CN114621527A - Antistatic wear-resistant plastic for vehicles and preparation method thereof - Google Patents
Antistatic wear-resistant plastic for vehicles and preparation method thereof Download PDFInfo
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- CN114621527A CN114621527A CN202210358173.5A CN202210358173A CN114621527A CN 114621527 A CN114621527 A CN 114621527A CN 202210358173 A CN202210358173 A CN 202210358173A CN 114621527 A CN114621527 A CN 114621527A
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- 239000004033 plastic Substances 0.000 title claims abstract description 59
- 229920003023 plastic Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 113
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 113
- 238000002156 mixing Methods 0.000 claims abstract description 108
- 239000002131 composite material Substances 0.000 claims abstract description 59
- -1 polypropylene Polymers 0.000 claims abstract description 59
- 239000004743 Polypropylene Substances 0.000 claims abstract description 34
- 229920001155 polypropylene Polymers 0.000 claims abstract description 34
- NLFXTGCQAOAMJY-UHFFFAOYSA-N 2,4,6-trinitrobenzenediazonium Chemical class [O-][N+](=O)C1=CC([N+]([O-])=O)=C([N+]#N)C([N+]([O-])=O)=C1 NLFXTGCQAOAMJY-UHFFFAOYSA-N 0.000 claims abstract description 25
- LXCMFWXRKJJBDY-UHFFFAOYSA-N 3,5-dihydroxybenzenecarboximidamide Chemical compound NC(=N)C1=CC(O)=CC(O)=C1 LXCMFWXRKJJBDY-UHFFFAOYSA-N 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 11
- XVZWMPLMWUJTCE-UHFFFAOYSA-N 6-ethenylnaphthalen-2-ol Chemical compound C1=C(C=C)C=CC2=CC(O)=CC=C21 XVZWMPLMWUJTCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 168
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 238000001816 cooling Methods 0.000 claims description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000008367 deionised water Substances 0.000 claims description 48
- 229910021641 deionized water Inorganic materials 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 39
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 34
- IAHOUQOWMXVMEH-UHFFFAOYSA-N 2,4,6-trinitroaniline Chemical compound NC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O IAHOUQOWMXVMEH-UHFFFAOYSA-N 0.000 claims description 32
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 32
- 230000004224 protection Effects 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 28
- 229910052786 argon Inorganic materials 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 17
- ABHOEQJNEOMTEK-UHFFFAOYSA-N 3,5-dihydroxybenzonitrile Chemical compound OC1=CC(O)=CC(C#N)=C1 ABHOEQJNEOMTEK-UHFFFAOYSA-N 0.000 claims description 16
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 235000010288 sodium nitrite Nutrition 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 11
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 11
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- 102000020897 Formins Human genes 0.000 claims description 2
- 108091022623 Formins Proteins 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 230000006750 UV protection Effects 0.000 abstract description 8
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 abstract description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 abstract description 7
- 239000012964 benzotriazole Substances 0.000 abstract description 7
- 229920001088 polycarbazole Polymers 0.000 abstract description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 238000010561 standard procedure Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- 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
- C08K9/10—Encapsulated ingredients
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- 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
-
- 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
- C08K9/02—Ingredients treated with inorganic substances
-
- 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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an antistatic wear-resistant plastic for a vehicle and a preparation method thereof, and relates to the technical field of plastics. When the antistatic wear-resistant plastic for the vehicle is prepared, the carbon nanofiber is wrapped by 3, 5-dihydroxybenzoamidine and 2,4, 6-trinitrobenzene diazonium salt, and hydrogen coupled ultrasonic treatment is utilized to form benzotriazole with a triazine ring and a hyperbranched structure, so that the composite carbon nanofiber is prepared; mixing propylene and 6-vinyl-2-naphthol to prepare a polypropylene prepolymer; and finally, mixing the polypropylene prepolymer and the composite carbon nanofibers, polymerizing the polypropylene prepolymer and the composite carbon nanofibers to form an interpenetrating network structure and a polycarbazole conductive path, and preparing the antistatic wear-resistant plastic for the vehicle. The antistatic wear-resistant plastic for the vehicle, prepared by the invention, has good impact strength, flame retardance, ultraviolet resistance and antistatic performance.
Description
Technical Field
The invention relates to the technical field of plastics, in particular to an antistatic wear-resistant plastic for a vehicle and a preparation method thereof.
Background
Under the promotion of dual factors of energy conservation and environmental protection, the China automobile manufacturing industry basically realizes plastification in the field of interior decoration, such as a storage battery shell, an instrument panel, a steering wheel and the like. Meanwhile, the new development route takes the light weight of the automobile as the main idea, mainly aims at further plastifying the outer covering part, and is mainly applied to automobile accessories such as bumpers, door inner decoration plates, plastic engine covers, plastic front fenders and the like of the typical passenger cars at present.
However, plastics are extremely easy to wear, and in order to expand the application of the plastics to the outer covering parts, carbon nano fibers are often added into the plastics by the technical personnel in the field to increase the wear resistance of the plastics for vehicles. In recent years, automobile spontaneous combustion events are gradually increased, and people are aware of the defects of flammability, tracking resistance, high brittleness, low impact strength and the like of plastics due to safety considerations, so that the automobile spontaneous combustion is easily caused, and people in the automobile are greatly injured in collision, and the problems greatly hinder the automobile plastification step, and become a difficult problem to be solved in the technical field of the current automobile plastics.
The invention focuses on the current situation, and solves the problem by preparing the antistatic wear-resistant plastic for the vehicle.
Disclosure of Invention
The invention aims to provide an antistatic wear-resistant plastic for vehicles and a preparation method thereof, and aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of antistatic wear-resistant plastic for vehicles is provided, wherein the antistatic wear-resistant plastic for vehicles is prepared by mixing polypropylene prepolymer and composite carbon nanofiber; the polypropylene prepolymer is prepared from propylene and 6-vinyl-2-naphthol; the composite carbon nanofiber is prepared by wrapping 3, 5-dihydroxybenzamidine and 2,4, 6-trinitrobenzene diazonium salt on the carbon nanofiber and performing hydrogen coupling ultrasonic treatment.
Preferably, the preparation method of the antistatic wear-resistant plastic for the vehicle comprises the following steps: under the condition of argon protection, mixing a polypropylene prepolymer, benzoyl peroxide and composite carbon nanofiber according to a mass ratio of 1: 0.007: 0.8-1: 0.009: 1, mixing, putting into a reaction kettle with the pressure of 0.6-0.8 MPa, stirring for 1-3 h at the speed of 500-700 r/min, then adding aluminum chloride with the mass of 0.003-0.005 times of that of the polypropylene prepolymer, heating to 180-190 ℃ at the speed of 9-11 ℃/min, continuing stirring for 11-13 h, naturally cooling to room temperature, cooling to 0-5 ℃ at the speed of 3-5 ℃/min, and sequentially mixing according to the mass ratio of 1: 1-1: 3, adding 98% concentrated sulfuric acid and deionized water by mass, wherein the mass of the 98% concentrated sulfuric acid is 2-4 times of that of the composite carbon nanofiber, stirring for 5-15 min at 800-1000 r/min, then dropwise adding 20-30% sodium nitrite solution 1-3 times of that of the composite carbon nanofiber at 60-80 drops/min, continuously stirring for 1-3 h, adding 0.01-0.03 times of that of the composite carbon nanofiber, continuously stirring for 50-70 min, dropwise adding 20-30% sodium bisulfite solution 1-3 times of that of the composite carbon nanofiber at 60-80 drops/min, continuously stirring for 10-20 min, heating to 120-140 ℃ at 4-6 ℃/min, dropwise adding 10-20% sulfuric acid solution at 60-80 drops/min to adjust the pH to 4-6, continuously stirring for 3-5 days, and (3) putting the mixture into a 230-250 ℃ double-screw extruder, and extruding and granulating at the rotating speed of 300-500 r/min to prepare the antistatic wear-resistant plastic for the vehicle.
Preferably, the preparation method of the polypropylene prepolymer is as follows: under the protection of argon at the temperature of 60-80 ℃, mixing propylene, 6-vinyl-2-naphthol and benzoyl peroxide according to the mass ratio of 1: 0.3: 0.006-1: 0.5: 0.008 mixing, putting into a reaction kettle with the pressure of 2-4 MPa, and stirring for 4-6 h at 500-700 r/min to prepare the polypropylene prepolymer.
Preferably, the preparation method of the composite carbon nanofiber comprises the following steps: under the condition of argon protection, mixing an azo intermediate, nickel powder, toluene and piperidine according to a mass ratio of 1: 0.02: 11: 0.5-1: 0.04: 13: 0.7, placing the mixture into a reaction kettle with the pressure of 0.4 to 0.6MPa, and controlling the temperature to be between 5 and 7m at 40 and 60 DEG C3And introducing hydrogen gas for min, continuing stirring for 4-6 h, naturally cooling to room temperature, filtering, washing with ethanol and deionized water for 2-4 times in sequence, and putting into an oven at 30-50 ℃ for drying for 1-3 h to prepare the composite carbon nanofiber.
Preferably, the preparation method of the azo intermediate is as follows: at the temperature of 0-4 ℃, mixing carbon nanofiber and concentrated sulfuric acid with the mass fraction of 98% according to the mass ratio of 1: 3-1: 5, mixing, stirring for 30-50 min at a speed of 500-700 r/min, performing ultrasonic treatment for 10-20 min at 30-40 kHz, filtering, washing for 2-4 times by using deionized water, and placing into an oven at 30-50 ℃ for drying for 1-3 h to prepare the pretreated carbon nanofiber; the method comprises the following steps of (1) mixing pretreated carbon nanofibers, 3, 5-dihydroxybenzamidine, copper acetate monohydrate, sodium carbonate and toluene according to a mass ratio of 1: 1: 0.1: 0.6: 13-1: 3: 0.3: 0.8: 15, stirring and refluxing for 23-25 h at 1200-1300 r/min, cooling to 0-5 ℃ at 5-7 ℃/min, and mixing according to a mass ratio of 1: 0.07: 0.001 to 1: 0.09: 0.003 of methanol, sodium hydroxide and sodium dodecyl benzene sulfonate are sequentially added, wherein the mass of the methanol is 20-30 times of that of the pretreated carbon nanofiber, the mixture is continuously stirred for 50-70 min, 2,4, 6-trinitrobenzene diazonium salt which is 1-3 times of that of the pretreated carbon nanofiber is added, the mixture is continuously stirred for 20-40 min, sodium hydroxide solution with the mass fraction of 20-30% is dripped at the speed of 60-80 drops/min to adjust the pH value to 7-9, and the mixture is continuously stirred for 1-2 h to prepare the azo intermediate.
Preferably, the length of the carbon nanofiber is 200-300 μm.
Preferably, the preparation method of the 2,4, 6-trinitrobenzene diazonium salt is as follows: mixing 2,4, 6-trinitroaniline, concentrated sulfuric acid with the mass fraction of 98% and deionized water according to the mass ratio of 1: 2: 2-1: 4: 4, mixing, stirring for 5-15 min at 800-1000 r/min, naturally cooling to 30-40 ℃, adding deionized water with the mass being 2-4 times that of 2,4, 6-trinitroaniline, continuously stirring for 5-15 min, cooling to 0-5 ℃ at 2-4 ℃, then dropwise adding a sodium nitrite solution with the mass fraction being 20-30% and the mass being 1-3 times that of 2,4, 6-trinitroaniline at 60-80 drops/min, continuously stirring for 1-3 h, adding urea with the mass being 0.01-0.03 time that of 2,4, 6-trinitroaniline, continuously stirring for 50-70 min, and filtering to prepare the 2,4, 6-trinitrobenzene diazonium salt.
Preferably, the preparation method of the 3, 5-dihydroxy benzamidine comprises the following steps: at the temperature of 30-40 ℃, mixing 3, 5-dihydroxy benzene oxime, ethanol and deionized water according to the mass ratio of 1: 9: 4-1: 11: 6, mixing, stirring for 30-50 min at 500-700 r/min, then adding nickel powder with the mass of 0.002-0.004 times of that of 3, 5-dihydroxy benzene oxime, putting into a reaction kettle with the pressure of 0.6-0.8 MPa, heating to 60-80 ℃ at 3-5 ℃/min, and preserving heat for 8-10 h at the stirring speed of 500-700 r/min under the protection of argon to prepare the 3, 5-dihydroxy benzene formamidine.
Preferably, the preparation method of the 3, 5-dihydroxy benzene oxime comprises the following steps: at the temperature of 30-40 ℃, mixing 3, 5-dihydroxy benzonitrile and ethanol according to the mass ratio of 1: 9-1: 11, stirring for 30-50 min at 500-700 r/min, then adding a hydroxylamine hydrochloride aqueous solution with the mass fraction of 19-21% and 9-10 times of the mass of 3, 5-dihydroxybenzonitrile, continuing stirring for 20-30 min, then dropwise adding a sodium carbonate solution with the mass fraction of 9-11% and 0.4-0.6 time of the mass of the hydroxylamine hydrochloride aqueous solution at 60-80 drops/min, continuing stirring for 50-60 min, naturally cooling to room temperature, standing for 1-3 h, and performing suction filtration under the condition of 10-20 Pa to prepare the 3, 5-dihydroxy benzene oxime.
Preferably, the particle size of the nickel powder is 30-50 nm.
Compared with the prior art, the invention has the following beneficial effects:
when the antistatic wear-resistant plastic for the vehicle is prepared, the carbon nanofiber is wrapped by 3, 5-dihydroxybenzamidine and 2,4, 6-trinitrobenzene diazonium salt, and the composite carbon nanofiber is prepared by hydrogen coupling ultrasonic treatment; mixing propylene and 6-vinyl-2-naphthol to prepare a polypropylene prepolymer; and finally, mixing the polypropylene prepolymer and the composite carbon nanofiber to prepare the antistatic wear-resistant plastic for the vehicle.
Firstly, a large number of free radicals such as hydroxyl and the like are formed on the surface of the carbon nanofiber, amidino on 3, 5-dihydroxybenzamidine reacts with the hydroxyl on the carbon nanofiber, and dehydrocyclization is carried out to form triazine ring, so that the flame retardant property of the composite carbon nanofiber is enhanced; the 2,4, 6-trinitrobenzene diazonium salt and part of phenol on the 3, 5-dihydroxy benzamidine are coupled to form an azo intermediate, the nitro group adjacent to the diazo group in the 2,4, 6-trinitrobenzene diazonium salt reacts with the azo intermediate to be cyclized under the action of hydrogen to form benzotriazole with a hyperbranched structure, and the other part of nitro group is reduced to form amino group under the action of hydrogen, so that the uvioresistant performance of the composite carbon nanofiber is enhanced.
Secondly, the polypropylene prepolymer quickly enters the cavity of the composite carbon nanofiber, the polypropylene prepolymer is polymerized, and part of propylene reacts with the other part of phenol in the composite carbon nanofiber for crosslinking to form an interpenetrating network structure, so that the impact strength of the antistatic wear-resistant plastic for the vehicle is enhanced; hydrazine groups formed by reducing the composite carbon nanofibers after the ammonia basis weight is nitrified react with naphthol in the polypropylene prepolymer to form carbazole, and polycarbazole formed by polymerizing the carbazole forms a conductive path with the carbon nanofibers, so that the antistatic property of the composite carbon nanofibers is enhanced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for detailed description, and the method for testing each index of the antistatic wear-resistant plastic for vehicles prepared in the following examples is as follows:
antistatic property: the antistatic property of the antistatic wear-resistant plastic for vehicles prepared by the same mass of the examples and the comparative examples is determined by measuring the volume resistivity according to the GB/T15662 standard method.
Impact strength: the impact strength of the antistatic abrasion-resistant plastic for vehicles prepared by taking the same mass of the examples and the comparative examples is measured according to the GB/T2546.2 standard method.
Flame retardancy: the flame retardance of the antistatic wear-resistant plastic for the vehicle prepared by the same mass of the example and the comparative example is tested by measuring the extreme oxygen index according to the GB/T2406 standard method.
Ultraviolet resistance: the automobile antistatic wear-resistant plastics prepared in the same mass of the examples and the comparative examples are subjected to an ultraviolet aging test according to a GB/T16422 standard method, and the impact strength of the automobile antistatic wear-resistant plastics subjected to ultraviolet aging is measured according to the GB/T2546.2 standard method to measure the ultraviolet resistance.
Example 1
The preparation method of the antistatic wear-resistant plastic for the vehicle comprises the following preparation steps:
(1) at the temperature of 30 ℃, mixing 3, 5-dihydroxy benzonitrile and ethanol according to the mass ratio of 1: 9, stirring for 30min at 500r/min, then adding a hydroxylamine hydrochloride aqueous solution with the mass fraction of 19 percent and 9 times of the mass of the 3, 5-dihydroxy benzonitrile, continuing to stir for 20min, then dropwise adding a sodium carbonate solution with the mass fraction of 9 percent and 0.4 time of the mass of the hydroxylamine hydrochloride aqueous solution at 60 drops/min, continuing to stir for 50min, and naturallyCooling to room temperature, standing for 1h, and performing suction filtration under the condition of 10Pa to prepare 3, 5-dihydroxy benzene oxime; at the temperature of 30 ℃, mixing 3, 5-dihydroxy benzene oxime, ethanol and deionized water according to the mass ratio of 1: 9: 4, mixing, stirring for 30min at 500r/min, then adding nickel powder with the particle size of 30nm, the mass of which is 0.002 times of that of the 3, 5-dihydroxy benzoxime, putting the nickel powder into a reaction kettle with the pressure of 0.6MPa, heating to 60 ℃ at 3 ℃/min, and preserving heat for 8h under the stirring speed of 500r/min and the protection of argon gas to prepare 3, 5-dihydroxy benzamidine; mixing 2,4, 6-trinitroaniline, concentrated sulfuric acid with the mass fraction of 98% and deionized water according to the mass ratio of 1: 2: 2, stirring at 800r/min for 5min, naturally cooling to 30 ℃, adding deionized water with the mass of 2 times that of 2,4, 6-trinitroaniline, continuing to stir for 5min, cooling to 0 ℃ at 2 ℃, then dropwise adding a sodium nitrite solution with the mass fraction of 20% which is 1 time that of 2,4, 6-trinitroaniline at 60 drops/min, continuing to stir for 1h, adding urea with the mass of 0.01 time that of 2,4, 6-trinitroaniline, continuing to stir for 50min, and filtering to prepare 2,4, 6-trinitrobenzene diazonium salt; at 0 ℃, carbon nano-fibers with the length of 200 mu m and concentrated sulfuric acid with the mass fraction of 98 percent are mixed according to the mass ratio of 1: 3, mixing, stirring for 30min at the speed of 500r/min, performing ultrasonic treatment for 10min at the frequency of 30kHz, filtering, washing for 2 times by using deionized water, and placing in an oven at the temperature of 30 ℃ for drying for 1h to prepare pretreated carbon nanofibers; the method comprises the following steps of mixing pretreated carbon nanofiber, 3, 5-dihydroxybenzamidine, copper acetate monohydrate, sodium carbonate and toluene according to a mass ratio of 1: 1: 0.1: 0.6: 13, stirring and refluxing for 23h at 1200r/min, cooling to 0 ℃ at 5 ℃/min, and mixing according to a mass ratio of 1: 0.07: 0.001 sequentially adding methanol, sodium hydroxide and sodium dodecyl benzene sulfonate, wherein the mass of the methanol is 20 times that of the pretreated carbon nano fibers, continuing to stir for 50min, adding 2,4, 6-trinitrobenzene diazonium salt which is 1 time that of the pretreated carbon nano fibers, continuing to stir for 20min, dropwise adding sodium hydroxide solution with the mass fraction of 20% at a rate of 60 drops/min to adjust the pH value to 7, and continuing to stir for 1h to prepare an azo intermediate; under the protection of argon, mixing an azo intermediate, nickel powder with the particle size of 30nm, toluene and piperidine according to the mass ratio of 1: 0.02: 11: 0.5 mixing, placing into a reaction kettle with a pressure of 0.4MPa, and heating at 40 deg.C for 5m3Introducing hydrogen gas at min, stirring for 4 hr, naturally cooling to room temperature, filtering, and filteringWashing with ethanol and deionized water for 2 times, and oven drying at 30 deg.C for 1 hr to obtain composite carbon nanofiber;
(2) under the protection of argon at 60 ℃, mixing propylene, 6-vinyl-2-naphthol and benzoyl peroxide according to the mass ratio of 1: 0.3: 0.006, putting into a 2MPa reaction kettle, and stirring at 500r/min for 4h to prepare a polypropylene prepolymer;
(3) under the condition of argon protection, mixing a polypropylene prepolymer, benzoyl peroxide and composite carbon nanofiber in a mass ratio of 1: 0.007: 0.8, placing the mixture into a reaction kettle with the pressure of 0.6MPa, stirring the mixture for 1h at the speed of 500r/min, then adding aluminum chloride with the mass of 0.003 time of that of the polypropylene prepolymer, heating the mixture to 180 ℃ at the speed of 9 ℃/min, continuing stirring the mixture for 11h, naturally cooling the mixture to room temperature, cooling the mixture to 0 ℃ at the speed of 3 ℃/min, and sequentially mixing the mixture according to the mass ratio of 1: 1 adding 98 percent of concentrated sulfuric acid and deionized water, wherein the mass of the 98 percent of concentrated sulfuric acid is 2 times of that of the composite carbon nanofiber, stirring at 800r/min for 5min, then dripping sodium nitrite solution with mass fraction of 20% and mass 1 time of composite carbon nanofiber at 60 drops/min, continuing stirring for 1h, adding urea with mass 0.01 time of composite carbon nanofiber, continuing stirring for 50min, dripping sodium bisulfite solution with mass fraction of 20% which is 1 time of the mass of the composite carbon nanofiber into the solution at a rate of 60 drops/min, continuously stirring the solution for 10min, heating to 120 deg.C at 4 deg.C/min, adding 10% sulfuric acid solution at 60 drops/min to adjust pH to 4, stirring for 3 days, placing into 230 deg.C twin-screw extruder, and extruding and granulating at the rotating speed of 300r/min to prepare the antistatic wear-resistant plastic for the vehicle.
Example 2
The preparation method of the antistatic wear-resistant plastic for the vehicle comprises the following preparation steps:
(1) at the temperature of 35 ℃, mixing 3, 5-dihydroxy benzonitrile and ethanol according to the mass ratio of 1: 10, stirring for 40min at 600r/min, then adding 20 percent of hydroxylamine hydrochloride aqueous solution which is 9.5 times of the mass of the 3, 5-dihydroxy benzonitrile, continuing to stir for 25min, then dropwise adding 10 percent of sodium carbonate solution which is 0.5 times of the mass of the hydroxylamine hydrochloride aqueous solution at 70 drops/min, continuing to stir for 55min, naturally cooling to room temperatureStanding for 2h at warm temperature, and performing suction filtration under the condition of 15Pa to prepare 3, 5-dihydroxy benzene oxime; at 35 ℃, mixing 3, 5-dihydroxy benzene oxime, ethanol and deionized water according to a mass ratio of 1: 10: 5, mixing, stirring for 40min at 600r/min, then adding nickel powder with the particle size of 40nm, the mass of which is 0.003 time of that of the 3, 5-dihydroxy benzene oxime, putting the nickel powder into a reaction kettle with the pressure of 0.7MPa, heating to 70 ℃ at 4 ℃/min, and preserving heat for 9h under the stirring speed of 600r/min and the protection of argon to prepare the 3, 5-dihydroxy benzamidine; mixing 2,4, 6-trinitroaniline, concentrated sulfuric acid with the mass fraction of 98% and deionized water according to the mass ratio of 1: 3: 3, mixing, stirring for 10min at 900r/min, naturally cooling to 35 ℃, adding deionized water with the mass of 3 times that of 2,4, 6-trinitroaniline, continuing to stir for 10min, cooling to 2 ℃ at 3 ℃, then dropwise adding a sodium nitrite solution with the mass fraction of 25% which is 2 times that of 2,4, 6-trinitroaniline at 70 drops/min, continuing to stir for 2h, adding urea with the mass of 0.02 time that of 2,4, 6-trinitroaniline, continuing to stir for 60min, and filtering to prepare 2,4, 6-trinitrobenzene diazonium salt; at 2 ℃, carbon nano-fibers with the length of 250 mu m and concentrated sulfuric acid with the mass fraction of 98 percent are mixed according to the mass ratio of 1: 4, mixing, stirring for 40min at the speed of 600r/min, carrying out ultrasonic treatment for 15min at 35kHz, filtering, washing for 3 times by using deionized water, and putting into an oven at the temperature of 40 ℃ for drying for 2h to prepare pretreated carbon nanofibers; the method comprises the following steps of mixing pretreated carbon nanofiber, 3, 5-dihydroxybenzamidine, copper acetate monohydrate, sodium carbonate and toluene according to a mass ratio of 1: 2: 0.2: 0.7: 14, stirring and refluxing for 24 hours at 1250r/min, cooling to 2 ℃ at 6 ℃/min, and mixing the components in a mass ratio of 1: 0.08: 0.002, sequentially adding methanol, sodium hydroxide and sodium dodecyl benzene sulfonate, wherein the mass of the methanol is 25 times that of the pretreated carbon nano fiber, continuing to stir for 60min, adding 2,4, 6-trinitrobenzene diazonium salt which is 2 times that of the pretreated carbon nano fiber, continuing to stir for 30min, dropwise adding sodium hydroxide solution with the mass fraction of 25% at 70 drops/min to adjust the pH value to 8, and continuing to stir for 1.5h to prepare an azo intermediate; under the protection of argon, mixing an azo intermediate, nickel powder with the particle size of 40nm, toluene and piperidine according to the mass ratio of 1: 0.03: 12: 0.6 mixing, placing into a reaction kettle with a pressure of 0.5MPa, and heating at 50 deg.C for 6m3Introducing hydrogen gas at min, stirring for 5 hr, naturally cooling to room temperature, filtering, and sequentially usingWashing with ethanol and deionized water for 3 times, and drying in a 40 ℃ oven for 2h to obtain the composite carbon nanofiber;
(2) under the protection of argon at 70 ℃, mixing propylene, 6-vinyl-2-naphthol and benzoyl peroxide according to the mass ratio of 1: 0.4: 0.007 percent, putting the mixture into a reaction kettle with the pressure of 3MPa, and stirring the mixture for 5 hours at the speed of 600r/min to prepare a polypropylene prepolymer;
(3) under the condition of argon protection, mixing a polypropylene prepolymer, benzoyl peroxide and composite carbon nanofiber according to a mass ratio of 1: 0.008: 0.9, placing the mixture into a reaction kettle with the pressure of 0.7MPa, stirring the mixture for 2 hours at the speed of 600r/min, then adding aluminum chloride with the mass of 0.004 time of that of the polypropylene prepolymer, heating the mixture to 185 ℃ at the speed of 10 ℃/min, continuing stirring the mixture for 12 hours, naturally cooling the mixture to room temperature, cooling the mixture to 2 ℃ at the speed of 4 ℃/min, and sequentially mixing the mixture according to the mass ratio of 1: 2 adding 98 percent of concentrated sulfuric acid and deionized water, wherein the mass of the 98 percent of concentrated sulfuric acid is 3 times of that of the composite carbon nanofiber, stirring at 900r/min for 10min, then dripping sodium nitrite solution with mass fraction of 25% and mass 2 times of composite carbon nanofiber at 70 drops/min, continuing stirring for 2h, adding urea with mass 0.02 time of composite carbon nanofiber, continuing stirring for 60min, dripping sodium bisulfite solution with mass fraction of 25% and 2 times of the composite carbon nanofiber mass at 70 drops/min, continuing stirring for 15min, heating to 130 deg.C at 5 deg.C/min, adding dropwise 15% sulfuric acid solution at 70 drops/min to adjust pH to 5, stirring for 4 days, placing into 240 deg.C twin-screw extruder, and extruding and granulating at the rotating speed of 400r/min to prepare the antistatic wear-resistant plastic for the vehicle.
Example 3
The preparation method of the antistatic wear-resistant plastic for the vehicle comprises the following preparation steps:
(1) at 40 ℃, mixing 3, 5-dihydroxy benzonitrile and ethanol according to a mass ratio of 1: 11, stirring for 50min at 700r/min, then adding 21 percent of hydroxylamine hydrochloride aqueous solution which is 10 times of the mass of the 3, 5-dihydroxy benzonitrile, continuing to stir for 30min, then dropwise adding 11 percent of sodium carbonate solution which is 0.6 times of the mass of the hydroxylamine hydrochloride aqueous solution at 80 drops/min, continuing to stir for 60min, naturally cooling to room temperature,standing for 3h, and performing suction filtration under the condition of 20Pa to prepare 3, 5-dihydroxy benzene oxime; at 40 ℃, mixing 3, 5-dihydroxy benzene oxime, ethanol and deionized water according to a mass ratio of 1: 11: 6, mixing, stirring for 50min at 700r/min, then adding nickel powder with the particle size of 50nm and the mass of 0.004 time of that of the 3, 5-dihydroxy benzene oxime, putting the nickel powder into a reaction kettle with the pressure of 0.8MPa, heating to 80 ℃ at the speed of 5 ℃/min, and preserving heat for 10h at the stirring speed of 700r/min and under the protection of argon gas to prepare the 3, 5-dihydroxy benzene formamidine; mixing 2,4, 6-trinitroaniline, concentrated sulfuric acid with the mass fraction of 98% and deionized water according to the mass ratio of 1: 4: 4, mixing, stirring for 15min at 1000r/min, naturally cooling to 40 ℃, adding deionized water with the mass of 4 times that of 2,4, 6-trinitroaniline, continuing to stir for 15min, cooling to 5 ℃ at 4 ℃, then dropwise adding a sodium nitrite solution with the mass fraction of 30% with the mass of 3 times that of 2,4, 6-trinitroaniline at 80 drops/min, continuing to stir for 3h, adding urea with the mass of 0.03 time that of 2,4, 6-trinitroaniline, continuing to stir for 70min, and filtering to prepare 2,4, 6-trinitrobenzene diazonium salt; at 4 ℃, carbon nano-fibers with the length of 300 mu m and concentrated sulfuric acid with the mass fraction of 98% are mixed according to the mass ratio of 1: 5, mixing, stirring for 50min at 700r/min, carrying out ultrasonic treatment for 20min at 40kHz, filtering, washing for 4 times by using deionized water, and putting into an oven at 50 ℃ for drying for 3h to prepare pretreated carbon nanofibers; the method comprises the following steps of mixing pretreated carbon nanofiber, 3, 5-dihydroxybenzamidine, copper acetate monohydrate, sodium carbonate and toluene according to a mass ratio of 1: 3: 0.3: 0.8: 15, stirring and refluxing for 25h at 1300r/min, cooling to 5 ℃ at 7 ℃/min, and mixing the components in a mass ratio of 1: 0.09: 0.003, sequentially adding methanol, sodium hydroxide and sodium dodecyl benzene sulfonate, wherein the mass of the methanol is 30 times of that of the pretreated carbon nano fiber, continuously stirring for 70min, adding 2,4, 6-trinitrobenzene diazonium salt which is 3 times of that of the pretreated carbon nano fiber, continuously stirring for 40min, dropwise adding a sodium hydroxide solution with the mass fraction of 30% at a rate of 80 drops/min to adjust the pH value to 9, and continuously stirring for 2h to prepare an azo intermediate; under the protection of argon, mixing an azo intermediate, nickel powder with the particle size of 50nm, toluene and piperidine according to the mass ratio of 1: 0.04: 13: 0.7 mixing, placing into a reaction kettle with the pressure of 0.6MPa, and heating at 60 deg.C for 7m3Introducing hydrogen gas at min, stirring for 6 hr, naturally cooling to room temperature, filtering, sequentially adding ethanolWashing with deionized water for 4 times, and drying in a 50 ℃ oven for 3h to obtain the composite carbon nanofiber;
(2) under the protection of argon at 80 ℃, mixing propylene, 6-vinyl-2-naphthol and benzoyl peroxide according to the mass ratio of 1: 0.5: 0.008 mixing, placing into a reaction kettle with 4MPa, and stirring for 6h at 700r/min to prepare a polypropylene prepolymer;
(3) under the condition of argon protection, mixing a polypropylene prepolymer, benzoyl peroxide and composite carbon nanofiber according to a mass ratio of 1: 0.009: 1, placing the mixture into a 0.8MPa reaction kettle, stirring the mixture for 3 hours at the speed of 700r/min, then adding aluminum chloride with the mass of 0.005 time that of the polypropylene prepolymer, heating the mixture to 190 ℃ at the speed of 11 ℃/min, continuing stirring the mixture for 13 hours, naturally cooling the mixture to room temperature, cooling the mixture to 5 ℃ at the speed of 5 ℃/min, and sequentially mixing the mixture according to the mass ratio of 1: 3 adding 98 percent of concentrated sulfuric acid and deionized water, wherein the mass of the 98 percent of concentrated sulfuric acid is 4 times of that of the composite carbon nanofiber, stirring for 15min at 1000r/min, then dripping 30% sodium nitrite solution with mass fraction 3 times of the mass of the composite carbon nanofiber at 80 drops/min, continuing stirring for 3h, adding urea with mass fraction 0.03 time of the mass of the composite carbon nanofiber, continuing stirring for 70min, dripping 30% sodium bisulfite solution 3 times of the composite carbon nanofiber mass at 80 drops/min, continuing stirring for 20min, heating to 140 deg.C at a rate of 6 deg.C/min, adding 80 drops/min dropwise 20% sulfuric acid solution to adjust pH to 6, stirring for 5 days, placing into a 250 deg.C twin-screw extruder, and extruding and granulating at the rotating speed of 500r/min to prepare the antistatic wear-resistant plastic for the vehicle.
Comparative example 1
Comparative example 1 differs from example 2 only in step (1), step (1) being modified: mixing 2,4, 6-trinitroaniline, concentrated sulfuric acid with the mass fraction of 98% and deionized water according to the mass ratio of 1: 3: 3, stirring for 10min at 900r/min, naturally cooling to 35 ℃, adding deionized water with the mass of 3 times of that of 2,4, 6-trinitroaniline, continuing to stir for 10min, cooling to 2 ℃ at 3 ℃, then dropwise adding sodium nitrite solution with the mass fraction of 25 percent, which is 2 times of that of 2,4, 6-trinitroaniline, at 70 drops/min, continuing to stir for 2h, adding urea with the mass of 0.02 time of that of 2,4, 6-trinitroaniline, continuing to stir for 60min,filtering to prepare 2,4, 6-trinitrobenzene diazonium salt; at 2 ℃, carbon nano-fibers with the length of 250 mu m and concentrated sulfuric acid with the mass fraction of 98 percent are mixed according to the mass ratio of 1: 4, mixing, stirring for 40min at the speed of 600r/min, carrying out ultrasonic treatment for 15min at 35kHz, filtering, washing for 3 times by using deionized water, and putting into an oven at the temperature of 40 ℃ for drying for 2h to prepare pretreated carbon nanofibers; mixing the pretreated carbon nanofiber, copper acetate monohydrate, sodium carbonate and toluene in a mass ratio of 1: 0.2: 0.7: 14, stirring and refluxing for 24 hours at 1250r/min, cooling to 2 ℃ at 6 ℃/min, and mixing according to a mass ratio of 1: 0.08: 0.002, sequentially adding methanol, sodium hydroxide and sodium dodecyl benzene sulfonate, wherein the mass of the methanol is 25 times that of the pretreated carbon nano fiber, continuing to stir for 60min, adding 2,4, 6-trinitrobenzene diazonium salt which is 2 times that of the pretreated carbon nano fiber, continuing to stir for 30min, dropwise adding sodium hydroxide solution with the mass fraction of 25% at 70 drops/min to adjust the pH value to 8, and continuing to stir for 1.5h to prepare an azo intermediate; under the protection of argon, mixing an azo intermediate, nickel powder with the particle size of 40nm, toluene and piperidine according to the mass ratio of 1: 0.03: 12: 0.6 mixing, placing into a reaction kettle with a pressure of 0.5MPa, and heating at 50 deg.C for 6m3Introducing hydrogen gas in the solution/min, continuing stirring for 5h, naturally cooling to room temperature, filtering, washing with ethanol and deionized water for 3 times in sequence, and placing in a 40 ℃ oven for drying for 2h to prepare the composite carbon nanofiber. The rest of the preparation steps are the same as example 2.
Comparative example 2
Comparative example 2 differs from example 2 only in step (1), step (1) being modified: at the temperature of 35 ℃, mixing 3, 5-dihydroxy benzonitrile and ethanol according to the mass ratio of 1: 10, stirring for 40min at 600r/min, then adding 20% hydroxylamine hydrochloride aqueous solution with the mass fraction 9.5 times that of the 3, 5-dihydroxybenzonitrile, continuing to stir for 25min, then dropwise adding 10% sodium carbonate solution with the mass fraction 0.5 times that of the hydroxylamine hydrochloride aqueous solution at 70 drops/min, continuing to stir for 55min, naturally cooling to room temperature, standing for 2h, and performing suction filtration under the condition of 15Pa to prepare 3, 5-dihydroxybenzoxime; at 35 ℃, mixing 3, 5-dihydroxy benzene oxime, ethanol and deionized water according to a mass ratio of 1: 10: 5 mixing, stirring at 600r/min for 40min, and adding granules with mass 0.003 times of that of 3, 5-dihydroxy benzene oximePutting nickel powder with the diameter of 40nm into a reaction kettle with the pressure of 0.7MPa, heating to 70 ℃ at the speed of 4 ℃/min, and preserving heat for 9 hours under the stirring speed of 600r/min and the protection condition of argon to prepare 3, 5-dihydroxy benzamidine; at 2 ℃, carbon nano-fibers with the length of 250 mu m and concentrated sulfuric acid with the mass fraction of 98% are mixed according to the mass ratio of 1: 4, mixing, stirring for 40min at the speed of 600r/min, carrying out ultrasonic treatment for 15min at 35kHz, filtering, washing for 3 times by using deionized water, and putting into an oven at the temperature of 40 ℃ for drying for 2h to prepare pretreated carbon nanofibers; the method comprises the following steps of mixing pretreated carbon nanofiber, 3, 5-dihydroxybenzamidine, copper acetate monohydrate, sodium carbonate and toluene according to a mass ratio of 1: 2: 0.2: 0.7: 14, stirring and refluxing for 24 hours at 1250r/min, cooling to 2 ℃ at 6 ℃/min, and mixing the components in a mass ratio of 1: 0.08: 0.002 adding methanol, sodium hydroxide and sodium dodecyl benzene sulfonate in turn, wherein the mass of methanol is 25 times of the mass of the pretreated carbon nanofiber, continuously stirring for 60min, placing into a reaction kettle with the pressure of 0.5MPa, and heating at 50 deg.C and 6m3Introducing hydrogen gas in the solution/min, continuing stirring for 5h, naturally cooling to room temperature, filtering, washing with ethanol and deionized water for 3 times in sequence, and placing in a 40 ℃ oven for drying for 2h to prepare the composite carbon nanofiber. The rest of the preparation steps are the same as example 2.
Comparative example 3
Comparative example 3 differs from example 2 only in step (1), step (1) being modified: at 35 ℃, mixing 3, 5-dihydroxy benzonitrile and ethanol according to a mass ratio of 1: 10, stirring for 40min at 600r/min, then adding 20% hydroxylamine hydrochloride aqueous solution with the mass fraction 9.5 times that of the 3, 5-dihydroxybenzonitrile, continuing to stir for 25min, then dropwise adding 10% sodium carbonate solution with the mass fraction 0.5 times that of the hydroxylamine hydrochloride aqueous solution at 70 drops/min, continuing to stir for 55min, naturally cooling to room temperature, standing for 2h, and performing suction filtration under the condition of 15Pa to prepare 3, 5-dihydroxybenzoxime; at 35 ℃, mixing 3, 5-dihydroxy benzene oxime, ethanol and deionized water according to a mass ratio of 1: 10: 5, mixing, stirring for 40min at 600r/min, then adding nickel powder with the particle size of 40nm, the mass of which is 0.003 time of that of the 3, 5-dihydroxy benzene oxime, putting the nickel powder into a reaction kettle with the pressure of 0.7MPa, heating to 70 ℃ at 4 ℃/min, and preserving heat for 9h under the stirring speed of 600r/min and the protection of argon to prepare the 3, 5-dihydroxy benzamidine; mixing 2,4, 6-trinitroaniline, concentrated sulfuric acid with the mass fraction of 98% and deionized water according to the mass ratio of 1: 3: 3, mixing, stirring for 10min at 900r/min, naturally cooling to 35 ℃, adding deionized water with the mass of 3 times that of 2,4, 6-trinitroaniline, continuing to stir for 10min, cooling to 2 ℃ at 3 ℃, then dropwise adding a sodium nitrite solution with the mass fraction of 25% which is 2 times that of 2,4, 6-trinitroaniline at 70 drops/min, continuing to stir for 2h, adding urea with the mass of 0.02 time that of 2,4, 6-trinitroaniline, continuing to stir for 60min, and filtering to prepare 2,4, 6-trinitrobenzene diazonium salt; at 2 ℃, carbon nano-fibers with the length of 250 mu m and concentrated sulfuric acid with the mass fraction of 98 percent are mixed according to the mass ratio of 1: 4, mixing, stirring for 40min at the speed of 600r/min, filtering, washing for 3 times by using deionized water, and placing in a drying oven at the temperature of 40 ℃ for drying for 2h to prepare pretreated carbon nanofibers; the method comprises the following steps of mixing pretreated carbon nanofiber, 3, 5-dihydroxybenzamidine, copper acetate monohydrate, sodium carbonate and toluene according to a mass ratio of 1: 2: 0.2: 0.7: 14, stirring and refluxing for 24 hours at 1250r/min, cooling to 2 ℃ at 6 ℃/min, and mixing the components in a mass ratio of 1: 0.08: 0.002, sequentially adding methanol, sodium hydroxide and sodium dodecyl benzene sulfonate, wherein the mass of the methanol is 25 times that of the pretreated carbon nano fiber, continuing to stir for 60min, adding 2,4, 6-trinitrobenzene diazonium salt which is 2 times that of the pretreated carbon nano fiber, continuing to stir for 30min, dropwise adding sodium hydroxide solution with the mass fraction of 25% at 70 drops/min to adjust the pH value to 8, and continuing to stir for 1.5h to prepare an azo intermediate; under the protection of argon, mixing an azo intermediate, nickel powder with the particle size of 40nm, toluene and piperidine according to the mass ratio of 1: 0.03: 12: 0.6, placing the mixture into a reaction kettle with the pressure of 0.5MPa, continuously stirring the mixture for 5 hours at the temperature of 50 ℃, naturally cooling the mixture to the room temperature, filtering the mixture, sequentially washing the mixture for 3 times by using ethanol and deionized water, and placing the mixture into an oven with the temperature of 40 ℃ to be dried for 2 hours to prepare the composite carbon nanofiber. The rest of the preparation steps are the same as example 2.
Comparative example 4
(1) At the temperature of 35 ℃, mixing 3, 5-dihydroxy benzonitrile and ethanol according to the mass ratio of 1: 10, stirring for 40min at 600r/min, then adding 20 percent of hydroxylamine hydrochloride aqueous solution which is 9.5 times of the mass of the 3, 5-dihydroxy benzonitrile, continuing to stir for 25min, and then dropwise adding 0.5 time of the mass of the hydroxylamine hydrochloride aqueous solution at 70 drops/minContinuously stirring 10% sodium carbonate solution for 55min, naturally cooling to room temperature, standing for 2h, and performing suction filtration under the condition of 15Pa to obtain 3, 5-dihydroxy benzene oxime; at 35 ℃, mixing 3, 5-dihydroxy benzene oxime, ethanol and deionized water according to a mass ratio of 1: 10: 5, mixing, stirring for 40min at 600r/min, then adding nickel powder with the particle size of 40nm, the mass of which is 0.003 time of that of the 3, 5-dihydroxy benzene oxime, putting the nickel powder into a reaction kettle with the pressure of 0.7MPa, heating to 70 ℃ at 4 ℃/min, and preserving heat for 9h under the stirring speed of 600r/min and the protection of argon to prepare the 3, 5-dihydroxy benzamidine; mixing 2,4, 6-trinitroaniline, concentrated sulfuric acid with the mass fraction of 98% and deionized water according to the mass ratio of 1: 3: 3, mixing, stirring for 10min at 900r/min, naturally cooling to 35 ℃, adding deionized water with the mass of 3 times that of 2,4, 6-trinitroaniline, continuing to stir for 10min, cooling to 2 ℃ at 3 ℃, then dropwise adding a sodium nitrite solution with the mass fraction of 25% which is 2 times that of 2,4, 6-trinitroaniline at 70 drops/min, continuing to stir for 2h, adding urea with the mass of 0.02 time that of 2,4, 6-trinitroaniline, continuing to stir for 60min, and filtering to prepare 2,4, 6-trinitrobenzene diazonium salt; at 2 ℃, carbon nano-fibers with the length of 250 mu m and concentrated sulfuric acid with the mass fraction of 98 percent are mixed according to the mass ratio of 1: 4, mixing, stirring for 40min at the speed of 600r/min, carrying out ultrasonic treatment for 15min at 35kHz, filtering, washing for 3 times by using deionized water, and putting into an oven at the temperature of 40 ℃ for drying for 2h to prepare pretreated carbon nanofibers; the method comprises the following steps of mixing pretreated carbon nanofiber, 3, 5-dihydroxybenzamidine, copper acetate monohydrate, sodium carbonate and toluene according to a mass ratio of 1: 2: 0.2: 0.7: 14, stirring and refluxing for 24 hours at 1250r/min, cooling to 2 ℃ at 6 ℃/min, and mixing the components in a mass ratio of 1: 0.08: 0.002, sequentially adding methanol, sodium hydroxide and sodium dodecyl benzene sulfonate, wherein the mass of the methanol is 25 times that of the pretreated carbon nano fiber, continuing to stir for 60min, adding 2,4, 6-trinitrobenzene diazonium salt which is 2 times that of the pretreated carbon nano fiber, continuing to stir for 30min, dropwise adding sodium hydroxide solution with the mass fraction of 25% at 70 drops/min to adjust the pH value to 8, and continuing to stir for 1.5h to prepare an azo intermediate; under the condition of argon protection, mixing an azo intermediate, nickel powder with the particle size of 40nm, toluene and piperidine according to the mass ratio of 1: 0.03: 12: 0.6 mixing, placing into a reaction kettle with a pressure of 0.5MPa, and heating at 50 deg.C for 6m3Min introductionContinuously stirring with hydrogen for 5h, naturally cooling to room temperature, filtering, washing with ethanol and deionized water for 3 times in sequence, and drying in a 40 ℃ oven for 2h to obtain the composite carbon nanofiber;
(2) under the protection of argon, mixing polypropylene, benzoyl peroxide and composite carbon nanofiber according to a mass ratio of 1: 0.008: 0.9, placing the mixture into a reaction kettle with the pressure of 0.7MPa, stirring the mixture for 2 hours at the speed of 600r/min, then adding aluminum chloride with the mass of 0.004 time of that of the polypropylene prepolymer, heating the mixture to 185 ℃ at the speed of 10 ℃/min, continuing stirring the mixture for 12 hours, naturally cooling the mixture to room temperature, cooling the mixture to 2 ℃ at the speed of 4 ℃/min, and sequentially mixing the mixture according to the mass ratio of 1: 2 adding 98 percent of concentrated sulfuric acid and deionized water, wherein the mass of the 98 percent of concentrated sulfuric acid is 3 times of that of the composite carbon nanofiber, stirring at 900r/min for 10min, then dripping sodium nitrite solution with mass fraction of 25% and mass 2 times of composite carbon nanofiber at 70 drops/min, continuing stirring for 2h, adding urea with mass 0.02 time of composite carbon nanofiber, continuing stirring for 60min, dripping sodium bisulfite solution with mass fraction of 25% and 2 times of the composite carbon nanofiber mass at 70 drops/min, continuing stirring for 15min, heating to 130 deg.C at 5 deg.C/min, adding dropwise 15% sulfuric acid solution at 70 drops/min to adjust pH to 5, stirring for 4 days, placing into 240 deg.C twin-screw extruder, and extruding and granulating at the rotating speed of 400r/min to prepare the antistatic wear-resistant plastic for the vehicle.
Examples of effects
The following table 1 shows the analysis results of the antistatic property, impact strength, flame retardancy, and ultraviolet resistance of the antistatic abrasion-resistant plastic for vehicles prepared by examples 1 to 3 of the present invention and comparative examples 1 to 4.
TABLE 1
From table 1, it can be seen that the antistatic wear-resistant plastics for vehicles prepared in examples 1, 2 and 3 have strong antistatic property, impact strength, flame retardance and ultraviolet resistance; from the comparison of experimental data of examples 1, 2 and 3 and comparative example 1, it can be found that the composite carbon nanofiber prepared by using 3, 5-dihydroxybenzamidine can form benzotriazole with triazine ring and hyperbranched structure, and the prepared antistatic wear-resistant plastic for vehicles has strong flame retardance and ultraviolet resistance; from the experimental data of examples 1, 2 and 3 and comparative example 2, it can be found that the composite carbon nanofiber prepared by using the 2,4, 6-trinitrobenzene diazonium salt can form benzotriazole with a hyperbranched structure, and then the benzotriazole and the polypropylene prepolymer are mixed to form an interpenetrating network structure and polycarbazole, so that the prepared antistatic wear-resistant plastic for the vehicle has strong antistatic property, impact strength and ultraviolet resistance; from the experimental data of the examples 1, 2 and 3 and the comparative example 3, it can be found that the composite carbon nanofiber prepared by using hydrogen coupled ultrasonic treatment can form benzotriazole, and the benzotriazole is subsequently mixed with the polypropylene prepolymer to form polycarbazole, so that the prepared antistatic wear-resistant plastic for the vehicle has strong antistatic property and ultraviolet resistance; from experimental data of examples 1, 2 and 3 and comparative example 4, it can be found that when the antistatic wear-resistant plastic for vehicles is prepared from the polypropylene prepolymer prepared from propylene and 6-vinyl-2-naphthol, an interpenetrating network structure and polycarbazole can be formed, and the prepared antistatic wear-resistant plastic for vehicles has strong antistatic property and impact strength.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The preparation method of the antistatic wear-resistant plastic for the vehicle is characterized in that the antistatic wear-resistant plastic for the vehicle is prepared by mixing a polypropylene prepolymer and composite carbon nanofibers; the polypropylene prepolymer is prepared from propylene and 6-vinyl-2-naphthol; the composite carbon nanofiber is prepared by wrapping 3, 5-dihydroxybenzamidine and 2,4, 6-trinitrobenzene diazonium salt on a carbon nanofiber and performing hydrogen coupling ultrasonic treatment.
2. The preparation method of the antistatic wear-resistant plastic for the vehicle as claimed in claim 1, wherein the preparation method of the antistatic wear-resistant plastic for the vehicle is as follows: under the condition of argon protection, mixing a polypropylene prepolymer, benzoyl peroxide and composite carbon nanofiber according to a mass ratio of 1: 0.007: 0.8-1: 0.009: 1, mixing, putting into a reaction kettle with the pressure of 0.6-0.8 MPa, stirring for 1-3 h at the speed of 500-700 r/min, then adding aluminum chloride with the mass of 0.003-0.005 times of that of the polypropylene prepolymer, heating to 180-190 ℃ at the speed of 9-11 ℃/min, continuing stirring for 11-13 h, naturally cooling to room temperature, cooling to 0-5 ℃ at the speed of 3-5 ℃/min, and sequentially mixing according to the mass ratio of 1: 1-1: 3 adding 98% concentrated sulfuric acid and deionized water, wherein the mass of the 98% concentrated sulfuric acid is 2-4 times of that of the composite carbon nanofiber, stirring for 5-15 min at 800-1000 r/min, then dripping 20-30% sodium nitrite solution with the mass of 1-3 times of that of the composite carbon nanofiber at 60-80 drops/min, continuing stirring for 1-3 h, adding 0.01-0.03 time of that of the composite carbon nanofiber, continuing stirring for 50-70 min, dripping 20-30% sodium bisulfite solution with the mass of 1-3 times of that of the composite carbon nanofiber at 60-80 drops/min, continuing stirring for 10-20 min, heating to 120-140 ℃ at 4-6 ℃/min, regulating the pH to 4-6 at 60-80 drops/min, continuing stirring for 3-5 days, and (3) putting the mixture into a 230-250 ℃ double-screw extruder, and extruding and granulating at the rotating speed of 300-500 r/min to prepare the antistatic wear-resistant plastic for the vehicle.
3. The preparation method of the antistatic wear-resistant plastic for the vehicle as claimed in claim 2, wherein the preparation method of the polypropylene prepolymer is as follows: under the protection of argon at the temperature of 60-80 ℃, mixing propylene, 6-vinyl-2-naphthol and benzoyl peroxide according to the mass ratio of 1: 0.3: 0.006-1: 0.5: 0.008 mixing, putting into a reaction kettle with the pressure of 2-4 MPa, and stirring for 4-6 h at 500-700 r/min to prepare the polypropylene prepolymer.
4. The preparation method of the antistatic wear-resistant plastic for the vehicle as claimed in claim 2, wherein the preparation method of the composite carbon nanofiber comprises the following steps: under the condition of argon protection, mixing an azo intermediate, nickel powder, toluene and piperidine according to a mass ratio of 1: 0.02: 11: 0.5-1: 0.04: 13: 0.7, placing the mixture into a reaction kettle with the pressure of 0.4 to 0.6MPa, and controlling the temperature to be between 5 and 7m at 40 and 60 DEG C3And introducing hydrogen gas for min, continuing stirring for 4-6 h, naturally cooling to room temperature, filtering, washing with ethanol and deionized water for 2-4 times in sequence, and putting into an oven at 30-50 ℃ for drying for 1-3 h to prepare the composite carbon nanofiber.
5. The preparation method of the antistatic wear-resistant plastic for the vehicles as claimed in claim 4, wherein the preparation method of the azo intermediate is as follows: at the temperature of 0-4 ℃, mixing carbon nanofibers and 98% concentrated sulfuric acid in a mass ratio of 1: 3-1: 5, mixing, stirring for 30-50 min at 500-700 r/min, performing ultrasonic treatment for 10-20 min at 30-40 kHz, filtering, washing for 2-4 times by using deionized water, and placing into an oven at 30-50 ℃ for drying for 1-3 h to prepare pretreated carbon nanofibers; the method comprises the following steps of mixing pretreated carbon nanofiber, 3, 5-dihydroxybenzamidine, copper acetate monohydrate, sodium carbonate and toluene according to a mass ratio of 1: 1: 0.1: 0.6: 13-1: 3: 0.3: 0.8: 15, stirring and refluxing for 23-25 h at 1200-1300 r/min, cooling to 0-5 ℃ at 5-7 ℃/min, and mixing according to a mass ratio of 1: 0.07: 0.001 to 1: 0.09: 0.003, sequentially adding methanol, sodium hydroxide and sodium dodecyl benzene sulfonate, wherein the mass of the methanol is 20-30 times of that of the pretreated carbon nano fiber, continuously stirring for 50-70 min, adding 2,4, 6-trinitrobenzene diazonium salt which is 1-3 times of that of the pretreated carbon nano fiber, continuously stirring for 20-40 min, dropwise adding a sodium hydroxide solution with the mass fraction of 20-30% at a rate of 60-80 drops/min to adjust the pH value to 7-9, and continuously stirring for 1-2 h to prepare the azo intermediate.
6. The preparation method of the antistatic wear-resistant plastic for the vehicle as claimed in claim 5, wherein the length of the carbon nanofiber is 200-300 μm.
7. The preparation method of the antistatic wear-resistant plastic for the vehicle as claimed in claim 5, wherein the preparation method of the 2,4, 6-trinitrobenzene diazonium salt is as follows: mixing 2,4, 6-trinitroaniline, concentrated sulfuric acid with the mass fraction of 98% and deionized water according to the mass ratio of 1: 2: 2-1: 4: 4, mixing, stirring for 5-15 min at 800-1000 r/min, naturally cooling to 30-40 ℃, adding deionized water with the mass being 2-4 times that of 2,4, 6-trinitroaniline, continuously stirring for 5-15 min, cooling to 0-5 ℃ at 2-4 ℃, then dropwise adding a sodium nitrite solution with the mass fraction being 20-30% and the mass being 1-3 times that of 2,4, 6-trinitroaniline at 60-80 drops/min, continuously stirring for 1-3 h, adding urea with the mass being 0.01-0.03 time that of 2,4, 6-trinitroaniline, continuously stirring for 50-70 min, and filtering to prepare the 2,4, 6-trinitrobenzene diazonium salt.
8. The preparation method of the antistatic wear-resistant plastic for the vehicles as claimed in claim 5, wherein the preparation method of the 3, 5-dihydroxybenzamidine is as follows: at the temperature of 30-40 ℃, mixing 3, 5-dihydroxy benzene oxime, ethanol and deionized water according to the mass ratio of 1: 9: 4-1: 11: 6, mixing, stirring for 30-50 min at 500-700 r/min, then adding nickel powder with the mass of 0.002-0.004 times of that of 3, 5-dihydroxy benzene oxime, putting into a reaction kettle with the pressure of 0.6-0.8 MPa, heating to 60-80 ℃ at 3-5 ℃/min, and preserving heat for 8-10 h at the stirring speed of 500-700 r/min under the protection of argon to prepare the 3, 5-dihydroxy benzene formamidine.
9. The preparation method of the antistatic wear-resistant plastic for the vehicles as claimed in claim 8, wherein the preparation method of the 3, 5-dihydroxy benzene oxime is as follows: at the temperature of 30-40 ℃, mixing 3, 5-dihydroxy benzonitrile and ethanol according to a mass ratio of 1: 9-1: 11, stirring for 30-50 min at 500-700 r/min, then adding 19-21% hydroxylamine hydrochloride aqueous solution 9-10 times of the mass of 3, 5-dihydroxy benzonitrile, continuing stirring for 20-30 min, then dropwise adding 9-11% sodium carbonate solution 0.4-0.6 times of the mass of hydroxylamine hydrochloride aqueous solution at 60-80 drops/min, continuing stirring for 50-60 min, naturally cooling to room temperature, standing for 1-3 h, and performing suction filtration under the condition of 10-20 Pa to prepare the 3, 5-dihydroxy benzene oxime.
10. The preparation method of the antistatic wear-resistant plastic for the vehicle as claimed in claim 4 or 8, wherein the particle size of the nickel powder is 30-50 nm.
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