面碳化增强体从侧喂料口加入挤出机；
    所述挤出造粒的温度为310～340℃。
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