CN118126478B - Wear-resistant antistatic polytetrafluoroethylene composite material and preparation process thereof - Google Patents
Wear-resistant antistatic polytetrafluoroethylene composite material and preparation process thereof Download PDFInfo
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- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 118
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 83
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 53
- 239000011737 fluorine Substances 0.000 claims abstract description 53
- 239000004642 Polyimide Substances 0.000 claims abstract description 40
- 229920001721 polyimide Polymers 0.000 claims abstract description 40
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 20
- HVBSAKJJOYLTQU-UHFFFAOYSA-M 4-aminobenzenesulfonate Chemical compound NC1=CC=C(S([O-])(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-M 0.000 claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 229910021389 graphene Inorganic materials 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000005457 ice water Substances 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 8
- HVBSAKJJOYLTQU-UHFFFAOYSA-N Sulfanilic acid Natural products NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 229950000244 sulfanilic acid Drugs 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VKPQLZPZPYQFOK-UHFFFAOYSA-N 2-acetamidobenzenesulfonyl chloride Chemical compound CC(=O)NC1=CC=CC=C1S(Cl)(=O)=O VKPQLZPZPYQFOK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000956 alloy Substances 0.000 abstract description 6
- 125000006337 tetrafluoro ethyl group Chemical group 0.000 abstract description 6
- 229910000601 superalloy Inorganic materials 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 230000002794 monomerizing effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229960005489 paracetamol Drugs 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to the technical field of polytetrafluoroethylene, and discloses a wear-resistant antistatic polytetrafluoroethylene composite material and a preparation process thereof. And simultaneously, 2, 3-tetrafluoro-1, 4-butanedium (p-aminobenzene sulfonate) and dianhydride compound are utilized for polymerization reaction to obtain fluorine-containing polyimide. Fluorine modified graphene and fluorine-containing polyimide are added into polytetrafluoroethylene, and the fluorine-containing graphene forms a continuous conductive path in the polytetrafluoroethylene, so that the volume resistivity of the polytetrafluoroethylene is remarkably reduced, and the conductivity and antistatic performance are improved. The fluorine-containing polyimide contains the same tetrafluoroethyl structural unit as polytetrafluoroethylene, has good interface compatibility with polytetrafluoroethylene, forms a high-performance alloy material with high compatibility, and improves the wear resistance and tensile property of the material.
Description
Technical Field
The invention relates to the technical field of polytetrafluoroethylene, in particular to a wear-resistant antistatic polytetrafluoroethylene composite material and a preparation process thereof.
Background
Polytetrafluoroethylene is a polymer material obtained by taking tetrafluoroethylene as a monomer and polymerizing, and has excellent performances of high and low temperature resistance, acid and alkali resistance, solvent resistance and the like; has wide application in the aspects of plastics, paint coatings, medical equipment and the like. The nano material such as graphene and the like and the high-performance polyimide, polyformaldehyde and other high-molecular polymers are utilized to carry out filling modification on polytetrafluoroethylene, so that the polytetrafluoroethylene can be endowed with antistatic, wear-resistant, high-strength and other performances. However, the compatibility of the graphene and polytetrafluoroethylene is poor, and the dispersibility is poor, so that the enhancement effect of the graphene on polytetrafluoroethylene can be influenced.
The polyimide as special engineering plastic has high mechanical strength, high wear resistance and high heat resistance, and may be used in producing excellent alloy material with polyurethane, polytetrafluoroethylene, polyoxymethylene, etc. Chinese patent CN105001566B discloses a polytetrafluoroethylene/polyimide composite material and a preparation method thereof, wherein polytetrafluoroethylene is modified by phenolphthalein type polyimide with a special structure, and the obtained composite material has better tensile strength, tensile modulus and stable size. However, the polytetrafluoroethylene/polyimide composite material of the patent does not show good wear resistance, antistatic property and the like.
Disclosure of Invention
The invention solves the problem of poor compatibility of graphene, polyimide and polytetrafluoroethylene, and improves the performances of wear resistance, antistatic property and the like of the polytetrafluoroethylene.
The invention provides the following technical scheme: a wear-resistant antistatic polytetrafluoroethylene composite material comprises 70-90 parts by weight of polytetrafluoroethylene, 10-30 parts by weight of fluorine-containing polyimide and 1-8 parts by weight of fluorine-modified graphene.
The preparation process of the fluorine-containing polyimide comprises the following steps: adding dianhydride compound and 2, 3-tetrafluoro-1, 4-butanediyl (sulfanilic acid ester) into a solvent, stirring at room temperature for reaction for 10-15h, then carrying out gradient heating treatment on the solution, cooling, discharging, and crushing to obtain fluorine-containing polyimide.
The preparation process of the fluorine modified graphene comprises the following steps: adding graphene oxide into a reaction solvent, uniformly mixing, adding 2, 3-tetrafluoro-1, 4-butanedium (p-aminobenzenesulfonate), reacting at 60-90 ℃ for 18-24h, filtering after the reaction, washing with ethanol, and drying to obtain fluorine modified graphene.
Wherein, in the preparation process of the fluorine-containing polyimide, the proportion of the dianhydride compound and the 2, 3-tetrafluoro-1, 4-butanedium (p-aminobenzene sulfonate) is 1mol (0.95-1.1 mol); the dianhydride compound is any one of pyromellitic anhydride, 3', 4' -diphenyl tetracarboxylic dianhydride and 3,3', 4' -diphenyl tetracarboxylic dianhydride.
Wherein the gradient heating treatment is sequentially carried out at 120 ℃ for 1h, at 150 ℃ for 2h, at 200 ℃ for 2h, at 260 ℃ for 1h and at 300 ℃ for 1h.
In the preparation process of the fluorine-containing polyimide, the solvent is any one of N, N-dimethylformamide and N, N-dimethylacetamide.
In the preparation process of the fluorine modified graphene, the reaction solvent is any one of ethanol, N-dimethylformamide and N, N-dimethylacetamide.
In the preparation process of the fluorine modified graphene, the proportion of graphene oxide to 2, 3-tetrafluoro-1, 4-butylene (p-aminobenzenesulfonate) is 1g (2-5 g).
Wherein, the preparation process of the 2, 3-tetrafluoro-1, 4-butylene (p-aminobenzenesulfonate) comprises the following steps: adding 1mol of acetamido benzenesulfonyl chloride and 2, 3-tetrafluoro-1, 4-butanediol into pyridine in a ratio of (2.4-3.2) mol under ice water bath, heating to 50-70 ℃, reacting for 18-24h, cooling the solution, adding into ice water to separate out precipitate, filtering, washing the precipitate with methanol, drying, adding into 5-8% hydrochloric acid solution in mass fraction, heating, condensing and refluxing for reacting for 8-12h, cooling, adding sodium hydroxide for neutralization, filtering, washing the precipitate with distilled water and methanol, and drying to obtain 2, 3-tetrafluoro-1, 4-butylene (sulfanilic acid ester). The reaction route is as follows:
The preparation process of the wear-resistant antistatic polytetrafluoroethylene composite material comprises the following steps: adding 70-90 parts by weight of polytetrafluoroethylene, 10-30 parts by weight of fluorine-containing polyimide and 1-8 parts by weight of fluorine-modified graphene into a high-speed mixer for uniform mixing, then placing the materials into a flat vulcanizing machine, and performing cold press molding for 5-10min under the pressure of 15-20 MPa; then placing the mixture in a sintering furnace, and sintering the mixture for 3 to 5 hours at 375 to 385 ℃ to obtain the wear-resistant antistatic polytetrafluoroethylene composite material.
The invention has the following technical effects:
The invention utilizes acetamido benzene sulfonyl chloride and 2, 3-tetrafluoro-1, 4-butanediol to carry out sulfonic acid esterification reaction, and then carries out hydrochloric acid hydrolysis to obtain novel diamine monomer 2, 3-tetrafluoro-1, 4-butane diol (p-amino benzene sulfonate) containing tetrafluoroethyl structure. Further utilizing the reaction of the amino group of 2, 3-tetrafluoro-1, 4-butanedium (p-aminobenzenesulfonate) with the carboxyl group and the epoxy group on the surface of the graphene oxide, realizing the surface modification of the graphene oxide and obtaining the fluorine modified graphene. Meanwhile, 2, 3-tetrafluoro-1, 4-butanediyl (p-aminobenzene sulfonate) and dianhydride compounds such as pyromellitic anhydride are utilized to carry out polymerization reaction, so that fluorine-containing polyimide is obtained, and a tetrafluoroethyl structural unit is introduced into a polyimide molecular chain.
According to the invention, fluorine modified graphene is added into polytetrafluoroethylene, and fluorine-containing groups are grafted on the surface of the graphene, so that the dispersibility of the graphene in the polytetrafluoroethylene is improved, the graphene forms a continuous conductive path in the polytetrafluoroethylene, the volume resistivity of the polytetrafluoroethylene is obviously reduced, and the conductivity and antistatic performance are improved.
According to the invention, fluorine-containing polyimide is added into polytetrafluoroethylene, the fluorine-containing polyimide contains the same tetrafluoroethyl structural unit as polytetrafluoroethylene, the interface compatibility with polytetrafluoroethylene is good, the polytetrafluoroethylene and the fluorine-containing polyimide form a high-performance alloy material with high compatibility, the polyimide has excellent wear resistance and mechanical strength, and meanwhile, the added fluorine-modified graphene is uniformly dispersed in a polytetrafluoroethylene matrix, so that the wear resistance and tensile property of the material are obviously improved.
Detailed Description
The present invention will be described in detail below with reference to specific examples for the purpose of understanding. It is specifically pointed out that the specific examples are for illustrative purposes only and that it is obvious that, within the scope of the invention, a person skilled in the art can make various modifications within the scope of the invention, based on the description herein.
The Graphene oxide model is Graphene-510, and the thickness is 3.4-8nm. The model of polytetrafluoroethylene is MP1100E. Acetaminophen sulfonyl chloride CAS accession number 121-60-8.2, 3-tetrafluoro-1, 4-butanediol CAS registry number 425-61-6. Pyromellitic anhydride CAS accession number 89-32-7.3,3', 4' -benzophenone tetracarboxylic dianhydride CAS registry number 2421-28-5.3,3', 4' -Biphenyltetracarboxylic dianhydride CAS registry number 2420-87-3.
Example 1
44Mmol of acetaminophenesulfonyl chloride and 15mmol of 2, 3-tetrafluoro-1, 4-butanediol are added into 20mL of pyridine under ice water bath, then the pyridine is heated to 50 ℃ for reaction for 24 hours, the solution is cooled and added into ice water to separate out precipitate, the precipitate is washed by methanol after filtration, dried and added into 5% hydrochloric acid solution by mass percent, heated to 110 ℃ and condensed and refluxed for reaction for 8 hours, sodium hydroxide is added after cooling to neutralize pH to 7, the precipitate is washed by distilled water and methanol after filtration, and 2, 3-tetrafluoro-1, 4-butanedium (p-aminobenzenesulfonate) is obtained after drying. The structural formula is as follows:。
10mmol of pyromellitic anhydride and 10mmol of 2, 3-tetrafluoro-1, 4-butanediyl (sulfanilic acid ester) are added into 80mL of N, N-dimethylformamide solvent, stirred at room temperature for reaction for 10h, and then the solution is subjected to gradient heating treatment: sequentially carrying out heat preservation at 120 ℃ for 1h, 150 ℃ for 2h, 200 ℃ for 2h, 260 ℃ for 1h, 300 ℃ for 1h, cooling and discharging, and crushing to obtain the fluorine-containing polyimide.
Adding 0.5g of graphene oxide into 150mL of ethanol solvent, uniformly mixing, adding 1g of 2, 3-tetrafluoro-1, 4-butylene (sulfanilate), reacting at 60 ℃ for 24 hours, filtering after the reaction, washing with ethanol, and drying to obtain fluorine modified graphene.
Adding 900g of polytetrafluoroethylene, 100g of fluorine-containing polyimide and 10g of fluorine-modified graphene into a high-speed mixer, uniformly mixing, then placing the materials into a flat vulcanizing machine, and cold-pressing and molding for 5min under the pressure of 15 MPa; then placing the mixture in a sintering furnace, and sintering the mixture for 3 hours at 385 ℃ to obtain the wear-resistant antistatic polytetrafluoroethylene composite material.
Example 2
36Mmol of acetaminophenesulfonyl chloride and 15mmol of 2, 3-tetrafluoro-1, 4-butanediol are added into 12mL of pyridine under ice water bath, then the pyridine is heated to 50 ℃ for reaction for 24 hours, the solution is cooled and added into ice water to separate out precipitate, the precipitate is washed by methanol after filtration, dried and added into 5% hydrochloric acid solution by mass percent, heated to 110 ℃ and condensed and refluxed for reaction for 12 hours, sodium hydroxide is added after cooling to neutralize pH to 7, the precipitate is washed by distilled water and methanol after filtration, and 2, 3-tetrafluoro-1, 4-butanedium (p-aminobenzenesulfonate) is obtained after drying.
10Mmol of 3,3', 4' -benzophenone tetracarboxylic dianhydride and 9.5mmol of 2, 3-tetrafluoro-1, 4-butanedium (sulfanilic acid ester) are added into 70mL of N, N-dimethylacetamide solvent, stirred at room temperature for reaction for 15h, and then the solution is subjected to gradient heating treatment: sequentially carrying out heat preservation at 120 ℃ for 1h, 150 ℃ for 2h, 200 ℃ for 2h, 260 ℃ for 1h, 300 ℃ for 1h, cooling and discharging, and crushing to obtain the fluorine-containing polyimide.
Adding 0.5g of graphene oxide into 200mL of N, N-dimethylacetamide solvent, uniformly mixing, adding 1.8g of 2, 3-tetrafluoro-1, 4-butylene (sulfanilic acid ester), reacting at 90 ℃ for 18 hours, filtering after the reaction, washing with ethanol, and drying to obtain fluorine modified graphene.
Adding 800g of polytetrafluoroethylene, 200g of fluorine-containing polyimide and 40g of fluorine-modified graphene into a high-speed mixer, uniformly mixing, then placing the materials into a flat vulcanizing machine, and cold-pressing and molding for 10min under the pressure of 20 MPa; then placing the mixture in a sintering furnace, and sintering the mixture at 375 ℃ for 5 hours to obtain the wear-resistant antistatic polytetrafluoroethylene composite material.
Example 3
48Mmol of acetaminophenesulfonyl chloride and 15mmol of 2, 3-tetrafluoro-1, 4-butanediol are added into 20mL of pyridine under ice water bath, then the pyridine is heated to 70 ℃ for reaction for 18 hours, the solution is cooled and added into ice water to separate out precipitate, the precipitate is washed by methanol after filtration, dried and added into hydrochloric acid solution with the mass fraction of 8%, heated to 110 ℃ and condensed and refluxed for reaction for 8 hours, sodium hydroxide is added after cooling to neutralize pH to 7, the precipitate is washed by distilled water and methanol after filtration, and 2, 3-tetrafluoro-1, 4-butanedium (p-aminobenzenesulfonate) is obtained after drying.
10Mmol of 3,3', 4' -biphenyl tetracarboxylic dianhydride and 11mmol of 2, 3-tetrafluoro-1, 4-butanediyl (sulfanilic acid ester) are added into 80mL of N, N-dimethylformamide solvent, stirred at room temperature for reaction for 12h, and then the solution is subjected to gradient heating treatment: sequentially carrying out heat preservation at 120 ℃ for 1h, 150 ℃ for 2h, 200 ℃ for 2h, 260 ℃ for 1h, 300 ℃ for 1h, cooling and discharging, and crushing to obtain the fluorine-containing polyimide.
Adding 0.5g of graphene oxide into 200mL of N, N-dimethylformamide solvent, uniformly mixing, adding 2.5g of 2, 3-tetrafluoro-1, 4-butylene (sulfanilate), reacting at 90 ℃ for 24 hours, filtering after the reaction, washing with ethanol, and drying to obtain fluorine modified graphene.
Adding 700g of polytetrafluoroethylene, 300g of fluorine-containing polyimide and 80g of fluorine-modified graphene into a high-speed mixer, uniformly mixing, then placing the materials into a flat vulcanizing machine, and cold-pressing and molding for 10min under the pressure of 20 MPa; then placing the mixture in a sintering furnace, and sintering the mixture for 5 hours at 380 ℃ to obtain the wear-resistant antistatic polytetrafluoroethylene composite material.
Comparative example 1
Placing 900g of polytetrafluoroethylene in a flat vulcanizing machine, and cold-pressing and molding for 5min under the pressure of 15 MPa; then placing the mixture in a sintering furnace, and sintering the mixture for 3 hours at 385 ℃ to obtain the polytetrafluoroethylene material.
Comparative example 2
900G of polytetrafluoroethylene, 100g of fluorine-containing polyimide (prepared by the process of the embodiment 1) and 10g of graphene oxide are added into a high-speed mixer to be uniformly mixed, and then the materials are placed into a flat vulcanizing machine to be subjected to cold press molding for 5min under the pressure of 15 MPa; then placing the mixture in a sintering furnace, and sintering the mixture for 3 hours at 385 ℃ to obtain the polytetrafluoroethylene composite material.
Comparative example 3
10Mmol of pyromellitic anhydride and 10mmol of 4,4' -biphenyldiamine are treated) Adding the mixture into 80mL of N, N-dimethylformamide solvent, stirring the mixture at room temperature for reaction for 10h, and then carrying out gradient heating treatment on the solution: sequentially carrying out heat preservation at 120 ℃ for 1h, 150 ℃ for 2h, 200 ℃ for 2h, 260 ℃ for 1h, 300 ℃ for 1h, cooling and discharging, and crushing to obtain polyimide.
Adding 900g of polytetrafluoroethylene, 100g of polyimide and 10g of fluorine modified graphene into a high-speed mixer, uniformly mixing, then placing the materials into a flat vulcanizing machine, and cold-pressing and molding for 5min under the pressure of 15 MPa; then placing the mixture in a sintering furnace, and sintering the mixture for 3 hours at 385 ℃ to obtain the polytetrafluoroethylene composite material.
And testing the volume resistivity of the polytetrafluoroethylene material by adopting a high resistance meter and a four-probe method.
The volume resistivity test results of the materials are shown in Table 1
TABLE 1 volume resistivity test of polytetrafluoroethylene materials
| Volume resistivity (Ω cm) | |
| Example 1 | 5.12×107 |
| Example 2 | 2.33×102 |
| Example 3 | 32.3 |
| Comparative example 1 | 8.69×1016 |
| Comparative example 2 | 9.35×108 |
| Comparative example 3 | 5.09×107 |
As is clear from Table 1, comparative example 1 was a pure polytetrafluoroethylene, and had a volume resistivity of 9.02X10 13. Omega. Cm, poor conductivity and poor antistatic properties. Through wear test, the wear amount reaches 816.9 mg, and the wear resistance is poor.
The polytetrafluoroethylene of the embodiments 1-3 is added with fluorine modified graphene, fluorine-containing groups are grafted on the surface of the graphene, so that the dispersibility of the graphene in the polytetrafluoroethylene is improved, the graphene forms a continuous conductive path in the polytetrafluoroethylene, the volume resistivity of the polytetrafluoroethylene is obviously reduced, and the conductivity and antistatic performance are improved. In comparative example 3, fluorine modified graphene is also added, and the volume resistivity of polytetrafluoroethylene is also low, so that the antistatic performance is excellent.
Compared with example 1, the graphene oxide added in comparative example 2 does not contain fluorine-containing groups, has poor compatibility with polytetrafluoroethylene, poor dispersibility, does not form a continuous conductive path in polytetrafluoroethylene well, and has a volume resistivity greater than that of example 1 and poor antistatic performance.
The abrasion resistance of the polytetrafluoroethylene material was tested according to the GB/T3960-2016 method. The load is 200N, the rotating speed is 200r/min, the wear time is 2h, and the mating part is a 45# steel ring.
The tensile properties of the polytetrafluoroethylene materials were tested according to the GB/T1040.1-2018 method.
The mechanical properties of each material are shown in Table 2.
TABLE 2 mechanical Property test of polytetrafluoroethylene materials
| Volume abrasion Rate [ mm 3/(N.m) ] | Tensile Strength (MPa) | Tensile modulus (MPa) | |
| Example 1 | 4.56×10-5 | 51.4 | 892.6 |
| Example 2 | 7.52×10-7 | 64.9 | 1048.0 |
| Example 3 | 3.59×10-7 | 53.3 | 852.3 |
| Comparative example 1 | 1.38×10-3 | 29.6 | 371.5 |
| Comparative example 2 | 7.40×10-5 | 45.2 | 822.7 |
| Comparative example 3 | 9.56×10-5 | 40.8 | 770.9 |
Comparative example 1 is pure polytetrafluoroethylene, and the volume abrasion rate reaches 1.38X10 -3 mm3/(N.m) through abrasion test, and the abrasion resistance is poor.
The fluorine-containing polyimide added in the embodiment 1-3 contains the same tetrafluoroethyl structural unit as polytetrafluoroethylene, has good interfacial compatibility with polytetrafluoroethylene, forms a high-performance alloy material with high compatibility, has excellent wear resistance and mechanical strength, and can obviously reduce the volume wear rate of the material and obviously improve the wear resistance and tensile property of the material by uniformly dispersing the heated fluorine-modified graphene in a polytetrafluoroethylene matrix.
Compared with the example 1, the fluorine-containing polyimide is added in the comparative example 2, the interface compatibility with polytetrafluoroethylene is good, and the fluorine-containing polyimide and the polytetrafluoroethylene form the compatible alloy composite material, so that the tensile property and the wear resistance of the polytetrafluoroethylene can be obviously improved. However, the added graphene oxide does not contain fluorine-containing groups, has poor compatibility with polytetrafluoroethylene, poor dispersibility and poor reinforcing effect on polytetrafluoroethylene, and results in lower wear resistance, tensile strength and tensile modulus than those of example 1.
The fluorine modified graphene is added in the comparative example 3, so that the compatibility with polytetrafluoroethylene is good, the dispersibility is excellent, and the tensile property of the polytetrafluoroethylene can be obviously improved, but the pyromellitic anhydride and the 4,4 '-biphenyl diamine are used as monomers, the obtained polyimide does not contain a tetrafluoroethyl structural unit, the interfacial compatibility with the polytetrafluoroethylene is poor, and the high-compatibility high-performance alloy material is difficult to form by the pyromellitic anhydride and the 4,4' -biphenyl diamine, so that the wear resistance and the tensile property of the material are lower than those of the 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 (7)
1. The wear-resistant antistatic polytetrafluoroethylene composite material is characterized by comprising 70-90 parts by weight of polytetrafluoroethylene, 10-30 parts by weight of fluorine-containing polyimide and 1-8 parts by weight of fluorine-modified graphene;
The preparation process of the fluorine-containing polyimide comprises the following steps: adding dianhydride compound and 2, 3-tetrafluoro-1, 4-butanedium (sulfanilic acid ester) into a solvent, stirring at room temperature for reaction for 10-15h, then carrying out gradient heating treatment on the solution, cooling, discharging, and crushing to obtain fluorine-containing polyimide;
the preparation process of the fluorine modified graphene comprises the following steps: adding graphene oxide into a reaction solvent, uniformly mixing, adding 2, 3-tetrafluoro-1, 4-butanedium (p-aminobenzenesulfonate), reacting at 60-90 ℃ for 18-24h, filtering after the reaction, washing and drying to obtain fluorine modified graphene;
The preparation process of the 2, 3-tetrafluoro-1, 4-butylene (p-aminobenzenesulfonate) comprises the following steps: adding acetamido benzenesulfonyl chloride and 2, 3-tetrafluoro-1, 4-butanediol into pyridine under ice water bath, heating to 50-70 ℃, reacting for 18-24 hours, cooling the solution, adding into ice water to separate out precipitate, filtering, washing the precipitate, drying, adding into 5-8% hydrochloric acid solution by mass percent, heating and condensing and refluxing for reacting for 8-12 hours, cooling, adding sodium hydroxide for neutralization, filtering, washing the precipitate with distilled water and methanol, and drying to obtain 2, 3-tetrafluoro-1, 4-butanedium (p-aminobenzenesulfonate);
The ratio of the acetamido benzenesulfonyl chloride to the 2, 3-tetrafluoro-1, 4-butanediol is (2.4-3.2) mol to 1mol;
In the preparation process of the fluorine-containing polyimide, the proportion of the dianhydride compound to the 2, 3-tetrafluoro-1, 4-butanedium (p-aminobenzene sulfonate) is 1mol (0.95-1.1 mol);
In the preparation process of the fluorine modified graphene, the proportion of graphene oxide to 2, 3-tetrafluoro-1, 4-butylene (p-aminobenzenesulfonate) is 1g (2-5 g).
2. The wear-resistant antistatic polytetrafluoroethylene composite according to claim 1, wherein the dianhydride compound is any one of pyromellitic anhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, and 3,3', 4' -biphenyl tetracarboxylic dianhydride.
3. The wear-resistant antistatic polytetrafluoroethylene composite material according to claim 1, wherein the gradient heating treatment is performed sequentially by heat preservation at 120 ℃ for 1h, heat preservation at 150 ℃ for 2h, heat preservation at 200 ℃ for 2h, heat preservation at 260 ℃ for 1h, and heat preservation at 300 ℃ for 1h.
4. The wear-resistant antistatic polytetrafluoroethylene composite material according to claim 1, wherein the solvent in the preparation process of the fluorine-containing polyimide is any one of N, N-dimethylformamide and N, N-dimethylacetamide.
5. The wear-resistant and antistatic polytetrafluoroethylene composite material according to claim 1, wherein in the preparation process of the fluorine modified graphene, the reaction solvent is any one of ethanol, N-dimethylformamide and N, N-dimethylacetamide.
6. A process for preparing the wear-resistant antistatic polytetrafluoroethylene composite material as claimed in any one of claims 1 to 5, wherein the process comprises the following steps: adding 70-90 parts by weight of polytetrafluoroethylene, 10-30 parts by weight of fluorine-containing polyimide and 1-8 parts by weight of fluorine modified graphene into a high-speed mixer for uniform mixing, and then placing the materials into a flat vulcanizing machine for cold press molding; and then sintering in a sintering furnace to obtain the wear-resistant antistatic polytetrafluoroethylene composite material.
7. The process for preparing the wear-resistant antistatic polytetrafluoroethylene composite material according to claim 6, wherein the cold press molding pressure is 15-20MPa, and the cold press time is 5-10min; the sintering temperature is 375-385 ℃, and the sintering time is 3-5h.
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