CN113842941A - Catalyst for cracking fluororesin and preparation method and application thereof - Google Patents
Catalyst for cracking fluororesin and preparation method and application thereof Download PDFInfo
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- CN113842941A CN113842941A CN202111110672.4A CN202111110672A CN113842941A CN 113842941 A CN113842941 A CN 113842941A CN 202111110672 A CN202111110672 A CN 202111110672A CN 113842941 A CN113842941 A CN 113842941A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 238000005336 cracking Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 25
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000009835 boiling Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 19
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 22
- 239000006116 anti-fingerprint coating Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 4
- JONNRYNDZVEZFH-UHFFFAOYSA-N 2-(2-butoxypropoxy)propyl acetate Chemical compound CCCCOC(C)COC(C)COC(C)=O JONNRYNDZVEZFH-UHFFFAOYSA-N 0.000 claims description 4
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 claims description 4
- CKCGJBFTCUCBAJ-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propyl acetate Chemical compound CCOC(C)COC(C)COC(C)=O CKCGJBFTCUCBAJ-UHFFFAOYSA-N 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 9
- 150000001265 acyl fluorides Chemical group 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000010702 perfluoropolyether Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a catalyst for cracking fluororesin, and a preparation method and application thereof. Wherein, the catalyst comprises the following components in parts by weight: 10-25 parts of polyvinyl butyral, 5-15 parts of a high-boiling point solvent, 1-10 parts of nano silicon dioxide, 10-30 parts of superfine aluminum oxide, 15-40 parts of superfine boron trioxide, 1-10 parts of titanium dioxide, 0.5-5 parts of superfine iron powder, 0.3-4 parts of superfine cobalt powder, 0.5-5 parts of superfine nickel powder and 0.5-5 parts of superfine copper powder.
Description
Technical Field
The invention relates to the field of catalytic cracking of fluororesin, in particular to a catalyst for cracking fluororesin, a preparation method and application thereof.
Background
Although the anti-fingerprint coating is widely applied in various industries, such as smart phones, automobiles, home offices, household appliances, glasses, airplanes, trains and the like, the anti-fingerprint coating is widely applied in the current market, but the production mode of the product is single and high in cost, and the large-scale popularization of the anti-fingerprint coating is influenced because the anti-fingerprint coating prepared by the prior art is mainly prepared from linear perfluoropolyether, the production of the raw material is mastered by a few manufacturers, the raw material is basically located abroad, the raw material is controlled during the production by domestic manufacturers, the neck problem is easy to occur, if other raw materials (such as fluororesin) are adopted to produce the anti-fingerprint coating, the quality of the produced anti-fingerprint coating is low, and the market requirement cannot be met, therefore, a new method is needed to be developed, and under the condition that the linear perfluoropolyether is not used, the high-quality anti-fingerprint coating is prepared, and the dependence of the production of the anti-fingerprint coating on linear perfluoropolyether is broken.
Disclosure of Invention
The invention aims to provide a catalyst for cracking fluororesin, and high-quality fingerprint-resistant coating can be obtained by cracking fluororesin by using the catalyst.
In order to achieve the above object, the present invention provides a catalyst for cracking a fluororesin, comprising, in parts by weight:
10-25 parts of polyvinyl butyral, 5-15 parts of a high boiling point solvent, 1-10 parts of nano silicon dioxide, 10-30 parts of superfine aluminum oxide, 15-40 parts of superfine boron trioxide, 1-10 parts of titanium dioxide, 0.5-5 parts of superfine iron powder, 0.3-4 parts of superfine cobalt powder, 0.5-5 parts of superfine nickel powder and 0.5-5 parts of superfine copper powder.
Optionally, the catalyst comprises, in parts by weight:
12-25 parts of polyvinyl butyral, 7-15 parts of a high boiling point solvent, 1-9 parts of nano silicon dioxide, 10-28 parts of superfine aluminum oxide, 15-36 parts of boron trioxide, 1-9 parts of titanium dioxide, 0.5-4.5 parts of superfine iron powder, 0.3-3.5 parts of superfine cobalt powder, 0.5-4.5 parts of superfine nickel powder and 1-5 parts of superfine copper powder.
Optionally, the catalyst comprises, in parts by weight:
15-25 parts of polyvinyl butyral, 10-15 parts of a high boiling point solvent, 2-9 parts of nano silicon dioxide, 13-28 parts of superfine aluminum oxide, 18-36 parts of diboron trioxide, 2-9 parts of titanium dioxide, 0.8-3.5 parts of superfine iron powder, 0.5-3.5 parts of superfine cobalt powder, 1-4.5 parts of superfine nickel powder and 1.5-5 parts of superfine copper powder.
Optionally, the PVB is resin with the molecular weight of 10000-200000.
Optionally, the high boiling point solvent includes one or a combination of two or more of diethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, dibasic ester, dipropylene glycol butyl ether acetate, dipropylene glycol ethyl ether acetate, isophorone, dimethylformamide, and dimethylsulfoxide.
Optionally, the D50 of the nano-silica is less than 500nm, the D50 of the superfine aluminum oxide is less than 10 μm, the D50 of the superfine boron trioxide is less than 10 μm, the D50 of the titanium dioxide is less than 10 μm, the D50 of the superfine iron powder is less than 25 μm, the D50 of the superfine cobalt powder is less than 25 μm, the D50 of the superfine nickel powder is less than 25 μm, and the D50 of the superfine copper powder is less than 25 μm.
The invention also provides a preparation method of the catalyst for cracking the fluororesin, which comprises the following steps:
step S1, adding polyvinyl butyral into a high boiling point solvent and dissolving in a water bath kettle to obtain a colorless and transparent solution;
step S2, adding the nano silicon dioxide into the colorless and transparent solution obtained in the step S1, stirring the mixture manually, and then uniformly stirring the mixture by using a dispersion machine to obtain a first mixture;
step S3, sequentially dispersing superfine aluminum oxide, superfine boron trioxide, titanium dioxide, superfine iron powder, superfine cobalt powder, superfine nickel powder and superfine copper powder in the mixture I and uniformly stirring to obtain a well-dispersed catalyst mixture;
step S4, kneading the dispersed catalyst mixture into balls;
s5, baking the round ball in a tunnel furnace to obtain a dried round ball;
s6, sintering the dried round balls in a muffle furnace, cooling and taking out the round balls to obtain catalyst balls with cage-shaped structures;
step S7, soaking the catalyst balls with cage structures in a mixed aqueous solution of nitric acid and saturated ammonium fluoride to obtain soaked catalyst balls;
and step S8, taking out the soaked catalyst balls, baking the catalyst balls in an oven to volatilize water on the surface and decompose ammonium fluoride to obtain a target catalyst, wherein the target catalyst is a catalyst ball with iron, cobalt, nickel, copper nitrate and corresponding fluoride attached to the surface.
Optionally, in the step S1, the solution is dissolved in a water bath at 80-100 ℃ to obtain a colorless and transparent solution.
Optionally, in step S4, kneading the dispersed catalyst mixture into 3-5mm round balls;
in the step S5, the round balls are placed in a tunnel furnace to be baked for 25-30 minutes at the temperature of 150-180 ℃;
in the step S6, the dried round ball is placed in a muffle furnace at the temperature of 550-650 ℃ and sintered for 5-10 minutes;
in the step S7, soaking the catalyst balls with the cage-shaped structures in a mixed aqueous solution of 0.1-0.5M nitric acid and saturated ammonium fluoride for 30-60 minutes;
and S8, taking out the soaked cage-shaped catalyst balls, and baking the cage-shaped catalyst balls in an oven at the temperature of 120-150 ℃ for 20-40 minutes.
The invention also provides an application of the catalyst in preparation of an anti-fingerprint coating.
The invention has the beneficial effects that: the invention provides a catalyst for cracking fluororesin, a preparation method and an application thereof, wherein the catalyst comprises the following components in parts by weight: 10-25 parts of polyvinyl butyral, 5-15 parts of a high-boiling point solvent, 1-10 parts of nano silicon dioxide, 10-30 parts of superfine aluminum oxide, 15-40 parts of superfine boron trioxide, 1-10 parts of titanium dioxide, 0.5-5 parts of superfine iron powder, 0.3-4 parts of superfine cobalt powder, 0.5-5 parts of superfine nickel powder and 0.5-5 parts of superfine copper powder.
Detailed Description
To further illustrate the technical means adopted by the present invention and the effects thereof, the following detailed description is given with reference to the preferred embodiments of the present invention.
The invention provides a catalyst for cracking fluororesin, which comprises the following components in parts by weight:
10-25 parts of Polyvinyl Butyral (PVB), 5-15 parts of a high-boiling-point solvent, 1-10 parts of nano silicon dioxide, 10-30 parts of superfine aluminum oxide, 15-40 parts of superfine boron trioxide, 1-10 parts of titanium dioxide, 0.5-5 parts of superfine iron powder, 0.3-4 parts of superfine cobalt powder, 0.5-5 parts of superfine nickel powder and 0.5-5 parts of superfine copper powder.
Specifically, the polyvinyl butyral in the catalyst has high viscosity after being dissolved, has excellent viscosity after being dried at low temperature, can well bond various powder materials in a formula together, and can be completely carbonized and decomposed at the temperature of more than 300 ℃, so that the finally formed catalyst has a good cage-shaped structure, the surface area of the catalyst is increased, and the catalyst has a better catalytic effect.
Furthermore, the high boiling point dissolution of the catalyst of the invention has good solubility to PVB, and can wet various powder materials, so that the powder materials can be well and uniformly mixed.
In addition, the nano silicon dioxide has small particle size, and can reduce the sintering temperature and energy consumption during high-temperature sintering.
And the superfine aluminum oxide, the superfine boron oxide, the titanium dioxide and the nano-silicon dioxide together form a glassy substance at a sintering temperature to form a cage-shaped framework of the final catalyst, and meanwhile, a little silicon dioxide, more aluminum oxide, boron oxide and titanium dioxide are adopted in the formula to enhance the hydrofluoric acid (HF) resistance of the cage-shaped structure.
Specifically, after being sintered at high temperature, iron powder, cobalt powder, nickel powder and copper powder are exposed on the surface of a glassy cage structure, and the metal powder on the surface forms metal fluoride by being etched by acid and fluorine salt, so that various fluororesins are catalytically cracked in a synergetic manner.
Preferably, in some embodiments of the present invention, the catalyst comprises, by weight, 12 to 25 parts of polyvinyl butyral, 7 to 15 parts of a high boiling point solvent, 1 to 9 parts of nano silica, 10 to 28 parts of ultrafine alumina, 15 to 36 parts of boron trioxide, 1 to 9 parts of titanium dioxide, 0.5 to 4.5 parts of ultrafine iron powder, 0.3 to 3.5 parts of ultrafine cobalt powder, 0.5 to 4.5 parts of ultrafine nickel powder, and 1 to 5 parts of ultrafine copper powder.
Preferably, in some embodiments of the present invention, the catalyst includes, by weight, 15 to 25 parts of polyvinyl butyral (PVB), 10 to 15 parts of a high boiling point solvent, 2 to 9 parts of nano silica, 13 to 28 parts of ultrafine aluminum oxide, 18 to 36 parts of boron trioxide, 2 to 9 parts of titanium dioxide, 0.8 to 3.5 parts of ultrafine iron powder, 0.5 to 3.5 parts of ultrafine cobalt powder, 1 to 4.5 parts of ultrafine nickel powder, and 1.5 to 5 parts of ultrafine copper powder.
Preferably, the PVB is resin with the molecular weight of 10000-200000.
More preferably, the PVB is resin with the molecular weight of 50000-150000.
Preferably, the high boiling point solvent includes one or a combination of two or more of diethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, dibasic ester, dipropylene glycol butyl ether acetate, dipropylene glycol ethyl ether acetate, isophorone, dimethylformamide, and dimethylsulfoxide.
More preferably, the high boiling point solvent includes one or a combination of two or more of diethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, dibasic ester, dipropylene glycol butyl ether acetate, and dipropylene glycol ethyl ether acetate.
Optionally, the nanosilica has a D50 of less than 500 nm.
Preferably, the D50 of the nano silicon dioxide is between 200 and 500nm, the particle size is too small, and the cost is high.
Optionally, the ultrafine alumina, ultrafine diboron trioxide and titanium dioxide D50 are less than 10 μm.
Preferably, the superfine aluminum oxide, the superfine boron trioxide and the titanium dioxide D50 are 2-10 μm, the particle size is too small, the cost is high, and the source is less.
Optionally, the superfine iron powder, the superfine cobalt powder, the superfine nickel powder and the superfine copper powder D50 are less than 25 μm.
Preferably, the D50 ranges from 10 to 25 μm, and the particle size is too small, so that the ultrafine iron powder, the ultrafine cobalt powder, the ultrafine nickel powder and the ultrafine copper powder is easily covered by glassy substances, cannot be exposed on the surface of a cage-shaped object, and cannot play a role in catalysis.
The invention also provides a preparation method of the catalyst for cracking the fluororesin, which comprises the following steps:
step S1, adding polyvinyl butyral into a high boiling point solvent and dissolving in a water bath kettle to obtain a colorless and transparent solution;
step S2, adding the nano silicon dioxide into the colorless and transparent solution obtained in the step S1, stirring the mixture manually, and then uniformly stirring the mixture by using a dispersion machine to obtain a first mixture;
step S3, sequentially dispersing superfine aluminum oxide, superfine boron trioxide, titanium dioxide, superfine iron powder, superfine cobalt powder, superfine nickel powder and superfine copper powder in the mixture I and uniformly stirring to obtain a well-dispersed catalyst mixture;
step S4, kneading the dispersed catalyst mixture into balls;
s5, baking the round ball in a tunnel furnace to obtain a dried round ball;
s6, sintering the dried round balls in a muffle furnace, cooling and taking out the round balls to obtain catalyst balls with cage-shaped structures;
step S7, soaking the catalyst balls with cage structures in a mixed aqueous solution of nitric acid and saturated ammonium fluoride to obtain soaked catalyst balls;
and step S8, taking out the soaked catalyst balls, baking the catalyst balls in an oven to volatilize water on the surface and decompose ammonium fluoride to obtain a target catalyst, wherein the target catalyst is a catalyst ball with iron, cobalt, nickel, copper nitrate and corresponding fluoride attached to the surface.
Optionally, in the step S1, the solution is dissolved in a water bath at 80-100 ℃ to obtain a colorless and transparent solution.
Optionally, in step S4, kneading the dispersed catalyst mixture into 3-5mm round balls;
in the step S5, the round balls are placed in a tunnel furnace to be baked for 25-30 minutes at the temperature of 150-180 ℃;
in the step S6, the dried round ball is placed in a muffle furnace at the temperature of 550-650 ℃ and sintered for 5-10 minutes;
in the step S7, soaking the catalyst balls with the cage-shaped structures in a mixed aqueous solution of 0.1-0.5M nitric acid and saturated ammonium fluoride for 30-60 minutes;
and S8, taking out the soaked cage-shaped catalyst balls, and baking the cage-shaped catalyst balls in an oven at the temperature of 120-150 ℃ for 20-40 minutes.
In detail, in some embodiments of the present invention, the specific steps of the preparation method of the catalyst for cracking fluororesin are as follows:
and (3) slowly adding PVB into a high-boiling-point solvent under the condition of low-speed stirring, and dissolving the PVB in a water bath kettle at the temperature of 80-100 ℃ to obtain a colorless and transparent solution.
Adding the nano silicon dioxide into the solution 1, manually stirring to prevent the nano silicon dioxide from floating into the air due to small particle size, basically wrapping the nano silicon dioxide by the solution, and then uniformly stirring by using a dispersion machine to obtain a product 2.
And dispersing the superfine aluminum oxide in the product 2 under the condition of low-speed stirring, and uniformly stirring at a high speed to obtain a product 3.
Under the condition of low-speed stirring, dispersing the superfine boron trioxide in the product 3, and uniformly stirring at high speed to obtain a product 4.
Under the condition of low-speed stirring, the titanium dioxide is dispersed in the product 4, and then the titanium dioxide is uniformly stirred at high speed to obtain a product 5.
Under the condition of low-speed stirring, the superfine iron powder is dispersed in the product 5, and then uniformly stirred at high speed to obtain the product 6.
Under the condition of low-speed stirring, the superfine cobalt powder is dispersed in the product 6, and then the mixture is uniformly stirred at a high speed to obtain a product 7.
Under the condition of low-speed stirring, the superfine nickel powder is dispersed in the product 7, and then the mixture is uniformly stirred at high speed to obtain a product 8.
Under the condition of low-speed stirring, dispersing the superfine copper powder in the obtained product 8, and then uniformly stirring at high speed to obtain a dispersed catalyst mixture.
The dispersed catalyst mixture was kneaded into 3-5mm round balls.
And (3) baking the round balls for 25-30 minutes at 150-180 ℃ in a well-ventilated tunnel furnace.
And (3) placing the dried round balls in a muffle furnace at 550-650 ℃, sintering for 5-10 minutes, cooling, and taking out the round balls to obtain the catalyst balls with cage-shaped structures.
Soaking the cage-shaped catalyst ball in 0.1-0.5M nitric acid and saturated ammonium fluoride mixed aqueous solution for 30-60 minutes.
And taking out the soaked cage-shaped catalyst balls, and baking the cage-shaped catalyst balls in an oven at the temperature of 120-150 ℃ for 20-40 minutes to volatilize water on the surface and decompose ammonium fluoride, so that the catalyst balls with nitrates of iron, cobalt, nickel and copper and corresponding fluorides attached to the surfaces are obtained.
In addition, the invention also provides an application of the catalyst in preparation of an anti-fingerprint coating.
Examples
As shown in the above examples, under the catalytic oxidation of the catalyst of the present invention, the terminal groups (including the branched terminal groups) on the fluororesin are oxidized into acyl fluoride groups, such resin has a plurality of active groups, and then a plurality of silane coupling agents can be grafted on a macromolecular chain, so as to form a plurality of anchor points with the substrate, thereby improving the adhesion between the fluororesin and the substrate, and consequently also improving the wear resistance of the fingerprint resistant coating.
Comparative example 1
As in the comparative example 1, the fluororesin mainly controlled by a few foreign manufacturers and having an acyl fluoride active group has a straight chain structure (both provided by domestic manufacturers are branched chain structures, and the content of the acyl fluoride group is much lower than that of foreign similar products), and there is no branched chain on the molecular chain, so that the prepared fingerprint-resistant coating has a tighter molecular arrangement, and the molecular chain has two acyl fluoride groups, which can react with the silane coupling agent to provide better adhesion to the substrate and improve the wear resistance of the fingerprint-resistant coating.
Comparative example 2
As in the comparative example 2, the fluororesin mainly controlled by a few foreign manufacturers has a linear structure (both provided by domestic manufacturers have a branched structure), and has no branched chain on a molecular chain, and the acyl fluoride formed after cracking also has a linear structure, and reacts with the silane coupling agent to prepare the fingerprint resistant coating with tighter molecular arrangement, so that the fingerprint resistant coating has better wear resistance.
Comparative example 3
As in the above comparative example 3, under the catalysis of the conventional catalyst, the macromolecular fluororesin is cracked into the smaller molecular fluororesin, and simultaneously, activated acyl fluoride groups are formed at the cracked positions, so that the subsequent connection of other small molecular silane coupling agents is facilitated, and the anchoring points are formed with the substrate, so that the anti-fingerprint coating is well attached to the substrate. However, due to the acyl fluoride groups formed by catalytic cracking, more branched chains are left on the main chain, and the branched chains are not favorable for the anti-fingerprint coating to form a tightly arranged fluorocarbon molecular layer on the substrate, so that the wear resistance of the anti-fingerprint coating is reduced, and the wear resistance is a key index for measuring the anti-fingerprint coating.
Table 1, the performance test results of the fingerprint resistant coatings prepared in the inventive examples and comparative examples 1 to 3
As can be seen from Table 1, the comprehensive performance of the anti-fingerprint coating prepared in the example of the invention is better than that of comparative example 3, and is basically equivalent to that of comparative example 1, which shows that the anti-fingerprint coating prepared by the catalyst of the invention has basically equivalent performance to that of the product prepared by the linear perfluoropolyether raw material.
The standard of the transmittance test basis is as follows: GB T5433 and 1985 methods for measuring the transmittance of daily glass;
the adhesion test is based on the following criteria: test for marking GB/T9286-1998 paint and varnish films
The standard of the adhesion test after boiling in water is as follows: GB5237-2008 poaching test method
The insulation resistance test is based on the following standards: GB/T3048.5-2007 electric wire and cable electric performance test method part 5: testing the insulation resistance;
the standard of the test basis of the water drop angle, the water drop angle after the wear resistance of the steel wool and the rubber wear-resistant water drop angle is as follows: GB/T30693-.
In conclusion, the invention provides a catalyst for cracking fluororesin, a preparation method and application thereof. Wherein, the catalyst comprises the following components in parts by weight: 10-25 parts of polyvinyl butyral, 5-15 parts of a high-boiling point solvent, 1-10 parts of nano silicon dioxide, 10-30 parts of superfine aluminum oxide, 15-40 parts of superfine boron trioxide, 1-10 parts of titanium dioxide, 0.5-5 parts of superfine iron powder, 0.3-4 parts of superfine cobalt powder, 0.5-5 parts of superfine nickel powder and 0.5-5 parts of superfine copper powder.
As described above, it will be apparent to those skilled in the art that other various changes and modifications may be made based on the technical solution and concept of the present invention, and all such changes and modifications are intended to fall within the scope of the appended claims.
Claims (10)
1. A catalyst for cracking a fluororesin, characterized by comprising, in parts by weight:
10-25 parts of polyvinyl butyral, 5-15 parts of a high boiling point solvent, 1-10 parts of nano silicon dioxide, 10-30 parts of superfine aluminum oxide, 15-40 parts of superfine boron trioxide, 1-10 parts of titanium dioxide, 0.5-5 parts of superfine iron powder, 0.3-4 parts of superfine cobalt powder, 0.5-5 parts of superfine nickel powder and 0.5-5 parts of superfine copper powder.
2. The catalyst for cracking fluororesin according to claim 1, comprising, in parts by weight:
12-25 parts of polyvinyl butyral, 7-15 parts of a high boiling point solvent, 1-9 parts of nano silicon dioxide, 10-28 parts of superfine aluminum oxide, 15-36 parts of boron trioxide, 1-9 parts of titanium dioxide, 0.5-4.5 parts of superfine iron powder, 0.3-3.5 parts of superfine cobalt powder, 0.5-4.5 parts of superfine nickel powder and 1-5 parts of superfine copper powder.
3. A catalyst for cracking a fluororesin according to claim 2, comprising, in parts by weight:
15-25 parts of polyvinyl butyral, 10-15 parts of a high boiling point solvent, 2-9 parts of nano silicon dioxide, 13-28 parts of superfine aluminum oxide, 18-36 parts of diboron trioxide, 2-9 parts of titanium dioxide, 0.8-3.5 parts of superfine iron powder, 0.5-3.5 parts of superfine cobalt powder, 1-4.5 parts of superfine nickel powder and 1.5-5 parts of superfine copper powder.
4. The catalyst for cracking fluororesin according to claim 1, wherein the PVB is a resin having a molecular weight of 10000 to 200000.
5. The catalyst for cracking a fluororesin according to claim 1, wherein the high-boiling solvent includes one or a combination of two or more of diethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, dibasic ester, dipropylene glycol butyl ether acetate, dipropylene glycol ethyl ether acetate, isophorone, dimethylformamide, and dimethylsulfoxide.
6. The catalyst for the decomposition of fluororesin according to claim 1, wherein said nanosilica has a D50 of less than 500nm, ultrafine alumina has a D50 of less than 10 μm, ultrafine diboron trioxide has a D50 of less than 10 μm, titanium dioxide has a D50 of less than 10 μm, ultrafine iron powder has a D50 of less than 25 μm, ultrafine cobalt powder has a D50 of less than 25 μm, ultrafine nickel powder has a D50 of less than 25 μm, and ultrafine copper powder has a D50 of less than 25 μm.
7. A method for preparing a catalyst for cracking a fluororesin, comprising the steps of:
step S1, adding polyvinyl butyral into a high boiling point solvent and dissolving in a water bath kettle to obtain a colorless and transparent solution;
step S2, adding the nano silicon dioxide into the colorless and transparent solution obtained in the step S1, stirring the mixture manually, and then uniformly stirring the mixture by using a dispersion machine to obtain a first mixture;
step S3, sequentially dispersing superfine aluminum oxide, superfine boron trioxide, titanium dioxide, superfine iron powder, superfine cobalt powder, superfine nickel powder and superfine copper powder in the mixture I and uniformly stirring to obtain a well-dispersed catalyst mixture;
step S4, kneading the dispersed catalyst mixture into balls;
s5, baking the round ball in a tunnel furnace to obtain a dried round ball;
s6, sintering the dried round balls in a muffle furnace, cooling and taking out the round balls to obtain catalyst balls with cage-shaped structures;
step S7, soaking the catalyst balls with cage structures in a mixed aqueous solution of nitric acid and saturated ammonium fluoride to obtain soaked catalyst balls;
and step S8, taking out the soaked catalyst balls, baking the catalyst balls in an oven to volatilize water on the surface and decompose ammonium fluoride to obtain a target catalyst, wherein the target catalyst is a catalyst ball with iron, cobalt, nickel, copper nitrate and corresponding fluoride attached to the surface.
8. The method for preparing a catalyst for cracking a fluororesin according to claim 7, wherein in the step S1, the catalyst is dissolved in a water bath at 80 to 100 ℃ to obtain a colorless transparent solution.
9. The method of preparing a catalyst for cracking a fluororesin according to claim 7, wherein in the step S4, the dispersed catalyst mixture is kneaded into round balls of 3 to 5 mm;
in the step S5, the round balls are placed in a tunnel furnace to be baked for 25-30 minutes at the temperature of 150-180 ℃;
in the step S6, the dried round ball is placed in a muffle furnace at the temperature of 550-650 ℃ and sintered for 5-10 minutes;
in the step S7, soaking the catalyst balls with the cage-shaped structures in a mixed aqueous solution of 0.1-0.5M nitric acid and saturated ammonium fluoride for 30-60 minutes;
and S8, taking out the soaked cage-shaped catalyst balls, and baking the cage-shaped catalyst balls in an oven at the temperature of 120-150 ℃ for 20-40 minutes.
10. Use of a catalyst according to any one of claims 1 to 6 in the preparation of an anti-fingerprint coating.
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