CN117285855B - Metal protective agent, metal protective coating, preparation method and application - Google Patents
Metal protective agent, metal protective coating, preparation method and application Download PDFInfo
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- CN117285855B CN117285855B CN202311590015.3A CN202311590015A CN117285855B CN 117285855 B CN117285855 B CN 117285855B CN 202311590015 A CN202311590015 A CN 202311590015A CN 117285855 B CN117285855 B CN 117285855B
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- protective agent
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 185
- 239000002184 metal Substances 0.000 title claims abstract description 184
- 239000003223 protective agent Substances 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000011253 protective coating Substances 0.000 title claims abstract description 26
- 239000004480 active ingredient Substances 0.000 claims abstract description 75
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 72
- 150000001265 acyl fluorides Chemical class 0.000 claims abstract description 33
- OSBJUINXNAJWND-UHFFFAOYSA-N CC1=CC=CC=C1OP(=O)(O)Cl Chemical compound CC1=CC=CC=C1OP(=O)(O)Cl OSBJUINXNAJWND-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000004381 surface treatment Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- -1 trihydroxyethyl isocyanurate Chemical compound 0.000 claims abstract description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 29
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 239000003085 diluting agent Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000000779 smoke Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000007865 diluting Methods 0.000 abstract description 2
- 239000003517 fume Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 238000004821 distillation Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000011241 protective layer Substances 0.000 description 10
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000006233 lamp black Substances 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000003666 anti-fingerprint Effects 0.000 description 2
- 239000002519 antifouling agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 description 1
- 239000010963 304 stainless steel Substances 0.000 description 1
- 241001539473 Euphoria Species 0.000 description 1
- 206010015535 Euphoric mood Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000036561 sun exposure Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 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
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33317—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group heterocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The invention belongs to the technical field of special polymer coating synthesis, and particularly relates to a metal protective agent, a metal protective coating, a preparation method and application. The effective component of the metal protective agent is a compound containing a perfluoropolyether chain. The preparation method of the metal protective agent comprises the steps of firstly preparing active ingredients; then diluting the prepared active ingredients; wherein the preparation raw materials of the active ingredients comprise trihydroxyethyl isocyanurate, o-tolyl chlorophosphate and perfluoropolyether acyl fluoride. The metal protective coating adopts the metal protective agent, and firstly, the metal protective agent is added into a solvent to dilute again to obtain a surface treatment liquid; and then coating the surface treatment liquid on a metal substrate, and curing to obtain the metal protective coating. The metal protective agent is applied to the surface of a metal substrate in high-temperature, oil fume and exposure use environments, and can endow the metal substrate with better temperature resistance, weather resistance, hydrophobicity and oleophobicity and certain wear resistance.
Description
Technical Field
The invention belongs to the technical field of special polymer coating synthesis, and particularly relates to a metal protective agent, a metal protective coating, a preparation method and application.
Background
With the rapid rise of living standard, the requirements of people on the use of electric appliances in daily life are increasingly increased, and not only are excellent product functions of the electric appliances expected, but also the electric appliances are expected to have the advantages of easy cleaning of the surfaces, high and low temperature resistance, no toxicity, water and oil repellency, weather resistance, aging resistance, high adhesive force and the like of the surface coatings.
A variety of different protective products, such as anti-fingerprint oil for protecting electronic touch screens, are currently on the market; an anti-fingerprint additive that protects against UV curable hard coatings; hydrophobic oleophobic nano-coatings for stainless steel protection, and the like. However, the product for protecting the metal of the electric appliance is relatively few, the performance of the product is single, and the product has problems in the aspects of temperature resistance, weather resistance, binding force, wear resistance and the like.
Patent CN101544724a discloses a method for preparing an acrylic polymer emulsion for a water-based metal protective paint, wherein the obtained metal protective paint is stable to heat and light, has very low surface tension and very good stain resistance, but has a glass transition temperature (Tg) of only 50 ℃, and is not suitable for use at an environmental temperature exceeding 50 ℃, namely, cannot be used under a high-temperature condition.
Patent CN101608306A discloses a surface treatment method of passivation solution and galvanized material, which can also be used for metal protection, the passivation solution is an aqueous solution containing water-soluble molybdenum compound, boric acid, water-soluble organic matter and silica sol, wherein the water-soluble organic matter is a mixture of alcohol and organic carboxylic acid. The patent aims to overcome the defect of poor corrosion resistance of the conventional galvanized material, and the attention of the patent is only corrosion resistance, and the passivation solution has relatively good corrosion resistance, but has relatively single performance and imperfect function, and does not pay attention to the performances of heat resistance, weather resistance, fingerprint resistance, wear resistance and other aspects.
Patent CN103031042a discloses a metal protective coating, a hot dip galvanized metal material and a hot dip aluminized zinc metal material, wherein the raw material mixture contains water-soluble silicate, an accelerator, a silane coupling agent, a silica filler, a water-soluble film-forming resin and water, and the protective film formed by the metal protective coating is improved in corrosion resistance, water resistance, heat resistance and fingerprint resistance, but because the silicate containing silicon, the silica filler and the silane coupling agent exist in the raw material of the metal protective coating, chemical bonding is difficult to occur between the metal protective coating and the metal, and the metal is mainly bonded on the surface of the metal by physical acting force to form a coating, so that the bonding force between the coating and the metal material is poor.
In addition, the active ingredients of the existing metal protective agent are mostly inorganic metal salts (such as zinc phosphate and molybdenum compounds) or organic coatings (acrylic ester protective coatings), and based on the requirement of binding force, various auxiliary agents such as silane coupling agents, silica sol and the like are required to be added into the metal protective agent, and the auxiliary agents and the active ingredients are physically mixed to prepare the required metal protective agent. The addition of the auxiliary agents causes the problems of thicker coating, reduced glossiness and complicated operation of the metal protective coating formed by the metal protective agent. Meanwhile, the auxiliary agent and the metal base material are physically combined, so that the combination force is poor, and the coating is at risk of falling off in the long term.
Disclosure of Invention
The invention aims to provide a metal protective agent, wherein the effective component of the metal protective agent is a compound containing a perfluoropolyether chain, and the perfluoropolyether chain, phosphate and isocyanurate containing benzene ring structures are simultaneously introduced into the molecular structure of the compound, so that the effective component of the metal protective agent has excellent heat resistance, weather resistance, hydrophobicity and oleophobicity and wear resistance, any other auxiliary agent is not required to be added, and the metal protective agent with excellent performance is obtained after the metal protective agent is diluted by only adopting the diluent, thereby avoiding the defects of thicker film layer, complex operation and poor binding force caused by the auxiliary agent.
The metal base material protected by the metal protective agent has excellent heat resistance (the metal base material is not fallen off after being baked at the high temperature of 200 ℃ for 8 hours), weather resistance, hydrophobicity and oleophobicity (the initial water contact angle can reach 116 degrees, the oil contact angle can reach 75 degrees) and wear resistance (the water contact angle can still reach 101 degrees after being rubbed 4000 times), so that the metal protective agent can be suitable for protecting the metal base material in use environments such as high temperature, lampblack or insolation.
The specific technical scheme is as follows:
a metal protective agent comprises a compound containing a perfluoropolyether chain as an active ingredient, wherein the structural formula of the compound is shown as a formula (a):
（a）；
in the formula, PFPE represents a perfluoropolyether chain.
The structure of the formula (a) contains phosphate groups, isocyanurate and perfluoropolyether chain segments, the three structures are divided into different parts, but are not required, wherein the phosphate groups can be chelated with metal elements, the binding force between the protective agent and the metal materials is increased, and the benzene ring on the phosphate can improve the temperature resistance; the isocyanurate not only can improve the temperature resistance and weather resistance, but also can play a role in connecting a perfluoropolyether chain and a phosphate group; the perfluor polyether chain segment promotes the hydrophobicity and the oleophobicity of the protective agent, and the three groups can react and simultaneously provide different effects for the effective components of the metal protective agent in a multi-dimensional manner.
In the invention, the perfluoropolyether chain contained in the compound serving as the effective component of the metal protective agent is Z-type perfluoropolyether chain or K-type perfluoropolyether chain.
The invention introduces the perfluoropolyether chain into the active ingredient compound of the metal protective agent through the reaction of the perfluoropolyether acyl fluoride and the hydroxyl. Although the structure of the perfluoropolyether chain in the prior art is mainly four, namely K, Z, D, Y type, the invention combines the wear resistance and the economic applicability of the metal protective agent, and preferably adopts two types of perfluoropolyether chains, namely Z type and K type.
The structural formula of the Z-type perfluoropolyether chain is as follows: CF (compact flash) 3 (CF 2 CF 2 O) p (CF 2 O) q CF 2 -。
The structural formula of the K-type perfluoropolyether chain is as follows: CF (compact flash) 3 CF 2 CF 2 O[CF(CF 3 )CF 2 O] n CF(CF 3 )-。
Preferably, the perfluoropolyether chain is a Z-type perfluoropolyether chain, and the structural formula of the Z-type perfluoropolyether chain is CF 3 (CF 2 CF 2 O) p (CF 2 O) q CF 2 -wherein p is an integer between 1 and 15 and q is an integer between 1 and 15. The structure of the Z-type perfluoropolyether chain is linear, which is helpful for improving the wear resistance of the protective agent.
In the present invention, the perfluoropolyether chain contained in the compound as an active ingredient of the metal protectant has a weight average molecular weight of 500 to 2000g/mol.
The molecular weight of the PFPE molecular chain is selected within the range by comprehensively considering the wear resistance, hydrophobicity and oleophobicity of the metal protective agent and whether the metal protective agent can form a uniform and thin coating on the metal surface. Taking K-type PFPE molecular chain as an example, when the molecular weight is larger than 2000g/mol, the viscosity of the PFPE molecular chain can reach 50CST, and if the molecular weight is continuously increased, the viscosity is continuously increased, so that the coating of the metal protective agent on the metal surface is not facilitated. And when the molecular weight of the PFPE molecular chain is lower than 500g/mol, firstly, the abrasion resistance is obviously reduced, and secondly, the synthesis difficulty of PFPE with lower molecular weight is increased, and the PFPE is difficult to obtain.
In the invention, the preparation raw materials of the effective components of the metal protective agent comprise trishydroxyethyl isocyanurate, o-tolyl chlorophosphate and perfluoropolyether acyl fluoride.
Trihydroxyethyl isocyanurate:. The tris (hydroxyethyl) isocyanurate has 3 hydroxyl groups which can react, so that the molecular structure of the obtained metal protective agent can be adjusted by adjusting the molar ratio of the reaction.
O-tolyl chlorophosphate:。
perfluoro polyether acyl fluoride, C 6 F 12 O 2 ，。
In the invention, the preparation raw material of the active ingredient of the metal protective agent is tris (hydroxyethyl) isocyanurate: o-tolyl chlorophosphate: the molar ratio of the perfluoro polyether acyl fluoride is 1:1:2-2.5.
In the invention, the metal protective agent also comprises a diluent; the metal protective agent contains 15-25wt% of effective components. Compared with the metal protective agent in the prior art, the metal protective agent has the advantages of less consumption of active ingredients, low viscosity, easy formation of a compact and uniform protective layer and lower use cost.
The preparation method of the metal protective agent comprises the steps of firstly preparing active ingredients; then diluting the prepared active ingredient. The method specifically comprises the following steps:
(1) Under the inert gas atmosphere, firstly, uniformly stirring the tris (hydroxyethyl) isocyanurate, an alkaline catalyst and a solvent to obtain a mixed solution;
then dropwise adding o-tolyl chlorophosphate into the mixed solution under the stirring condition, and reacting for 6-8 hours at the temperature of 85-95 ℃ after the dropwise adding is finished to obtain an intermediate A.
(2) Under the inert gas atmosphere, the obtained intermediate A is dissolved in a solvent, then the perfluoropolyether acyl fluoride is added, and the mixture is reacted for 4 to 6 hours at the constant temperature of 55 to 65 ℃ to obtain an active ingredient solution.
(3) And (3) adding a diluent into the active ingredient solution obtained in the step (2) for dilution, and thus obtaining the metal protective agent.
The synthetic route is as follows:
；
wherein PFPE-COF represents perfluoropolyether acyl fluoride.
In the invention, in the step (1) of the preparation method of the metal protective agent, the alkaline catalyst comprises the following components: the mol ratio of the trihydroxyethyl isocyanuric acid ester is 0.05-0.15:1; intermediate a in step (2): the molar ratio of the perfluoro polyether acyl fluoride is 1 (2-2.5).
In the invention, the alkaline catalyst in the step (1) of the preparation method of the metal protective agent is one or more of potassium hydroxide, sodium hydroxide, potassium carbonate and triethylamine. Preferably, the basic catalyst is potassium hydroxide.
In the invention, the solvent in the step (1) of the preparation method of the metal protective agent is one or more of anhydrous methanol, anhydrous ethanol and hydrofluoroether. Preferably, the solvent is absolute ethanol.
In the invention, the solvent in the step (2) of the preparation method of the metal protective agent is hydrofluoroether.
In the invention, the diluent in the step (3) of the preparation method of the metal protective agent is hydrofluoroether.
A metal protective coating adopts the metal protective agent or the metal protective agent prepared by the preparation method.
The metal protective agent is coated on a substrate, the thickness of the formed metal protective coating is generally 60-80nm, and the surface of the metal protective coating is compact and uniform and is abrasion-resistant, hydrophobic and oleophobic and resistant to high temperature and ultraviolet rays. However, if the existing metal protective agent is intended to form the metal protective coating with the above effects, the thickness of the coating needs to be at least several hundred nanometers and even micrometers. In this way, the risk of film falling off is increased and the use cost is higher.
The preparation method of the metal protective coating comprises the following steps:
(1) Adding the metal protective agent into a solvent hydrofluoroether to obtain a surface treatment liquid with the metal protective agent content of 2-5 wt%;
(2) And (3) coating the surface treatment liquid obtained in the step (1) on a metal substrate, and curing for 15-20min at 130-150 ℃ to obtain the metal protective coating.
Therefore, the effective components in the metal protective agent have excellent heat resistance, weather resistance, hydrophobicity and oleophobicity and wear resistance, and the effectiveness of the components is exerted to the greatest extent, so that when the metal protective agent is used for forming a metal protective coating, the metal protective agent is firstly diluted again to form a surface treatment liquid with the metal protective agent content of only 2-5 wt%o, and then sprayed on a metal substrate for curing, and the formed metal protective coating still has excellent protective effect. Thus, compared with the existing metal protective agent, the metal protective agent achieves the same protective effect, the dosage of the metal protective agent only needs 40-50% of the dosage of the existing metal protective agent, and the use cost is greatly reduced.
The metal protective agent or the metal protective agent prepared by the preparation method is applied to the protection of smoke machines, kitchen ranges and automobile metal shells. The metal protective agent has better temperature resistance, weather resistance, hydrophobicity and oleophobicity and certain wear resistance, and can be well suitable for high temperature, lampblack or insolation conditions, so that the metal protective agent can be applied to the relevant fields of smoke machines, kitchen ranges and the like with higher temperature and more greasy dirt in use environments; the method can also be applied to the fields of automobile metal shells and the like which are always in the exposure environment.
The beneficial effects of the invention are as follows: the invention directly endows the effective components of the metal protective agent with various effects by chemical means, and can form a thin, compact and uniform protective coating with strong binding force on the metal surface by using the low-concentration metal protective agent by a simple and efficient method, so that the glossiness of a base material is not changed, and the use cost is reduced.
(1) The active ingredients of the metal protective agent of the invention simultaneously introduce a perfluoropolyether chain, a phosphate group, a benzene ring and an isocyanurate structure, so that the metal base material can be used for a long time even if being exposed to high temperature, lampblack and high ultraviolet environment.
(2) The base material has better temperature resistance, weather resistance, hydrophobicity and oleophobicity and certain wear resistance, the initial contact angle reaches 110 degrees, the oil contact angle reaches 75 degrees, and the surface of the treated base material can resist steel wool friction 3000-4000 times. After baking at 200 ℃ for 8 hours, the coating did not fall off and the water contact angle was still greater than 100 °.
(3) The technical scheme provided by the invention is simple to operate and mild in condition.
Drawings
FIG. 1 is a spectrum of nuclear magnetic resonance hydrogen spectrum of perfluoropolyether chain compound containing effective component of metal protectant described in example 4.
Detailed Description
For a better understanding of the present invention, the present invention is further illustrated by the following examples.
1. The sources of the reagents used are as follows:
the hydrofluoroether solvent was HFE-7200 available from 3M company.
The perfluoropolyether acyl fluoride is a commercial product.
Trihydroxyethyl isocyanurate, o-tolyl chlorophosphate, and triethylamine were purchased from Alatine.
Methanol, ethanol, KOH, potassium carbonate were all purchased from Kande Co., ltd.
2. The chromatographic column separation is operated as follows: the chromatographic column is separated by using a sand plate chromatographic column, the outer diameter of the chromatographic column is 46mm, the aperture of a throttle is 2mm, the height of a packed column is 6-8cm, and the size of silica gel is 200-300 meshes.
3. The operation of the reduced pressure distillation is as follows: the reduced pressure distillation temperature is 45-65deg.C, the time is 10-30min, and the pressure is-0.1 MPa.
4. The extraction operation is as follows: the extractant is methanol, the extraction temperature is normal temperature, and the product is positioned in the lower layer.
5. The filtering operation is as follows: the filtration was carried out using a mobile phase filter of model euphoria F10401L (with a flange with a sand core).
Example 1
The structural formula of the effective component of the metal protective agent containing the perfluoropolyether chain compound is shown as the following formula:
。
wherein PFPE is a Z-type perfluoropolyether chain having a molecular chain structure of CF 3 (CF 2 CF 2 O) p (CF 2 O) q CF 2 -, p is 2 and q is 2.
The metal protective agent consists of a diluent and the active ingredients, wherein the content of the active ingredients is 15wt%, and the active ingredients are raw material of the tris (hydroxyethyl) isocyanurate: o-tolyl chlorophosphate: the molar ratio of the perfluoro polyether acyl fluoride is 1:1:2.5.
The preparation method of the metal protective agent comprises the following steps:
(1) Into a four-necked flask equipped with a stirring device, a thermometer and a condenser, 20g (0.077 mol) of tris (hydroxyethyl) isocyanurate, 0.5g (0.0089 mol) of potassium hydroxide and 40g of absolute ethanol were charged under an inert gas atmosphere, and stirred until dissolved.
23g (0.0775 mol) of o-tolyl chlorophosphate was slowly dropped into the mixture under stirring by using a constant pressure dropping funnel, and reacted at 90℃for 6 hours.
After the completion of the reaction, 40g of intermediate A was obtained by separation with a column chromatography and distillation under reduced pressure.
(2) 40g of intermediate A was dissolved in 150g of a hydrofluoroether solvent, 96g (0.192 mol) of perfluoropolyether acyl fluoride (Mw weight average molecular weight=500 g/mol) was added and reacted at 60℃for 4 hours.
After the reaction is finished, extracting, filtering by a precise instrument and distilling under reduced pressure to obtain an active ingredient solution.
(3) And (3) adding a diluent of hydrofluoroether into the active ingredient solution obtained in the step (2) to dilute until the content of the active ingredient is 15wt%, thus obtaining the metal protective agent.
Example 2
The structural formula of the effective component of the metal protective agent containing the perfluoropolyether chain compound is shown as the following formula:
。
wherein the PFPE has the structural formula of CF 3 (CF 2 CF 2 O) p (CF 2 O) q CF 2 -, p is 5, q is 5.
The content of active ingredients in the metal protective agent is 20wt% and the raw material of the active ingredients is the tris (hydroxyethyl) isocyanurate: o-tolyl chlorophosphate: the molar ratio of the perfluoro polyether acyl fluoride is 1:1:2.
The preparation method of the metal protective agent comprises the following steps:
(1) Into a four-necked flask equipped with a stirring device, a thermometer and a condenser, 20g (0.077 mol) of tris (hydroxyethyl) isocyanurate, 0.5g (0.0089 mol) of sodium hydroxide and 40g of absolute ethanol were charged under an inert gas atmosphere, and stirred until dissolved.
23g (0.0775 mol) of o-tolyl chlorophosphate was slowly dropped into the mixture under stirring by using a constant pressure dropping funnel, and reacted at 90℃for 6 hours.
After the completion of the reaction, 40g of intermediate A was obtained by separation with a column chromatography and distillation under reduced pressure.
(2) 40g of intermediate A was dissolved in 200g of a hydrofluoroether solvent, 153g (0.153 mol) of perfluoropolyether acyl fluoride (Mw=1000 g/mol) was added and reacted at 60℃for 4.5h.
After the reaction is finished, extracting, filtering by a precise instrument and distilling under reduced pressure to obtain an active ingredient solution.
(3) And (3) adding a diluent of hydrofluoroether into the active ingredient solution obtained in the step (2) to dilute until the content of the active ingredient is 20wt%, thus obtaining the metal protective agent.
Example 3
The structural formula of the effective component of the metal protective agent containing the perfluoropolyether chain compound is shown as the following formula:
。
wherein the PFPE has the structural formula of CF 3 (CF 2 CF 2 O) p (CF 2 O) q CF 2 P is 8,q and 7.
The content of active ingredients in the metal protective agent is 25wt%, and the active ingredients are raw material of the tris (hydroxyethyl) isocyanurate: o-tolyl chlorophosphate: the molar ratio of the perfluoro polyether acyl fluoride is 1:1:2.
The preparation method of the metal protective agent comprises the following steps:
(1) Into a four-necked flask equipped with a stirring device, a thermometer and a condenser, 20g (0.077 mol) of tris (hydroxyethyl) isocyanurate, 0.5g (0.0089 mol) of potassium hydroxide and 40g of anhydrous methanol were charged under an inert gas atmosphere, and stirred until dissolved.
23g (0.0775 mol) of o-tolyl chlorophosphate was slowly dropped into the mixture under stirring by using a constant pressure dropping funnel, and reacted at 90℃for 6 hours.
After the completion of the reaction, 40g of intermediate A was obtained by separation with a column chromatography and distillation under reduced pressure.
(2) 40g of intermediate A was dissolved in 300g of a hydrofluoroether solvent, 230g (0.153 mol) of perfluoropolyether acyl fluoride (Mw=1500 g/mol) was added and reacted at 60℃for 5h.
After the reaction is finished, extracting, filtering by a precise instrument and distilling under reduced pressure to obtain an active ingredient solution.
(3) And (3) adding a diluent of hydrofluoroether into the active ingredient solution obtained in the step (2) to dilute until the content of the active ingredient is 25wt%, thus obtaining the metal protective agent.
Example 4
The structural formula of the effective component of the metal protective agent containing the perfluoropolyether chain compound is shown as the following formula:
。
wherein the PFPE has the structural formula of CF 3 (CF 2 CF 2 O) p (CF 2 O) q CF 2 -, p is 10 and q is 11.
The content of active ingredients in the metal protective agent is 20wt% and the raw material of the active ingredients is the tris (hydroxyethyl) isocyanurate: o-tolyl chlorophosphate: the molar ratio of the perfluoro polyether acyl fluoride is 1:1:2.
The preparation method of the metal protective agent comprises the following steps:
(1) Into a four-necked flask equipped with a stirring device, a thermometer and a condenser, 20g (0.077 mol) of tris (hydroxyethyl) isocyanurate, 0.5g (0.0089 mol) of triethylamine and 40g of absolute ethanol were charged under an inert gas atmosphere, and stirred until dissolved.
23g (0.0775 mol) of o-tolyl chlorophosphate was slowly dropped into the mixture under stirring by using a constant pressure dropping funnel, and reacted at 90℃for 6 hours.
After the completion of the reaction, 40g of intermediate A was obtained by separation with a column chromatography and distillation under reduced pressure.
(2) 40g of intermediate A was dissolved in 400g of a hydrofluoroether solvent, and 306g (0.153 mol) of perfluoropolyether acyl fluoride (Mw=2000 g/mol) was added and reacted at 60℃for 6h.
After the reaction is finished, extracting, filtering by a precise instrument and distilling under reduced pressure to obtain an active ingredient solution.
(3) And (3) adding a diluent of hydrofluoroether into the active ingredient solution obtained in the step (2) to dilute until the content of the active ingredient is 20wt%, thus obtaining the metal protective agent.
As shown in fig. 1: the peaks at 2.2ppm and 3.85-3.89ppm in the spectrum are methyl peaks on benzene ring, the peak at 4.29-4.43ppm is methylene peak directly connected with nitrogen atom, the peak at 4.40-4.43ppm is methylene peak connected with ester group, the peak at 4.29-4.34ppm is methylene peak connected with oxygen and phosphoric acid group, the peak area ratio of the two peaks is 2:1, and the peak at 7.05-7.36ppm is hydrogen peak on benzene ring, which can prove that the reaction happens successfully.
Example 5
The structural formula of the effective component of the metal protective agent containing the perfluoropolyether chain compound is shown as the following formula:
。
wherein the PFPE has the structural formula of CF 3 (CF 2 CF 2 O) p (CF 2 O) q CF 2 -, p is 10 and q is 11.
The content of active ingredients in the metal protective agent is 20wt% and the raw material of the active ingredients is the tris (hydroxyethyl) isocyanurate: o-tolyl chlorophosphate: the molar ratio of the perfluoro polyether acyl fluoride is 1:1:2.
The preparation method of the metal protective agent comprises the following steps:
(1) Into a four-necked flask equipped with a stirring device, a thermometer and a condenser, 20g (0.077 mol) of tris (hydroxyethyl) isocyanurate, 0.5g (0.0089 mol) of potassium hydroxide and 40g of absolute ethanol were charged under an inert gas atmosphere, and stirred until dissolved.
23g (0.0775 mol) of o-tolyl chlorophosphate was slowly dropped into the mixture under stirring by using a constant pressure dropping funnel, and the mixture was reacted at 95℃for 7 hours.
After the completion of the reaction, 40g of intermediate A was obtained by separation with a column chromatography and distillation under reduced pressure.
(2) 40g of intermediate A was dissolved in 400g of a hydrofluoroether solvent, and 306g (0.153 mol) of perfluoropolyether acyl fluoride (Mw=2000 g/mol) was added and reacted at 65℃for 4h.
And after the reaction is accepted, extracting, filtering by a precise instrument and distilling under reduced pressure to obtain an active ingredient solution.
(3) And (3) adding a diluent of hydrofluoroether into the active ingredient solution obtained in the step (2) to dilute until the content of the active ingredient is 20wt%, thus obtaining the metal protective agent.
Example 6
The structural formula of the effective component of the metal protective agent containing the perfluoropolyether chain compound is shown as the following formula:
。
wherein the PFPE has the structural formula of CF 3 (CF 2 CF 2 O) p (CF 2 O) q CF 2 -, p is 10 and q is 11.
The content of active ingredients in the metal protective agent is 20wt% and the raw material of the active ingredients is the tris (hydroxyethyl) isocyanurate: o-tolyl chlorophosphate: the molar ratio of the perfluoro polyether acyl fluoride is 1:1:2.
The preparation method of the metal protective agent comprises the following steps:
(1) Into a four-necked flask equipped with a stirring device, a thermometer and a condenser, 20g (0.077 mol) of tris (hydroxyethyl) isocyanurate, 0.5g (0.0089 mol) of potassium hydroxide and 40g of absolute ethanol were charged under an inert gas atmosphere, and stirred until dissolved.
23g (0.0775 mol) of o-tolyl chlorophosphate was slowly dropped into the mixture under stirring by using a constant pressure dropping funnel, and reacted at 85℃for 8 hours.
After the completion of the reaction, 40g of intermediate A was obtained by separation with a column chromatography and distillation under reduced pressure.
(2) 40g of intermediate A was dissolved in 400g of a hydrofluoroether solvent, and 306g (0.153 mol) of perfluoropolyether acyl fluoride (Mw=2000 g/mol) was added and reacted at 55℃for 5h.
And after the reaction is accepted, extracting, filtering by a precise instrument and distilling under reduced pressure to obtain an active ingredient solution.
(3) And (3) adding a diluent of hydrofluoroether into the active ingredient solution obtained in the step (2) to dilute until the content of the active ingredient is 20wt%, thus obtaining the metal protective agent.
Example 7
The structural formula of the effective component of the metal protective agent containing the perfluoropolyether chain compound is shown as the following formula:
。
wherein PFPE is a K-type perfluoropolyether chain, and the molecular chain structure is CF 3 CF 2 CF 2 O[CF(CF 3 )CF 2 O] n CF(CF 3 )-，n=4，Mw=1000g/mol。
The content of active ingredients in the metal protective agent is 20wt% and the raw material of the active ingredients is the tris (hydroxyethyl) isocyanurate: o-tolyl chlorophosphate: the molar ratio of the perfluoro polyether acyl fluoride is 1:1:2.
The preparation method of the metal protectant in this example is the same as that in example 2.
And adding a diluent hydrofluoroether into the obtained active ingredient solution to dilute until the content of the active ingredient is 20wt%, thus obtaining the metal protective agent.
Comparative example 1
The structural formula of the metal protective agent of the comparative example, the effective component of which contains the perfluoropolyether chain compound, is shown as the following formula:
。
wherein the PFPE has the structural formula of CF 3 (CF 2 CF 2 O) p (CF 2 O) q CF 2 -, p is 2,q is 2.
The content of active ingredients in the metal protective agent is 20wt% and the raw material of the active ingredients is the tris (hydroxyethyl) isocyanurate: o-tolyl chlorophosphate: the molar ratio of the perfluoro polyether acyl fluoride is 1:2:2.5.
The preparation method of the metal protective agent in the comparative example comprises the following steps:
(1) 20g (0.077 mol) of tris (hydroxyethyl) isocyanurate, 2g (0.036 mol) of potassium hydroxide and 100g of absolute ethanol were charged into a four-necked flask equipped with a stirring device, a thermometer and a condenser under an inert gas atmosphere, and stirred until dissolved.
46g (0.155 mol) of o-tolyl chlorophosphate was slowly dropped into the mixture under stirring by using a constant pressure dropping funnel, and reacted at 90℃for 6 hours.
After the completion of the reaction, 40g of intermediate A was obtained by separation with a column chromatography and distillation under reduced pressure.
(2) 40g of intermediate A was dissolved in 200g of fluoroether solvent, 96g (0.192 mol) of perfluoropolyether acyl fluoride (Mw=500 g/mol) was added thereto and reacted at 60℃for 4 hours.
After the reaction is finished, extracting, filtering by a precise instrument and distilling under reduced pressure to obtain an active ingredient solution.
(3) And (3) adding a diluent of hydrofluoroether into the active ingredient solution obtained in the step (2) to dilute until the content of the active ingredient is 20wt%, thus obtaining the metal protective agent of the comparative example.
Structurally, the metal protectant active ingredient in this comparative example contains 2 phosphate groups and 1 PFPE molecular chain in its structure.
Comparative example 2
The structural formula of the metal protective agent of the comparative example, the effective component of which contains the perfluoropolyether chain compound, is shown as the following formula:
。
wherein the PFPE has the structural formula of CF 3 O(CF 2 CF 2 O) p (CF 2 O) q CF 2 -, p is 5, q is 5.
The metal protective agent comprises 25 weight percent of active ingredients, wherein the active ingredients are prepared from the raw materials of trishydroxyethyl isocyanurate and perfluoropolyether acyl fluoride, and the trishydroxyethyl isocyanurate: the molar ratio of the perfluoro polyether acyl fluoride is 1:2.
The preparation method of the metal protective agent comprises the following specific steps:
20g (0.077 mol) of tris (hydroxyethyl) isocyanurate are dissolved in 400g of hydrofluoroether solvent, and 153g (0.153 mol) of perfluoropolyether acyl fluoride (Mw=1000 g/mol) are added and reacted at 60℃for 4.5h.
After the reaction is finished, extracting and decompressing and distilling to obtain an active ingredient solution.
And (3) adding a diluent hydrofluoroether into the obtained active ingredient solution to dilute until the content of the active ingredient is 25wt%, thus obtaining the metal protective agent of the comparative example.
Comparative example 3
The structural formula of the active ingredient compound of the metal protective agent of the comparative example is shown as the following formula:
。
the metal protective agent comprises 20 weight percent of active ingredients, wherein the active ingredients are prepared from the raw materials of trishydroxyethyl isocyanurate and o-tolyl chlorophosphate, and the trishydroxyethyl isocyanurate is prepared from the following components in percentage by weight: the molar ratio of the o-tolyl chlorophosphate is 1:1.
The preparation method of the metal protective agent comprises the following specific steps:
20g (0.077 mol) of tris (hydroxyethyl) isocyanurate, 0.5g (0.0089 mol) of potassium hydroxide and 40g of absolute ethanol were charged into a four-necked flask equipped with a stirring device, a thermometer and a condenser under an inert gas atmosphere, and stirred until dissolved.
23g (0.0775 mol) of o-tolyl chlorophosphate was slowly dropped into the mixture under stirring by using a constant pressure dropping funnel, and reacted at 90℃for 6 hours.
Separating by chromatography column and distilling under reduced pressure after reaction to obtain effective component solution.
And (3) adding a diluent hydrofluoroether into the obtained active ingredient solution to dilute until the content of the active ingredient is 25wt%, thus obtaining the metal protective agent of the comparative example.
Comparative example 4
The structural formula of the metal protective agent of the comparative example is shown as follows:
。
wherein the PFPE has the structural formula of CF 3 (CF 2 CF 2 O) p (CF 2 O) q CF 2 -, p is 10 and q is 11.
The content of active ingredients in the metal protective agent is 25wt%, and the active ingredients are raw material of the tris (hydroxyethyl) isocyanurate: o-tolyl chlorophosphate: the molar ratio of the perfluoro polyether acyl fluoride is 1:1:2.
The preparation method of the metal protective agent comprises the following steps:
(1) 20g (0.077 mol) of tris (hydroxyethyl) isocyanurate, 0.5g (0.0089 mol) of potassium hydroxide and 40g of absolute ethanol were charged into a four-necked flask equipped with a stirring device, a thermometer and a condenser under an inert gas atmosphere, and stirred until dissolved.
23g (0.0775 mol) of o-tolyl chlorophosphate was slowly dropped into the mixture under stirring by using a constant pressure dropping funnel, and the mixture was reacted at 50℃for 4 hours.
After the completion of the reaction, 40g of intermediate A was obtained by separation with a column chromatography and distillation under reduced pressure.
(2) 40g of intermediate A was dissolved in 400g of a hydrofluoroether solvent, and 306g (0.153 mol) of perfluoropolyether acyl fluoride (Mw=2000 g/mol) was added and reacted at 90℃for 8h.
After the reaction is finished, extracting, filtering by a precise instrument and distilling under reduced pressure to obtain an active ingredient solution.
(3) And (3) adding a diluent of hydrofluoroether into the active ingredient solution obtained in the step (2) to dilute until the content of the active ingredient is 25wt%, thus obtaining the metal protective agent of the comparative example.
Experimental example 1
1. The purpose of the experiment is as follows: the properties of the metal shield formed using the metal shield described in examples 1 to 7 and comparative examples 1 to 4, including temperature resistance, weather resistance, hydrophobicity, oleophobicity and abrasion resistance, were examined.
2. The experimental method comprises the following steps:
(1) The stock solutions of the metal protectants obtained in examples 1 to 7 and comparative examples 1 to 4 were dissolved in a hydrofluoroether solvent and diluted to a concentration of 20% by weight to obtain a diluted solution of the stock solution of the metal protectant.
(2) 1g of stock solution dilution with the mass fraction of 20wt% obtained in the step (1) is taken and added into 199g of hydrofluoroether solvent, so as to obtain 5 wt%o of surface treatment solution.
(3) Spraying the surface treatment liquid prepared in the step (2) on a 304 stainless steel sheet, and curing for 30min at 130 ℃ to obtain the metal protective layer with the thickness of 65 nm.
(4) The contact angle, the friction resistance, the weather resistance and the temperature resistance of the metal protective layer are tested, and the specific operation is as follows:
a. water and oil contact angle test: the measurement is carried out at room temperature, the sample to be measured is tiled on a horizontal platform of a contact angle tester, the size of water drops/oil drops is 2 mu L, 3 points are measured on the same sample, and the average value is taken.
b. Abrasion resistance test: the stainless steel sheet was placed horizontally, and steel wool (Bonstar#0000, size 5 mm. Times.10 mm) was brought into contact with the side of the stainless steel sheet coated with the surface treatment liquid, and a load of 1kg was applied thereto, and the steel wool was reciprocated at a speed of 50 times/min. The static contact angle of water was measured at regular intervals (1000 times) until the measurement of the water contact angle was terminated at less than 100 °.
c. Weather resistance test: the irradiation illuminance was 0.63W/m using a UV-B313 UV light source 2 The static contact angle of water is measured on the surface of the irradiated stainless steel sheet coated with the surface treatment liquid, and the contact angle can be maintained for a time of 100 ° or more.
d. Temperature resistance test: the sample stainless steel sheet is baked for 8 hours at 180-200 ℃, and the water contact angle is detected until the measured value is smaller than 100 degrees.
3. Experimental results:
1. the water and oil contact angles represent the hydrophobicity and oleophobicity of the metal protective layer formed by the obtained metal protective agent, and the test results are shown in table 1.
TABLE 1 results of Metal protective layer Water and oil contact Angle test
。
2. The wear resistance can show the binding force strength of the metal protective layer formed by the obtained metal protective agent to a certain extent, and the test results are shown in table 2.
Table 2 results of abrasion resistance test of metal protective layer
。
3. The weathering resistance QUV aging test is an artificial weathering test method for simulating the exposure of materials in outdoor environments, such as durability under conditions of sun exposure, uv radiation, and humidity changes. The QUV test can help determine the life of a material and evaluate its performance change under different circumstances. The test results are shown in Table 3.
TABLE 3 weathering resistance test results of metal protective layer
。
4. The test results of the temperature resistance are shown in table 4.
TABLE 4 results of temperature resistance test of metallic protective layer
。
From the data, the metal protective layer formed by the metal protective agent has better hydrophobicity, good wear resistance, good weather resistance and good temperature resistance, wherein each performance of the embodiment 4 is optimal. Therefore, the metal protective agent is applied to the surface of a metal substrate in high-temperature, oil fume and exposure use environments, and can endow the metal substrate with better temperature resistance, weather resistance, hydrophobicity and oleophobicity and certain wear resistance.
Claims (8)
1. The metal protective agent is characterized in that the active ingredient is a compound containing a perfluoropolyether chain, and the structural formula of the compound is shown as a formula (a):
（a）；
wherein PFPE represents a perfluoropolyether chain;
the perfluoropolyether chain is a Z-type perfluoropolyether chain or a K-type perfluoropolyether chain;
the weight average molecular weight of the perfluoropolyether chain is 500-2000g/mol;
the preparation raw materials of the active ingredients comprise trihydroxyethyl isocyanurate, o-tolyl chlorophosphate and perfluoropolyether acyl fluoride;
the tris (hydroxyethyl) isocyanurate: o-tolyl chlorophosphate: the molar ratio of the perfluoro polyether acyl fluoride is 1:1:2-2.5;
the active ingredients are prepared by the following steps:
(1) Under the inert gas atmosphere, firstly, mixing and stirring the tri-hydroxyethyl isocyanurate, the alkaline catalyst and the solvent to obtain a mixed solution;
then dropwise adding o-tolyl chlorophosphate into the mixed solution under the stirring condition, and reacting for 6-8 hours at the temperature of 85-95 ℃ after the dropwise adding is finished to obtain an intermediate A;
(2) Under the inert gas atmosphere, the obtained intermediate A is dissolved in a solvent, then the perfluoro polyether acyl fluoride is added, and the reaction is carried out for 4 to 6 hours at the temperature of 55 to 65 ℃ to obtain an active ingredient solution.
2. The metal shielding agent of claim 1, further comprising a diluent; the content of the effective components in the metal protective agent is 15-25wt%.
3. The metal protectant of claim 1, wherein in step (1), the basic catalyst: the mol ratio of the trihydroxyethyl isocyanuric acid ester is 0.05-0.15:1;
intermediate a in step (2): the molar ratio of the perfluoro polyether acyl fluoride is 1 (2-2.5).
4. The metal shielding agent according to claim 1, wherein the basic catalyst in the step (1) is one or more of potassium hydroxide, sodium hydroxide, potassium carbonate and triethylamine;
the solvent in the step (1) is one or more of absolute methanol, absolute ethanol and hydrofluoroether;
the solvent in the step (2) is hydrofluoroether.
5. A metal protective coating employing the metal protective agent of any one of claims 1-4.
6. The metallic protective coating of claim 5, wherein the metallic protective agent is coated on the substrate at a thickness of 60-80nm.
7. The method of producing a metallic protective coating as claimed in claim 5 or 6, comprising the steps of:
(1) Adding the metal protective agent into a solvent to obtain a surface treatment liquid with the metal protective agent content of 2-5 wt%;
(2) And (3) coating the surface treatment liquid obtained in the step (1) on a metal substrate, and curing for 15-20min at 130-150 ℃ to obtain the metal protective coating.
8. Use of the metal protective agent according to any one of claims 1 to 4 or the metal protective coating according to claim 5 for the protection of smoke machines, kitchen ranges and automotive metal housings.
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| CN116003770A (en) * | 2022-12-23 | 2023-04-25 | 湖南柯盛新材料有限公司 | Perfluoro polyether phosphate compound and preparation method and application thereof |
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