CN114262433A - Coupling agent and polyaryletherketone composite material prepared from same - Google Patents
Coupling agent and polyaryletherketone composite material prepared from same Download PDFInfo
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- CN114262433A CN114262433A CN202111345385.1A CN202111345385A CN114262433A CN 114262433 A CN114262433 A CN 114262433A CN 202111345385 A CN202111345385 A CN 202111345385A CN 114262433 A CN114262433 A CN 114262433A
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- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 239000007822 coupling agent Substances 0.000 title claims abstract description 66
- 229920006260 polyaryletherketone Polymers 0.000 title abstract description 11
- 239000004696 Poly ether ether ketone Substances 0.000 claims abstract description 87
- 229920002530 polyetherether ketone Polymers 0.000 claims abstract description 87
- 239000000945 filler Substances 0.000 claims abstract description 77
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 42
- 239000004917 carbon fiber Substances 0.000 claims abstract description 42
- 239000003571 electronic cigarette Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000000835 fiber Substances 0.000 claims description 50
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims description 40
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- 238000000034 method Methods 0.000 claims description 34
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 26
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- 239000000843 powder Substances 0.000 claims description 21
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- 238000000576 coating method Methods 0.000 claims description 16
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 14
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
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- 239000000178 monomer Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- IYRWEQXVUNLMAY-UHFFFAOYSA-N fluoroketone group Chemical group FC(=O)F IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 claims description 9
- 239000002109 single walled nanotube Substances 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229920002748 Basalt fiber Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 239000005083 Zinc sulfide Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 6
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
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- YGROSAOZMCLHSW-UHFFFAOYSA-N (4-chlorophenyl)-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(Cl)C=C1 YGROSAOZMCLHSW-UHFFFAOYSA-N 0.000 claims description 2
- HLRVUOFDBXRZBI-UHFFFAOYSA-N 4-fluoro-4'-hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(F)C=C1 HLRVUOFDBXRZBI-UHFFFAOYSA-N 0.000 claims description 2
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- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 28
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Abstract
The invention provides a coupling agent, a filler containing the coupling agent and a composite material of carbon fibers, wherein the coupling agent is more uniformly attached to the surfaces of the filler and the carbon fibers by utilizing the solubility of the coupling agent PEK-LK in an organic solvent, and meanwhile, the PEK-LK is used as one member of polyaryletherketone, has similar manufacturability with polyetheretherketone, and also ensures that the coupling agent is not decomposed in a high-temperature environment, thereby greatly exerting the effect of the coupling agent. In addition, the problem that the surface of the product has snowflake appearance is solved, and the mechanical property of the composite material is improved, so that the composite material is particularly suitable for preparing wafer boxes, electronic cigarettes, medical appliances and ceramic materials in the semiconductor industry.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a coupling agent, a preparation method thereof and application of the coupling agent in the field of polyaryletherketone composite materials.
Background
Under the background of a new era, scientific technology is continuously developed, and the development and progress of various industries are greatly promoted. The polyaryletherketone is used as a novel polymer material in many fields due to excellent performance, and the polyetheretherketone is the most representative polyaryletherketone material and is applied to various fields such as aerospace, automobile parts, electronic and electrical appliances, energy sources, wires and cables, medical treatment and the like due to excellent thermal stability, chemical resistance, mechanical properties, electrical insulation and fatigue resistance.
Semiconductors are the heart of the electronics industry, the foundation of the information industry, and wafer fabrication is the heart of the semiconductor industry chain. In recent years, with the continuous improvement and gradual development and expansion of the technical research and development level of semiconductor wafer enterprises, the requirements for wafer carriers are also more demanding, traditional materials such as PP and PFA cannot meet the requirements, PEEK plays a main role in manufacturing the wafer carriers by virtue of excellent comprehensive properties such as wear resistance and heat resistance, the appearance, mechanical properties and antistatic level of common PEEK materials cannot meet the use requirements of the wafer carriers, and the performance of a polyether-ether-ketone composite material added with carbon fibers and/or fillers meets the use requirements of the wafer carriers, but the carbon fibers and/or fillers and polyether-ether-ketone are not uniformly blended, so that the wafer carriers are greatly influenced.
The ceramic material is a traditional biomedical material, has high strength, but is relatively high in brittleness, relatively poor in corrosion resistance and wear resistance, inferior to an organic polymer material, difficult to machine and form, and generally needs high-temperature sintering, but the ceramic material is compounded with a polyether-ether-ketone material, so that the modulus of the polyether-ether-ketone can be effectively improved on the premise of meeting the toughness of an implant-grade material, and the toughness and the rigidity of the polyether-ether-ketone can reach ideal critical points. The ceramic PEEK composite material obtained by the conventional mixing process and the coupling agent has the defects that the components are difficult to uniformly disperse.
When the electronic cigarette works, a high-temperature environment exists around the electronic cigarette, and the temperature can reach about 300 ℃. Generally, these parts need to satisfy two conditions: temperature resistance and heat insulation. Therefore, the PEEK is a very suitable material, the temperature resistance level is just suitable, the cost performance is highest, the price of materials such as PEK and PEKEKK is doubled compared with the PEEK, and the temperature resistance level of the materials such as PEI/PPSU is not enough compared with the PEI/PPSU at the bottom end of the PEEK. Meanwhile, PEEK also has the characteristics of corrosion resistance (smoke corrosion resistance), FDA (food and drug administration) compliance and the like. The heat resistance of the PEEK can be increased by a common PEEK composite material process, but the increase is small.
Disclosure of Invention
The invention aims to provide a coupling agent, which can be used for more uniformly attaching or coating a filler and carbon fibers after being grafted by phenolphthalein and fluoroketone, and is beneficial to preparing a polyaryletherketone composite material.
A coupling agent selected from one of the following structures:
it is a second object of the present invention to provide a method for preparing a coupling agent.
(1) The preparation method of the Phenolphthalein (PLK) monomer comprises the following steps:
adding polyphenolic PPL, a silane coupling agent and sodium hydroxide into a three-neck flask, adding 500mL of solvent anhydrous ethanol 200-; wherein the molar ratio of PPL to the silane coupling agent to the sodium hydroxide is 1: (0.01-0.2): (1-3);
(2) preparation of coupling agent PEK-LK:
adding Phenolphthalein (PLK), fluoroketone and potassium carbonate into a three-neck flask, adding a solvent of 300-500mL toluene and 300-500mL dimethyl sulfoxide, introducing nitrogen, stirring, heating to 110-160 ℃ for reaction for 1-6 hours, evaporating the toluene, slowly heating to 190 ℃ for reaction for 2-8 hours, diluting the obtained yellow sticky substance with N, N-dimethylformamide, standing overnight, and layering. Slowly pouring the obtained supernatant into a mixed settling agent prepared from ethanol and hydrochloric acid to separate out a large amount of white products, repeatedly boiling the white products with deionized water, and drying the white products in a vacuum drying oven to obtain a product PEK-LK; wherein the molar ratio of PLK, fluoroketone and potassium carbonate is 1: (0.5-2): (0.5-3).
Preferably, the coupling agent is selected from silane coupling agents KH550, KH560 or KH570.
Preferably, the fluoroketone monomer is one of 4,4 ' -difluorobenzophenone, 4-chloro-4 ' -fluorobenzophenone and 4-fluoro-4 ' -hydroxybenzophenone.
Preferably, the Phenolphthalein (PLK) has a structure that is one of the following:
preferably, the molar ratio of PPL, silane coupling agent, and sodium hydroxide is 1: (0.03-0.18): (1-2).
Preferably, the molar ratio of PLK, fluoroketone and potassium carbonate is 1: (0.8-2): (1-3).
Preferably, the mol ratio of the ethanol to the hydrochloric acid in the settling liquid is 0.2-2. The preferred molar ratio is 1.
Preferably, the organic solvent is one of tetrahydrofuran and chloroform.
The third purpose of the invention is to provide a composite material, which is characterized in that the PEEK is added with the fiber and the filler which are coated by the coupling agent, so that the surfaces of the filler and the fiber are changed from hydrophilicity to lipophilicity, and the filler, the fiber and the PEEK are tightly combined with each other, thereby improving the mechanical property of the composite material.
A composite material is composed of the following components in parts by weight: PEEK: 50-90 parts of fiber: 0-30 parts of filler: 0-30 parts of filler which is pretreated by PEK-LK, and fiber which is pretreated by PEK-LK.
Preferably, the method for pretreating the filler by the coupling agent PEK-LK is a water dispersion method.
Preferably, the method for pretreating the fiber by the coupling agent PEK-LK is an impregnation method.
Preferably, the composite material consists of the following components in parts by weight: PEEK: 50-90 parts of fiber: 1-30 parts of filler: 1-20 parts. Further, PEEK: 65-85 parts of fiber: 10-25 parts of filler: 5-20 parts of a coupling agent PEK-LK: 1-3 parts, more preferably, PEEK: 65-85 parts of fiber: 10-20 parts of filler: 5-15 parts of a coupling agent PEK-LK: 1-3 parts.
Preferably, the filler is selected from one or more of conductive carbon black, colloidal graphite powder, single-wall or multi-wall carbon nanotubes with the diameter of 1-10 μm, titanium dioxide, aluminum oxide, zirconium dioxide, silicon nitride, zinc sulfide, barium sulfate and pigment carbon black.
Preferably, the fiber is selected from one or more of polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, glass fiber, quartz fiber and basalt fiber.
Preferably, the filler is selected from one or more of conductive carbon black, colloidal graphite powder and single-walled or multi-walled carbon nanotubes with the diameter of 1-10 microns, the fiber is selected from polyacrylonitrile-based carbon fiber and asphalt-based carbon fiber, and the polyether-ether-ketone composite material prepared by the technical scheme is suitable for preparing a crystal box in the field of semiconductors.
Preferably, the filler is selected from one or more of titanium dioxide, aluminum oxide, zirconium dioxide and silicon nitride, the fiber is selected from glass fiber or quartz fiber, more preferably, the fiber is glass fiber with monofilament diameter of 10-20 μm or quartz fiber with monofilament diameter of 10-20 μm, and the polyether-ether-ketone composite material prepared by the technical scheme is suitable for the medical and electronic fields, such as the manufacture of electronic component bases, artificial bones and teeth.
Preferably, the fiber is glass fiber, basalt fiber or quartz fiber, the filler is one or more of alumina, zinc sulfide, barium sulfate and pigment carbon black, and the polyetheretherketone composite material prepared by the technical scheme is suitable for manufacturing electronic cigarettes, especially shells of electronic cigarettes.
A fourth object of the present invention is to provide a method for preparing a composite material having significantly improved mechanical properties.
A method of making a composite material comprising the steps of:
(1) adding the dried PEEK coarse powder and the filler into a low-speed mixer for mixing at the speed of 200r/min for 10-20min to obtain a mixture;
(2) extruding and granulating the mixture obtained in the step (1) by using a double-screw extruder, feeding fibers laterally, wherein the extrusion temperature is 320-390 ℃, and the cooling mode is air cooling to obtain uniform granules;
preferably, the method further comprises the step of pretreating the filler: PEK-LK and filler are dispersed in water according to the weight ratio of 1: (0.8-1.5) dispersing in deionized water, stirring at high speed for 0.5-4 hours, filtering, and drying the obtained filter cake in a drying oven at 160 ℃ for 10-16 hours to obtain the filler.
Preferably, the method further comprises the step of pretreating the fibers: dissolving PEK-LK in an organic solvent according to a certain proportion, wherein the concentration of the PEK-LK is 0.2-1 g/mL, uniformly coating the solution on the surface of the carbon fiber by using a glass rod, naturally volatilizing the carbon fiber in the air, and then placing the carbon fiber in infrared searchlighting equipment for 1-6 hours until the solvent is completely volatilized, so as to obtain the carbon fiber with the thickness of 20 microns of coating.
Preferably, the process for drying polyetheretherketone is: and (3) drying the PEEK coarse powder in an oven at the temperature of 140-160 ℃ for 4-6 hours.
The fifth purpose of the invention is to provide the application of the polyetheretherketone composite material, and the polyetheretherketone composite material is suitable for preparing wafer boxes, electronic cigarettes, medical apparatuses and ceramic materials in the semiconductor industry.
Has the advantages that: 1. under the same process conditions, the PEK-LK coated fibers and the filler are easier to be uniformly mixed with the polyether-ether-ketone powder, so that the mechanical property of the prepared polyether-ether-ketone composite material is greatly improved, and the composite material has excellent uniformity in all directions. 2. The surface of the filler is changed from hydrophilicity to lipophilicity by physically coating the coupling agent and the filler, physical winding is generated between the filler and the fiber, the inorganic material and the polyether-ether-ketone are combined more tightly, and the strength, the cohesive force, the electrical property, the hydrophobicity, the ageing resistance and the like of the material are obviously improved. 3. The solubility of PEK-LK in organic solvent is utilized, PEK-LK is used as one member of polyaryletherketone, the PEK-LK has similar manufacturability with polyetheretherketone, and the coupling agent is not decomposed in high temperature environment, so that the effect of the coupling agent is greatly exerted.
Drawings
FIG. 1 is a basic circuit diagram for measuring surface resistivity using guard electrodes;
fig. 2 is a resistance test pattern of the composite material prepared in comparative example 1.
Fig. 3 is a sample resistance test of the composite material prepared in example 2.
Reference numerals: 1. a protected electrode; 2. the electrodes are not protected; 3. and protecting the electrode.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Test method
Coating thickness test
Coating thickness test method for PEK-LK coated fibres the coating thickness test method was determined with reference to the measurement method of GB/T13452.2-2008 paint and varnish film thickness, namely: the test is carried out using a depth micrometer or dial depth gauge, the coating is removed from the measurement area, the zero point of the instrument is checked and zeroed by using a reference plate, and then:
when the depth micrometer is used, the support legs are placed on the surface of the coating, the measuring rod is positioned above the exposed area, and the measuring rod is rotated downwards until the contact contacts with the substrate and touches the toothed bar;
in using a depth dial gauge, the contact element is placed over the exposed substrate with its contact pin placed on the coating (care should be taken to ensure that the contact pin is perpendicular to the sample surface if the dial gauge is of the type having a contact pin).
The coating thickness value can be read directly from the depth number.
Surface resistance test
The test method of the surface resistance refers to the GB/T1410-2006 volume surface resistivity test method for testing, namely:
preparing a sample: the invention adopts a square plate with the thickness of 60mm multiplied by 2mm as a test part for standby;
sample treatment: when measuring the surface resistance, the surface is not cleaned unless otherwise required. The surface portion to be tested should not be touched by anything except that the untouched surface of another sample of the same material may touch the sample to be tested. The samples were conditioned as in GB/T10580-2015.
A predetermined DC voltage is applied to measure the resistance between electrodes 1 and 2 of two measuring electrodes (FIG. 1) on the surface of the sample. The resistance should be measured after 1min of the electrochemical time, even if the current has not reached a steady state within this time.
Calculation of surface resistivity: it should be calculated as follows:
in the formula:
ρ — surface resistivity in ohms (Ω);
RXmeasured surface resistance, sheetThe bit is ohm (omega);
p-effective perimeter in meters (m) (or centimeters (cm)) of the protected electrode in a particular electrode-using device;
g-the distance between the two electrodes in meters (m) (or centimeters (cm));
reproducibility: since the resistance of a given sample varies with the test conditions and the material is not homogeneous from sample to sample, the reproducibility of the measurement is usually not close to + -10%, but there is often a large dispersion (the ratio of the measured values may be 10 to 1 under approximately the same conditions). In order for measurements to be comparable on similar samples, the measurements must be performed at approximately equal potential gradients.
Preparation of coupling agent PEK-LK
Examples 1a-1c preparation of coupling agents
1) Preparation of Phenolphthalein (PLK) monomer:
adding 1mol of PPL, 0.1mol of coupling agent, 2mol of sodium hydroxide (analytically pure) and 300mL of absolute ethyl alcohol (analytically pure) into a three-neck flask, gradually dissolving under stirring, heating to 65 ℃, adding 0.1mol of KI, then reacting for 14 hours, dropwise adding hydrochloric acid to adjust the pH value to 6, carrying out suction filtration, placing filtrate into a rotary evaporator, evaporating the solution to dryness at 80 ℃ to obtain light yellow crystals, repeatedly washing with deionized water, and then placing into a 160 ℃ oven to dry for 6 hours to obtain the target product phenolphthalein PLK.
2) Preparation of coupling agent PEK-LK:
1mol of phenolphthalein PLK prepared in the step 1), 1mol of 4, 4' -difluorobenzophenone (analytically pure), 2mol of potassium carbonate (analytically pure), 380mL of toluene (analytically pure) and 340mL of dimethyl sulfoxide (analytically pure) are added into a three-neck flask, nitrogen is introduced for stirring, the temperature is firstly raised to 140 ℃ for reaction for 6 hours, then the toluene is evaporated out, the temperature is slowly raised to 175 ℃ for reaction for 2 hours, and the obtained yellow sticky matter is diluted by N, N-dimethylformamide and stands overnight for layering. The resulting supernatant was slowly poured into a flask consisting of 1:1, precipitating a large amount of white products in a mixed settling agent prepared from ethanol and hydrochloric acid, repeatedly boiling and washing with deionized water, and drying in a vacuum drying oven to obtain the product PEK-LK.
The experimental scheme is detailed in the table I
TABLE 1 EXAMPLES 1a-1c coupling agent type and product type
| Examples | 1a | 1b | 1c |
| Coupling agent | KH550 | KH560 | KH570 |
| Phenolphthalein PLK | PLK-550 | PLK-560 | PLK-570 |
| PEK-LK model | PEK-LK-550 | PEK-LK-560 | PEK-LK-570 |
Wherein the PLK-550 prepared in the step 1) has a structure as follows:
the structure of the prepared PLK-560 is:
the structure of the prepared PLK-570 is:
the solution was tested at 25 ℃ using a nuclear magnetic resonance analyzer (Bruker, Germany, 400MHz, TMS internal standard) to obtain13C NMR spectrum, the carbon groups on the three aromatic ring skeletons are chemically migrated in slightly different chemical environments as follows:
(1) PLK-560 was shown at 43.6ppm
(2) PLK-570 expressed in 31.5ppm
(3) PLK-550 was shown to be 28.9ppm
The structure of the coupling agent prepared in the step 2) is as follows:
the structure of PEK-LK-550 is:
the structure of the prepared PEK-LK-560 is as follows:
the structure of the prepared PEK-LK-570 is as follows:
the solution was tested at 25 ℃ using a nuclear magnetic resonance analyzer (Bruker, Germany, 400MHz, TMS internal standard) to obtain13C NMR spectrum, the carbon groups on the three aromatic ring skeletons are chemically migrated in slightly different chemical environments as follows:
(1) PEK-LK-560 expressed in 43.6ppm
(2) PEK-LK-570 expressed at 31.5ppm
(3) PEK-LK-550 manifested in 28.9ppm
Preparation of composite material-suitable for making wafer cassettes
Example 2 composite Material prepared from polyetheretherketone, coupling agent PEK-LK-550, carbon fibers and conductive carbon Black Filler
Step 1 preparation of coupling agent PEK-LK-550 following the procedure of example 1a
mixing PEK-LK-550 and conductive carbon black in deionized water according to the mass ratio of 1:1 by a water dispersion method, stirring at a high speed for 4 hours, filtering, and drying the obtained filter cake in a drying oven at 160 ℃ for 14 hours to obtain the conductive carbon black.
Step 3 preparation of carbon fiber pretreated by PEK-LK-550
PEK-LK-550 is dissolved in tetrahydrofuran according to the proportion of 0.4Kg/1L, the solution is evenly coated on the surface of the asphalt-based carbon fiber by a glass rod, the asphalt-based carbon fiber is placed in air to be naturally volatilized, then the asphalt-based carbon fiber is placed in infrared searchlighting equipment for 4 hours until the solvent is completely volatilized, and the carbon fiber with the thickness of 20 mu m is obtained by testing according to a coating testing method.
Step 42000g preparation of polyetheretherketone composite:
(1) drying the PEEK coarse powder in a drying oven at 160 ℃ for 6 hours;
(2) adding 1500g of dried PEEK coarse powder and 200g of pretreated conductive carbon black into a low-speed mixer for mixing at the speed of 200r/min for 15min to obtain a mixture;
(3) and (3) carrying out extrusion granulation on the mixture obtained in the step (2) by using a double-screw extruder, feeding the pretreated carbon fibers on the side, setting the addition of the mixture to be 15% of the total mass of the composite material, wherein the extrusion temperature is 320 ℃/350 ℃/350 ℃/350 ℃/375 ℃/375 ℃, and the cooling mode is air cooling, so as to obtain material particles with uniform particles (the fibers and the fillers in the step 4 of all the embodiments in the patent are pretreated by using a coupling agent).
Example 3 composite Material prepared from polyetheretherketone, coupling agent PEK-LK-550, carbon fiber and colloidal graphite powder
Step 1 preparation of Phenolphthalein (PLK) monomer: following the procedure of example 1a, only the following changes were made: the amounts of the components were changed to 1mol of PPL, 0.05mol of KH550, 1.5mol of sodium hydroxide (analytical grade), and 500mL of absolute ethanol (analytical grade).
Preparation of intermediate PEK-LK: following the procedure of example 1a, only the following changes were made: the amounts of the individual components were changed to 1mol of PLK, 1.2mol of 4, 4' -difluorobenzophenone (analytical grade), 2.3mol of potassium carbonate (analytical grade), 420mL of toluene (analytical grade) and 380mL of dimethyl sulfoxide (analytical grade).
the preparation method of step 2 in example 2 was followed, except that the filler was changed to colloidal graphite powder.
Step 3, preparation of carbon fibers:
according to the preparation method of step 3 in the embodiment 2, only the carbon fiber is changed into the polyacrylonitrile-based carbon fiber, and the solvent is changed into the chloroform.
Step 42000g preparation of polyetheretherketone composite:
prepared according to the preparation method and process of example 2.
Example 4 composite material prepared from polyetheretherketone, coupling agent PEK-LK-550, carbon fibers and single-walled carbon nanotube filler
Step 1 preparation of Phenolphthalein (PLK) monomer: according to the preparation method of example 2, the amounts of the components were changed to 1mol of PPL, 0.08mol of KH550, 1.7mol of sodium hydroxide (analytical grade), and 450mL of absolute ethanol (analytical grade).
Preparation of intermediate PEK-LK: according to the preparation method of example 2, the amounts of the components were changed to 1mol of PLK, 1.1mol of 4, 4' -difluorobenzophenone (analytically pure), 2.4mol of potassium carbonate (analytically pure), 400mL of toluene (analytically pure) and 330mL of dimethyl sulfoxide (analytically pure).
the preparation method of example 2 was followed, and the filler was changed to 5 μm single-walled carbon nanotubes.
Step 3, pretreating carbon fibers by using PEK-LK-550:
the procedure of example 2 was followed except that the solvent was chloroform.
Step 42000g preparation of polyetheretherketone composite:
prepared according to the preparation method and process of example 2.
Example 5 composite materials prepared from polyetheretherketone, PEK-LK-560 carbon fibers, and Single-walled carbon nanotube Filler
This example was prepared in the same manner as example 2, except that in step 1 the coupling agent was replaced with KH550 and KH560.
Example 6 composite materials prepared from polyetheretherketone, PEK-LK-570 carbon fibers, and Single-walled carbon nanotube Filler
This example was prepared in the same manner as example 2, except that in step 1 the coupling agent was replaced with KH550 and KH570.
Comparative example 1:
preparation of 2000g of a conventional PEEK composite (fillers and fibers not pretreated):
(1) drying the PEEK coarse powder in a drying oven at 160 ℃ for 6 hours;
(2) adding 1500g of dried PEEK coarse powder and 200g of conductive carbon black into a low-speed mixer for mixing at the speed of 200r/min for 15min to obtain a mixture;
(3) extruding and granulating the PEEK coarse powder obtained in the step (2) by using a double-screw extruder, feeding the carbon fiber on the side, wherein the extrusion temperature is 320 ℃/375 ℃/375 ℃/375 ℃/375 ℃, and the cooling mode is air cooling, so that material particles with uniform particles are obtained;
preparation of test panels:
the pellets obtained in examples 2 to 6 and comparative example 1 were injection-molded by an injection molding machine to obtain a square plate for resistance test of 60 mm. times.60 mm. times.2 mm, a bar for dumbbell type tensile test of 10 mm. times.4 mm and a bar for bending test of 80 mm. times.10 mm. times.4 mm, at an injection molding temperature of 385 ℃ and a mold temperature of 180 ℃.
The polyetheretherketone composites prepared in examples 2 to 6 and comparative example 1 were each tested for mechanical properties, with reference to ISO 527, for tensile strength at 23 ℃; the flexural strength and flexural modulus were tested at 23 ℃ according to ISO 178.
The test results are summarized in Table 2
As can be seen from the Table, the resistivity of each region of the test sample of the composite materials of examples 2-6 is uniform and is not less than 104The surfaces of the test boards of example 2 and comparative example 1 were photographed with cameras, respectively, and the appearances of the surfaces are shown in fig. 2-3, which show that the filler and the fiber are uniformly distributed in the system by uniform resistivity and appearance without snowflake, the performances of the three coupling agents on the filler and the carbon fiber are basically the same, the problem of snowflake external application on the surface of the product is also solved, the mechanical properties of the composite material are also improved, which is more obvious in the composite examples 2-4. The filler and the fiber are physically coated by the coupling agent, so that the surfaces of the filler and the fiber are changed from hydrophilicity to lipophilicity, physical winding is generated between the filler and the fiber, the inorganic material and the polyether-ether-ketone are combined more tightly, the solubility of the PEK-LK in an organic solvent is utilized, the PEK-LK is used as one member of the polyaryletherketone, the PEK-LK has similar manufacturability with the polyether-ether-ketone, and the coupling agent is not decomposed in a high-temperature environment, so that the effectiveness of the coupling agent is greatly exerted, and the strength, the cohesive force, the electrical property, the hydrophobicity, the ageing resistance and the like of the material are obviously improved.
Preparation of composite materials-for medical and electronic applications
Example 7 composite prepared from polyetheretherketone, PEK-LK-550, alumina Filler
Step 1 preparation of coupling agent PEK-LK-550 following the procedure of example 1a
Mixing PEK-LK and the alumina ceramic filler in deionized water according to the mass ratio of 1:1 by a water dispersion method, stirring at a high speed for 4 hours, filtering, and drying the obtained filter cake in a drying oven at 160 ℃ for 14 hours to obtain the alumina ceramic filler.
Step 32000 g of preparation of the polyetheretherketone composite material:
(1) drying the PEEK coarse powder in a drying oven at 160 ℃ for 6 hours;
(2) adding 1500g of dried PEEK coarse powder and 200g of alumina ceramic filler into a low-speed mixer for mixing at the speed of 200r/min for 15min to obtain a mixture;
(3) extruding and granulating the mixture obtained in the step (2) by using a double-screw extruder, wherein the extrusion temperature is 320 ℃/350 ℃/350 ℃/350 ℃/350 ℃/350 ℃/375 ℃/375 ℃, and the cooling mode is air cooling, so that material particles with uniform particles are obtained;
example 8 composite Material prepared from polyetheretherketone, PEK-LK-550, glass fibers and titanium dioxide ceramic Filler
Step 1 preparation of Phenolphthalein (PLK) monomer: according to the preparation method of step 1 of example 7, the amounts of the components were changed to 1mol of PPL, 0.05mol of KH550, 1.5mol of sodium hydroxide, analytically pure, and 500mL of absolute ethanol, analytically pure.
Preparation of intermediate PEK-LK: according to the preparation method of example 7, the amounts of the components were changed to 1mol of PLK, 1.2mol of 4, 4' -difluorobenzophenone (analytically pure), 2.3mol of potassium carbonate (analytically pure), 420mL of toluene (analytically pure) and 380mL of dimethyl sulfoxide (analytically pure).
The preparation of example 7 was followed, changing the ceramic filler to titanium dioxide.
Step 3, pretreating the glass fiber by using PEK-LK-550:
PEK-LK is dissolved in tetrahydrofuran according to the proportion of 0.4Kg/1L, the solution is evenly coated on the surface of the glass fiber by a glass rod, the glass fiber is firstly placed in the air to be naturally volatilized, and then the glass fiber is placed in infrared searchlighting equipment for 4 hours until the solvent is completely volatilized, so that the glass fiber with the thickness of 20 mu m coating is obtained.
Step 42000g preparation of polyetheretherketone composite:
prepared according to the preparation method and procedure of example 7.
Example 9 composite Material prepared from polyetheretherketone, PEK-LK-550, Quartz fiber and zirconia ceramic Filler
Step 1 preparation of Phenolphthalein (PLK) monomer: according to the preparation method of example 7, the amounts of the components were changed to 1mol of PPL, 0.08mol of KH550, 1.7mol of sodium hydroxide (analytical grade), and 450mL of absolute ethanol (analytical grade).
Preparation of intermediate PEK-LK: according to the preparation method of example 7, the amounts of the components were changed to 1mol of PLK, 1.1mol of 4, 4' -difluorobenzophenone (analytically pure), 2.4mol of potassium carbonate (analytically pure), 400mL of toluene (analytically pure) and 330mL of dimethyl sulfoxide (analytically pure).
The preparation of example 7 was followed, except that the ceramic filler was changed to a zirconium dioxide ceramic filler.
Step 3, pretreating quartz fibers by using PEK-LK-550:
the preparation of example 8 was followed, the fiber being changed to quartz fiber and the solvent to chloroform.
Step 42000g preparation of polyetheretherketone composite:
prepared according to the preparation method and procedure of example 7.
Example 10 composite material prepared from polyetheretherketone, PEK-LK-560, glass fibers and alumina ceramic filler this example was the same as example 8 except that the coupling agent was replaced with KH550 to KH560 in step 1.
Example 11 composite Material made from polyetheretherketone, PEK-LK-570 glass fibers and alumina ceramic Filler
This example was prepared in the same manner as example 8, except that in step 1 the coupling agent was replaced with KH550 and KH570.
Comparative example 2:
2000g of conventional PEEK composite preparation (filler and fibres not pretreated):
(4) drying the PEEK coarse powder in a drying oven at 160 ℃ for 6 hours;
(5) adding 1500g of dried PEEK coarse powder and 200g of aluminum oxide into a low-speed mixer for mixing at the speed of 200r/min for 15min to obtain a mixture;
(6) extruding and granulating the PEEK coarse powder obtained in the step (2) by using a double-screw extruder, feeding the glass fiber on the side, wherein the extrusion temperature is 320 ℃/375 ℃/375 ℃/375 ℃/375 ℃/375 ℃, and the cooling mode is air cooling, so as to obtain material particles with uniform particles;
(7) and (4) carrying out injection molding on the granules obtained in the step (3) by using an injection molding machine, wherein the injection molding temperature is 385 ℃, and the mold temperature is 180 ℃. The appearance of the resistance test specimen is detailed in fig. 2.
Preparation of test panels:
pellets obtained in examples 7 to 11 and comparative example 2 were injection-molded by an injection molding machine to give dumbbell-type tensile test specimens of 10 mm. times.4 mm and bending test specimens of 80 mm. times.10 mm. times.4 mm at an injection molding temperature of 385 ℃ and a mold temperature of 180 ℃.
The polyetheretherketone composites prepared in examples 7 to 11 and comparative example 2 were each tested for mechanical properties, with reference to ISO 527, for tensile strength at 23 ℃; the flexural strength and flexural modulus were tested at 23 ℃ according to ISO 178 (insulation of the filler in the composite materials prepared in examples 7 to 11 and comparative example 2, without resistance testing).
The test results are summarized in Table 3
| Numbering | Tensile Strength (MPa) | Flexural Strength (MPa) | Flexural modulus (GPa) |
| Example 7 | 103.2 | 162.19 | 4.7 |
| Example 8 | 155.8 | 235.9 | 7.1 |
| Example 9 | 154.4 | 233.3 | 6.7 |
| Example 10 | 151.7 | 230.6 | 7.0 |
| Example 11 | 153.1 | 232.8 | 6.9 |
| Comparative example 2 | 85.9 | 141.8 | 3.6 |
As can be seen from Table 3, the PEK-LK in the present patent utilizes the solubility of the PEK-LK in the organic solvent to more uniformly attach the coupling agent to the surfaces of the ceramic filler and the glass fiber or the quartz fiber, so that the mechanical properties of the composite material are improved, and meanwhile, the PEK-LK as one member of the polyaryletherketone has a similar manufacturability to the polyetheretherketone, so that the coupling agent is not decomposed in a high temperature environment, and the utility of the coupling agent is greatly exerted, thereby the performance is more obvious in the composite examples 8-11.
The composites prepared in examples 8-11 are suitable for use in medical and electronic applications.
Preparation of composite material-suitable for electronic cigarette
Example 12 composite Material made from polyetheretherketone, PEK-LK-550, glass fibers and alumina, pigment carbon Black Filler
Step 1 preparation of PEK-LK-550 following the procedure of example 1a
Step 2PEK-LK-550 pretreatment filler
Mixing PEK-LK, alumina and pigment carbon black in deionized water in a mass ratio of 1:1:0.1 by a water dispersion method, stirring at a high speed for 4 hours, filtering, and drying the obtained filter cake in a drying oven at 160 ℃ for 14 hours to obtain the filler.
Step 3PEK-LK-550 pretreatment of glass fiber
PEK-LK is dissolved in tetrahydrofuran according to the proportion of 0.4Kg/1L, the solution is evenly coated on the surface of the glass fiber by a glass rod, the glass fiber is firstly placed in the air to be naturally volatilized, and then the glass fiber is placed in infrared searchlighting equipment for 4 hours until the solvent is completely volatilized, so that the glass fiber with the thickness of 20 mu m coating is obtained.
Step 42000g preparation of polyetheretherketone composite:
(1) drying the PEEK coarse powder in a drying oven at 160 ℃ for 6 hours;
(2) 1500g of dried PEEK coarse powder and 200g of pretreated aluminum oxide and pigment carbon black filler are added into a low-speed mixer to be mixed, the speed is 200r/min, and the time is 15min, so that a mixture is obtained;
(3) extruding and granulating the mixture obtained in the step (2) by using a double-screw extruder, feeding the pretreated glass fiber on the side, setting the addition of the glass fiber to be 15% of the total mass of the composite material, wherein the extrusion temperature is 320 ℃/350 ℃/350 ℃/350 ℃/350 ℃/350 ℃/375 ℃/375 ℃, and the cooling mode is air cooling to obtain uniform granules;
example 13 composite Material made from polyetheretherketone, PEK-LK-550, basalt fiber and Zinc sulfide, pigment carbon Black Filler
Step 1 preparation of Phenolphthalein (PLK) monomer: according to the preparation method of step 1 of example 12, the amounts of the components were changed to 1mol of PPL, 0.05mol of KH550, 1.5mol of sodium hydroxide, analytically pure, and 500mL of absolute ethanol, analytically pure.
Preparation of intermediate PEK-LK: according to the preparation method of example 12, the amounts of the components were changed to 1mol of PLK, 1.2mol of 4, 4' -difluorobenzophenone, analytically pure, 2.3mol of potassium carbonate, analytically pure, 420mL of toluene, analytically pure and 380mL of dimethyl sulfoxide, analytically pure.
Step 2PEK-LK-550 pretreatment of colloidal graphite powder
The procedure of example 12 was followed, except that the filler was changed to zinc sulfide and pigment carbon black.
Step 3, pretreating basalt fibers by using PEK-LK-550:
according to the preparation method of example 12, the fiber was changed to basalt fiber, and the solvent was changed to chloroform.
Step 4, preparation of the polyether-ether-ketone composite material:
prepared according to the preparation method and procedure of example 12.
Example 14 composite Material made from PEEK-LK-550, Quartz fibers and barium sulfate, pigment carbon Black Filler
Step 1 preparation of Phenolphthalein (PLK) monomer: according to the preparation method of example 12, the amount of each component was changed to 1mol of PPL, 0.08mol of KH550, 1.7mol of sodium hydroxide, analytically pure, and 450mL of absolute ethanol, analytically pure.
Preparation of intermediate PEK-LK: according to the preparation method of example 12, the amounts of the components were changed to 1mol of PLK, 1.1mol of 4, 4' -difluorobenzophenone, analytically pure, 2.4mol of potassium carbonate, analytically pure, 400mL of toluene, analytically pure and 330mL of dimethyl sulfoxide, analytically pure.
the procedure of example 12 was followed except that the fillers were changed to barium sulfate and pigment carbon black.
Step 3, pretreating quartz fibers by using PEK-LK-550:
the preparation of example 12 was followed, the fiber being changed to quartz fiber and the solvent to chloroform.
Step 4, preparation of the polyether-ether-ketone composite material:
prepared according to the preparation method and procedure of example 12.
Example 15 composite Material made from polyetheretherketone, PEK-LK-560, glass fibers and alumina, pigment carbon Black Filler
This example was prepared in the same manner as example 12, except that in step 1 the coupling agent was replaced with KH550 and KH560.
Example 16 composite Material made from polyetheretherketone, PEK-LK-570, glass fibers and alumina, pigment carbon Black Filler
This example was prepared in the same manner as example 12, except that in step 1 the coupling agent was replaced with KH550 and KH570.
Comparative example 3:
2000g of conventional PEEK preparation (filler and fibres not pretreated):
(8) drying the PEEK coarse powder in a drying oven at 160 ℃ for 6 hours;
(9) 1500g of dried PEEK coarse powder and 200g of alumina and pigment carbon black are added into a low-speed mixer to be mixed, the speed is 200r/min, and the time is 15min, so that a mixture is obtained;
(10) extruding and granulating the PEEK coarse powder obtained in the step (2) by using a double-screw extruder, feeding the glass fiber on the side, wherein the extrusion temperature is 320 ℃/375 ℃/375 ℃/375 ℃/375 ℃/375 ℃, and the cooling mode is air cooling, so as to obtain material particles with uniform particles;
preparation of test panels:
pellets obtained in examples 12 to 16 and comparative example 3 were injection-molded by an injection molding machine to give dumbbell-type tensile test specimens of 10 mm. times.4 mm and bending test specimens of 80 mm. times.10 mm. times.4 mm at an injection molding temperature of 385 ℃ and a mold temperature of 180 ℃.
The polyetheretherketone composites prepared in examples 2 to 6 and comparative example 1 were each tested for mechanical properties, with reference to ISO 527, for tensile strength at 23 ℃; the flexural strength and flexural modulus were tested at 23 ℃ according to ISO 178.
The test results are summarized in Table 4
As can be seen from the Table I, the filler and carbon fibers in the composites of examples 12-16 are uniformly distributed compared to comparative example 3, and the properties of the three coupling agents are substantially the same for the filler and carbon fibers; the method utilizes the solubility of the PEK-LK in the organic solvent to more uniformly attach the coupling agent to the surfaces of the filler and the carbon fiber, and simultaneously, the PEK-LK is used as one member of the polyaryletherketone, has similar manufacturability with the polyetheretherketone, and also ensures that the coupling agent is not decomposed in a high-temperature environment, thereby greatly exerting the effect of the coupling agent. In addition, the problem that the snowflake-shaped external application is caused on the surface of the product is solved, the mechanical property of the composite material is improved, and the phenomenon is obvious in the composite examples 12 to 16.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (22)
1. A coupling agent, characterized in that said coupling agent is selected from the following structures:
or;
or;
2. a process for preparing the coupling agent of claim 1, comprising the steps of:
(1) PPL, a coupling agent and sodium hydroxide are added into a reaction container, 500mL of anhydrous ethanol 200-plus-one is added, stirring and heating are carried out to 50-70 ℃, 0.05-0.15mol of KI is added for reaction for 8-18 hours, hydrochloric acid is dropwise added to adjust the PH value to 6, suction filtration is carried out, filtrate is evaporated to dryness at the temperature of 60-90 ℃ to obtain light yellow crystals, and the light yellow crystals are cleaned and dried to obtain PLK; wherein the molar ratio of PPL to the silane coupling agent to the sodium hydroxide is 1: (0.01-0.2): (1-3);
(2) adding PLK, fluoroketone and potassium carbonate into a reaction container, adding 500mL of 300-plus-500 mL of methylbenzene and 500mL of 300-plus-500 mL of dimethyl sulfoxide, introducing nitrogen and stirring, heating to 110-plus-160 ℃ for reaction for 1-6 hours, then evaporating the methylbenzene, slowly heating to 140-plus-190 ℃ for reaction for 2-8 hours, diluting the obtained yellow sticky matter with N, N-dimethylformamide, standing and layering, slowly pouring the obtained supernatant into a mixed settling agent prepared from ethanol and hydrochloric acid, precipitating a large amount of white products, repeatedly boiling and washing the white products, and drying to obtain PEK-LK; wherein the molar ratio of PLK, fluoroketone and potassium carbonate is 1: (0.5-2): (0.5-3).
3. The process for preparing a coupling agent according to claim 2, wherein the coupling agent is selected from the group consisting of silane coupling agents KH550, KH560 or KH570.
4. The method of preparing a coupling agent according to claim 2, wherein the structure of PLK is one of the following structures:
5. the method of claim 2, wherein the molar ratio of PPL, coupling agent, and sodium hydroxide is 1: (0.03-0.18): (1-2), the molar ratio of PLK, fluoroketone and potassium carbonate is 1: (0.8-2): (1-3), the mol ratio of ethanol to hydrochloric acid in the settling liquid is 0.2-2, and the organic solvent is one of tetrahydrofuran and trichloromethane.
6. The method of claim 2, wherein the fluoroketone monomer is one of 4,4 ' -difluorobenzophenone, 4-chloro-4 ' -fluorobenzophenone, and 4-fluoro-4 ' -hydroxybenzophenone.
7. The composite material is characterized by comprising 50-90 parts by weight of PEEK, 0-30 parts by weight of carbon fibers and 0-30 parts by weight of filler, wherein the filler is pretreated by a coupling agent PEK-LK, and the fibers are pretreated by the coupling agent PEK-LK.
8. The composite of claim 7, wherein the coupling agent PEK-LK pretreats the filler by water dispersion.
9. The composite material of claim 7, wherein the coupling agent PEK-LK pretreats the fibers by impregnation.
10. The composite material of claim 7, comprising 50-90 parts PEEK, 1-30 parts fiber, 1-20 parts filler.
11. The composite material of claim 7, wherein the filler is selected from one or more of conductive carbon black, colloidal graphite powder, 1-10 μm single or multi-walled carbon nanotubes, titanium dioxide, aluminum oxide, zirconium dioxide, silicon nitride, zinc sulfide, barium sulfate, and pigment carbon black.
12. The composite material of claim 7, wherein the fibers are selected from one or more of polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, glass fibers, quartz fibers, and basalt fibers.
13. The composite material of claim 7, wherein the filler is selected from one or more of conductive carbon black, colloidal graphite powder, single-walled or multi-walled carbon nanotubes of 1-10 μm, and the fiber is selected from polyacrylonitrile-based carbon fiber and pitch-based carbon fiber.
14. The composite material of claim 7, wherein the filler is selected from one or more of titanium dioxide, aluminum oxide, zirconium dioxide and silicon nitride, and the fiber is selected from glass fiber or quartz fiber.
15. The composite material of claim 7, wherein the fibers are glass fibers, basalt fibers or quartz fibers, and the filler is one or more of alumina, zinc sulfide, barium sulfate and pigment carbon black.
16. A method of making the composite material of any one of claims 7-15, comprising:
(1) adding the dried PEEK coarse powder and the filler into a mixer for mixing at the speed of 100-300r/min for 10-20min to obtain a mixture;
(2) and (3) extruding and granulating the mixture obtained in the step (1) by using a double-screw extruder, feeding the fibers laterally, wherein the extrusion temperature is 320-390 ℃, and the cooling mode is air cooling to obtain uniform granules.
17. The method of making a composite material of claim 16, further comprising the step of pretreating the filler by: PEK-LK and filler are dispersed in water according to the weight ratio of 1: (0.8-1.5) dispersing in deionized water, stirring at high speed for 0.5-4 hours, filtering, and drying the obtained filter cake in a drying oven at 160 ℃ for 10-16 hours to obtain the filler.
18. The method of making a composite material of claim 16, further comprising the step of pretreating the fibers by: dissolving PEK-LK in an organic solvent according to a certain proportion, wherein the concentration of the PEK-LK is 0.2-1 g/mL, uniformly coating the solution on the surface of the carbon fiber by using a glass rod, naturally volatilizing the carbon fiber in the air, and then placing the carbon fiber in infrared searchlighting equipment for 1-6 hours until the solvent is completely volatilized, so as to obtain the carbon fiber with the thickness of 20 microns of coating.
19. A method of making a composite material as claimed in claim 16 wherein the process of drying the PEEK coarse powder is: and (3) drying the PEEK coarse powder in an oven at the temperature of 140-160 ℃ for 4-6 hours.
20. A wafer pod, prepared from the composite material of any one of claims 7-13.
21. Use of the composite material according to any one of claims 7-12, 14 in medical and electronic applications.
22. An electronic cigarette comprising an electronic cigarette housing made from the composite material of any of claims 7-12, 15.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005314566A (en) * | 2004-04-28 | 2005-11-10 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| CN102250446A (en) * | 2011-06-10 | 2011-11-23 | 吉林大学 | High-dimension-stability and friction-resistant polyether-ether-ketone composite material and preparation method thereof |
| US20140205816A1 (en) * | 2011-07-08 | 2014-07-24 | Sumitomo Bakelite Co., Ltd. | Dicing-tape-integrated adhesive sheet, semiconductor device, multilayered circuit board and electronic component |
| CN113563577A (en) * | 2021-07-26 | 2021-10-29 | 长春工业大学 | Phenolphthalein modified polyaryletherketone water-based sizing agent and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005314566A (en) * | 2004-04-28 | 2005-11-10 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| CN102250446A (en) * | 2011-06-10 | 2011-11-23 | 吉林大学 | High-dimension-stability and friction-resistant polyether-ether-ketone composite material and preparation method thereof |
| US20140205816A1 (en) * | 2011-07-08 | 2014-07-24 | Sumitomo Bakelite Co., Ltd. | Dicing-tape-integrated adhesive sheet, semiconductor device, multilayered circuit board and electronic component |
| CN113563577A (en) * | 2021-07-26 | 2021-10-29 | 长春工业大学 | Phenolphthalein modified polyaryletherketone water-based sizing agent and preparation method and application thereof |
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