CN114262433B - Coupling agent and polyaryletherketone composite material prepared from coupling agent - Google Patents
Coupling agent and polyaryletherketone composite material prepared from coupling agent Download PDFInfo
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- CN114262433B CN114262433B CN202111345385.1A CN202111345385A CN114262433B CN 114262433 B CN114262433 B CN 114262433B CN 202111345385 A CN202111345385 A CN 202111345385A CN 114262433 B CN114262433 B CN 114262433B
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- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 239000007822 coupling agent Substances 0.000 title claims abstract description 71
- 229920006260 polyaryletherketone Polymers 0.000 title abstract description 8
- 239000004696 Poly ether ether ketone Substances 0.000 claims abstract description 83
- 229920002530 polyetherether ketone Polymers 0.000 claims abstract description 83
- 239000000945 filler Substances 0.000 claims abstract description 80
- 239000000835 fiber Substances 0.000 claims abstract description 62
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims description 65
- 238000000034 method Methods 0.000 claims description 49
- 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 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 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 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 26
- 239000004917 carbon fiber Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000003365 glass fiber Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 16
- 239000006229 carbon black Substances 0.000 claims description 15
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- 239000000049 pigment Substances 0.000 claims description 14
- 239000010453 quartz Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- IYRWEQXVUNLMAY-UHFFFAOYSA-N fluoroketone group Chemical group FC(=O)F IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000002109 single walled nanotube Substances 0.000 claims description 9
- 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 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 229920002748 Basalt fiber Polymers 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 239000005083 Zinc sulfide Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000006185 dispersion Substances 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
- 239000004408 titanium dioxide Substances 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
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000001376 precipitating effect Effects 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
- 239000006228 supernatant Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 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
- 238000001914 filtration Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000011304 carbon pitch Substances 0.000 claims 1
- 235000012054 meals Nutrition 0.000 claims 1
- 239000011295 pitch Substances 0.000 claims 1
- 239000003571 electronic cigarette Substances 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 3
- 241000533950 Leucojum Species 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 238000001746 injection moulding Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- -1 poly (arylene ether ketone Chemical class 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 239000008187 granular material Substances 0.000 description 6
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000011152 fibreglass Substances 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000007781 pre-processing Methods 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
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- 238000009827 uniform distribution Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
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- 239000003921 oil Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920001660 poly(etherketone-etherketoneketone) Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000001039 zinc pigment Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a coupling agent, a composite material containing the coupling agent, and a filler and a fiber, wherein the coupling agent is more uniformly attached to the surfaces of the filler and the fiber by utilizing the solubility of the coupling agent PEK-LK in an organic solvent, and meanwhile, the PEK-LK is taken as a member of polyaryletherketone, has similar manufacturability with the polyether etherketone, and also ensures that the coupling agent is not decomposed in a high-temperature environment, so that the effect of the coupling agent is greatly exerted. 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 equipment 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 and a preparation method thereof, and application of the coupling agent in the field of polyaryletherketone composite materials.
Background
Under the background of new times, the scientific technology is continuously developed, and the development and progress of a plurality of industries are greatly promoted. Among them, poly (arylene ether ketone) is used as a novel polymer material in many fields due to its excellent properties, and poly (arylene ether ketone) is the most representative poly (arylene ether ketone) material, and is used in many fields such as aerospace, automobile parts, electronic and electric appliances, energy, electric wires and cables, medical treatment, etc. due to its excellent thermal stability, chemical resistance, mechanical properties, electrical insulation and fatigue resistance.
Semiconductors are the core of the electronics industry, the foundation of the information industry, and wafer fabrication is the core of the semiconductor industry chain. In recent years, with the continuous improvement of the technical development level of semiconductor wafer enterprises, the development and expansion of the technology are gradually advanced, the requirements on the wafer carrier are more severe, the traditional materials such as PP, PFA and the like cannot meet the requirements, PEEK plays a main role of a wafer carrier manufacturing material with the excellent comprehensive properties such as wear resistance, heat resistance and the like, the appearance, mechanical properties and antistatic grade of the common PEEK material cannot meet the use requirements of the wafer carrier, the performance of the polyether-ether-ketone composite material added with fibers and/or fillers meets the use requirements of the wafer carrier, but the blending of the fibers and/or fillers and the polyether-ether-ketone is uneven, and the use of the wafer carrier is greatly influenced.
The ceramic material is a traditional biomedical material, has high strength, high brittleness, relatively poor corrosion resistance and wear resistance, is not an organic polymer material, is difficult to process and form, and is usually sintered at high temperature, but 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 implantation-level material, and the toughness and the rigidity of the polyether-ether-ketone reach ideal critical points. The ceramic PEEK composite material obtained by the conventional mixing process and the coupling agent is difficult to uniformly disperse among the components.
The periphery of the electronic cigarette is provided with a high-temperature environment when in operation, and the temperature can reach 300 ℃. Typically this part of the component needs to fulfil two conditions: temperature resistance and heat insulation. Therefore, PEEK is a very suitable material, the temperature resistance grade is just suitable, the cost performance is highest, the price of materials such as PEK, PEKEKK and the like at the higher end of PEEK is doubled, and the temperature resistance grade of PEI/PPSU and the like at the lower end of PEEK is insufficient. Meanwhile, PEEK also has the characteristics of corrosion resistance (smoke and oil corrosion resistance), compliance with the FDA and the like. The common PEEK composite material process can increase the heat resistance of PEEK, but the increase is not large.
Disclosure of Invention
The invention aims to provide a coupling agent, which can be used for more uniformly attaching or coating fillers and fibers after being grafted by phenolphthalein and fluoroketone, thereby being beneficial to preparing polyaryletherketone composite materials.
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 modified Phenolphthalein (PLK) monomer comprises the following steps:
Adding phenolphthalein PPL, a silane coupling agent and sodium hydroxide into a three-neck flask, adding 200-500mL of absolute ethyl alcohol serving as a solvent, gradually dissolving under stirring, heating to 50-70 ℃, adding 0.05-0.15mol of KI, reacting for 8-18 hours, dripping hydrochloric acid to adjust the pH value to 6, carrying out suction filtration, placing filtrate into a rotary evaporator, evaporating the solution at 60-90 ℃ to obtain light yellow crystals, repeatedly cleaning with deionized water, and then placing the solution into a 160 ℃ oven for drying for 2-6 hours to obtain the product modified Phenolphthalein (PLK); wherein, the mole ratio of the phenolphthalein PPL, the silane coupling agent and the sodium hydroxide is 1: (0.01-0.2): (1-3);
(2) Preparation of coupling agent PEK-LK:
Adding modified Phenolphthalein (PLK), fluoroketone and potassium carbonate into a three-neck flask, adding 300-500mL of toluene and 300-500mL of dimethyl sulfoxide as solvents, introducing nitrogen, stirring, heating to 110-160 ℃ to react for 1-6 hours, then steaming out toluene, slowly heating to 140-190 ℃ to react for 2-8 hours, diluting the obtained yellow sticky material with N, N-dimethylformamide, standing and layering overnight. Slowly pouring the obtained supernatant into a mixed sedimentation agent prepared from ethanol and hydrochloric acid, precipitating a large amount of white products, repeatedly boiling and washing with deionized water, and drying in a vacuum drying oven to obtain a product PEK-LK; wherein, the mole 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 modified Phenolphthalein (PLK) has a structure of one of the following structures:
Preferably, the molar ratio of phenolphthalein 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 sedimentation liquid is 0.2-2. The preferred molar ratio is 1.
Preferably, the organic solvent is one of tetrahydrofuran and chloroform.
The third object of the invention is to provide a composite material, wherein fibers and fillers coated by a coupling agent are added into PEEK, so that the surfaces of the fillers and the fibers are changed from hydrophile to lipophile, and the fillers, the fibers and the PEEK are tightly combined with each other, thereby improving the mechanical properties of the composite material.
A composite material consists 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 the 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 coupling agent PEK-LK:1-3 parts, more preferably PEEK:65-85 parts of fiber: 10-20 parts of filler: 5-15 parts of 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 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-wall or multi-wall carbon nanotubes with the diameter of 1-10 mu m, and the fiber is selected from polyacrylonitrile-based carbon fiber and asphalt-based carbon fiber.
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 the monofilament diameter of 10-20 mu m or quartz fiber with the monofilament diameter of 10-20 mu m, 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 element bases, artificial bones and teeth.
Preferably, the fiber is glass fiber, basalt fiber or quartz fiber, the filler is one or more of aluminum oxide, zinc sulfide, barium sulfate and pigment carbon black, and the polyether-ether-ketone composite material prepared by the technical scheme is suitable for manufacturing electronic cigarettes, in particular to shells of the electronic cigarettes.
The fourth object of the invention is to provide a method for preparing a composite material, wherein the mechanical properties of the prepared composite material are remarkably improved.
A method of preparing 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, and feeding the fiber side by side, wherein the extrusion temperature is 320 DEG C
Cooling at 390 ℃ below zero in an air cooling mode to obtain material particles with uniform particles;
Preferably, the method further comprises the step of pre-treating said filler: PEK-LK and filler were mixed in a 1: (0.8-1.5) in mass ratio, stirring at high speed for 0.5-4 hours, suction filtering, and drying the obtained filter cake in a 160 ℃ oven for 10-16 hours to obtain the filler.
Preferably, the method further comprises the step of pre-treating the fibers: and (3) 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 fiber by using a glass rod, naturally volatilizing the solution in air, and then placing the solution in infrared searchlighting equipment for 1-6 hours until the solvent is completely volatilized, thus obtaining the fiber with the coating thickness of 20 mu m.
Preferably, the process for drying the polyether-ether-ketone comprises the following steps: and (3) placing the PEEK coarse powder into an oven at 140-160 ℃ for drying for 4-6 hours.
The fifth object of the invention is to provide application of the polyether-ether-ketone composite material, which is suitable for preparing wafer boxes, electronic cigarettes, medical instruments and ceramic materials in the semiconductor industry.
The beneficial effects are that: 1. under the same technological condition, the PEK-LK coated fiber and filler are easier to be mixed uniformly with the PEEK powder, the mechanical property of the prepared PEEK composite material is greatly improved, and the uniformity of the composite material in all directions is more excellent. 2. The coupling agent and the filler are physically coated, so that the surface of the filler is changed from hydrophilcity to lipophilicity, physical winding is generated between the filler and the two inorganic materials of the fiber, and the combination of the inorganic materials and the polyether-ether-ketone is tighter, so that the strength, the adhesive 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 an organic solvent is utilized, PEK-LK is taken as a member of polyaryletherketone, has similar manufacturability with polyether-ether-ketone, and also ensures that the coupling agent is not decomposed in a high-temperature environment, thereby greatly exerting the effect of the coupling agent.
Drawings
FIG. 1 is a basic circuit diagram for measuring surface resistivity using guard electrodes;
fig. 2 is a resistance test panel of the composite material prepared in comparative example 1.
Fig. 3 is a resistance test panel of the composite material prepared in example 2.
Reference numerals: 1. a protected electrode; 2. the electrode is not protected; 3. protecting the electrode.
Detailed Description
Embodiments of the present invention are described in detail below. The following examples are illustrative only and are not to be construed as limiting the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Test method
Coating thickness test
The coating thickness test method of PEK-LK coated fiber is measured by referring to the measuring method of GB/T13452.2-2008 color paint and varnish film thickness, namely: testing is performed using a depth micrometer or a depth dial gauge, the coating of the measurement area is removed, the instrument is zeroed by checking the zero point with a reference plate, and then:
when the depth micrometer is used, the supporting feet are placed on the surface of the coating, so that the measuring rod is positioned above the exposed area, and the measuring rod is rotated downwards until the contact contacts the substrate and touches the toothed bar;
in using the depth dial gauge, the contact element is placed over the exposed substrate with its contact feet placed on the coating (if the dial gauge is of the contact foot type, care should be taken to ensure that the contact feet are perpendicular to the sample surface).
The coating thickness value can be read directly from the depth scale.
Surface resistance test
The surface resistance test method refers to the GB/T1410-2006 volume surface resistivity test method, namely:
Sample preparation: the invention adopts a square plate with the thickness of 60mm multiplied by 2mm as a test piece for standby;
Sample treatment: the surface resistance is measured without cleaning the surface unless otherwise required. The surface measured portion should not be touched by anything other than the untouched surface of another sample of the same material that is accessible to the sample under test. The samples were conditioned as required in GB/T10580-2015.
A predetermined dc voltage is applied to measure the resistance between the electrodes 1 and 2 of the two measuring electrodes (fig. 1) on the surface of the sample. The resistance should be measured after an electrochemical time of 1min, even though the current has not yet reached a steady state during this time.
Calculation of surface resistivity: the calculation should be as follows:
Wherein:
ρ—surface resistivity in ohms (Ω);
r X -the measured surface resistance in ohms (Ω);
P-the effective perimeter of the protected electrode in meters (m) (or centimeters (cm)) in the electrode device of particular use;
g-the distance between two electrodes in meters (m) (or centimeters (cm));
reproducibility: because the resistance of a given sample varies with test conditions and the material varies from sample to sample, the non-reproducibility of the measurement is typically not close to + -10%, but often there is a greater dispersion (the ratio of measured values may be 10 to 1 under approximately the same conditions). In order for measurements performed on similar samples to be comparable, 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 modified Phenolphthalein (PLK) monomers:
Adding 1mol of phenolphthalein PPL,0.1mol of a 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 0.1molKI, then reacting for 14 hours, dripping hydrochloric acid to adjust the pH value to 6, carrying out suction filtration, placing filtrate into a rotary evaporator, evaporating the solution at 80 ℃ to obtain light yellow crystals, repeatedly cleaning with deionized water, and then placing the solution into a 160 ℃ oven to dry for 6 hours to obtain the target product modified phenolphthalein PLK.
2) Preparation of coupling agent PEK-LK:
1mol of modified phenolphthalein PLK prepared in 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 and stirred, the temperature is firstly increased to 140 ℃ for reaction for 6 hours, then toluene is distilled off, the temperature is slowly increased to 175 ℃ for reaction for 2 hours, and the obtained yellow sticky matter is diluted by N, N-dimethylformamide and then is stood for overnight layering. The resulting supernatant was slowly poured into a liquid medium consisting of a molar ratio 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 shown in Table I
Table 1 examples 1a-1c coupling agent model and product model table
| Examples | 1a | 1b | 1c |
| Coupling agent | KH550 | KH560 | KH570 |
| Modified 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 the structure as follows:
the structure of the PLK-560 prepared was:
The structure of the PLK-570 prepared was:
the solution was tested using a nuclear magnetic resonance analyzer (Bruker, 400mhz, tms internal standard, germany) at 25 ℃ to give 13 C NMR spectra, with the carbon groups on the three aromatic ring backbones undergoing chemical migration in slightly different chemical environments, as shown below:
(1) PLK-560 was found at 43.6ppm
(2) PLK-570 was shown at 31.5ppm
(3) PLK-550 was shown at 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:
the solution was tested using a nuclear magnetic resonance analyzer (Bruker, 400mhz, tms internal standard, germany) at 25 ℃ to give 13 C NMR spectra, with the carbon groups on the three aromatic ring backbones undergoing chemical migration in slightly different chemical environments, as shown below:
(1) PEK-LK-560 is shown at 43.6ppm
(2) PEK-LK-570 is present at 31.5ppm
(3) PEK-LK-550 is shown at 28.9ppm
Preparation of composite materials-suitable for manufacturing wafer cassettes
Example 2 composite materials prepared from polyetheretherketone, coupling agent PEK-LK-550, carbon fiber and conductive carbon black filler
Step 1 preparation of coupling agent PEK-LK-550 according to the method of example 1a
Step 2, the conductive carbon black filler is pretreated by PEK-LK-550:
and mixing PEK-LK-550 and conductive carbon black in a mass ratio of 1:1 in deionized water by utilizing a water dispersion method, stirring at a high speed for 4 hours, carrying out suction filtration, and drying the obtained filter cake in a 160 ℃ oven for 14 hours to obtain the conductive carbon black.
Step 3 preparation of carbon fiber pretreated with PEK-LK-550
And (3) dissolving PEK-LK-550 in tetrahydrofuran according to the proportion of 0.4Kg/1L, uniformly coating the solution on the surface of the asphalt-based carbon fiber by using a glass rod, naturally volatilizing in air, then placing in infrared searchlighting equipment for 4 hours until the solvent is completely volatilized, and testing according to a coating test method to obtain the carbon fiber with the coating thickness of 20 mu m.
Step 4, preparation of 2000g of polyether-ether-ketone composite material:
(1) Drying PEEK coarse powder in a drying oven at 160 ℃ for 6 hours;
(2) 1500g of dried PEEK coarse powder and 200g of pretreated conductive carbon black are added 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, feeding the pretreated carbon fiber side, setting the addition of the carbon fiber accounting for 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 uniformly-granular granules (the fiber and the filler in step 4 of all the embodiments in the patent are pretreated by the coupling agent).
Example 3 composite materials prepared from polyetheretherketone, coupling agent PEK-LK-550, carbon fiber and colloidal graphite powder
Step 1 preparation of modified Phenolphthalein (PLK) monomer: according to the method of example 1a, only the following is changed: the amounts of the components were changed to 1mol phenolphthalein PPL,0.05mol KH550,1.5mol sodium hydroxide (analytically pure), 500mL absolute ethanol (analytically pure).
Preparation of intermediate PEK-LK: according to the method of example 1a, only the following is changed: the amounts of the components were changed to 1mol PLK,1.2mol 4,4' -difluorobenzophenone (analytically pure), 2.3mol potassium carbonate (analytically pure), 420mL toluene (analytically pure) and 380mL dimethyl sulfoxide (analytically pure).
Step 2, pretreating the colloidal graphite powder by PEK-LK-550:
According to the preparation method of the step 2 in the example 2, only the filler is changed into the colloidal graphite powder.
Step3, preparation of carbon fibers:
According to the preparation method of the step 3 in the example 2, only the carbon fiber is changed into the polyacrylonitrile-based carbon fiber, and the solvent is changed into the chloroform.
Step 4, preparation of 2000g of polyether-ether-ketone composite material:
prepared according to the method and process of example 2.
Example 4 composite materials prepared from polyetheretherketone, coupling agent PEK-LK-550, carbon fiber and Single wall carbon nanotube filler
Step 1 preparation of modified Phenolphthalein (PLK) monomer: the preparation method of example 2 was followed, changing the amount of each component to 1mol phenolphthalein PPL,0.08mol KH550,1.7mol sodium hydroxide (analytically pure), and 450mL absolute ethanol (analytically pure).
Preparation of intermediate PEK-LK: the amounts of the components were changed to 1mol PLK,1.1mol 4,4' -difluorobenzophenone (analytically pure), 2.4mol potassium carbonate (analytically pure), 400mL toluene (analytically pure) and 330mL dimethyl sulfoxide (analytically pure) according to the preparation method of example 2.
Step 2, pretreating the single-walled carbon nanotubes by using PEK-LK-550:
The preparation method of example 2 was followed, except that the filler was changed to single-walled carbon nanotubes of 5. Mu.m.
Step 3, pretreating the carbon fiber with PEK-LK-550:
the preparation method of example 2 was followed, the solvent being changed to chloroform.
Step 4, preparation of 2000g of polyether-ether-ketone composite material:
prepared according to the method and process of example 2.
Example 5 composite materials prepared from polyetheretherketone, PEK-LK-560 carbon fiber and Single wall carbon nanotube filler
This example was prepared in the same manner as in example 2, except that the coupling agent was replaced with KH560 in step 1.
Example 6 composite materials prepared from polyetheretherketone, PEK-LK-570 carbon fiber and Single wall carbon nanotube filler
This example was prepared in the same manner as in example 2, except that the coupling agent was replaced with KH570 from KH550 in step 1.
Comparative example 1:
2000g of conventional PEEK composite (filler and fiber were not pretreated):
(1) Drying 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 carbon fiber at the side, wherein the extrusion temperature is 320 ℃/375 ℃/375 ℃/375 ℃/375 ℃/375 ℃/375 ℃/375 ℃, and cooling the PEEK coarse powder by air cooling to obtain uniformly-granular material particles;
Preparation of test templates:
The pellets obtained in examples 2 to 6 and comparative example 1 were subjected to injection molding by an injection molding machine, respectively, to obtain a square plate for resistance test of 60mm×60mm×2mm, a dumbbell-shaped tensile test bar of 10mm×4mm, and a bending test bar of 80mm×10mm×4mm, the injection molding temperature was 385 ℃, and the mold temperature was 180 ℃.
The mechanical properties were tested on the polyether-ether-ketone composites prepared in examples 2 to 6 and comparative example 1, respectively, and tensile strength was tested at 23 ℃ with reference to ISO 527; the flexural strength and flexural modulus were tested at 23℃with reference to ISO 178.
The test results are summarized in Table 2
As can be seen from the table I, compared with comparative example 1, the resistivity of each area of the test panels of the composite materials of examples 2 to 6 is uniform and is not lower than 10 4, and the surfaces of the test panels of example 2 and comparative example 1 are photographed by cameras respectively, the appearance of the surfaces is shown in fig. 2 to 3, the uniform distribution of the filler and the fiber in the system is illustrated by the uniform resistivity and the snowflake-free appearance, the performances of the three coupling agents on the filler and the carbon fiber are basically the same, the problem of snowflake-shaped external application on the surfaces of the products is solved, the mechanical properties of the composite materials are also improved, and the appearance is obvious in the composite examples 2 to 4. The coupling agent is used for physically coating the filler and the fiber, 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 combination of the inorganic material and the polyether-ether-ketone is tighter, meanwhile, the solubility of PEK-LK in an organic solvent is utilized, the PEK-LK is used as a member of the polyether-ether-ketone, 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 effect of the coupling agent is greatly exerted, and the strength, the adhesive 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 materials prepared from polyetheretherketone, PEK-LK-550, alumina filler
Step 1 preparation of coupling agent PEK-LK-550 according to the method of example 1a
Step 2 pretreatment of alumina ceramic Filler with PEK-LK-550
And mixing PEK-LK and alumina ceramic filler in a mass ratio of 1:1 in deionized water by utilizing a water dispersion method, stirring at a high speed for 4 hours, carrying out suction filtration, and drying the obtained filter cake in a 160 ℃ oven for 14 hours to obtain the alumina ceramic filler.
Step 3 preparation of 2000g of polyether-ether-ketone composite material:
(1) Drying PEEK coarse powder in a drying oven at 160 ℃ for 6 hours;
(2) 1500g of dried PEEK coarse powder and 200g of alumina ceramic filler are added 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 as to obtain material particles with uniform particles;
example 8 composite materials prepared from polyetheretherketone, PEK-LK-550, fiberglass, and titanium dioxide ceramic filler
Step 1 preparation of modified Phenolphthalein (PLK) monomer: the preparation method of the step 1 of the example 7 is followed, wherein the amount of each component is changed to 1mol of phenolphthalein PPL,0.05mol KH550,1.5mol sodium hydroxide, analytically pure and 500mL of absolute ethanol.
Preparation of intermediate PEK-LK: the preparation of example 7 was followed, changing the amounts of the components to 1mol PLK,1.2mol 4,4' -difluorobenzophenone (analytically pure), 2.3mol potassium carbonate (analytically pure), 420mL toluene (analytically pure) and 380mL dimethyl sulfoxide (analytically pure).
Step 2 pretreatment of titanium Titania ceramic Filler with PEK-LK-550
The preparation method of example 7 was followed, changing the ceramic filler to titanium dioxide.
Step 3 pretreatment of glass fiber with PEK-LK-550:
And (3) dissolving PEK-LK in tetrahydrofuran according to the proportion of 0.4Kg/1L, uniformly coating the solution on the surface of the glass fiber by using a glass rod, naturally volatilizing in air, and then placing in an infrared searchlighting device for 4 hours until the solvent is completely volatilized, thus obtaining the glass fiber with the coating thickness of 20 mu m.
Step 4, preparation of 2000g of polyether-ether-ketone composite material:
prepared according to the method and process for preparation of example 7.
Example 9 composite materials made from polyetheretherketone, PEK-LK-550, quartz fibers and zirconia ceramic filler
Step 1 preparation of modified Phenolphthalein (PLK) monomer: the preparation method of example 7 was followed, changing the amount of each component to 1mol phenolphthalein PPL,0.08mol KH550,1.7mol sodium hydroxide (analytically pure), and 450mL absolute ethanol (analytically pure).
Preparation of intermediate PEK-LK: the preparation of example 7 was followed, changing the amounts of the components to 1mol PLK,1.1mol 4,4' -difluorobenzophenone (analytically pure), 2.4mol potassium carbonate (analytically pure), 400mL toluene (analytically pure) and 330mL dimethyl sulfoxide (analytically pure).
Step 2 pretreatment of zirconium dioxide ceramic filler with PEK-LK-550
The preparation method of example 7 was followed, changing the ceramic filler to a zirconium dioxide ceramic filler.
Step 3, the quartz fiber is pretreated by PEK-LK-550:
according to the preparation method of example 8, the fiber is changed to quartz fiber, and the solvent is changed to chloroform.
Step 4, preparation of 2000g of polyether-ether-ketone composite material:
prepared according to the method and process for preparation of example 7.
Example 10 composite materials made from polyetheretherketone, PEK-LK-560, fiberglass, and alumina ceramic filler
This example was prepared in the same manner as in example 8, except that the coupling agent was replaced with KH560 in step 1.
Example 11 composite materials made from polyetheretherketone, PEK-LK-570 glass fibers and alumina ceramic filler
This example was prepared in the same manner as in example 8, except that the coupling agent was replaced with KH570 from KH550 in step 1.
Comparative example 2:
2000g of conventional PEEK composite preparation (filler and fiber were not pretreated):
(4) Drying 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 glass fiber at the side, wherein the extrusion temperature is 320 ℃/375 ℃/375 ℃/375 ℃/375 ℃, and cooling the PEEK coarse powder by air cooling to obtain uniformly-granular material particles;
(7) And (3) carrying out injection molding on the granules obtained in the step (3) by an injection molding machine, wherein the injection molding temperature is 385 ℃, and the mold temperature is 180 ℃. The appearance of the resistance test sample is shown in detail in fig. 2.
Preparation of test templates:
The pellets obtained in examples 7 to 11 and comparative example 2 were subjected to injection molding by an injection molding machine, respectively, to obtain dumbbell tensile test bars of 10mm×4mm and bending test bars of 80mm×10mm×4mm, at an injection molding temperature of 385℃and a mold temperature of 180 ℃.
The mechanical properties were tested on the polyether-ether-ketone composites prepared in examples 7 to 11 and comparative example 2, respectively, and tensile strength was tested at 23 ℃ with reference to ISO 527; with reference to ISO 178, flexural strength and flexural modulus (insulation of the fillers in the composites prepared in this example 7-11 and comparative example 2, no resistance test was performed) were tested at 23 ℃.
The test results are summarized in Table 3
| Numbering device | 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 solubility of PEK-LK in organic solvent is utilized, the coupling agent is more uniformly attached to the surfaces of ceramic filler and glass fiber or quartz fiber, the mechanical property of the composite material is also improved, and meanwhile, PEK-LK is taken as a member of polyaryletherketone, has similar manufacturability with polyether etherketone, and the coupling agent is not decomposed in a high-temperature environment, so that the effect of the coupling agent is greatly exerted, and the coupling agent is obviously shown in composite examples 8-11.
The composites prepared in examples 8-11 are suitable for use in the medical and electronic fields.
Preparation of composite material-suitable for electronic cigarette
Example 12 composite materials made from polyetheretherketone, PEK-LK-550, fiberglass and alumina, pigment carbon black filler
Step1 preparation of PEK-LK-550 according to the method of example 1a
Step 2PEK-LK-550 pretreatment Filler
And mixing PEK-LK, alumina and pigment carbon black in a mass ratio of 1:1:0.1 in deionized water by using a water dispersion method, stirring at a high speed for 4 hours, carrying out suction filtration, and placing the obtained filter cake in a 160 ℃ oven for drying for 14 hours to obtain the filler.
Step 3PEK-LK-550 pretreatment glass fiber
And (3) dissolving PEK-LK in tetrahydrofuran according to the proportion of 0.4Kg/1L, uniformly coating the solution on the surface of the glass fiber by using a glass rod, naturally volatilizing in air, and then placing in an infrared searchlighting device for 4 hours until the solvent is completely volatilized, thus obtaining the glass fiber with the coating thickness of 20 mu m.
Step 4, preparation of 2000g of polyether-ether-ketone composite material:
(1) Drying PEEK coarse powder in a drying oven at 160 ℃ for 6 hours;
(2) 1500g of dried PEEK coarse powder and 200g of pretreated alumina and pigment carbon black filler are added 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, feeding the pretreated glass fiber side, setting the addition of 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, so as to obtain uniformly-granular material particles;
Example 13 composite Material prepared from polyetheretherketone, PEK-LK-550, basalt fiber and Zinc sulfide, pigment carbon black filler
Step 1 preparation of modified Phenolphthalein (PLK) monomer: the preparation method of step 1 of example 12 was followed, changing the amounts of the components to 1mol phenolphthalein PPL,0.05mol KH550,1.5mol sodium hydroxide, analytically pure, 500mL absolute ethanol.
Preparation of intermediate PEK-LK: the preparation was carried out according to the method of example 12, changing the amounts of the individual components to 1mol PLK,1.2mol 4,4' -difluorobenzophenone, analytically pure, 2.3mol potassium carbonate, analytically pure, 420mL toluene, analytically pure and 380mL dimethyl sulfoxide.
Step 2PEK-LK-550 pretreatment of the colloidal graphite powder
The preparation method of example 12 was followed, except that the filler was changed to zinc sulfide and pigment carbon black.
Step 3, preprocessing basalt fibers by PEK-LK-550:
according to the preparation method of example 12, the fiber is changed to basalt fiber, and the solvent is changed to chloroform.
Step 4, preparing a polyether-ether-ketone composite material:
Prepared according to the method and process for preparation of example 12.
Example 14 composite materials prepared from PEK-LK-550, quartz fibers and barium sulfate, pigment carbon black filler
Step 1 preparation of modified Phenolphthalein (PLK) monomer: the preparation method of example 12 was followed, changing the amount of each component to 1mol phenolphthalein PPL,0.08mol KH550,1.7mol sodium hydroxide, analytically pure, absolute 450mL ethanol.
Preparation of intermediate PEK-LK: the preparation was carried out as in example 12, changing the amounts of the individual components to 1mol PLK,1.1mol4,4' -difluorobenzophenone, analytically pure, 2.4mol potassium carbonate, analytically pure, 400mL toluene, analytically pure and 330mL dimethyl sulfoxide.
Step 2, preprocessing barium sulfate and pigment carbon black by PEK-LK-550:
the preparation method of example 12 was followed, except that the filler was changed to barium sulfate and pigment carbon black.
Step 3, preprocessing quartz fiber by PEK-LK-550:
According to the preparation method of example 12, the fiber is changed to quartz fiber, and the solvent is changed to chloroform.
Step 4, preparing a polyether-ether-ketone composite material:
Prepared according to the method and process for preparation of example 12.
Example 15 composite materials prepared from polyetheretherketone, PEK-LK-560, glass fibers and alumina, pigment carbon black filler
This example was prepared in the same manner as in example 12, except that the coupling agent was replaced with KH560 in step 1.
Example 16 composite materials made from polyetheretherketone, PEK-LK-570, glass fibers and alumina, pigment carbon black filler
This example was prepared in the same manner as in example 12, except that the coupling agent was replaced with KH570 from KH550 in step 1.
Comparative example 3:
2000g of conventional PEEK was prepared (filler and fiber were not pretreated):
(8) Drying PEEK coarse powder in a drying oven at 160 ℃ for 6 hours;
(9) Adding 1500g of dried PEEK coarse powder, 200g of alumina and pigment carbon black into a low-speed mixer for mixing at the speed of 200r/min for 15min to obtain a mixture;
(10) Extruding and granulating the PEEK coarse powder obtained in the step (2) by using a double-screw extruder, feeding glass fiber at the side, wherein the extrusion temperature is 320 ℃/375 ℃/375 ℃/375 ℃/375 ℃, and cooling the PEEK coarse powder by air cooling to obtain uniformly-granular material particles;
Preparation of test templates:
the pellets obtained in examples 12 to 16 and comparative example 3 were subjected to injection molding by an injection molding machine, respectively, to obtain dumbbell tensile test bars of 10 mm. Times.4 mm and bending test bars of 80 mm. Times.10 mm. Times.4 mm, at an injection molding temperature of 385℃and a mold temperature of 180 ℃.
The mechanical properties were tested on the polyether-ether-ketone composites prepared in examples 2 to 6 and comparative example 1, respectively, and tensile strength was tested at 23 ℃ with reference to ISO 527; the flexural strength and flexural modulus were tested at 23℃with reference to ISO 178.
The test results are summarized in Table 4
As can be seen from table one, the composite materials of examples 12 to 16 have a uniform distribution of filler and carbon fiber, and the properties of the three coupling agents on the filler and carbon fiber are substantially the same, as compared to comparative example 3; the PEK-LK is used as a member of the polyaryletherketone, has similar manufacturability with the polyetheretherketone, and prevents the coupling agent from being decomposed in a high-temperature environment, so that the utility of the coupling agent is greatly exerted. In addition, the problem of snowflake-shaped external application on the surface of the product is solved, and the mechanical property of the composite material is improved, so that the composite material is obviously represented in the composite examples 12-16.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means 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 present invention. In this specification, schematic representations of the above terms are not necessarily directed 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, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (17)
1. A coupling agent, characterized in that the coupling agent is selected from the following structures:
PEK-LK-550 or;
PEK-LK-560 or;
The preparation method of the PEK-LK-570 coupling agent comprises the following steps:
(1) Adding phenolphthalein PPL, a silane coupling agent and sodium hydroxide into a reaction container, adding 200-500mL of absolute ethyl alcohol, stirring and heating to 50-70 ℃, adding 0.05-0.15mol of KI to react for 8-18 hours, dripping hydrochloric acid to adjust pH to 6, carrying out suction filtration, evaporating filtrate at 60-90 ℃ to obtain light yellow crystals, cleaning the light yellow crystals, and drying to obtain PLK; wherein the silane coupling agent is selected from silane coupling agents KH550, KH560 or KH570, and the molar ratio of the phenolphthalein PPL, the silane coupling agent and the sodium hydroxide is 1: (0.01-0.2): (1-3);
(2) Adding PLK, fluoroketone and potassium carbonate into a reaction container, adding 300-500mL of toluene and 300-500mL of dimethyl sulfoxide, introducing nitrogen, stirring, heating to 110-160 ℃ to react for 1-6 hours, then steaming out toluene, slowly heating to 140-190 ℃ to react for 2-8 hours, diluting the obtained yellow sticky material with N, N-dimethylformamide, standing for 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 a coupling agent PEK-LK; wherein, the mole ratio of PLK, fluoroketone and potassium carbonate is 1: (0.5-2): (0.5-3).
2. A method of preparing the coupling agent of claim 1, comprising the steps of:
(1) Adding phenolphthalein PPL, a silane coupling agent and sodium hydroxide into a reaction container, adding 200-500mL of absolute ethyl alcohol, stirring and heating to 50-70 ℃, adding 0.05-0.15mol of KI to react for 8-18 hours, dripping hydrochloric acid to adjust pH to 6, carrying out suction filtration, evaporating filtrate at 60-90 ℃ to obtain light yellow crystals, cleaning the light yellow crystals, and drying to obtain PLK; wherein the silane coupling agent is selected from silane coupling agents KH550, KH560 or KH570, and the molar ratio of the phenolphthalein PPL, the silane coupling agent and the sodium hydroxide is 1: (0.01-0.2): (1-3);
(2) Adding PLK, fluoroketone and potassium carbonate into a reaction container, adding 300-500mL of toluene and 300-500mL of dimethyl sulfoxide, introducing nitrogen, stirring, heating to 110-160 ℃ to react for 1-6 hours, then steaming out toluene, slowly heating to 140-190 ℃ to react for 2-8 hours, diluting the obtained yellow sticky material with N, N-dimethylformamide, standing for 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 a coupling agent PEK-LK; wherein, the mole ratio of PLK, fluoroketone and potassium carbonate is 1: (0.5-2): (0.5-3).
3. The method of preparing a coupling agent of claim 2, wherein the PLK has a structure of one of the following structures:
PEK-550；
PEK-560；
PEK-570。
4. The method for preparing a coupling agent according to claim 2, wherein the molar ratio of phenolphthalein PPL, silane coupling agent and sodium hydroxide is 1: (0.03-0.18): (1-2), the mole ratio of PLK, fluoroketone and potassium carbonate is 1: (0.8-2): (1-3), wherein the mol ratio of ethanol to hydrochloric acid in the mixed sedimentation agent is 0.2-2.
5. The method for preparing a coupling agent according to claim 2, wherein the fluoroketone monomer is one of 4,4' -difluorobenzophenone, 4-chloro-4 ' -fluorobenzophenone, and 4-fluoro-4 ' -hydroxybenzophenone.
6. A composite material comprising, by weight, 50-90 parts of PEEK, 1-30 parts of fibers pretreated with the coupling agent PEK-LK according to claim 1, and 1-20 parts of filler pretreated with the coupling agent PEK-LK according to claim 1.
7. The composite material according to claim 6, wherein the method of pretreating the filler with the coupling agent PEK-LK is a water dispersion method.
8. The composite material of claim 6, wherein the method of pretreating the fibers with the coupling agent PEK-LK is an impregnation method.
9. The composite material according to claim 6, 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.
10. The composite material of claim 6, 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.
11. The composite material according to claim 6, wherein the filler is selected from one or more of conductive carbon black, colloidal graphite powder, single-wall or multi-wall carbon nanotubes of 1-10 μm, and the fiber is selected from polyacrylonitrile-based carbon fiber or pitch-based carbon fiber.
12. The composite material according to claim 6, 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.
13. The composite material of claim 6, wherein the fibers are glass fibers, basalt fibers or quartz fibers, and the filler is one or more of aluminum oxide, zinc sulfide, barium sulfate and pigment carbon black.
14. A method of preparing the composite material of any one of claims 6-13, comprising:
(1) Adding the dried PEEK coarse powder and the filler pretreated by the coupling agent into a mixer for mixing at the speed of 100-300r/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, and feeding the fiber pretreated by the coupling agent to the side, wherein the extruding temperature is 320-390 ℃, and the cooling mode is air cooling, so as to obtain the material particles with uniform particles.
15. The method of preparing a composite material according to claim 14, wherein the step of pre-treating the filler comprises: PEK-LK and filler were mixed in a 1: (0.8-1.5) in mass ratio, stirring at high speed for 0.5-4 hours, suction filtering, and drying the obtained filter cake in a 160 ℃ oven for 10-16 hours to obtain the filler.
16. A method of preparing a composite material according to claim 14, wherein the step of pre-treating the fibers is: and (3) 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 fiber by using a glass rod, naturally volatilizing the solution in air, and then placing the fiber in infrared searchlighting equipment for 1-6 hours until the solvent is completely volatilized, thus obtaining the fiber with the coating thickness of 20 mu m.
17. The method of preparing a composite material of claim 14, wherein the process of drying the PEEK meal is: and (3) placing the PEEK coarse powder into an oven at 140-160 ℃ for drying for 4-6 hours.
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| 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 |
| 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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| JP2013038405A (en) * | 2011-07-08 | 2013-02-21 | Sumitomo Bakelite Co Ltd | Dicing tape integrated adhesive sheet, semiconductor device, multilayer circuit board, and electronic component |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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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