CN115491089B - Modified carbon nano tube-fluorocarbon resin and application thereof in wear-resistant aluminum veneers - Google Patents
Modified carbon nano tube-fluorocarbon resin and application thereof in wear-resistant aluminum veneers Download PDFInfo
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- CN115491089B CN115491089B CN202211200797.0A CN202211200797A CN115491089B CN 115491089 B CN115491089 B CN 115491089B CN 202211200797 A CN202211200797 A CN 202211200797A CN 115491089 B CN115491089 B CN 115491089B
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- 229920005989 resin Polymers 0.000 title claims abstract description 49
- 239000011347 resin Substances 0.000 title claims abstract description 49
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 39
- 150000001721 carbon Chemical class 0.000 title claims abstract description 22
- -1 perfluorooctanoyl-triazaheptane Chemical compound 0.000 claims abstract description 39
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003973 paint Substances 0.000 claims abstract description 17
- 238000005507 spraying Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 33
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 239000003377 acid catalyst Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000013530 defoamer Substances 0.000 claims description 8
- AQQBRCXWZZAFOK-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(Cl)=O AQQBRCXWZZAFOK-UHFFFAOYSA-N 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- KNORWRWRHNHJAV-UHFFFAOYSA-N tert-butyl n-[2-[2-[(2-methylpropan-2-yl)oxycarbonylamino]ethylamino]ethyl]carbamate Chemical compound CC(C)(C)OC(=O)NCCNCCNC(=O)OC(C)(C)C KNORWRWRHNHJAV-UHFFFAOYSA-N 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 229920003180 amino resin Polymers 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000005299 abrasion Methods 0.000 claims 1
- 239000002518 antifoaming agent Substances 0.000 claims 1
- 239000002041 carbon nanotube Substances 0.000 abstract description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 14
- MXFJAOPLNIKOCW-UHFFFAOYSA-K F[C+3].[F-].[F-].[F-] Chemical compound F[C+3].[F-].[F-].[F-] MXFJAOPLNIKOCW-UHFFFAOYSA-K 0.000 abstract description 8
- 239000002033 PVDF binder Substances 0.000 abstract description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000000051 modifying effect Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- 238000010559 graft polymerization reaction Methods 0.000 abstract description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 abstract description 2
- 229920005548 perfluoropolymer Polymers 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000012043 crude product Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000001953 recrystallisation Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 5
- 239000004640 Melamine resin Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
- B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of fluorocarbon resin, and discloses a modified carbon nano tube-fluorocarbon resin and application thereof in wear-resistant aluminum veneers, wherein 4, 4-diphenylmethane diisocyanate and perfluorooctanoyl-triazaheptane are subjected to in-situ graft polymerization on the surface of a carbon nano tube by an in-situ polymerization method, and a polymer molecular chain containing perfluoroalkyl is grafted on the surface of the carbon nano tube. Filling and modifying fluorocarbon resin, and after the carbon nano-tube is grafted by the perfluoropolymer, the compatibility with polyvinylidene fluoride fluorocarbon resin is good, so that the problems of uneven dispersion and agglomeration of the carbon nano-tube are overcome. The fluorocarbon resin has better reinforcing and modifying effects. The modified carbon nano tube-fluorocarbon resin finishing paint is used for carrying out fluorocarbon spraying treatment on the aluminum veneer, the surface of the fluorocarbon aluminum veneer has higher hardness, wear resistance and impact resistance, and the performances of salt spray resistance, acid resistance and the like are also obviously improved.
Description
Technical Field
The invention relates to the technical field of fluorocarbon resin, in particular to modified carbon nano tube-fluorocarbon resin and application thereof in wear-resistant aluminum veneers.
Background
The polyvinylidene fluoride fluorocarbon resin has the advantages of excellent weather resistance, water resistance, chemical resistance and the like, and is widely applied to the aspects of aluminum veneers, coil coating, kitchen cooking appliances, precise instrument coating and the like. At present, the aluminum veneer is usually treated by fluorocarbon resin through fluorocarbon two-coating one-baking, fluorocarbon three-coating one-baking and other processes, so that the corrosion resistance and the service life of the aluminum veneer are improved, the performances of the fluorocarbon resin such as wear resistance, impact resistance and the like are enhanced, and the practical application of the fluorocarbon resin in the aspects of the aluminum veneer and the like is expanded, so that the aluminum veneer has important excellent performances.
The inorganic nano material is added into fluorocarbon resin to endow fluorocarbon resin coating with unique performance, such as reported in low-temperature preparation of self-cleaning fluorocarbon aluminum veneer of nanometer titanium dioxide 2 The sol is coated on the surface of the fluorocarbon aluminum veneer, and the unique self-cleaning effect is shown; the carbon nano tube is used as a high-strength carbon nano material and widely applied to high polymer materials such as fluorocarbon resin, for example, the dispersion of the carbon nano tube in the fluorocarbon resin and the influence of the carbon nano tube on the optical performance are disclosed, a ball milling dispersion process is adopted to prepare a carbon nano tube butyl acetate dispersion liquid, and then the carbon nano tube butyl acetate dispersion liquid is added into the fluorocarbon resin to prepare a coating, so that the thermal performance and the optical performance of a fluorocarbon resin coating are improved.
Disclosure of Invention
(one) solving the technical problems
The invention provides a modified carbon nano tube-fluorocarbon resin applied to an aluminum veneer, which enhances the comprehensive performance of the fluorocarbon aluminum veneer.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions: preferably, the modified carbon nanotube-fluorocarbon resin comprises 100 parts by weight of fluorocarbon resin, 8-12 parts by weight of amino resin, 0.5-0.8 parts by weight of acid catalyst, 0.2-1 part by weight of perfluoro modified carbon nanotube, 0.1-0.5 part by weight of leveling agent, 0.2-0.5 part by weight of defoamer and 0.2-0.6 part by weight of dispersant.
Preferably, the preparation method of the perfluoro modified carbon nano tube comprises the following steps:
s1, dissolving 100 parts by weight of perfluorooctanoyl chloride into a reaction solvent at 0-5 ℃, then dropwise adding 60-75 parts by weight of 1, 7-bis-Boc-1, 4, 7-triazaheptane and 40-60 parts by weight of triethylamine, stirring 1-2 h, then stirring at 20-35 ℃ for reaction 3-8 h, removing the solvent by rotary evaporation after the reaction, washing the product by using a saturated sodium chloride solution, and then adding the crude product into chloroform for recrystallization to obtain perfluorooctanoyl amide-bis-Boc-triazaheptane.
S2, dissolving perfluoro-octanamide-bis-Boc-triazaheptane into 1, 4-dioxane, then dropwise adding hydrochloric acid solution, stirring at 20-35 ℃ for reaction for 2-6 h, adding dichloromethane and saturated sodium bicarbonate after the reaction, drying and concentrating an organic phase after extraction and separation, and adding a crude product into chloroform for recrystallization to obtain perfluoro-octanamide-triazaheptane;
s3, ultrasonically dispersing 100 parts by weight of hydroxylated carbon nano tube into N, N-dimethylformamide, then adding 2000-3500 parts by weight of 4, 4-diphenylmethane diisocyanate and 30-80 parts by weight of dibutyltin dilaurate, stirring and reacting at 55-65 ℃ for 6-12 h, then adding 3800-6000 parts by weight of perfluorooctanoyl amide-triazaheptane, stirring and polymerizing for 3-8 h in 70-85, filtering a solvent after the reaction, and washing a product with acetone to obtain the perfluoro modified carbon nano tube;
preferably, the reaction solvent in S1 includes dichloromethane, chloroform, and tetrahydrofuran.
Preferably, the mass fraction of the hydrochloric acid solution in the S2 is 10-18%.
Preferably, the modified carbon nano tube-fluorocarbon resin is applied to the wear-resistant aluminum veneer.
Preferably, the preparation process of the wear-resistant aluminum veneer comprises the following steps: adding 100 parts by weight of fluorocarbon resin, 0.1-0.5 part by weight of flatting agent, 0.2-0.5 part by weight of defoamer and 0.2-0.6 part by weight of dispersant into a xylene solvent, uniformly stirring, adding 0.2-1 part by weight of perfluorinated modified carbon nano tube, adding 8-12 parts by weight of amino resin and 0.5-0.8 part by weight of acid catalyst after ultrasonic dispersion to obtain modified carbon nano tube-fluorocarbon resin finishing paint, then carrying out primer spraying and flash drying on an aluminum veneer, carrying out finishing paint spraying and flash drying, and baking for 20-30 min at 170-185 ℃ to obtain the wear-resistant aluminum veneer.
(III) beneficial technical effects
Compared with the prior art, the invention has the following beneficial technical effects: and carrying out amidation reaction on perfluoro octanoyl chloride and 1, 7-bis-Boc-1, 4, 7-triazaheptane, then removing N-Boc protection by hydrochloric acid solution to synthesize perfluoro octanoyl amido-triazaheptane monomer, then carrying out surface modification on the hydroxylated carbon nano tube by using excessive 4, 4-diphenylmethane diisocyanate, and carrying out in-situ graft polymerization on unreacted 4, 4-diphenylmethane diisocyanate and perfluoro octanoyl amido-triazaheptane on the surface of the carbon nano tube by an in-situ polymerization method to obtain the perfluoro modified carbon nano tube.
And polymer molecular chains containing perfluoroalkyl groups are grafted on the surface of the carbon nano tube. The perfluoromodified carbon nano tube is used for filling and modifying fluorocarbon resin, and after the carbon nano tube is grafted by the perfluoropolymer, the compatibility with polyvinylidene fluoride fluorocarbon resin is good, so that the problems of uneven dispersion and agglomeration of the carbon nano tube are overcome. The fluorocarbon resin has better reinforcing and modifying effects.
The modified carbon nano tube-fluorocarbon resin finishing paint is used for carrying out fluorocarbon spraying treatment on the aluminum veneer, the surface of the fluorocarbon aluminum veneer has higher hardness, wear resistance and impact resistance, and the performances of salt spray resistance, acid resistance and the like are also obviously improved.
Description of the embodiments
Examples
(1) 2g of perfluorooctanoyl chloride is dissolved in 15 mL of dichloromethane, chloroform and tetrahydrofuran at 5 ℃, then 1.2 g of 1, 7-bis-Boc-1, 4, 7-triazaheptane and 1 g of triethylamine are added dropwise, 1 h is stirred and then the reaction is carried out at 35 ℃ again, 4 h of the reaction is stirred, the solvent is removed by rotary evaporation, saturated sodium chloride solution is used for washing the product, and then the crude product is added into chloroform for recrystallization, thus obtaining perfluorooctanoyl amide-bis-Boc-triazaheptane.
(2) The perfluoro-octanamide-bis-Boc-triazepan of 1 g is dissolved in 1, 4-dioxane of 20 mL, then 3 mL of 15% hydrochloric acid solution is added dropwise, stirring reaction is carried out at 35 ℃ for 2 h, dichloromethane and saturated sodium bicarbonate are added after the reaction, the organic phase is dried and concentrated after extraction separation, and the crude product is added into chloroform for recrystallization, thus obtaining perfluoro-octanamide-triazepan.
(3) Ultrasonically dispersing 0.1 g hydroxylated carbon nano tube into N, N-dimethylformamide, then adding 2g of 4, 4-diphenylmethane diisocyanate and 0.08 g of dibutyltin dilaurate, stirring at 65 ℃ for reaction 12 h, then adding 3.8 g of perfluorooctanoyl-triazaheptane, stirring for polymerization at 85 for 4 h, filtering a solvent after the reaction, and washing a product by acetone to obtain the perfluoro modified carbon nano tube.
(4) Adding 50 g polyvinylidene fluoride fluorocarbon resin, 0.1 g leveling agent FC805, 0.25g defoamer CK-D266 and 0.15g dispersant BKY110 into a xylene solvent, stirring uniformly, adding 0.1 g perfluoro modified carbon nano tube, adding 5g hexamethoxy methyl melamine resin and 0.25g acid catalyst BKY450 after ultrasonic dispersion to obtain modified carbon nano tube-fluorocarbon resin finishing paint, then carrying out primer spraying and flash drying on an aluminum veneer through polyester resin, carrying out finishing paint spraying, and flash drying for 10 min at 100 ℃, and finally baking for 30 min at 170 ℃ to obtain the wear-resistant aluminum veneer.
Examples
(1) 2. 2g of perfluorooctanoyl chloride is dissolved in 10 mL of dichloromethane, chloroform and tetrahydrofuran at 0 ℃, 1.5 g of 1, 7-bis-Boc-1, 4, 7-triazaheptane and 1.2 g of triethylamine are then added dropwise, 2 h is stirred and then the reaction is carried out at 25 ℃ with stirring for 5 h, the solvent is removed by rotary evaporation after the reaction, the product is washed by saturated sodium chloride solution, and then the crude product is added into chloroform for recrystallization, thus obtaining perfluorooctanoyl amide-bis-Boc-triazaheptane.
(2) The perfluoro-octanamide-bis-Boc-triazepan of 1 g is dissolved in 1, 4-dioxane of 20 mL, then 3 mL of 15% hydrochloric acid solution is added dropwise, stirring reaction is carried out at 20 ℃ for 6 h, dichloromethane and saturated sodium bicarbonate are added after the reaction, the organic phase is dried and concentrated after extraction separation, and the crude product is added into chloroform for recrystallization, thus obtaining perfluoro-octanamide-triazepan.
(3) Ultrasonically dispersing 0.1 g hydroxylated carbon nano tube into N, N-dimethylformamide, then adding 2g of 4, 4-diphenylmethane diisocyanate and 0.03 g of dibutyltin dilaurate, stirring at 60 ℃ for reaction of 10 h, then adding 3.8 g of perfluorooctanoyl-triazaheptane, stirring for polymerization of 8 h in 85, filtering a solvent after the reaction, and washing a product by acetone to obtain the perfluoro modified carbon nano tube.
(4) Adding 50 g of polyvinylidene fluoride fluorocarbon resin, 0.25g of flatting agent FC805, 0.2g of defoamer CK-D266 and 0.1 g of dispersant BKY110 into a xylene solvent, uniformly stirring, adding 0.1 g of perfluorinated carbon nano tube, adding 4 g of hexamethoxymethyl melamine resin and 0.3 g of acid catalyst BKY450 after ultrasonic dispersion to obtain modified carbon nano tube-fluorocarbon resin finishing paint, then carrying out primer spraying and flash drying on an aluminum veneer through polyester resin, carrying out finishing paint spraying, and flash drying for 10 min at 90 ℃, and finally baking for 25 min at 185 ℃ to obtain the wear-resistant aluminum veneer.
Examples
(1) 2g of perfluorooctanoyl chloride is dissolved into 20 mL of dichloromethane, chloroform and tetrahydrofuran at 0 ℃, then 1 g of 1, 7-bis-Boc-1, 4, 7-triazaheptane and 0.8 g of triethylamine are added dropwise, 2 h is stirred and then the reaction is carried out at 20 ℃ again, 5 h is carried out by stirring, the solvent is removed by rotary evaporation after the reaction, saturated sodium chloride solution is used for washing the product, and then the crude product is added into chloroform for recrystallization, thus obtaining perfluorooctanoyl amide-bis-Boc-triazaheptane.
(2) The perfluoro-octanamide-bis-Boc-triazepan of 1 g is dissolved in 1, 4-dioxane of 20 mL, then 18% hydrochloric acid solution of 3 mL is added dropwise, stirring reaction is carried out at 20 ℃ for 6 h, dichloromethane and saturated sodium bicarbonate are added after the reaction, the organic phase is dried and concentrated after extraction separation, and the crude product is added into chloroform for recrystallization, thus obtaining perfluoro-octanamide-triazepan.
(3) Ultrasonically dispersing 0.1 g hydroxylated carbon nano tube into N, N-dimethylformamide, then adding 2.6 g of 4, 4-diphenylmethane diisocyanate and 0.05 g of dibutyltin dilaurate, stirring at 65 ℃ for reaction of 6 h, then adding 4.2 g of perfluorooctanoyl-triazaheptane, stirring for polymerization of 8 h in 75, filtering a solvent after the reaction, and washing a product by acetone to obtain the perfluoro modified carbon nano tube.
(4) Adding 50 g of polyvinylidene fluoride fluorocarbon resin, 0.2g of flatting agent FC805, 0.25g of defoamer CK-D266 and 0.1 g of dispersant BKY into a xylene solvent, stirring uniformly, adding 0.2g of perfluorinated modified carbon nano-tube, adding 4.5 g of hexamethoxy methyl melamine resin and 0.28 g of acid catalyst BKY450 into the mixture after ultrasonic dispersion to obtain modified carbon nano-tube-fluorocarbon resin finish paint, then carrying out primer spraying and flash drying on an aluminum veneer through polyester resin, carrying out finish paint spraying, and flash drying for 10 min at 80 ℃, and finally baking for 30 min at 180 ℃ to obtain the wear-resistant aluminum veneer.
Examples
(1) 2. 2g of perfluorooctanoyl chloride is dissolved in 20 mL of dichloromethane, chloroform and tetrahydrofuran at 0 ℃, then 1.2 g of 1, 7-bis-Boc-1, 4, 7-triazaheptane and 1 g of triethylamine are added dropwise, 2 h is stirred and then the reaction is carried out at 20 ℃ again, 4 h is carried out under stirring, the solvent is removed by rotary evaporation after the reaction, saturated sodium chloride solution is used for washing the product, and then the crude product is added into chloroform for recrystallization, thus obtaining perfluorooctanoyl amide-bis-Boc-triazaheptane.
(2) The perfluoro-octanamide-bis-Boc-triazepan of 1 g is dissolved in 1, 4-dioxane of 20 mL, then 3 mL of 10% hydrochloric acid solution is added dropwise, the mixture is stirred at 20 ℃ for 4 h, methylene dichloride and saturated sodium bicarbonate are added after the reaction, the organic phase is dried and concentrated after extraction and separation, and the crude product is added into chloroform for recrystallization, thus obtaining perfluoro-octanamide-triazepan.
(3) Ultrasonically dispersing 0.1 g hydroxylated carbon nano tube into N, N-dimethylformamide, then adding 3 g of 4, 4-diphenylmethane diisocyanate and 0.07 g of dibutyltin dilaurate, stirring at 65 ℃ for reaction 8 h, then adding 5.5 g of perfluorooctanoyl-triazaheptane, stirring for polymerization 3 h in 85, filtering a solvent after the reaction, and washing a product by acetone to obtain the perfluoro modified carbon nano tube.
(4) Adding 50 g of polyvinylidene fluoride fluorocarbon resin, 0.15g of flatting agent FC805, 0.1 g of defoamer CK-D266 and 0.3 g of dispersant BKY into a xylene solvent, stirring uniformly, adding 0.1 g of perfluorinated carbon nano tube, adding 6 g of hexamethoxymethyl melamine resin and 0.4 g of acid catalyst BKY450 after ultrasonic dispersion to obtain modified carbon nano tube-fluorocarbon resin finishing paint, then carrying out primer spraying and flash drying on an aluminum veneer through polyester resin, carrying out finishing paint spraying, and flash drying for 10 min at 80 ℃, and finally baking for 20 min at 185 ℃ to obtain the wear-resistant aluminum veneer.
Comparative example 1
(1) Adding 50 g polyvinylidene fluoride fluorocarbon resin, 0.15g flatting agent FC805, 0.2g defoamer CK-D266 and 0.1 g dispersant BKY into a xylene solvent, stirring uniformly, adding 0.1 g carbon nano tube, adding 4.5 g hexamethoxymethyl melamine resin and 0.3 g acid catalyst BKY450 after ultrasonic dispersion to obtain modified carbon nano tube-fluorocarbon resin finishing paint, then carrying out primer spraying and flash drying on an aluminum veneer through polyester resin, carrying out finishing paint spraying, and flash drying for 10 min at 100 ℃, and finally baking for 30 min at 170 ℃ to obtain the wear-resistant aluminum veneer.
The wear resistance of the surface of a wear resistant aluminum veneer was measured with reference to ASTM D968-2015. And (5) determining the performance of the wear-resistant aluminum veneer according to the JG/T331-2011 standard.
The modified carbon nano tube-fluorocarbon resin finishing paint is used for carrying out spray coating treatment on the aluminum veneer, so that the hardness, impact resistance and wear resistance of the obtained fluorocarbon aluminum veneer are obviously improved.
Claims (4)
1. A preparation method of modified carbon nano tube-fluorocarbon resin is characterized in that: the modified carbon nano tube-fluorocarbon resin comprises 100 parts by weight of fluorocarbon resin, 8-12 parts by weight of amino resin, 0.5-0.8 part by weight of acid catalyst, 0.2-1 part by weight of perfluoro modified carbon nano tube, 0.1-0.5 part by weight of flatting agent, 0.2-0.5 part by weight of defoaming agent and 0.2-0.6 part by weight of dispersing agent; the preparation method of the perfluoro modified carbon nano tube comprises the following steps:
s1, dissolving 100 parts by weight of perfluorooctanoyl chloride into a reaction solvent at 0-5 ℃, then dropwise adding 60-75 parts by weight of 1, 7-bis-Boc-1, 4, 7-triazaheptane and 40-60 parts by weight of triethylamine, stirring 1-2 h, then stirring at 20-35 ℃ for reaction for 3-8 h, removing the solvent after the reaction, washing, and recrystallizing to obtain perfluorooctanoyl amide-bis-Boc-triazaheptane;
s2, dissolving perfluoro-octanamido-bis-Boc-triazaheptane into 1, 4-dioxane, then dropwise adding hydrochloric acid solution, stirring at 20-35 ℃ for reaction for 2-6 h, and extracting, separating, drying, concentrating and recrystallizing after the reaction to obtain perfluoro-octanamido-triazaheptane;
s3, ultrasonically dispersing 100 parts by weight of hydroxylated carbon nano tube into N, N-dimethylformamide, then adding 2000-3500 parts by weight of 4, 4-diphenylmethane diisocyanate and 30-80 parts by weight of dibutyltin dilaurate, stirring and reacting at 55-65 ℃ for 6-12 h, then adding 3800-6000 parts by weight of perfluorooctanoyl amide-triazaheptane, stirring and polymerizing for 3-8 h in 70-85, filtering and washing after the reaction, and obtaining the perfluoro modified carbon nano tube.
2. The method for preparing the modified carbon nanotube-fluorocarbon resin as claimed in claim 1, wherein: the reaction solvent in the step S1 comprises any one or combination of dichloromethane, chloroform and tetrahydrofuran.
3. The method for preparing the modified carbon nanotube-fluorocarbon resin as claimed in claim 1, wherein: the mass fraction of the hydrochloric acid solution in the S2 is 10-18%.
4. The use of the modified carbon nanotube-fluorocarbon resin obtained by the preparation method of any one of claims 1 to 3 in abrasion-resistant aluminum veneers, characterized in that: the preparation process of the wear-resistant aluminum veneer comprises the following steps: adding 100 parts by weight of fluorocarbon resin, 0.1-0.5 part by weight of flatting agent, 0.2-0.5 part by weight of defoamer and 0.2-0.6 part by weight of dispersing agent into a xylene solvent, uniformly stirring, adding 0.2-1 part by weight of perfluorinated modified carbon nano tube, adding 8-12 parts by weight of amino resin and 0.5-0.8 part by weight of acid catalyst after ultrasonic dispersion to obtain modified carbon nano tube-fluorocarbon resin as finish paint, then carrying out primer spraying and flash drying on an aluminum veneer, carrying out finish paint spraying and flash drying, and baking for 20-30 min at 170-185 ℃ to obtain the wear-resistant aluminum veneer.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108948949A (en) * | 2018-06-01 | 2018-12-07 | 合肥奇呗数字科技有限公司 | A kind of conductive anti-corrosion coating and preparation method thereof |
| CN111961381A (en) * | 2020-09-02 | 2020-11-20 | 江苏华夏制漆科技有限公司 | anti-H2Long-acting paint film of S gas erosion |
| CN114045071A (en) * | 2022-01-14 | 2022-02-15 | 佛山市南海宇诚装饰材料有限公司 | Building aluminum veneer curtain wall finish paint and preparation method thereof |
| CN114273188A (en) * | 2022-01-14 | 2022-04-05 | 佛山市南海宇诚装饰材料有限公司 | Fluorine-carbon aluminum veneer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108948949A (en) * | 2018-06-01 | 2018-12-07 | 合肥奇呗数字科技有限公司 | A kind of conductive anti-corrosion coating and preparation method thereof |
| CN111961381A (en) * | 2020-09-02 | 2020-11-20 | 江苏华夏制漆科技有限公司 | anti-H2Long-acting paint film of S gas erosion |
| CN114045071A (en) * | 2022-01-14 | 2022-02-15 | 佛山市南海宇诚装饰材料有限公司 | Building aluminum veneer curtain wall finish paint and preparation method thereof |
| CN114273188A (en) * | 2022-01-14 | 2022-04-05 | 佛山市南海宇诚装饰材料有限公司 | Fluorine-carbon aluminum veneer and preparation method thereof |
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