CN113842941B - Catalyst for cracking fluorine resin, preparation method and application thereof - Google Patents
Catalyst for cracking fluorine resin, preparation method and application thereof Download PDFInfo
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- CN113842941B CN113842941B CN202111110672.4A CN202111110672A CN113842941B CN 113842941 B CN113842941 B CN 113842941B CN 202111110672 A CN202111110672 A CN 202111110672A CN 113842941 B CN113842941 B CN 113842941B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000005336 cracking Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920005989 resin Polymers 0.000 title claims description 9
- 239000011347 resin Substances 0.000 title claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 4
- 239000011737 fluorine Substances 0.000 title claims description 4
- 229910052731 fluorine Inorganic materials 0.000 title claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000009835 boiling Methods 0.000 claims abstract description 23
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 22
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 22
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000006116 anti-fingerprint coating Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000003776 cleavage reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 230000007017 scission Effects 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- 229910052810 boron oxide Inorganic materials 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 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
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 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
- 239000008188 pellet Substances 0.000 claims description 6
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 4
- ZIKLJUUTSQYGQI-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxypropoxy)propane Chemical compound CCOCC(C)OCC(C)OCC ZIKLJUUTSQYGQI-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- 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 4
- 229940019778 diethylene glycol diethyl ether Drugs 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
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 3
- 230000003666 anti-fingerprint Effects 0.000 abstract description 15
- 239000003973 paint Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000010702 perfluoropolyether Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 9
- 150000001265 acyl fluorides Chemical group 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229960002050 hydrofluoric acid Drugs 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
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- 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
-
- B01J35/51—
-
- B01J35/61—
-
- 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
Abstract
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 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, and the catalyst disclosed by the invention is used for carrying out fluororesin cracking in a matching way, so that the requirement of raw material cracking of high-quality anti-fingerprint paint can be met, the raw material acquisition cost of the anti-fingerprint paint is reduced, the market competitiveness of the anti-fingerprint paint is improved, and the dependence of production of the anti-fingerprint paint on linear perfluoropolyether is broken.
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
The anti-fingerprint coating is applied to various industries, such as smart phones, automobiles, home offices, household appliances, glasses, airplanes, trains and the like, although the current market application of the anti-fingerprint coating is very wide, the production mode of the product is very single and the cost is high, and the large-scale popularization of the anti-fingerprint coating is influenced.
Disclosure of Invention
The invention aims to provide a catalyst for cracking fluororesin, which can obtain high-quality anti-fingerprint paint by using the catalyst grade to crack the fluororesin.
In order to achieve the above object, the present invention provides a catalyst for cleavage of fluororesin, comprising, in parts by weight:
10 to 25 parts of polyvinyl butyral, 5 to 15 parts of high boiling point solvent, 1 to 10 parts of nano silicon dioxide, 10 to 30 parts of superfine aluminum oxide, 15 to 40 parts of superfine boron trioxide, 1 to 10 parts of titanium dioxide, 0.5 to 5 parts of superfine iron powder, 0.3 to 4 parts of superfine cobalt powder, 0.5 to 5 parts of superfine nickel powder and 0.5 to 5 parts of superfine copper powder.
Alternatively, the catalyst comprises, in parts by weight:
12 to 25 parts of polyvinyl butyral, 7 to 15 parts of high boiling point solvent, 1 to 9 parts of nano silicon dioxide, 10 to 28 parts of superfine aluminum oxide, 15 to 36 parts of boron trioxide, 1 to 9 parts of titanium dioxide, 0.5 to 4.5 parts of superfine iron powder, 0.3 to 3.5 parts of superfine cobalt powder, 0.5 to 4.5 parts of superfine nickel powder and 1 to 5 parts of superfine copper powder.
Alternatively, the catalyst comprises, in parts by weight:
15 to 25 parts of polyvinyl butyral, 10 to 15 parts of high boiling point solvent, 2 to 9 parts of nano silicon dioxide, 13 to 28 parts of superfine aluminum oxide, 18 to 36 parts of boron trioxide, 2 to 9 parts of titanium dioxide, 0.8 to 3.5 parts of superfine iron powder, 0.5 to 3.5 parts of superfine cobalt powder, 1 to 4.5 parts of superfine nickel powder and 1.5 to 5 parts of superfine copper powder.
Optionally, the PVB is resin with molecular weight between 10000 and 200000.
Optionally, the high boiling point solvent comprises one or more of diethylene glycol butyl ether acetate, diethylene glycol diethyl ether acetate, dibasic ester, dipropylene glycol butyl ether acetate, dipropylene glycol diethyl ether acetate, isophorone, dimethylformamide and dimethyl sulfoxide.
Alternatively, the D50 of the nano silicon dioxide is less than 500nm, the D50 of the superfine aluminum oxide is less than 10 mu m, the D50 of the superfine boron oxide is less than 10 mu m, the D50 of the titanium dioxide is less than 10 mu m, the D50 of the superfine iron powder is less than 25 mu m, the D50 of the superfine cobalt powder is less than 25 mu m, the D50 of the superfine nickel powder is less than 25 mu m, and the D50 of the superfine copper powder is less than 25 mu m.
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 the polyvinyl butyral in a water bath kettle to obtain a colorless transparent solution;
step S2, adding nano silicon dioxide into the colorless transparent solution in the step S1, stirring by hand, and then uniformly stirring by using a dispersing machine to obtain a mixture I;
step S3, sequentially dispersing superfine aluminum oxide, superfine boron oxide, 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 dispersed catalyst mixture;
s4, kneading the dispersed catalyst mixture into spheres;
s5, placing the pellets in a tunnel furnace for baking to obtain dried pellets;
s6, sintering the dried spheres in a muffle furnace, cooling and taking out the spheres to obtain catalyst spheres with cage structures;
step S7, soaking the catalyst balls with the cage-shaped structures in a mixed aqueous solution of nitric acid and saturated ammonium fluoride to obtain soaked catalyst balls;
and S8, taking out the soaked catalyst balls, baking 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, dissolving in a water bath kettle at the temperature of 80-100 ℃ to obtain colorless transparent solution.
Optionally, in the step S4, the dispersed catalyst mixture is kneaded into 3-5mm spheres;
in the step S5, the ball is put into a tunnel furnace to be baked for 25-30 minutes at 150-180 ℃;
in the step S6, the dried spheres are placed in a muffle furnace at 550-650 ℃ and sintered for 5-10 minutes;
in the step S7, the catalyst balls with the cage-shaped structures are soaked in a mixed aqueous solution of 0.1-0.5M nitric acid and saturated ammonium fluoride for 30-60 minutes;
and in the step S8, the soaked cage-shaped catalyst balls are taken out and baked in an oven at 120-150 ℃ for 20-40 minutes.
The invention also provides application of the catalyst in preparation of anti-fingerprint paint.
The invention has the beneficial effects that: the invention provides a catalyst for cracking fluororesin, a preparation method and application thereof, and the catalyst comprises the following components in parts by weight: 10-25 parts of polyvinyl butyral, 5-15 parts of 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, and the catalyst disclosed by the invention is used for carrying out fluororesin cracking in a matching way, so that the requirement of raw material cracking of high-quality anti-fingerprint paint can be met, the raw material acquisition cost of the anti-fingerprint paint is reduced, the market competitiveness of the anti-fingerprint paint is improved, and the dependence of production of the anti-fingerprint paint on linear perfluoropolyether is broken.
Detailed Description
The technical means adopted by the present invention and the effects thereof are further described in detail below in connection with preferred embodiments of the present invention.
The invention provides a catalyst for cracking fluororesin, which comprises the following components in parts by weight:
10 to 25 parts of polyvinyl butyral (Polyvinyl Butyral, PVB), 5 to 15 parts of high boiling point solvent, 1 to 10 parts of nano silicon dioxide, 10 to 30 parts of superfine aluminum oxide, 15 to 40 parts of superfine diboron trioxide, 1 to 10 parts of titanium dioxide, 0.5 to 5 parts of superfine iron powder, 0.3 to 4 parts of superfine cobalt powder, 0.5 to 5 parts of superfine nickel powder and 0.5 to 5 parts of superfine copper powder.
Specifically, the polyvinyl butyral in the catalyst disclosed by the invention has high viscosity after dissolution and excellent viscosity after low-temperature drying, various powder materials in a formula can be well bonded together, and meanwhile, the polyvinyl butyral 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 in the catalyst has good solubility to PVB, and can moisten 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 sintering temperature and energy consumption during high-temperature sintering.
The superfine aluminum oxide, the superfine boron oxide, the titanium dioxide and the nano silicon dioxide together form a glassy substance at the sintering temperature to form a cage-shaped framework of the final catalyst, and meanwhile, less silicon dioxide and more aluminum oxide, boron oxide and titanium dioxide are adopted in the formula to enhance the hydrofluoric acid (HydroFluoricAcid, HF) resistance of the cage-shaped structure.
Specifically, after high-temperature sintering, iron powder, cobalt powder, nickel powder and copper powder are exposed on the surface of a glassy cage structure, and metal powder on the surface forms metal fluoride through etching of acid and fluoride salt to cooperatively catalyze and crack various fluororesin.
Preferably, in some embodiments of the present invention, the catalyst of the present invention comprises, in parts 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 ultra-fine aluminum oxide, 15 to 36 parts of diboron trioxide, 1 to 9 parts of titanium dioxide, 0.5 to 4.5 parts of ultra-fine iron powder, 0.3 to 3.5 parts of ultra-fine cobalt powder, 0.5 to 4.5 parts of ultra-fine nickel powder, and 1 to 5 parts of ultra-fine copper powder.
Preferably, in some embodiments of the present invention, the catalyst of the present invention comprises, in parts by weight, 15 to 25 parts of polyvinyl butyral (PVB for short), 10 to 15 parts of a high boiling point solvent, 2 to 9 parts of nano silica, 13 to 28 parts of ultra-fine aluminum oxide, 18 to 36 parts of boron trioxide, 2 to 9 parts of titanium dioxide, 0.8 to 3.5 parts of ultra-fine iron powder, 0.5 to 3.5 parts of ultra-fine cobalt powder, 1 to 4.5 parts of ultra-fine nickel powder, and 1.5 to 5 parts of ultra-fine copper powder.
Preferably, the PVB is a resin with a molecular weight between 10000 and 200000.
More preferably, the PVB is a resin having a molecular weight between 50000 and 150000.
Preferably, the high boiling point solvent comprises one or more of diethylene glycol butyl ether acetate, diethylene glycol diethyl ether acetate, dibasic ester, dipropylene glycol butyl ether acetate, dipropylene glycol diethyl ether acetate, isophorone, dimethylformamide and dimethyl sulfoxide.
More preferably, the high boiling point solvent includes one or a combination of more than two of diethylene glycol butyl ether acetate, diethylene glycol diethyl ether acetate, dibasic ester, dipropylene glycol butyl ether acetate and dipropylene glycol diethyl ether acetate.
Optionally, the D50 of the nanosilica is less than 500nm.
Preferably, the D50 of the nano silicon dioxide is 200-500 nm, the particle size is too small, and the cost is high.
Optionally, the ultra-fine aluminum oxide, ultra-fine boron oxide, and titanium dioxide D50 is less than 10 μm.
Preferably, the superfine aluminum oxide, the superfine boron oxide and the titanium dioxide D50 are between 2 and 10 mu m, the particle size is too small, the cost is high, and the sources are also few.
Optionally, the D50 of the superfine iron powder, the superfine cobalt powder, the superfine nickel powder and the superfine copper powder is less than 25 μm.
Preferably, the D50 of the superfine iron powder, the superfine cobalt powder, the superfine nickel powder and the superfine copper powder is 10-25 mu m, the particle size is too small, the superfine iron powder, the superfine cobalt powder, the superfine nickel powder and the superfine copper powder are easily covered by glassy substances, the superfine cobalt powder, the superfine nickel powder, the superfine copper powder and the superfine copper powder cannot be exposed on the surface of a cage, and the catalysis effect cannot be achieved.
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 the polyvinyl butyral in a water bath kettle to obtain a colorless transparent solution;
step S2, adding nano silicon dioxide into the colorless transparent solution in the step S1, stirring by hand, and then uniformly stirring by using a dispersing machine to obtain a mixture I;
step S3, sequentially dispersing superfine aluminum oxide, superfine boron oxide, 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 dispersed catalyst mixture;
s4, kneading the dispersed catalyst mixture into spheres;
s5, placing the pellets in a tunnel furnace for baking to obtain dried pellets;
s6, sintering the dried spheres in a muffle furnace, cooling and taking out the spheres to obtain catalyst spheres with cage structures;
step S7, soaking the catalyst balls with the cage-shaped structures in a mixed aqueous solution of nitric acid and saturated ammonium fluoride to obtain soaked catalyst balls;
and S8, taking out the soaked catalyst balls, baking 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, dissolving in a water bath kettle at the temperature of 80-100 ℃ to obtain colorless transparent solution.
Optionally, in the step S4, the dispersed catalyst mixture is kneaded into 3-5mm spheres;
in the step S5, the ball is put into a tunnel furnace to be baked for 25-30 minutes at 150-180 ℃;
in the step S6, the dried spheres are placed in a muffle furnace at 550-650 ℃ and sintered for 5-10 minutes;
in the step S7, the catalyst balls with the cage-shaped structures are soaked in a mixed aqueous solution of 0.1-0.5M nitric acid and saturated ammonium fluoride for 30-60 minutes;
and in the step S8, the soaked cage-shaped catalyst balls are taken out and baked in an oven at 120-150 ℃ for 20-40 minutes.
In detail, in some embodiments of the present invention, the preparation method of the catalyst for cleavage of fluororesin comprises the following specific steps:
PVB is slowly added into a high boiling point solvent under the condition of low-speed stirring, and is dissolved in a water bath kettle at 80-100 ℃ to obtain colorless transparent solution.
Adding nano silicon dioxide into the product 1, stirring by hand, preventing the nano silicon dioxide from drifting into the air because of small particle size, basically wrapping the nano silicon dioxide by the solution, and stirring uniformly by using a dispersing machine to obtain the product 2.
Under the condition of low-speed stirring, superfine aluminum oxide is dispersed in the product 2, and then the product 3 is obtained after high-speed stirring.
Under the condition of low-speed stirring, superfine diboron trioxide is dispersed in the product 3, and then the mixture is uniformly stirred at a high speed to obtain the product 4.
Under the condition of low-speed stirring, titanium dioxide is dispersed in the product 4, and then the mixture is uniformly stirred at a high speed to obtain the product 5.
Under the condition of low-speed stirring, the superfine iron powder is dispersed in the product 5, and then the product 6 is obtained after high-speed stirring.
Under the condition of low-speed stirring, the superfine cobalt powder is dispersed in the product 6, and then the product 7 is obtained after high-speed stirring.
Under the condition of low-speed stirring, superfine nickel powder is dispersed in the product 7, and then the product 8 is obtained after high-speed stirring.
Under the condition of low-speed stirring, the superfine copper powder is dispersed in the obtained product 8, and then the mixture is uniformly stirred at a high speed to obtain a dispersed catalyst mixture.
The dispersed catalyst mixture was kneaded into 3-5mm spheres.
And placing the ball into a well-ventilated tunnel furnace and baking for 25-30 minutes at 150-180 ℃.
And (3) placing the dried spheres in a muffle furnace at 550-650 ℃, sintering for 5-10 minutes, cooling, and taking out the spheres to obtain the catalyst spheres with cage structures.
The cage-shaped catalyst balls are soaked in a mixed water solution of 0.1-0.5M nitric acid and saturated ammonium fluoride for 30-60 minutes.
Taking out the soaked cage-shaped catalyst balls, and baking the cage-shaped catalyst balls in an oven at 120-150 ℃ for 20-40 minutes to volatilize water on the surface and decompose ammonium fluoride, so as to obtain the catalyst balls with iron, cobalt, nickel, copper nitrate and corresponding fluoride on the surface.
In addition, the invention also provides application of the catalyst in preparation of anti-fingerprint paint.
Examples
As in the examples described above, under catalytic oxidation of the catalyst of the present invention, the end groups (including branched end groups) on the fluororesin are oxidized to acyl fluoride groups, and such resins have a plurality of reactive groups which can subsequently be attached to a macromolecular chain with a plurality of silane coupling agents, which can form a plurality of anchor points with the substrate, thereby improving the adhesion of the fluororesin to the substrate and consequently also improving the abrasion resistance of the anti-fingerprint coating.
Comparative example 1
As in the comparative example 1, the fluororesin with the acyl fluoride active group mainly controlled by a few foreign manufacturers is of a straight-chain structure (the domestic manufacturers provide branched structures, the content of the acyl fluoride groups is much lower than that of similar foreign products), no branched chain exists on the molecular chain, the prepared anti-fingerprint coating is compact in molecular arrangement, and two acyl fluoride groups are arranged on the molecular chain, so that the anti-fingerprint coating can react with a silane coupling agent to provide better adhesive force to a substrate, and the wear resistance of the anti-fingerprint coating is improved.
Comparative example 2
As in comparative example 2, the fluororesin mainly controlled by a few foreign manufacturers is of a linear structure (branched structure is provided by domestic manufacturers), no branched chain exists on the molecular chain, and the acyl fluoride formed after cracking is of a linear structure and reacts with the silane coupling agent, so that the prepared anti-fingerprint coating has relatively compact molecular arrangement, and has relatively good wear resistance.
Comparative example 3
As in comparative example 3 above, under the catalysis of conventional catalyst, the macromolecular fluororesin is cleaved into smaller molecular fluororesin, and at the same time, an activated acyl fluoride group is formed at the cleavage site, which is favorable for subsequent connection with other small molecular silane coupling agents and formation of anchor points with the substrate, so that the anti-fingerprint coating is better attached to the substrate. However, because the acyl fluoride groups formed by catalytic cracking leave more branched chains on the main chain, the branched chains are unfavorable for the anti-fingerprint coating to form a fluorocarbon molecular layer which is closely arranged 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, results of the anti-fingerprint coating performance test prepared in examples of the present invention and comparative examples 1 to 3
As can be seen from Table 1, the combination properties of the anti-fingerprint coating prepared in the examples of the present invention are superior to those of comparative example 3 and substantially equivalent to those of comparative example 1, indicating that the anti-fingerprint coating prepared by the catalyst of the present invention has substantially equivalent properties to those of the product prepared from the linear perfluoropolyether raw material.
The transmittance test is based on the following criteria: GB T5433-1985 daily glass transmittance measuring method;
the adhesion test is based on the following criteria: cross-cut test of GB/T9286-1998 color and clearcoat films
The standard of the adhesion test after boiling in water is as follows: GB5237-2008 water boiling test method
The insulation resistance test is based on the following criteria: GB/T3048.5-2007 part 5 of the wire and cable electrical property test method: testing insulation resistance;
the standard of the test basis of the water drop angle, the water drop angle after wear-resistant steel wool and the rubber wear-resistant water drop angle is as follows: a friction resistance test method for a GB/T30693-2014 plastic film and water contact angle measurement and a QB/T2702-2005 coated spectacle lens.
In summary, 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 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, and the catalyst disclosed by the invention is used for carrying out fluororesin cracking in a matching way, so that the requirement of raw material cracking of high-quality anti-fingerprint paint can be met, the raw material acquisition cost of the anti-fingerprint paint is reduced, the market competitiveness of the anti-fingerprint paint is improved, and the dependence of production of the anti-fingerprint paint on linear perfluoropolyether is broken.
In the above, it should be apparent to those skilled in the art that various other modifications and variations can be made in accordance with the technical solution and the technical idea of the present invention, and all such modifications and variations are intended to fall within the scope of the claims of the present invention.
Claims (8)
1. The preparation method of the catalyst for the cracking of the fluororesin is characterized by comprising the following raw materials 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;
the D50 of the nano silicon dioxide is smaller than 500nm, the D50 of the superfine aluminum oxide is smaller than 10 mu m, the D50 of the superfine boron trioxide is smaller than 10 mu m, the D50 of the titanium dioxide is smaller than 10 mu m, the D50 of the superfine iron powder is smaller than 25 mu m, the D50 of the superfine cobalt powder is smaller than 25 mu m, the D50 of the superfine nickel powder is smaller than 25 mu m, and the D50 of the superfine copper powder is smaller than 25 mu m;
the method specifically comprises the following steps:
step S1, adding polyvinyl butyral into a high-boiling point solvent and dissolving the polyvinyl butyral in a water bath kettle to obtain a colorless transparent solution;
step S2, adding nano silicon dioxide into the colorless transparent solution in the step S1, stirring by hand, and then uniformly stirring by using a dispersing machine to obtain a mixture I;
step S3, sequentially dispersing superfine aluminum oxide, superfine boron oxide, 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 dispersed catalyst raw material mixture;
s4, kneading the dispersed catalyst raw material mixture into spheres;
s5, placing the pellets in a tunnel furnace for baking to obtain dried pellets;
s6, sintering the dried spheres in a muffle furnace, cooling and taking out the spheres to obtain catalyst spheres with cage structures;
step S7, soaking the catalyst balls with the cage-shaped structures in a mixed aqueous solution of nitric acid and saturated ammonium fluoride to obtain soaked catalyst balls;
and S8, taking out the soaked catalyst balls, baking 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.
2. The method for preparing a catalyst for cleavage of fluorine resin according to claim 1, wherein the catalyst raw material 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.
3. The method for preparing a catalyst for cleavage of fluorine resin according to claim 2, wherein the catalyst raw material 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 boron 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 method for preparing a catalyst for the cleavage of fluororesin according to claim 1, wherein the polyvinyl butyral is a resin having a molecular weight of 10000 to 200000.
5. The method for preparing a catalyst for cleavage of fluororesin according to claim 1, wherein the high boiling point solvent comprises one or a combination of two or more of diethylene glycol butyl ether acetate, diethylene glycol diethyl ether acetate, dibasic ester, dipropylene glycol butyl ether acetate, dipropylene glycol diethyl ether acetate, isophorone, dimethylformamide and dimethylsulfoxide.
6. The method for preparing a catalyst for the cleavage of fluororesin according to claim 1, wherein in the step S1, the solution is dissolved in a water bath at 80 to 100 ℃ to obtain a colorless transparent solution.
7. The method for preparing a catalyst for cleavage of fluororesin according to claim 1, wherein in the step S4, the dispersed catalyst raw material mixture is kneaded into 3-5mm spheres;
in the step S5, the round balls are placed in a tunnel furnace and baked for 25-30 minutes at 150-180 ℃;
in the step S6, the dried spheres are placed in a muffle furnace at 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 in the step S8, the soaked cage-shaped catalyst balls are taken out and baked in an oven at 120-150 ℃ for 20-40 minutes.
8. Use of a catalyst obtainable by a process according to any one of claims 1 to 7 in the preparation of an anti-fingerprint coating.
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