CN116355337B - Fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene and preparation process thereof - Google Patents
Fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene and preparation process thereof Download PDFInfo
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- CN116355337B CN116355337B CN202310642030.1A CN202310642030A CN116355337B CN 116355337 B CN116355337 B CN 116355337B CN 202310642030 A CN202310642030 A CN 202310642030A CN 116355337 B CN116355337 B CN 116355337B
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- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 63
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 63
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 63
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 58
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 58
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 32
- 239000011737 fluorine Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 238000005245 sintering Methods 0.000 claims abstract description 25
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 22
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 22
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 11
- PPHHAZOVVZBSCM-UHFFFAOYSA-N 4-chloro-3-(trifluoromethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C(C(F)(F)F)=C1 PPHHAZOVVZBSCM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 238000000465 moulding Methods 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000007723 die pressing method Methods 0.000 claims 3
- 238000000748 compression moulding Methods 0.000 claims 1
- 229920002313 fluoropolymer Polymers 0.000 abstract description 13
- 239000004811 fluoropolymer Substances 0.000 abstract description 13
- 238000005299 abrasion Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000003825 pressing Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000012043 crude product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
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Abstract
The invention relates to the technical field of polytetrafluoroethylene, and discloses a fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene and a preparation process thereof, wherein the invention utilizes 4-chloro-3- (trifluoromethyl) benzoic acid, hydroquinone, potassium carbonate and thionyl chloride as reactants to prepare a novel compound Ph (OPhCF) 3 COCl） 2 And (3) carrying out in-situ polymerization reaction on the monomer and p-phenylenediamine on the surface of the aminated carbon nanotube to obtain a fluoropolymer grafted carbon nanotube, and then carrying out mould pressing and sintering processes on the fluoropolymer grafted carbon nanotube and polytetrafluoroethylene to obtain the fluoropolymer-carbon nanotube modified polytetrafluoroethylene material. After the polytetrafluoroethylene is filled and modified by the fluorine-containing polymer grafted carbon nano tube, the mechanical property and hardness of the polytetrafluoroethylene material are effectively improved, and the abrasion resistance is also obviously improved.
Description
Technical Field
The invention relates to the technical field of polytetrafluoroethylene, in particular to a fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene and a preparation process thereof.
Background
The polytetrafluoroethylene has good self-lubricity, strong stability, good corrosion resistance and chemical resistance, can be widely applied to the fields of coating, friction-resistant materials, equipment container inner liners and the like, plays an important role in the fields of electric industry, aerospace, electronic appliances and the like, and has the problems of poor mechanical properties such as tensile property, hardness and the like in the traditional polytetrafluoroethylene, and the traditional polytetrafluoroethylene modification method mainly comprises filling modification, irradiation grafting and the like.
The carbon nano tube is a nano material with excellent comprehensive performance, and is used for filling modification, so that the performances of polytetrafluoroethylene stretching, hardness, wear resistance and the like are effectively enhanced; in recent years, improving the compatibility between the carbon nanotubes and the matrix and improving the dispersion performance of the carbon nanotubes is a research hot spot, and the patent with publication No. CN112812477B obviously improves the interfacial compatibility of the carbon nanotubes and polytetrafluoroethylene by heating a fluorine-containing silane coupling agent, so that the filling modified polytetrafluoroethylene material with high conductivity, high mechanical strength and low density is obtained. The fluorocarbon nano tube and the bismaleimide resin are compounded in the patent with the publication number of CN101284929B, and the obtained material has the advantages of high strength, high temperature resistance, low friction, super wear resistance and the like. The invention aims to provide the fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene with strong tensile property, high hardness and good wear resistance.
Disclosure of Invention
(one) solving the technical problems
The invention provides a fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene and a preparation process thereof, which solve the problems of poor tensile property and hardness and low wear resistance of polytetrafluoroethylene.
(II) technical scheme
A preparation process of fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene comprises the following steps:
(1) Adding aminated carbon nanotube into N-methyl pyrrolidone solvent, dispersing, adding compound Ph (OPhCF) into ice water bath 3 COCl） 2 And (3) stirring and dissolving p-phenylenediamine and triethylamine, then reacting, dropwise adding a hydrochloric acid solution to adjust the pH to 4-5 after the reaction, carrying out suction filtration, and washing with water and ethanol in sequence to obtain the fluoropolymer grafted carbon nano tube.
(2) Adding fluorine-containing polymer grafted carbon nano tube into acetone solvent, dispersing, adding polytetrafluoroethylene, uniformly mixing in a high-speed mixer, volatilizing to remove the solvent, molding the material in a molding press at room temperature, and finally sintering in a sintering furnace to obtain fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene.
Further, the aminated carbon nanotube, the compound Ph (OPhCF 3 COCl） 2 The mass ratio of the p-phenylenediamine to the triethylamine is 1 (0.5-4) (0.3-2.6) (0.2-1.8).
Further, the temperature of the reaction in the step (1) is 40-65 ℃ and the time is 24-72 h.
Further, in the step (2), the mass ratio of the fluoropolymer grafted carbon nano tube to the polytetrafluoroethylene is 0.02-0.1:1.
Further, the molding pressure in the molding press in the step (2) is 35-50 MPa, and the molding time is 3-8 min.
Further, the sintering temperature in the sintering furnace in the step (2) is 330-360 ℃ and the sintering time is 2-4 h.
Further, the compound Ph (OPhCF) in the step (1) 3 COCl） 2 The preparation method of (2) comprises the following steps:
s1, adding 4-chloro-3- (trifluoromethyl) benzoic acid, hydroquinone and potassium carbonate into acetonitrile, uniformly stirring, reacting at 65-85 ℃ for 2-5 h, distilling under reduced pressure, and recrystallizing the crude product with dichloromethane to obtain a compound Ph (OPhCF) 3 COOH） 2 。
S2, adding a compound Ph (OPhCF) into thionyl chloride 3 COOH） 2 And N, N-dimethylformamide under the protection of nitrogen, reacting at 55-70deg.C for 3-6 h, distilling under reduced pressure, and recrystallizing the crude product with dichloromethane to obtain compound Ph (OPhCF) 3 COCl） 2 。
Further, the mass ratio of the 4-chloro-3- (trifluoromethyl) benzoic acid, hydroquinone and potassium carbonate in the S1 is 3.5-5:1:2.2-3.
Further, thionyl chloride, compound Ph (OPhCF 3 COOH） 2 And N, N-dimethylformamide in a mass ratio of 10-25:1:0.02-0.04.
(III) beneficial technical effects
1. The invention uses 4-chloro-3- (trifluoromethyl) benzoic acid, hydroquinone, potassium carbonate and thionyl chloride as reactants to prepare a novel compound Ph (OPhCF) 3 COCl） 2 And (3) carrying out in-situ polymerization reaction on the monomer and p-phenylenediamine on the surface of the aminated carbon nanotube to obtain a fluoropolymer grafted carbon nanotube, and then carrying out mould pressing and sintering processes on the fluoropolymer grafted carbon nanotube and polytetrafluoroethylene to obtain the fluoropolymer-carbon nanotube modified polytetrafluoroethylene material.
2. The polymer grafted by the carbon nano tube has fluorine-containing groups, has good compatibility with polytetrafluoroethylene, and can be well dispersed in a polytetrafluoroethylene matrix in the mixing process; meanwhile, the carbon nano tube grafted polymer contains a rigid and high-temperature-resistant polyaramid structure, and the polymer also maintains good structural stability in the sintering process and cannot be thermally decomposed; the carbon nano tube and the surface grafted fluorine-containing polymer have synergistic enhancement effect, and after filling modification, the mechanical property of polytetrafluoroethylene is greatly improved, the mechanical property and hardness of the polytetrafluoroethylene material are effectively improved, and the abrasion resistance is also obviously improved.
Drawings
FIG. 1 is Compound Ph (OPhCF 3 COCl） 2 Is a preparation reaction diagram of (2).
FIG. 2 is Compound Ph (OPhCF 3 COCl） 2 Nuclear magnetic hydrogen spectrogram of (2).
FIG. 3 is an infrared spectrum of a fluoropolymer grafted carbon nanotube.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Aminated carbon nanotubes: brand number: DZ-138. Fineness is 8-15nm. Large-scale nano (guangdong) limited.
Polytetrafluoroethylene: brand MP1200. High-trauma plastic materials Co., ltd.
Example 1
(1) Adding 4.5 g of 4-chloro-3- (trifluoromethyl) benzoic acid, 1 g of hydroquinone and 2.7 g of potassium carbonate into 80 mL of acetonitrile, uniformly stirring, reacting at 70 ℃ to obtain 4 h, distilling under reduced pressure, and recrystallizing the crude product with dichloromethane to obtain a compound Ph (OPhCF 3 COOH） 2 。
(2) To 75 g thionyl chloride was added 3 g of compound Ph (OPhCF 3 COOH） 2 And 0.12. g N, N-dimethylformamide under nitrogen protection at 55deg.C, vacuum distillation, and recrystallizing the crude product with dichloromethane to give compound Ph (OPhCF) 3 COCl） 2 The method comprises the steps of carrying out a first treatment on the surface of the Molecular formula C 22 H 10 Cl 2 O 4 F 6 ； 1 H NMR(400MHz，CDCl 3 )：δ80.2-7.79 (m, 4H)，7.44-7.28(m, 6H)，7.24-7.10 (m, 4H)。
(3) Adding 0.5 g aminated carbon nanotubes to 50 mL N-methylpyrrolidone solvent, dispersing, adding 0.25 g compound Ph (OPhCF) into ice water bath 3 COCl） 2 0.15 g p-phenylenediamine and 0.1 g triethylamine, stirring and dissolving, reacting at 40deg.C for 72 h, dropwise adding hydrochloric acid solution to adjust pH to 4, suction filtering, washing with water and ethanol sequentially to obtain fluoropolymer grafted carbon nanotube, 1698 cm in infrared spectrum -1 Is the characteristic peak of the polymer amide bond C=O, 1523cm -1 Is a bending absorption peak of N-H of an amide bond, 1592cm -1 Is the vibration peak of the benzene ring framework.
(4) Adding 0.4 g fluorine-containing polymer grafted carbon nano tube into acetone solvent, dispersing, adding 20 g polytetrafluoroethylene, uniformly mixing in a high-speed mixer, volatilizing to remove the solvent, molding the material in a molding press at room temperature of 35 MPa for 8 min for molding, and finally sintering in a sintering furnace at 360 ℃ for 2 h to obtain fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene.
Example 2
(1) 4.5 g of 4-chloro-3- (trifluoromethyl) benzoic acid, 1 g of hydroquinone and 2.8 g of potassium carbonate are added into 50 mL of acetonitrile, stirred uniformly, reacted at 85 ℃ for 2 h, distilled under reduced pressure, and the crude product is recrystallized by methylene dichloride to obtain a compound Ph (OPhCF) 3 COOH） 2 。
(2) To 30 g of thionyl chloride was added 3 g of compound Ph (OPhCF 3 COOH） 2 And 0.06 g N, NReacting dimethylformamide with nitrogen at 60 ℃ for 3 h, distilling under reduced pressure, and recrystallizing the crude product with dichloromethane to obtain compound Ph (OPhCF) 3 COCl） 2 。
(3) Adding 0.5 g aminated carbon nanotubes to 80. 80 mL N-methylpyrrolidone solvent, dispersing, adding 2 g compound Ph (OPhCF) into ice water bath 3 COCl） 2 And (2) carrying out reaction after stirring and dissolving p-phenylenediamine of 1.3 g and triethylamine of 0.9 g, wherein the reaction temperature is 65 ℃ and the reaction time is 24 h, dropwise adding hydrochloric acid solution to adjust the pH value to 5 after the reaction, carrying out suction filtration, and washing with water and ethanol in sequence to obtain the fluoropolymer grafted carbon nano tube.
(4) Adding 0.8 g fluorine-containing polymer grafted carbon nano tube into acetone solvent, dispersing, adding 20 g polytetrafluoroethylene, uniformly mixing in a high-speed mixer, volatilizing to remove the solvent, molding the material in a molding press at room temperature of 50 MPa for 3 min for molding, and finally sintering in a sintering furnace at 330 ℃ for 4 h to obtain fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene.
Example 3
(1) Adding 3.5 g of 4-chloro-3- (trifluoromethyl) benzoic acid, 1 g of hydroquinone and 2.2 g of potassium carbonate into 50 mL of acetonitrile, uniformly stirring, reacting at 65 ℃ for 5 h, distilling under reduced pressure, and recrystallizing the crude product with dichloromethane to obtain a compound Ph (OPhCF) 3 COOH） 2 。
(2) To 60 g thionyl chloride was added 3 g of compound Ph (OPhCF 3 COOH） 2 And 0.1. g N, N-dimethylformamide under nitrogen protection at 60℃under reduced pressure to give compound Ph (OPhCF) 3 COCl） 2 。
(3) Adding 0.5 g aminated carbon nanotubes to 100N-methylpyrrolidone solvent of mL, dispersing, adding 1.5 g of compound Ph (OPhCF) in ice water bath 3 COCl） 2 1.1 g of p-phenylenediamine and 0.7 g of triethylamine are stirred and dissolved for reaction at 50 ℃ for 36 h,and (3) dropwise adding a hydrochloric acid solution to adjust the pH to 5 after the reaction, carrying out suction filtration, and washing with water and ethanol in sequence to obtain the fluoropolymer grafted carbon nanotube.
(4) Adding 1.2 g fluorine-containing polymer grafted carbon nano tube into acetone solvent, dispersing, adding 20 g polytetrafluoroethylene, uniformly mixing in a high-speed mixer, volatilizing to remove the solvent, molding the material in a molding press at room temperature of 40 MPa for 5 min for molding, and finally sintering in a sintering furnace at 330 ℃ for 4 h to obtain fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene.
Example 4
(1) 5 g of 4-chloro-3- (trifluoromethyl) benzoic acid, 1 g of hydroquinone and 3 g of potassium carbonate are added into 100 mL of acetonitrile, stirred uniformly, reacted at 65 ℃ for 4 h, distilled under reduced pressure, and the crude product is recrystallized by methylene chloride to obtain a compound Ph (OPhCF) 3 COOH） 2 。
(2) To 30 g of thionyl chloride was added 3 g of compound Ph (OPhCF 3 COOH） 2 And 0.06. g of N, N-dimethylformamide under nitrogen protection at 70℃under reduced pressure to give compound Ph (OPhCF) 3 COCl） 2 。
(3) Adding 0.5 g aminated carbon nanotubes to 80. 80 mL N-methylpyrrolidone solvent, dispersing, adding 0.8 g compound Ph (OPhCF) into ice water bath 3 COCl） 2 And 0.5 g of p-phenylenediamine and 0.3 g of triethylamine are stirred and dissolved for reaction, the reaction temperature is 65 ℃, the reaction time is 36 h, a hydrochloric acid solution is dropwise added after the reaction to adjust the pH to 4, the suction filtration is carried out, and the water and the ethanol are sequentially used for washing, so that the fluoropolymer grafted carbon nano tube is prepared.
(4) Adding 0.6 g fluorine-containing polymer grafted carbon nano tube into acetone solvent, dispersing, adding 20 g polytetrafluoroethylene, uniformly mixing in a high-speed mixer, volatilizing to remove the solvent, molding the material in a molding press at room temperature of 50 MPa for 5 min for molding, and finally sintering in a sintering furnace at 350 ℃ for 3 h to obtain fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene.
Example 5
(1) 5 g of 4-chloro-3- (trifluoromethyl) benzoic acid, 1 g of hydroquinone and 3 g of potassium carbonate are added into 100 mL of acetonitrile, stirred uniformly, reacted at 85 ℃ for 2 h, distilled under reduced pressure, and the crude product is recrystallized by methylene chloride to obtain a compound Ph (OPhCF) 3 COOH） 2 。
(2) To 50 g thionyl chloride was added 3 g of compound Ph (OPhCF 3 COOH） 2 And 0.06. g of N, N-dimethylformamide under nitrogen protection at 55℃under reduced pressure to give compound Ph (OPhCF) 3 COCl） 2 。
(3) Adding 0.5 g aminated carbon nanotubes to 100N-methylpyrrolidone solvent of mL, dispersing, adding 2 g of compound Ph (OPhCF) in ice water bath 3 COCl） 2 And 1.3 g of p-phenylenediamine and 0.9 g of triethylamine are stirred and dissolved for reaction, the reaction temperature is 40 ℃, the reaction time is 36 h, a hydrochloric acid solution is dropwise added after the reaction to adjust the pH to 5, the suction filtration is carried out, and the water and the ethanol are sequentially used for washing, so that the fluoropolymer grafted carbon nano tube is prepared.
(4) Adding 2 g fluorine-containing polymer grafted carbon nano tube into acetone solvent, dispersing, adding 20 g polytetrafluoroethylene, uniformly mixing in a high-speed mixer, volatilizing to remove the solvent, molding the material in a molding press at room temperature of 35 MPa for 6 min for molding, and finally sintering in a sintering furnace at 350 ℃ for 2 h to obtain fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene.
Comparative example 1
Adding 0.4 g of aminated carbon nano tube into acetone solvent, dispersing, adding 20 g of polytetrafluoroethylene, uniformly mixing in a high-speed mixer, volatilizing to remove the solvent, molding the material in a molding press at room temperature of 35 MPa for 8 min for molding, and finally sintering in a sintering furnace at 360 ℃ for 2 h to obtain the carbon nano tube modified polytetrafluoroethylene.
The tensile properties of polytetrafluoroethylene were tested by a tensile tester at a loading rate of 10 mm/min, and standard GB/T1040.1-2018 was implemented. The friction resistance was tested by a frictional wear tester at a rate of 100 r/min, a load of 200N and a wear time of 180 min. Hardness was tested by a Shore durometer, standard GB/T2411-2008 was performed.
Table 1 tensile properties and hardness of polytetrafluoroethylene were tested.
| Tensile Strength (MPa) | Elongation at break (%) | Shore hardness of | |
| Example 1 | 35.9 | 291.0 | 58.6 |
| Example 2 | 42.7 | 342.4 | 60.2 |
| Example 3 | 52.4 | 405.7 | 65.7 |
| Example 4 | 46.2 | 379.2 | 68.2 |
| Example 5 | 40.8 | 332.7 | 68.0 |
| Comparative example 1 | 33.7 | 280.2 | 54.6 |
After polytetrafluoroethylene is filled and modified by the fluorine-containing polymer grafted carbon nano tube, the polytetrafluoroethylene material prepared in the examples 1-5 has the tendency that the tensile strength and the elongation at break are increased and then reduced along with the increase of the content of the fluorine-containing polymer grafted carbon nano tube, and the tensile strength and the elongation at break of the polytetrafluoroethylene material prepared in the example 3 are the largest and reach 52.4 MPa and 405.7%; the shore hardness of the polytetrafluoroethylene material of example 4 showed a tendency of gradually increasing and then slowly decreasing, and the shore hardness was 68.2 at the maximum, because the carbon nanotubes and the surface-grafted fluoropolymer have a synergistic enhancement effect, and the mechanical properties of polytetrafluoroethylene are greatly improved. The polytetrafluoroethylene material of comparative example 1, to which only carbon nanotubes were added, had much lower tensile properties and hardness than examples 1-5.
Table 2 abrasion resistance test of polytetrafluoroethylene.
| Pre-wear mass (g) | Post-wear mass (g) | Actual wear (g) | Wear Rate (%) | |
| Example 1 | 50.242 | 49.981 | 0.261 | 0.519 |
| Example 2 | 49.811 | 49.577 | 0.234 | 0.470 |
| Example 3 | 50.110 | 49.894 | 0.216 | 0.431 |
| Example 4 | 49.787 | 49.598 | 0.189 | 0.380 |
| Example 5 | 49.904 | 49.724 | 0.180 | 0.361 |
| Comparative example 1 | 50.209 | 49.898 | 0.311 | 0.619 |
The abrasion loss of the polytetrafluoroethylene material is smaller and smaller along with the increase of the content of the fluorine-containing polymer grafted carbon nano tube, the abrasion loss rate of the polytetrafluoroethylene material is lower and lower, the minimum abrasion loss rate of the example 5 is 0.361%, and the abrasion loss rate is far lower than that of the polytetrafluoroethylene material prepared in the comparative example 1.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. A preparation process of fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene is characterized in that: the preparation process comprises the following steps:
(1) Adding aminated carbon nanotube into N-methyl pyrrolidone solvent, dispersing, adding compound Ph (OPhCF) into ice water bath 3 COCl） 2 P-phenylenediamine and triethylamine, wherein the carbon nanotubes are aminated, compound Ph (OPhCF 3 COCl） 2 The mass ratio of p-phenylenediamine to triethylamine is 1 (0.5-4) (0.3-2.6) (0.2-1.8), stirring and dissolving, reacting, dripping hydrochloric acid solution to adjust pH to 4-5 after the reaction, filtering, and washing to obtain the fluorine-containing polymer grafted carbon nano tube;
(2) Adding fluorine-containing polymer grafted carbon nano tubes into an acetone solvent, dispersing, adding polytetrafluoroethylene, wherein the mass ratio of the fluorine-containing polymer grafted carbon nano tubes to the polytetrafluoroethylene is 0.02-0.1:1, uniformly mixing in a high-speed mixer, volatilizing to remove the solvent, then carrying out compression molding on the materials in a molding press at room temperature, and finally sintering in a sintering furnace to obtain fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene;
the compound Ph (OPhCF) in the step (1) 3 COCl） 2 The preparation method of (2) comprises the following steps:
s1, adding 4-chloro-3- (trifluoromethyl) benzoic acid, hydroquinone and potassium carbonate into acetonitrile, uniformly stirring, reacting at 65-85 ℃ for 2-5 h, distilling under reduced pressure, and recrystallizing to obtain a compound Ph (OPhCF) 3 COOH） 2 ；
S2, adding a compound Ph (OPhCF) into thionyl chloride 3 COOH） 2 And N, N-dimethylformamide under the protection of nitrogen, reacting at 55-70deg.C for 3-6 h, distilling under reduced pressure, and recrystallizing to obtain compound Ph (OPhCF) 3 COCl） 2 。
2. The process for preparing the fluoropolymer-carbon nanotube modified polytetrafluoroethylene according to claim 1, wherein: the reaction temperature in the step (1) is 40-65 ℃ and the reaction time is 24-72 h.
3. The process for preparing the fluoropolymer-carbon nanotube modified polytetrafluoroethylene according to claim 1, wherein: the pressure of the die pressing in the die pressing machine in the step (2) is 35-50 MPa, and the die pressing time is 3-8 min.
4. The process for preparing the fluoropolymer-carbon nanotube modified polytetrafluoroethylene according to claim 1, wherein: the sintering temperature in the sintering furnace in the step (2) is 330-360 ℃ and the sintering time is 2-4 h.
5. The process for preparing the fluoropolymer-carbon nanotube modified polytetrafluoroethylene according to claim 1, wherein: the mass ratio of the 4-chloro-3- (trifluoromethyl) benzoic acid, hydroquinone and potassium carbonate in the S1 is 3.5-5:1:2.2-3.
6. According to claimThe preparation process of the fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene is characterized by comprising the following steps of: thionyl chloride in S2, compound Ph (OPhCF) 3 COOH） 2 And N, N-dimethylformamide in a mass ratio of 10-25:1:0.02-0.04.
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| CN104877283A (en) * | 2015-06-25 | 2015-09-02 | 河南泛锐复合材料研究院有限公司 | Method for preparing anti-static carbon nanomaterial-polytetrafluoroethylene composite material |
| KR20190014006A (en) * | 2019-01-18 | 2019-02-11 | 엘에프피(주) | Polytetra fluoroethylene-carbon nano tube composite fabrication method with good electronic property |
| CN112812477A (en) * | 2021-02-07 | 2021-05-18 | 成都希瑞方晓科技有限公司 | Filled modified polytetrafluoroethylene and preparation method thereof |
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| CN104877283A (en) * | 2015-06-25 | 2015-09-02 | 河南泛锐复合材料研究院有限公司 | Method for preparing anti-static carbon nanomaterial-polytetrafluoroethylene composite material |
| KR20190014006A (en) * | 2019-01-18 | 2019-02-11 | 엘에프피(주) | Polytetra fluoroethylene-carbon nano tube composite fabrication method with good electronic property |
| CN112812477A (en) * | 2021-02-07 | 2021-05-18 | 成都希瑞方晓科技有限公司 | Filled modified polytetrafluoroethylene and preparation method thereof |
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