CN111849161B - Thermoplastic composite material, preparation method thereof and high-precision plastic part - Google Patents

Thermoplastic composite material, preparation method thereof and high-precision plastic part Download PDF

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CN111849161B
CN111849161B CN201910341191.0A CN201910341191A CN111849161B CN 111849161 B CN111849161 B CN 111849161B CN 201910341191 A CN201910341191 A CN 201910341191A CN 111849161 B CN111849161 B CN 111849161B
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thermal expansion
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negative thermal
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CN111849161A (en
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彭雪松
胡邦红
曹娟娟
史华良
章园红
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Huawei Technologies Co Ltd
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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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
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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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The embodiment of the invention provides a thermoplastic composite material taking engineering plastics as a matrix, which comprises the following components in parts by weight: 20-80 parts of thermoplastic engineering plastic, 20-80 parts of functional filler, 1-10 parts of coupling agent, 0.5-1 part of antioxidant and 0.5-2 parts of other auxiliary agents, wherein the functional filler comprises 0-80 parts of negative thermal expansion material and 0-80 parts of silicon dioxide microspheres, and the total weight parts of the thermoplastic engineering plastic and the functional filler is 100 parts. The thermoplastic composite material has extremely low linear thermal expansion coefficient, good heat resistance and high stability, can be used for preparing high-precision structural members such as optical communication equipment and 5G equipment, and improves the long-term running precision of precision equipment products. The embodiment of the invention also provides a preparation method of the composite material and a high-precision plastic part.

Description

Thermoplastic composite material, preparation method thereof and high-precision plastic part
Technical Field
The invention relates to the technical field of resin composite materials, in particular to a thermoplastic composite material with an ultralow thermal expansion coefficient, a preparation method thereof and a high-precision plastic part.
Background
The thermoplastic engineering plastic has the characteristics of high rigidity, small creep, high comprehensive strength and good molding processability, and can be used as an engineering structural material instead of metal. However, compared with metal, the intermolecular acting force of the thermoplastic engineering plastic is weaker, the thermal expansion coefficient is relatively larger, and therefore, the dimensional stability is lower, when the thermoplastic engineering plastic is used for forming precision parts, the parts are subjected to thermal deformation under the temperature change due to the influence of thermal expansion and cold contraction, so that the long-term operation precision of the parts is reduced, and the application of the thermoplastic engineering plastic to precision equipment and instruments is limited.
Therefore, in order to satisfy the requirement of high dimensional stability of precision parts, it is necessary to develop a thermoplastic composite material having a low thermal expansion coefficient and high stability.
Disclosure of Invention
In view of this, a first aspect of embodiments of the present invention provides a thermoplastic composite material, which has an ultra-low thermal expansion coefficient, good heat resistance and high stability, and can be used for preparing high-precision components, and improve the long-term operation precision of precision equipment and instruments, so as to solve the problem that the existing thermoplastic engineering plastics are difficult to meet the requirement of high dimensional stability of precision components under the condition of impact change of external temperature due to a large thermal expansion coefficient.
Specifically, in a first aspect, an embodiment of the present invention provides a thermoplastic composite material, where the composite material includes the following components in parts by weight:
Figure BDA0002040749820000011
the functional filler comprises 0-80 parts of negative thermal expansion material and 0-80 parts of silicon dioxide microbeads, and the total weight of the thermoplastic engineering plastic and the functional filler is 100 parts.
In the first aspect of the present invention, further, the negative thermal expansion material is 20 to 80 parts by weight, and the silica micro beads are 0 to 20 parts by weight. Further, the negative thermal expansion material is 30-70 parts by weight; further 45-70 parts and 50-70 parts. Further, the weight portion of the silicon dioxide micro-beads is 0-10.
In the first aspect of the present invention, further, the weight part of the silica micro beads is 40 to 80 parts, and the weight part of the negative thermal expansion material is 0 to 30 parts. Further, the silica micro beads are 50 to 80 parts by weight, and further 60 to 70 parts by weight.
In the first aspect of the present invention, the ratio of the thermoplastic engineering plastic to the functional filler is 1:0.25-4 by weight, further 1:1-4 by weight, and further 1:1-3 by weight or 1:1.5-2.5 by weight. The thermoplastic composite materials with different thermal expansion coefficients can be obtained by controlling the weight part ratio of the thermoplastic engineering plastic to the functional filler.
In the first aspect of the present invention, the negative thermal expansion material has an average linear expansion coefficient in a temperature range of-60 ℃ to 350 ℃ which is a negative value in at least one of three-dimensional directions. Specifically, the negative thermal expansion material comprises one or more of pyrophosphate, pyrotungstate, tungstate, manganese nitrogen compounds, cordierite, beta-eucryptite and garnet negative thermal expansion materials. More specifically, the pyrophosphate-based negative thermal expansion material comprises ZrP2O7The pyrotungstate negative thermal expansion material comprises ZrW2O8The tungstate negative thermal expansion material comprises Al2W3O12、Y2W3O12、Sc2W3O12The manganese nitrogen compound negative thermal expansion material comprises Mn3AN, said Mn3A in AN is one or more of Zn, Ga, Cu, Fe and Ge, and the cordierite negative thermal expansion material comprises Mg2Al4Si5O18The beta-eucryptite negative thermal expansion material comprises LiAl2Si2O8The garnet negative thermal expansion material comprises NaZr2(PO4)3、KZr2(PO4)3。
In the first aspect of the present invention, the particle size of the silica micro beads is in the range of 1 μm to 50 μm, and the silica micro beads are solid microspheres or hollow microspheres.
In the first aspect of the present invention, further, the weight portion of the engineering thermoplastic is 20 to 60 parts, and the weight portion of the functional filler is 40 to 80 parts.
In the first aspect of the present invention, the engineering thermoplastic may be a conventional thermoplastic, and specifically may include one or more of polyamide, polycarbonate, polyoxymethylene, modified polyphenylene ether, thermoplastic polyester, polyphenylene sulfide, polyetherimide, liquid crystal polymer, polyethersulfone, polyaryletherketone, and fluororesin.
In the first aspect of the present invention, the coupling agent includes one or more of a silane coupling agent, a titanate coupling agent. The antioxidant comprises one or more of hindered phenol, aromatic amine, phosphite ester and thioester antioxidant. The other auxiliary agents comprise one or more of a toughening agent, a lubricant, an antistatic agent and a toner.
In a first aspect of the invention, the thermoplastic composite has an ultra-low coefficient of thermal expansion, in particular the thermoplastic composite has an average coefficient of thermal expansion of 0-23 x 10 in the temperature interval-60 ℃ to 350 ℃-6/℃。
The thermoplastic composite material provided by the first aspect of the embodiment of the invention has good heat resistance and ultralow thermal expansion coefficient (0-23 x 10)-6v/DEG C), and the coefficient of thermal expansion is adjustable within a certain range, and the material can be used for forming precise structural members, can quickly form high-precision plastic parts through an injection molding process, and can be used for products with extremely high requirements on dimensional precision, such as optical communication parts, high-precision antenna parts and the like.
The second aspect of the embodiments of the present invention provides a method for preparing a thermoplastic composite material, including the following steps:
according to the parts by weight, 20-80 parts of functional filler and 1-10 parts of coupling agent are added into a high-speed mixer to be uniformly mixed, and the mixture is obtained after drying; the functional filler comprises 0-80 parts of negative thermal expansion material and 0-80 parts of silicon dioxide micro-beads;
and adding the mixture, 20-80 parts of thermoplastic engineering plastic, 0.5-1 part of antioxidant and 0.5-2 parts of other auxiliary agents into a double-screw extruder together for mixing, and extruding and granulating to obtain the thermoplastic composite material, wherein the total weight part of the thermoplastic engineering plastic and the functional filler is 100 parts.
In the second aspect of the present invention, the screw rotation speed of the twin-screw extruder is 150-300 rpm, and the extrusion temperature is 180-380 ℃.
In the second aspect of the present invention, the mixing time is 1min to 30 min.
The preparation method of the thermoplastic composite material provided by the second aspect of the embodiment of the invention has simple process and is suitable for large-scale industrial production.
A third aspect of embodiments of the present invention provides a high-precision plastic part, which is prepared from the thermoplastic composite material according to the first aspect of the present invention. Specifically, the high-precision plastic part comprises an antenna bracket, an antenna shell, a diffraction grating, an optical fiber connector, a mobile phone precision structural part and the like.
The high-precision composite material part provided by the third aspect of the embodiment of the invention has high dimensional precision, high reliability of temperature impact resistance and long fatigue life under long-term work.
Detailed Description
The present invention will be further described with reference to specific examples.
The expansion and contraction with heat is the basic property of most substances, and the property brings many adverse effects to the manufacturing industry, especially in the fields of precision equipment manufacturing and precision testing, the influence of the thermal deformation generated by the processed or measured object due to the temperature change on the actual processing precision and measurement precision is not negligible. For these products with high requirements for long-term dimensional stability, good dimensional stability is required from the starting material, and among the commonly used engineering structural materials, the plastic materials have the greatest influence on the dimensions with the change of environmental temperature. The engineering plastic has good rigidity, mechanical strength, heat resistance and physical and chemical resistance, and is lighter than metal and higher in forming efficiency. However, since the thermal expansion coefficient of the thermoplastic engineering plastic is relatively large due to weak intermolecular force, when the thermoplastic engineering plastic is used for molding precision parts, the long-term running precision of the obtained precision parts is reduced due to the influence of expansion caused by heat and contraction caused by cold of the material, thereby limiting the application of the thermoplastic resin to precision equipment and instruments.
In order to solve the above problems, an embodiment of the present invention provides a thermoplastic composite material, where the composite material includes the following components in parts by weight:
Figure BDA0002040749820000031
the functional filler comprises 0-80 parts of negative thermal expansion material and 0-80 parts of silicon dioxide microbeads, and the total weight of the thermoplastic engineering plastic and the functional filler is 100 parts.
The thermoplastic composite material provided by the embodiment of the invention is obtained by compounding the negative thermal expansion material and/or the silicon dioxide microspheres and the thermoplastic engineering plastic, has an ultralow thermal expansion coefficient, and the thermal expansion coefficient is adjustable in a certain range.
In an embodiment of the present invention, optionally, the negative thermal expansion material is 20 to 80 parts by weight, and the silica micro beads are 0 to 20 parts by weight. Further, the negative thermal expansion material is 30-70 parts by weight; further 45-70 parts and 50-70 parts. In some embodiments, the weight fraction of the silica micro beads is 0, and in other embodiments, the weight fraction of the silica micro beads is greater than 0 and less than or equal to 20. Further, the weight portion of the silicon dioxide micro-beads is 0-10. In the system of the embodiment of the invention, the negative thermal expansion material is used as a main functional filler, and a small amount of silica microspheres are added to serve as a forming auxiliary agent, so that the fluidity and the formability of the composite material can be improved. Because the negative thermal expansion material has negative thermal expansion coefficient, and the thermal expansion coefficients of the components of the composite material have additive property according to the composite material mixing law (ROM), the composite material of the embodiment has ultralow thermal expansion coefficient, and the thermal expansion coefficient can be adjusted in a certain range by controlling the type and the addition amount of the negative thermal expansion material.
The negative thermal expansion material is a compound with a negative average linear expansion coefficient or average volume expansion coefficient in a certain temperature range, and has the properties of thermal shrinkage and cold expansion in a specific temperature range. In particular, in the embodiment of the invention, the linear expansion coefficient of the negative thermal expansion material in the temperature range of-60-350 ℃ is negative in at least one direction in three-dimensional directions, namely, the negative thermal expansion material shows a phenomenon of thermal shrinkage and cold expansion in at least one direction. In an embodiment of the present invention, the negative thermal expansion material includes at least one of an isotropic negative thermal expansion material and an anisotropic negative thermal expansion material. Specifically, the linear expansion coefficient of the isotropic negative thermal expansion material is negative in all directions; further, the linear expansion coefficient is equal to a negative value in each direction, and the isotropic negative thermal expansion material shows uniform expansion behavior in each direction. The anisotropic negative thermal expansion material means that the linear expansion coefficient is negative in some directions and positive or zero in other directions, and thus shows inconsistent expansion behavior in all directions. In the embodiment of the invention, the negative thermal expansion material is preferably an isotropic negative thermal expansion material, and because the expansion behaviors in all directions are consistent, the composite material can have more uniform and stable thermal stress, so that the composite material part further has higher stability, fatigue life and thermal shock resistance.
In the embodiment of the present invention, the negative thermal expansion material may include different kinds, and specifically, the negative thermal expansion material may be one or more selected from the group consisting of pyrophosphates, pyrotungstates, tungstates, manganese nitrides, cordionites, β -eucryptites, and garnet negative thermal expansion materials. More specifically, the pyrophosphate-based negative thermal expansion material comprises ZrP2O7(ii) a The pyrotungstate negative thermal expansion material comprises ZrW2O8(ii) a The tungstate negative thermal expansion material comprises Al2W3O12、Y2W3O12、Sc2W3O12(ii) a The manganese nitrogen compound negative thermal expansion material comprises Mn3AN, said Mn3A in AN is one or more of Zn, Ga, Cu, Fe and Ge, wherein Mn can be partially substituted by other elements (such as Fe and the like); the cordierite-based negative thermal expansion material includes Mg2Al4Si5O18(ii) a The beta-eucryptite negative thermal expansion material comprises LiAl2Si2O8(ii) a The garnet negative thermal expansion material comprises NaZr2(PO4)3、KZr2(PO4)3. The above specific negative thermal expansion materials are only examples, and the present invention is not limited to the above listed negative thermal expansion materials.
The different types of negative thermal expansion materials described above differ in their negative expansion mechanism. For example, pyrophosphates (e.g. ZrP)2O7) Pyrotungstates (e.g. ZrW)2O8) The reason is that M1-O-M2 bonds (M1 and M2 are metal atoms, O is a bridge atom) exist in the crystal structure, the bonds of the M-O bonds are strong enough, the bond length cannot change along with the temperature, the energy required by the transverse thermal vibration of the oxygen bridge atom is low, and therefore when the oxygen atom vibrates transversely, the distance between the non-bonded M1 and the non-bonded M2 is reduced, the crystal structure is rotationally coupled, and finally the total volume of the crystal is reduced, and the crystal shows the properties of thermal shrinkage and cold expansion. In the manganese nitrogen compound material, the manganese nitrogen compound with an anti-perovskite structure can generate magnetic transformation under a certain temperature condition, and Mn is used3CuN is taken as an example, when the temperature is reduced, when the lattice expansion amount caused by magnetic order is larger than the lattice contraction amount caused by phonon thermal vibration, the material shows negative thermal expansion behavior, and the adjustable range of the thermal expansion coefficient of the manganese-nitrogen compound material is larger and can reach-25 ppm multiplied by 10 to the maximum-6V. C. The expansion characteristics of the beta-eucryptites are anisotropic, beta-eucryptites being a hexagonal system resembling high temperature quartz, Li rising as temperature rises+Can migrate from the tetrahedral coordination center to the octahedral position, and the phase change process can cause the a-axis and the b-axis of the crystal to expand and the c-axis to contract, thereby showing the characteristic of negative expansion in a single direction.
Due to the addition of the negative thermal expansion material, the composite material has the advantages of reduced thermal expansion coefficient, better heat resistance and more excellent flame retardant property compared with an engineering plastic base material, and different property improvements are reflected, for example, the composite material also has the advantages of high dielectric constant and low dielectric loss, and because part of the negative thermal expansion material (such as a manganese nitrogen compound) has good metallicity and mechanical strength, the thermoplastic composite material with high mechanical strength, good electric conductivity and good heat conductivity can be obtained by compounding the negative thermal expansion material with the thermoplastic engineering plastic.
In another embodiment of the present invention, optionally, the weight part of the silica micro beads is 40 to 80 parts, and the weight part of the negative thermal expansion material is 0 to 30 parts. Further, the silicon dioxide micro-beads are 50-80 parts by weight, and further 60-70 parts by weight. In some embodiments, the weight part of the negative thermal expansion material is 0 parts, and in other embodiments, the weight part of the negative thermal expansion material may be greater than 0 parts and less than or equal to 30 parts, further may be greater than 0 parts and less than or equal to 20 parts, and further may be greater than 0 parts and less than or equal to 10 parts. The silicon dioxide micro-beads have very low thermal expansion coefficient, the spherical filler can play a role in improving the fluidity and the formability of the composite material, the composite material with the ultralow thermal expansion coefficient can be obtained by compounding the spherical filler with thermoplastic engineering plastic, the thermal expansion coefficient can be adjusted within a certain range by controlling the adding amount of the silicon dioxide micro-beads, and in addition, the silicon dioxide micro-beads are easy to obtain, so that the preparation cost of the composite material can be greatly reduced. In the system using the silica micro beads as the main functional filler in the embodiment, the thermal expansion coefficient can be further reduced by adding a small amount of negative thermal expansion material.
In the embodiment of the present invention, optionally, the particle size of the silica micro beads is in the range of 1 μm to 50 μm, and further, the particle size of the silica micro beads is in the range of 1 μm to 20 μm. In the embodiment of the invention, the silica micro-beads can be solid micro-beads or hollow micro-beads.
The thermoplastic engineering plastic is a kind of resin capable of being heated, softened and cooled repeatedly, its molecular structure is linear or non-cross-linked structure with a few branched chains, and the resin is heated and melted in the course of forming, and then flows with the action of shearing, and can be shaped in the mould, and then cooled and shaped to obtain the product with required shape. Compared with general plastics, the engineering plastics have excellent heat resistance and cold resistance, have excellent mechanical properties in a wide temperature range, and are suitable for being used as structural materials. In the embodiment of the present invention, the engineering thermoplastic may be one or more of conventional types, including but not limited to polyamide, polycarbonate, polyoxymethylene, modified polyphenylene oxide, thermoplastic polyester, polyphenylene sulfide, polyether imide, liquid crystal polymer, polyether sulfone, polyaryletherketone and fluorine resin, and the polyphenylene sulfide may be linear polyphenylene sulfide. Among other things, selecting engineering plastics with relatively low coefficients of thermal expansion allows for lower coefficient of thermal expansion thermoplastic composites.
In the embodiment of the invention, according to the product precision requirement, the expansion coefficient of the composite material can be actively regulated and controlled by designing the type and the mass ratio of the functional filler and the thermoplastic engineering plastic so as to obtain the composite material with different thermal expansion coefficients. Alternatively, the ratio of the parts by weight of the engineering thermoplastic to the functional filler may be 1:0.25-4, further, the ratio of the parts by weight of the engineering thermoplastic to the functional filler may be 1:1-4, and further, the ratio of the parts by weight of the engineering thermoplastic to the functional filler may be 1:1-3 or 1: 1.5-2.5.
In an embodiment of the present invention, the coupling agent includes one or more of a silane coupling agent and a titanate coupling agent. The silane coupling agent may be, but is not limited to, silane coupling agents KH-550, KH-560, KH-570. The titanate coupling agent may specifically be, but is not limited to, titanate coupling CS-101, titanate coupling agent 109.
In an embodiment of the present invention, the antioxidant comprises one or more of hindered phenols, aromatic amines, phosphites, and thioesters. The other auxiliary agents comprise one or more of a toughening agent, a lubricant, an antistatic agent and a toner. Specifically, the antioxidant may be one or more selected from the following designations: antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 626, antioxidant 300, antioxidant 1330, antioxidant 619F or antioxidant 168. The antistatic agent can be carbon black, and the toner can be carbon black 660R, titanium dioxide ZR-940D and the like.
In the embodiment of the present invention, the lubricant may be, but not limited to, one or more of ethylene-propylene copolymer (AC540), paraffin wax, liquid paraffin, zinc stearate, lead stearate, barium stearate, calcium stearate, and pentaerythritol stearate. The toughening agent may be, but is not limited to, one or more of ethylene-octene copolymer (POE), polypropylene grafted maleic anhydride, maleic anhydride grafted ethylene-1-octene copolymer, butadiene-styrene rubber, chlorinated polyethylene, methacrylate-butadiene-styrene terpolymer (MBS), ethylene-vinyl acetate copolymer (EVA), butyl acrylate-methyl methacrylate copolymer, or ethylene-methyl methacrylate copolymer.
In the embodiment of the present invention, further optionally, the weight portion of the thermoplastic engineering plastic may specifically be 20 to 60 parts, and the weight portion of the functional filler is 40 to 80 parts; furthermore, the weight portion of the thermoplastic engineering plastic can be 20-50 parts, and the weight portion of the functional filler is 50-80 parts. In the embodiment of the invention, the weight part of the coupling agent can be 1-5 parts or 1-3 parts.
In an embodiment of the invention, the thermoplastic composite has an average coefficient of thermal expansion of 0 to 23 x 10 in the temperature range of-60 ℃ to 350 ℃-6The temperature per DEG C can be used as a molding raw material to be applied to the field of manufacturing of high-precision plastic parts. The thermal expansion coefficient of the composite material depends mainly on the thermal expansion coefficients of both the engineering thermoplastic and the negative thermal expansion material, so that the specific value of the average thermal expansion coefficient differs for systems of different components, in particular the average thermal expansion coefficient may be 0-20 x 10-6/℃、0-15×10-6/° C or 0-10 × 10-6/. degree.C., it should be noted that the negative thermal expansion property at different temperatures is not good due to different negative thermal expansion materialsAlso, the thermoplastic composite of certain embodiments of the present invention may therefore have a lower average coefficient of thermal expansion for a certain temperature interval within the temperature interval of-60 ℃ to 350 ℃.
The thermoplastic composite material provided by the embodiment of the invention has an ultralow thermal expansion coefficient, is adjustable within a certain range, has good heat resistance and high stability, can be used in the field of precision device molding, can prepare high-precision plastic parts with high dimensional stability, improves the reliability of long-term temperature impact resistance of finished products of parts, and reduces the maintenance cost.
Correspondingly, the embodiment of the invention also provides a preparation method of the thermoplastic composite material, which comprises the following steps:
s10, adding 20-80 parts of functional filler and 1-10 parts of coupling agent into a high-speed mixer according to parts by weight, uniformly mixing, and drying to obtain a mixture; the functional filler comprises 0-80 parts of negative thermal expansion material and 0-80 parts of silicon dioxide micro-beads;
and S20, adding the mixture, 20-80 parts of thermoplastic engineering plastic, 0.5-1 part of antioxidant and 0.5-2 parts of other auxiliary agents into a double-screw extruder together for mixing, and extruding and granulating to obtain the thermoplastic composite material, wherein the total weight part of the thermoplastic engineering plastic and the functional filler is 100 parts.
In the embodiment of the present invention, in step S10, the mixing time of the raw materials in the high-speed mixer is 1min to 30min, and further may be 5min to 20 min; the stirring speed of the high-speed mixer may be 500 rpm to 1000 rpm, and further may be 600 rpm to 800 rpm. The drying temperature is 100-140 ℃, particularly 120 ℃, and the drying time is 2-3 h. The functional filler (comprising the negative thermal expansion material and the silicon dioxide microspheres) and the coupling agent are mixed in advance, so that the coupling agent is combined with the surface of the functional filler in advance through chemical action to obtain a surface with better affinity to an engineering plastic matrix, and the functional filler can be better dispersed in a subsequent resin system, so that a thermoplastic composite material product with more uniform components and better performance can be obtained.
In an embodiment of the present invention, in step S10, the negative thermal expansion material has a negative linear expansion coefficient in at least one of three-dimensional directions within a temperature range of-60 ℃ to 350 ℃. In an embodiment of the present invention, the negative thermal expansion material includes at least one of an isotropic negative thermal expansion material and an anisotropic negative thermal expansion material. Specifically, the linear expansion coefficient of the isotropic negative thermal expansion material is negative in all directions; further, the linear expansion coefficient is equal to a negative value in each direction, and the isotropic negative thermal expansion material shows uniform expansion behavior in each direction. The anisotropic negative thermal expansion material means that the linear expansion coefficient is negative in some directions and positive or zero in other directions, and thus shows inconsistent expansion behavior in all directions. In the embodiment of the invention, the negative thermal expansion material is preferably an isotropic negative thermal expansion material, and because the expansion behaviors in all directions are consistent, the thermoplastic composite material can have more uniform and stable thermal stress, so that the thermoplastic composite material product has higher stability, fatigue life and thermal shock resistance.
Specifically, in the embodiment of the present invention, the negative thermal expansion material may be one or more selected from pyrophosphates, pyrotungstates, tungstates, manganese nitrogen compounds, cordierite, β -eucryptite, and garnet negative thermal expansion materials. More specifically, the pyrophosphate-based negative thermal expansion material comprises ZrP2O7(ii) a The pyrotungstate negative thermal expansion material comprises ZrW2O8(ii) a The tungstate negative thermal expansion material comprises Al2W3O12、Y2W3O12、Sc2W3O12(ii) a The manganese nitrogen compound negative thermal expansion material comprises Mn3AN, said Mn3A in AN is one or more of Zn, Ga, Cu, Fe and Ge, wherein Mn can be partially substituted by other elements (such as Fe and the like); the cordierite-based negative thermal expansion material includes Mg2Al4Si5O18(ii) a The beta-eucryptite negative thermal expansion material comprises LiAl2Si2O8(ii) a The garnet negative thermal expansion material comprises NaZr2(PO4)3、KZr2(PO4)3. The above specific negative thermal expansion materials are only examples, and the present invention is not limited to the above listed negative thermal expansion materials.
In an embodiment of the present invention, the coupling agent includes one or more of a silane coupling agent and a titanate coupling agent.
In the embodiment of the invention, in step S20, the screw rotation speed of the twin-screw extruder is 150-. Further, the rotation speed is 200-300 rpm. The specific extrusion temperature can be determined according to the type of the selected resin and the relative proportion of the added negative thermal expansion material so as to achieve the purpose of fully plasticizing the mixed material, and the specific extrusion temperature can be 200 ℃, 280 ℃, 300 ℃, 320 ℃, 350 ℃ and 380 ℃.
In embodiments of the present invention, the engineering resin may be of a conventional type, including, but not limited to, one or more of polyamide, polycarbonate, polyoxymethylene, modified polyphenylene ether, thermoplastic polyester, polyphenylene sulfide, polyetherimide, liquid crystal polymer, polyethersulfone, polyaryletherketone, and fluororesin. Specifically, the thermal expansion coefficient, the moldability and the mechanical properties can be selected comprehensively according to the requirements. The thermoplastic engineering plastics are generally dried in advance and then mixed with other raw materials.
In one embodiment of the invention, the negative thermal expansion material is 20-80 parts by weight, and the silica micro-beads are 0-20 parts by weight. Further, the negative thermal expansion material is 30-70 parts by weight, further 45-70 parts by weight and 50-70 parts by weight. Wherein, in some embodiments, the weight part of the silica micro beads is 0 part, and in other embodiments, the weight part of the silica micro beads is more than 0 part and less than or equal to 10 parts. Further, the weight portion of the silicon dioxide micro-beads is 0-10.
In another embodiment of the invention, the silica micro beads are 40 to 80 parts by weight, and the negative thermal expansion material is 0 to 30 parts by weight. Further, the silicon dioxide micro-beads are 50-80 parts by weight, and further 60-70 parts by weight. In some embodiments, the negative thermal expansion material is 0 parts by weight, and in other embodiments, the negative thermal expansion material is greater than 0 parts and less than or equal to 30 parts by weight.
In the embodiment of the present invention, optionally, the particle size of the silica micro beads is in the range of 1 μm to 50 μm, further, the particle size of the silica micro beads is in the range of 10 μm to 30 μm, and further, the particle size of the silica micro beads is in the range of 10 μm to 20 μm. In the embodiment of the invention, the silica micro-beads can be solid micro-beads or hollow micro-beads.
In the embodiment of the invention, according to the product precision requirement, the expansion coefficient of the composite material can be actively regulated and controlled by designing the type and the mass ratio of the functional filler and the engineering plastic so as to obtain the thermoplastic composite material with different thermal expansion coefficients. Considering the molding property, the mechanical property, the thermal expansion coefficient and the like, optionally, the ratio of the parts by weight of the engineering thermoplastic to the functional filler may be 1:0.25-4, further, the ratio of the parts by weight of the engineering thermoplastic to the functional filler may be 1:1-3, and further, the ratio of the parts by weight of the engineering thermoplastic to the functional filler may be 1: 1.5-2.5.
In an embodiment of the present invention, the coupling agent includes one or more of a silane coupling agent and a titanate coupling agent. The antioxidant comprises one or more of hindered phenol, aromatic amine, phosphite ester and thioester antioxidant. The other auxiliary agents comprise one or more of a toughening agent, a lubricant, an antistatic agent and a toner.
In the embodiment of the present invention, further optionally, the weight portion of the thermoplastic engineering plastic may specifically be 20 to 60 parts, and the weight portion of the functional filler is 40 to 80 parts; furthermore, the weight portion of the thermoplastic engineering plastic can be 20-50 parts, and the weight portion of the functional filler is 50-80 parts. In the embodiment of the invention, the weight part of the coupling agent can be 1-5 parts or 1-3 parts.
In the embodiment of the invention, the average thermal expansion coefficient of the prepared thermoplastic composite material in the temperature range of-60-350 ℃ is 0-23 multiplied by 10-6/℃。
The preparation method of the thermoplastic composite material provided by the embodiment of the invention has a simple process and is suitable for large-scale industrial production.
The thermoplastic composite material provided by the embodiment of the invention has an ultralow thermal expansion coefficient, is adjustable in a certain range, has good heat resistance and high stability, can be used in the fields of optical communication and 5G equipment precision device molding, can prepare high-precision plastic parts with high dimensional stability, improves the long-term temperature impact resistance reliability of finished products of the parts, and reduces the maintenance cost.
The following examples are intended to illustrate the invention in more detail.
Example 1
A thermoplastic composite material comprises the following components in parts by weight: 30 parts of linear polyphenylene sulfide and ZrW (ZrW)2O8)60 parts of SiO210 parts of microbeads, 1.5 parts of silane coupling agent, 0.5 part of antioxidant and 1 part of other auxiliary agents.
The preparation method of the thermoplastic composite material of the embodiment comprises the following steps:
s10, mixing pyrotungstate (ZrW)2O8)、SiO2Adding the microbeads and the silane coupling agent into a high-speed mixer, mixing for 20min at a stirring speed of 800 r/min, and drying for 2h at 120 ℃ to obtain a mixture;
s20, adding the pre-dried polyphenylene sulfide, the mixture, the antioxidant and the processing aid into a double-screw extruder, mixing and dispersing, wherein the screw rotating speed of the double-screw extruder is 200 revolutions per minute, the processing temperature is 320 ℃, and obtaining plastic granules after extrusion and cooling, namely the thermoplastic polyphenylene sulfide composite material of the embodiment.
The thermoplastic composite material obtained in the embodiment 1 of the invention has an average thermal expansion coefficient of 0-23 x 10 within the temperature range of-60 ℃ to 350 DEG C-6Range of/° cWithin the enclosure, specifically, about 11.3 × 10-6/° c, and has isotropic negative thermal expansion behavior due to ZrW2O8Has negative thermal expansion coefficient of-8.8 x 10 in a wide temperature range (0.3K-1050K)-6/° c, and the shrinkage is kept uniform in each direction. The thermoplastic polyphenylene sulfide composite material of the embodiment also has the characteristics of good heat resistance, high mechanical strength and excellent flame retardant property.
Example 2
A thermoplastic composite material comprises the following components in parts by weight: 30 parts of linear polyphenylene sulfide and pyrophosphate (ZrP)2O7)60 parts of SiO210 parts of microbeads, 1.5 parts of silane coupling agent, 0.5 part of antioxidant and 1 part of other auxiliary agents.
The preparation method of the thermoplastic composite material of the embodiment comprises the following steps:
s10, dissolving pyrophosphate (ZrP)2O7)、SiO2Adding the microbeads and the silane coupling agent into a high-speed mixer, mixing for 30min at a stirring speed of 600 revolutions per minute, and drying for 3h at 120 ℃ to obtain a mixture;
s20, adding the pre-dried polyphenylene sulfide, the mixture, the antioxidant and the processing aid into a double-screw extruder, mixing and dispersing, wherein the screw rotating speed of the double-screw extruder is 300 revolutions per minute, the processing temperature is 320 ℃, and obtaining plastic granules after extrusion and cooling, namely the thermoplastic polyphenylene sulfide composite material of the embodiment.
The thermoplastic composite material obtained in the embodiment 1 of the invention has an average thermal expansion coefficient of 0-23 x 10 within the temperature range of-60 ℃ to 350 DEG C-6In the range of/° C, specifically, the average coefficient of thermal expansion in the temperature range of 100 ℃ to 350 ℃ is about 10.0 × 10-6/° c, and has isotropic negative thermal expansion behavior. This is because ZrP2O7Has a negative thermal expansion coefficient of-10.8 x 10 in a wider temperature range of 373-773K-6/℃。
Example 3
A thermoplastic composite material comprises the following components in parts by weight: 36 parts of linear polyphenylene sulfideNitrogen manganese magnetic compound ((Mn)0.96Fe0.04)3(Zn0.5Ge0.5) N)44 parts of SiO220 parts of microbeads, 3 parts of silane coupling agent, 0.5 part of antioxidant and 1 part of other auxiliary agent.
The preparation method of the thermoplastic composite material of the embodiment comprises the following steps:
s10, mixing nitrogen and manganese magnetic compound ((Mn)0.96Fe0.04)3(Zn0.5Ge0.5)N)、SiO2Adding the microbeads and the silane coupling agent into a high-speed mixer, mixing for 25min at the stirring speed of 700 r/min, and drying for 2h at 130 ℃ to obtain a mixture;
s20, adding the pre-dried polyphenylene sulfide, the mixture, the antioxidant and the processing aid into a double-screw extruder, mixing and dispersing, wherein the screw rotating speed of the double-screw extruder is 150 revolutions per minute, the processing temperature is 320 ℃, and obtaining plastic granules after extrusion and cooling, namely the thermoplastic polyphenylene sulfide composite material of the embodiment.
The thermoplastic composite material obtained in the embodiment 3 of the invention has an average thermal expansion coefficient of 0-23 x 10 within the temperature range of-60 ℃ to 350 DEG C-6In the range of/° C, specifically, the average coefficient of thermal expansion in the temperature range of 43 ℃ to 113 ℃ is about 10.8 × 10-6/° c, and has isotropic negative thermal expansion behavior. This is because (Mn)0.96Fe0.04)3(Zn0.5Ge0.5) The thermal expansion coefficient of N reaches-25 x 10 in the range of 316K-386K-6The negative expansion effect is significant/° c. In this embodiment, the thermal expansion coefficient of the thermoplastic polyphenylene sulfide composite material of this embodiment can be controlled by changing the metal ratio in the nitrogen-manganese compound. In addition, due to (Mn)0.96Fe0.04)3(Zn0.5Ge0.5) N has good metallicity and mechanical strength, so the thermoplastic polyphenylene sulfide composite material has high mechanical strength and good electric conductivity and heat conductivity.
Example 4
A thermoplastic composite material comprises the following components in parts by weight: polyetherimide (PEI)25 parts of scandium tungstate (Sc)2W3O12)60 parts of powder, SiO215 parts of microbeads, 2.5 parts of titanate coupling agent, 0.5 part of antioxidant and 2 parts of other auxiliary agents.
The preparation method of the thermoplastic composite material of the embodiment comprises the following steps:
s10, mixing scandium tungstate powder and SiO2Adding the microbeads and the titanate coupling agent into a high-speed mixer, mixing for 25min at the stirring speed of 800 r/min, and drying for 2h at 120 ℃ to obtain a mixture;
s20, adding the polyether imide after being pre-dried, the mixture, the antioxidant and the processing aid into a double-screw extruder together for mixing and dispersing, wherein the screw rotating speed of the double-screw extruder is 250 revolutions per minute, the processing temperature is 350 ℃, and plastic granules are obtained after extrusion and cooling, namely the thermoplastic polyether imide composite material of the embodiment.
The thermoplastic composite material obtained in the embodiment 4 of the invention has an average thermal expansion coefficient of 0-23 x 10 within the temperature range of-60 ℃ to 350 DEG C-6In the range of/° C, specifically, the average coefficient of thermal expansion in the temperature range of-60 ℃ to 177 ℃ is about 14.5 × 10-6V. C. Wherein Sc2W3O12The powder has a thermal expansion coefficient of-2.2 × 10 in the range of 10K-450K-6/℃。
Example 5
A thermoplastic composite material comprises the following components in parts by weight: polyetherimide (PEI)35 parts, beta-eucryptite LiAl2Si2O850 parts of powder, SiO215 parts of microbeads, 2 parts of titanate coupling agent, 0.5 part of antioxidant and 1.5 parts of other auxiliary agents.
The preparation method of the thermoplastic composite material of the embodiment comprises the following steps:
s10, mixing beta-eucryptite LiAl2Si2O8Powder, SiO2Adding the microbeads and the titanate coupling agent into a high-speed mixer, mixing for 25min at the stirring speed of 800 r/min, and drying for 2h at 120 ℃ to obtain a mixture;
s20, adding the polyether imide after being pre-dried, the mixture, the antioxidant and the processing aid into a double-screw extruder together for mixing and dispersing, wherein the screw rotating speed of the double-screw extruder is 200 revolutions per minute, the processing temperature is 350 ℃, and plastic granules are obtained after extrusion and cooling, namely the thermoplastic polyether imide composite material of the embodiment.
The thermoplastic composite material obtained in the embodiment 5 of the invention has an average thermal expansion coefficient of 0-23 x 10 within the temperature range of-60 ℃ to 350 DEG C-6In the range of/° C, specifically, the average coefficient of thermal expansion in the temperature range of 25 ℃ to 350 ℃ is about 14.5 × 10-6V. C. Wherein beta-eucryptite LiAl2Si2O8The thermal expansion coefficient in the temperature range of 298K-1273K is-6.2 x 10-6/℃。
Example 6
A thermoplastic composite material comprises the following components in parts by weight: liquid Crystalline Polymer (LCP)40 parts, ZrW2O860 parts of powder, 2 parts of silane coupling agent, 0.5 part of antioxidant and 0.5 part of processing aid.
The preparation method of the liquid crystal polymer composite material comprises the following steps:
s10, mixing ZrW2O8Adding the powder and a silane coupling agent into a high-speed mixer, mixing for 25min at a stirring speed of 800 r/min, and drying for 2h at 120 ℃ to obtain a mixture;
s20, adding the liquid crystal polymer, the mixture, the antioxidant and the processing aid into a double-screw extruder, mixing and dispersing, wherein the screw rotating speed of the double-screw extruder is 200 revolutions per minute, the processing temperature is 200 ℃, and plastic granules are obtained after extrusion and cooling, namely the liquid crystal polymer composite material of the embodiment.
The thermoplastic composite material obtained in the embodiment 6 of the invention has an average thermal expansion coefficient of 0-23 x 10 within the temperature range of-60 ℃ to 350 DEG C-6In the range of/° c, specifically, the average linear coefficient of thermal expansion in the perpendicular flow direction is about 18.7 x 10-6The dimensional accuracy of the LCP composite material in the vertical flow direction can be improved.
Example 7
A thermoplastic composite material comprises the following components in parts by weight: 30 parts of linear polyphenylene sulfide and SiO270 parts of microbeads, 1 part of silane coupling agent, 0.4 part of antioxidant and 1 part of other auxiliary agents.
The preparation method of the thermoplastic composite material of the embodiment comprises the following steps:
s10, mixing SiO2Adding the microbeads and the silane coupling agent into a high-speed mixer, mixing for 20min at a stirring speed of 600 revolutions per minute, and drying for 2h at 120 ℃ to obtain a mixture;
s20, adding the pre-dried polyphenylene sulfide, the mixture, the antioxidant and the processing aid into a double-screw extruder, mixing and dispersing, wherein the screw rotating speed of the double-screw extruder is 200 revolutions per minute, the processing temperature is 320 ℃, and obtaining plastic granules after extrusion and cooling, namely the thermoplastic polyphenylene sulfide composite material of the embodiment.
The thermoplastic composite material obtained in the embodiment has an average thermal expansion coefficient of 0-23 x 10 in a temperature range of-60 ℃ to 350 DEG C-6In the range of/° C, specifically, about 18X 10-6/° c, and has isotropic negative thermal expansion behavior. The thermoplastic polyphenylene sulfide composite material with low thermal expansion coefficient of the embodiment is prepared from SiO2The lubricating effect of the microbeads has good flowability and formability.
Example 8
A thermoplastic composite material comprises the following components in parts by weight: 40 parts of linear polyphenylene sulfide and SiO240 parts of microbead, beta-eucryptite LiAl2Si2O820 parts of powder, 1.5 parts of silane coupling agent, 0.4 part of antioxidant and 1 part of other auxiliary agent.
The preparation method of the thermoplastic composite material of the embodiment comprises the following steps:
s10, mixing SiO2Microbead, beta-eucryptite LiAl2Si2O8Adding the powder and a silane coupling agent into a high-speed mixer, mixing for 20min at a stirring speed of 600 revolutions per minute, and drying for 2h at 120 ℃ to obtain a mixture;
s20, adding the pre-dried polyphenylene sulfide, the mixture, the antioxidant and the processing aid into a double-screw extruder, mixing and dispersing, wherein the screw rotating speed of the double-screw extruder is 200 revolutions per minute, the processing temperature is 320 ℃, and obtaining plastic granules after extrusion and cooling, namely the thermoplastic polyphenylene sulfide composite material of the embodiment.
The thermoplastic composite material obtained in the embodiment has an average thermal expansion coefficient of 0-23 x 10 in a temperature range of-60 ℃ to 350 DEG C-6In the range of/° C, specifically, about 20X 10-6/° c, and has isotropic negative thermal expansion behavior. The filler of the embodiment is SiO2The micro-beads are compounded with beta-eucryptite to obtain the composite material with good fluidity and low thermal expansion coefficient.
The thermoplastic composite material prepared in the embodiment of the invention is used as a raw material, and high-precision plastic parts with different structures can be prepared and obtained through injection molding and other modes. Specifically, the high-precision plastic part can comprise an antenna support/shell, a diffraction grating, an optical fiber connector, a mobile phone precision structural part and the like, and the composite material provided by the embodiment of the invention is used for preparation, so that the thermal shock resistance and the long-term working reliability of the device can be greatly improved.

Claims (17)

1. The thermoplastic composite material is characterized by comprising the following components in parts by weight:
Figure FDA0003381282890000011
the functional filler comprises more than 0 part and less than or equal to 80 parts of negative thermal expansion material and 0-80 parts of silicon dioxide micro-beads, and the total weight part of the thermoplastic engineering plastic and the functional filler is 100 parts; the thermoplastic engineering plastic comprises one or more of polyamide, polycarbonate, polyformaldehyde, modified polyphenyl ether, thermoplastic polyester, polyphenylene sulfide, polyetherimide, liquid crystal polymer, polyether sulfone, polyaryletherketone and fluororesin; the average thermal expansion coefficient of the thermoplastic composite material in the temperature range of-60 ℃ to 350 ℃ is 0-23×10-6/℃。
2. The composite material of claim 1, wherein the negative thermal expansion material is 20 to 80 parts by weight, and the silica micro beads are 0 to 20 parts by weight.
3. The composite material of claim 2, wherein the negative thermal expansion material is present in an amount of 30 to 70 parts by weight.
4. The composite material of claim 1, wherein the silica micro beads are present in an amount of 50 to 80 parts by weight, and the negative thermal expansion material is present in an amount of greater than 0 parts and less than or equal to 30 parts by weight.
5. The composite material according to any one of claims 1 to 4, wherein the ratio of parts by weight of the engineering thermoplastic to the functional filler is from 1:1 to 4.
6. The composite material of claim 1, wherein the negative thermal expansion material has an average linear expansion coefficient in a temperature range of-60 ℃ to 350 ℃ that is negative in at least one of three dimensions.
7. The composite material of claim 1, wherein the negative thermal expansion material comprises one or more of pyrophosphates, pyrotungstates, tungstates, manganese nitrogenates, cordierite, β -eucryptites, garnet-like negative thermal expansion materials.
8. The composite material of claim 7, wherein the pyrophosphate-based negative thermal expansion material comprises ZrP2O7The pyrotungstate negative thermal expansion material comprises ZrW2O8The tungstate negative thermal expansion material comprises Al2W3O12、Y2W3O12、Sc2W3O12The manganese nitrogen compound negative thermal expansion material comprises Mn3AN, said Mn3A in AN is one or more of Zn, Ga, Cu, Fe and Ge, and the cordierite negative thermal expansion material comprises Mg2Al4Si5O18The beta-eucryptite negative thermal expansion material comprises LiAl2Si2O8The garnet negative thermal expansion material comprises NaZr2(PO4)3、KZr2(PO4)3。
9. The composite material of claim 1, wherein the silica microbeads range in size from 1 μ ι η to 50 μ ι η, the silica microbeads being either solid or hollow.
10. The composite material of claim 1, wherein the coupling agent comprises one or more of a silane coupling agent, a titanate coupling agent.
11. The composite material of claim 1, wherein the antioxidant comprises one or more of hindered phenolic, aromatic amine, phosphite, and thioester antioxidants.
12. The composite of claim 1, wherein the other additives include one or more of a toughening agent, a lubricant, an antistatic agent, and a toner.
13. A method of making a thermoplastic composite, comprising the steps of:
according to the parts by weight, 20-80 parts of functional filler and 1-10 parts of coupling agent are added into a high-speed mixer to be uniformly mixed, and the mixture is obtained after drying; the functional filler comprises more than 0 part and less than or equal to 80 parts of negative thermal expansion material and 0-80 parts of silicon dioxide micro-beads;
mixing the mixture with 20-80 parts of thermoplastic engineering plastic, 0.5-1 part of antioxidant and 0 part of5-2 parts of other auxiliary agents are added into a double-screw extruder together for mixing, and extrusion granulation is carried out to obtain the thermoplastic composite material, wherein the total weight part of the thermoplastic engineering plastic and the functional filler is 100 parts; the thermoplastic engineering plastic comprises one or more of polyamide, polycarbonate, polyformaldehyde, modified polyphenyl ether, thermoplastic polyester, polyphenylene sulfide, polyetherimide, liquid crystal polymer, polyether sulfone, polyaryletherketone and fluororesin; the average thermal expansion coefficient of the thermoplastic composite material in the temperature range of-60 ℃ to 350 ℃ is 0 to 23 multiplied by 10-6/℃。
14. The method of claim 13, wherein the twin-screw extruder has a screw speed of 150-.
15. The method of claim 13, wherein the mixing time is from 1min to 30 min.
16. A high precision plastic part characterized in that it is produced using a thermoplastic composite material according to any one of claims 1 to 12.
17. The high-precision plastic part of claim 16, wherein the high-precision plastic part comprises an antenna mount, an antenna housing, a diffraction grating, a fiber optic connector, or a cell phone precision structure.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101134846A (en) * 2006-08-31 2008-03-05 东莞银禧塑胶有限公司 Antistatic reinforced polyphenylene sulfide composite material and method for making same
JP2008247973A (en) * 2007-03-29 2008-10-16 Toppan Printing Co Ltd Foamed molding
CN104496183A (en) * 2014-12-26 2015-04-08 上海天马有机发光显示技术有限公司 Low-temperature seal glass material and preparation method of composite filler
CN108250751A (en) * 2018-02-07 2018-07-06 深圳华力兴新材料股份有限公司 The NMT technologies polyphenyl thioether resin composition and preparation method of a kind of low-k

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101134846A (en) * 2006-08-31 2008-03-05 东莞银禧塑胶有限公司 Antistatic reinforced polyphenylene sulfide composite material and method for making same
JP2008247973A (en) * 2007-03-29 2008-10-16 Toppan Printing Co Ltd Foamed molding
CN104496183A (en) * 2014-12-26 2015-04-08 上海天马有机发光显示技术有限公司 Low-temperature seal glass material and preparation method of composite filler
CN108250751A (en) * 2018-02-07 2018-07-06 深圳华力兴新材料股份有限公司 The NMT technologies polyphenyl thioether resin composition and preparation method of a kind of low-k

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