CN114410218A - Preparation method of polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-titanium dioxide composite coating - Google Patents
Preparation method of polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-titanium dioxide composite coating Download PDFInfo
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- CN114410218A CN114410218A CN202210165854.XA CN202210165854A CN114410218A CN 114410218 A CN114410218 A CN 114410218A CN 202210165854 A CN202210165854 A CN 202210165854A CN 114410218 A CN114410218 A CN 114410218A
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- titanium dioxide
- stearic acid
- polyphenylene sulfide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 69
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 68
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 61
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 61
- 238000000576 coating method Methods 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000011248 coating agent Substances 0.000 title claims abstract description 47
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008117 stearic acid Substances 0.000 claims abstract description 13
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 12
- AVYGCQXNNJPXSS-UHFFFAOYSA-N 2,5-dichloroaniline Chemical compound NC1=CC(Cl)=CC=C1Cl AVYGCQXNNJPXSS-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 43
- 230000007797 corrosion Effects 0.000 abstract description 42
- -1 stearic acid modified titanium dioxide Chemical class 0.000 abstract description 3
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 abstract 1
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000005028 tinplate Substances 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GMMZXKSNKIUKOW-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].C(C)O Chemical class [O-2].[O-2].[Ti+4].C(C)O GMMZXKSNKIUKOW-UHFFFAOYSA-N 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005616 pyroelectricity Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 1
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
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- 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
- C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
- C09D181/02—Polythioethers; Polythioether-ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Abstract
The invention provides a preparation method of a polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-titanium dioxide composite coating, which is obtained by mixing stearic acid modified titanium dioxide with aminated polyphenylene sulfide and polyvinylidene fluoride, adding a catalyst isobutyl titanate, and carrying out curing reaction for 2-3 h at 180-220 ℃. The aminated polyphenylene sulfide has excellent corrosion resistance, the mechanical property and the corrosion resistance of the coating can be improved by adding the polyvinylidene fluoride, and the hydrophobicity of the surface of the coating can be improved by the modified titanium dioxide, so that the composite coating has lower corrosion current density, excellent hydrophobicity and corrosion resistance. The composite coating can play a role in protecting the metal surface, and can also be used for protecting a ship body and constructing objects on land.
Description
Technical Field
The invention relates to polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-TiO2A preparation method of a composite coating belongs to the technical field of composite materials and the field of anticorrosive coatings.
Background
Polyphenylene sulfide is a high performance engineering polymer with high thermal stability, good mechanical properties, chemical resistance, flammability and high dimensional stability. Therefore, the outstanding characteristics of PPS make it widely used in various fields of filters for chemical and industrial facilities, heat sensors, automobiles, aerospace industry, and oceans. PPS is called "plastic gold", and is called six special engineering plastics together with Polysulfone (PSF), Polyarylate (PAR), polyether ether ketone (PEEK), Polyimide (PI) and Liquid Crystal Polymer (LCP), and is also one of eight aerospace materials. The high-quality composite material is characterized in that a main chain formed by connecting a rigid benzene ring and a flexible thioether bond has the characteristics of rigidity and flexibility, the microscopic form of the polyphenylene sulfide has structures such as lamellar, hollow spherical, rod-shaped and flower-shaped structures, and the polyphenylene sulfide has good compatibility, so that the polyphenylene sulfide can be modified by means of blending, chemical mixing and the like, and the high-quality composite material is obtained and used in the field of coatings with anticorrosion performance.
The polyvinylidene fluoride (PVDF) resin is a vinylidene fluoride (VDF) homopolymer or a copolymer of VDF and other small amount of fluorine-containing vinyl monomers, the relative molecular mass is 40-60 ten thousand, and the repeating unit is-CH2-CF2-，CH2And CF2The alternate arrangement of the elements enables the PVDF resin to have the characteristics of both fluororesin and general resin and have excellent comprehensive performance, and the most common processes for preparing the PVDF resin are emulsion polymerization and suspension polymerization. The PVDF resin has the special performances of good chemical corrosion resistance, high temperature resistance, oxidation resistance, weather resistance, ultraviolet ray resistance, radiation resistance, piezoelectricity, pyroelectricity and the like, the application range of the PVDF resin is continuously expanded, and the PVDF resin is second to polytetrafluoroethylene in fluororesinThe 2 nd large variety of (PTFE) is widely applied to three fields of chemical equipment, electronics and electrics and architectural coatings.
Besides good catalytic performance, the titanium dioxide nano-particles can be used as a coating capable of degrading toxic gases, have good chemical stability and decontamination and self-cleaning performance, and not only are the dielectric properties of the titanium dioxide nano-particles improved, but also the super-hydrophobic properties of the titanium dioxide nano-particles can be fully reflected after the titanium dioxide nano-particles are modified by stearic acid.
Disclosure of Invention
The invention aims to provide polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-TiO2A preparation method of the composite coating.
Polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-TiO2Preparation of composite coatings
The invention relates to polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-TiO2The preparation of the composite coating comprises the following process steps:
(1) preparation of aminated polyphenylene sulfide: anhydrous sodium sulfide, p-dichlorobenzene and 2, 5-dichloroaniline are used as raw materials, N-methyl pyrrolidone is used as a solvent, isopropyl titanate is used as a catalyst, nitrogen is used as protective gas, the reaction is carried out for 1.5 to 2.5 hours at 260 to 280 ℃ in an alkaline environment, and the aminated polyphenylene sulfide is obtained by washing, filtering and drying and is marked as PPS-NH2. Wherein the mass ratio of the 2, 5-dichloroaniline to the anhydrous sodium sulfide is 1: 10-1: 15; the mass ratio of the 2, 5-dichloroaniline to the p-dichlorobenzene is 1: 10-1: 12; the mass ratio of the 2, 5-dichloroaniline to the isopropyl titanate is 1: 0.02-1: 0.05.
(2) Stearic acid-TiO2The preparation of (1): dissolving stearic acid and titanium dioxide in ethanol according to the mass ratio of 1.1: 1-1.2: 1, magnetically stirring for 1.5-2.5 h at room temperature, centrifugally washing, and drying to obtain modified titanium dioxide (stearic acid-TiO)2）。
(3) Polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-TiO2Preparing a composite coating: preparing a polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-titanium dioxide composite coating: adding aminated polyphenylene sulfide and polyvinylidene fluoride into ethanol solution of modified titanium dioxide, and performing ultrasonic dispersion and uniform mixingCombining; uniformly spraying the mixture on the surface of the metal by using a spray gun, and curing the mixture for 2 to 3 hours at 220 ℃ to obtain a polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-titanium dioxide composite coating, which is marked as PVDF/PPS-NH2Stearic acid-TiO2。Wherein the mass ratio of the aminated polyphenylene sulfide to the polyvinylidene fluoride is 1: 0.1-1: 1; polyvinylidene fluoride and stearic acid-TiO2The mass ratio of (A) to (B) is 12: 1-1: 9.
Structure and performance of polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-titanium dioxide composite coating
1. Infrared spectroscopic analysis
FIG. 1 shows stearic acid and TiO2And stearic acid-TiO2Infrared spectrum of composite material, stearic acid-TiO in composite material2Stearic acid and TiO can be found in the mid-infrared spectrogram2The characteristic peaks of (a) are all present, and the new peak just makes a mixed peak of the two, confirming the successful preparation of the composite material.
2. Analysis of hydrophobic Properties
FIG. 2 is a graph of the wetting properties of aminated polyphenylene sulfide carboxylic, polyvinylidene fluoride/aminated polyphenylene sulfide and composites with varying amounts thereof. It can be seen from the figure that the hydrophobic angle CA of the pure aminated polyphenylene sulfide is about 140 degrees, a certain amount of PVDF is added, the CA can reach 144.34 degrees, the CA of a single modified titanium dioxide coating can reach 149 degrees, and when PVDF and stearic acid-TiO are added, the PVDF and the modified titanium dioxide are added2When the content ratio is 9:1, the CA is 146.37 degrees; PVDF and stearic acid-TiO2The CA is 147.83 degrees when the content ratio is 7: 3; PVDF and stearic acid-TiO2At a content ratio of 5:5, CA is 151.29 degrees, PVDF and stearic acid-TiO2When the content ratio is 3:7, the CA reaches the maximum value of 152.27 degrees, the influence of the modified titanium dioxide on the hydrophobicity of the coating can be obviously judged, and PVDF and stearic acid-TiO2The hydrophobic property is best when the content ratio is 3: 7.
3. Polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-TiO2Impedance property of composite coating
FIG. 3 shows zeta potential polarization curves of aminated polyphenylene sulfide/polyvinylidene fluoride/stearic acid-titanium dioxide composite coatings with modified titanium dioxide content for different polyvinylidene fluorides. Test solution3.5% NaCl solution, test items: polarization curve, corrosion potential, corrosion current. The data obtained as shown in FIG. 3 were analyzed as follows, pure PPS-NH when not doped2The corrosion potential Ec of (1) Ec = 538mV and the corrosion current ic = 4.207X 10-5A/cm2High corrosion current values indicate PPS-NH2The corrosion resistance of the coating is poor, and the impedance of the coating doped with PVDF is improved to a certain extent by adding a certain amount of PVDF into the original PPS coating. When PVDF and stearic acid-TiO2When the mass ratio of (A) to (B) is 9:1, the corrosion potential of the composite coating is Ec = -645mV, and the corrosion current is ic = 8.832 × 10-6A/cm2The corrosion current becomes lower and the corrosion resistance of the composite coating is improved. When PVDF and stearic acid-TiO2At a content ratio of 7:3, PVDF/PPS-NH2Stearic acid-TiO2The corrosion potential of the composite coating is-629 mV, and the corrosion current value is ic =6.171 multiplied by 10-6A/cm2Lower corrosion current, indicating stearic acid-TiO2Certain content increase improves PVDF/PPS-NH2Stearic acid-TiO2Corrosion resistance of the composite coating. When PVDF and modified TiO2When the content ratio is 3:7, the corrosion potential is-301 mV, and the corrosion current is 3.085X 10 at the lowest-8 A/cm2Having maximum corrosion potential and minimum corrosion current when PVDF and modified TiO2When the content ratio is increased to 1:9, the corrosion potential is-429 mv, and the corrosion current becomes ic =2.182 × 10-8A/cm2Indicating that the stearic acid-TiO is continuously increased2At the content, the corrosion resistance is reduced, but pure PPS-NH2The corrosion resistance is higher than pure PPS-NH2Much higher. Taken together, it is shown that the added PVDF and modified TiO2The ratio of (A) to (B) is 3:7, the corrosion resistance of the composite coating is optimal.
In conclusion, the invention successfully prepares the polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-TiO2The stearic acid and the titanium dioxide are subjected to certain chemical bond reaction through free hydrogen bonds on the surface of the titanium dioxide and the stearic acid, and the stearic acid and the titanium dioxide are also subjected to action in a physical mixing mode, specifically, the stearic acid is in a fluid state to titanium dioxide particlesCoating is carried out, so that the modified titanium dioxide not only can keep the original good stability, but also has excellent hydrophobic property; the aminated polyphenylene sulfide, polyvinylidene fluoride and modified titanium dioxide are mixed to prepare the composite coating, so that the mechanical property and toughness of the original aminated polyphenylene sulfide are greatly improved, and the impedance of the composite coating is increased to a certain extent; the composite coating has lower corrosion current density, and the hydrophobicity and the corrosion resistance of the composite coating are greatly improved. The composite coating can play a role in protecting the metal surface, has an antifouling effect and has a wide application prospect in an anticorrosive and antifouling environment.
Drawings
FIG. 1 shows stearic acid and TiO2And stearic acid-TiO2Infrared spectrum of the composite material.
FIG. 2 is a wet performance diagram of aminated polyphenylene sulfide, modified titanium dioxide and polyvinylidene fluoride/aminated polyphenylene sulfide composite coating.
FIG. 3 is a zeta potential polarization curve diagram of polyvinylidene fluoride/aminated thiophenyl sulfide composite coatings with different modified titanium dioxide contents.
Detailed Description
The preparation and properties of the polyvinylidene fluoride/aminated polyphenylene sulfide/modified titanium dioxide composite coating of the present invention are further illustrated by the following specific examples.
Example 1
(1) Preparation of aminated polyphenylene sulfide: weighing 86.7 g of sodium sulfide nonahydrate, adding into 250mL of N-dimethyl pyrrolidone, reacting for 1.5 h at 160 ℃ in a nitrogen atmosphere to obtain a green anhydrous sodium sulfide solution, and pouring into a reaction kettle while the solution is hot; then weighing 0.2 g of catalyst isopropyl titanate, 60.13 g of p-dichlorobenzene and 5.5 g of 2, 5-dichloroaniline, adding the catalyst isopropyl titanate, introducing nitrogen, removing air in the kettle, reacting at 270 ℃ for 2 hours, repeatedly washing with deionized water and ethanol after the reaction is finished, carrying out hot filtration at 50 ℃, and freeze-drying to obtain aminated polyphenylene sulfide, which is marked as PPS-NH2。
(2) Stearic acid-TiO2The preparation of (1): dissolving stearic acid and titanium dioxide in ethanol at a ratio of 1.2:1And magnetically stirring for 2 hours at room temperature, centrifugally washing with ethanol, and drying to obtain the modified titanium dioxide.
(3) Polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-TiO2Preparing a composite coating: 0.03g of polyvinylidene fluoride and 0.1g of aminated polyphenylene sulfide are added into 0.07g of modified titanium dioxide ethanol solution with the concentration of 0.014g/mL in a physical mixing mode for ultrasonic dispersion, and then are uniformly sprayed on a clean and dry tinplate with the size of 20 multiplied by 50 multiplied by 1 mm at the speed of 5 seconds by a spray gun, and are cured for 3 hours in a tubular furnace at the temperature of 200 ℃, and then the corrosion resistance test is carried out. The corrosion resistance test is shown in FIG. 3, the corrosion potential Ec = -301mV, and the corrosion current ic = 3.085 × 10-8A/cm2。
Example 2
(1) Preparation of aminated polyphenylene sulfide: the same as example 1;
(2) stearic acid-TiO2Preparation of hydrophobic material: the same as example 1;
(3) polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-TiO2Preparing a composite coating: 0.09g of polyvinylidene fluoride and 0.1g of aminated polyphenylene sulfide are added into an ethanol solution with the concentration of 0.002g/mL and 0.01g of modified titanium dioxide by a physical mixing mode for ultrasonic dispersion, and then the mixture is uniformly sprayed on a clean and dry tinplate with the size of 20 multiplied by 50 multiplied by 1 mm at the speed of 5 seconds by a spray gun, cured for 3 hours in a tubular furnace at the temperature of 200 ℃, and then subjected to an anticorrosion test. The corrosion resistance test is shown in FIG. 3, the corrosion potential Ec = -645mV, and the corrosion current ic = 8.832 × 10-6A/cm2。
Example 3
(1) Preparation of aminated polyphenylene sulfide: the same as example 1;
(2) stearic acid-TiO2Preparation of hydrophobic material: the same as example 1;
(3) polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-TiO2Preparing a composite coating: adding 0.07g of polyvinylidene fluoride and 0.1g of aminated polyphenylene sulfide into 0.03g of modified titanium dioxide ethanol solution with the concentration of 0.006g/mL in a physical mixing mode, performing ultrasonic dispersion, and performing secondary/5 s treatment by using a spray gunThe coating is sprayed uniformly at a rate onto a clean and dry tinplate with a size of 20X 50X 1 mm, cured in a tube furnace at 200 ℃ for 3 h, and then subjected to an anticorrosion test. The corrosion resistance is tested as shown in FIG. 3, the corrosion potential Ec = -629mV, and the corrosion current is ic =6.171 × 10-6A/cm2。
Example 4
(1) Preparation of aminated polyphenylene sulfide: the same as example 1;
(2) stearic acid-TiO2Preparation of hydrophobic material: the same as example 1;
(3) polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-TiO2Preparing a composite coating: 0.01g of polyvinylidene fluoride and 0.1g of aminated polyphenylene sulfide are added into an ethanol solution with the concentration of 0.018g/mL and containing 0.09g of modified titanium dioxide by a physical mixing mode for ultrasonic dispersion, and then the mixture is uniformly sprayed on a clean and dry tinplate with the size of 20 multiplied by 50 multiplied by 1 mm at the speed of 5 seconds by a spray gun, cured for 3 hours in a tubular furnace at the temperature of 200 ℃, and then subjected to an anticorrosion test. The corrosion resistance test is shown in FIG. 3, the corrosion potential Ec = -429mV, and the corrosion current ic =2.182 × 10-8A/cm2。
Claims (7)
1. A preparation method of a polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-titanium dioxide composite coating comprises the following process steps:
(1) preparation of aminated polyphenylene sulfide: anhydrous sodium sulfide, p-dichlorobenzene and 2, 5-dichloroaniline are used as raw materials, N-methyl pyrrolidone is used as a solvent, isopropyl titanate is used as a catalyst, nitrogen is used as protective gas, the reaction is carried out for 1.5 to 2.5 hours at 260 to 280 ℃ in an alkaline environment, and the aminated polyphenylene sulfide PPS-NH is obtained by washing, filtering and drying2；
(2) Stearic acid-TiO2The preparation of (1): dissolving stearic acid and titanium dioxide in ethanol, stirring for 1.5-2.5 h at room temperature, centrifugally washing, and drying to obtain modified titanium dioxide;
(3) preparing a polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-titanium dioxide composite coating: adding aminated polyphenylene sulfide and polyvinylidene fluoride into an ethanol solution of modified titanium dioxide, and performing ultrasonic dispersion and uniform mixing; and uniformly spraying the mixture on the surface of the metal by using a spray gun, and curing and reacting for 2-3 h at 220 ℃ to obtain the polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-titanium dioxide composite coating.
2. The method for preparing a polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-titanium dioxide composite coating according to claim 1, wherein: in the step (1), the mass ratio of the 2, 5-dichloroaniline to the anhydrous sodium sulfide is 1: 10-1: 15.
3. The method for preparing a polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-titanium dioxide composite coating according to claim 1, wherein: in the step (1), the mass ratio of the 2, 5-dichloroaniline to the p-dichlorobenzene is 1: 10-1: 12.
4. The method for preparing a polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-titanium dioxide composite coating according to claim 1, wherein: in the step (1), the mass ratio of the 2, 5-dichloroaniline to the isopropyl titanate is 1: 0.02-1: 0.05.
5. The method for preparing a polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-titanium dioxide composite coating according to claim 1, wherein: in the step (2), the mass ratio of stearic acid to titanium dioxide is 1.1: 1-1.2: 1.
6. The method for preparing a polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-titanium dioxide composite coating according to claim 1, wherein: in the step (3), the mass ratio of the aminated polyphenylene sulfide to the polyvinylidene fluoride is 1: 0.1-1: 1.
7. The method for preparing a polyvinylidene fluoride/aminated polyphenylene sulfide/stearic acid-titanium dioxide composite coating according to claim 1, wherein: in the step (3), the mass ratio of the polyvinylidene fluoride to the modified titanium dioxide is 12: 1-1: 9.
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|---|---|---|---|---|
| CN114933712A (en) * | 2022-06-23 | 2022-08-23 | 西北师范大学 | Preparation and application of reduced graphene oxide grafted aminated polyphenylene sulfide composite material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3931421A (en) * | 1972-10-19 | 1976-01-06 | Phillips Petroleum Company | Coating with a dispersion of an arylene sulfide polymer containing high molecular weight fluorocarbon polymer |
| JPH0598158A (en) * | 1991-10-11 | 1993-04-20 | Dainippon Ink & Chem Inc | Slurry composition |
| JPH05295300A (en) * | 1992-04-20 | 1993-11-09 | Furukawa Electric Co Ltd:The | Powder-coating composition composed of polyphenylene sulfide resin |
| JPH0617475B1 (en) * | 1986-12-26 | 1994-03-09 | Idemitsu Petrochemical Co | |
| CN110194839A (en) * | 2019-06-25 | 2019-09-03 | 西北师范大学 | A kind of preparation and application of graphene quantum dot/polyphenyl thioether composite material |
| CN113308115A (en) * | 2021-06-11 | 2021-08-27 | 西北师范大学 | Preparation and application of modified zinc oxide-attapulgite/carboxylated polyphenylene sulfide composite material |
| CN113337205A (en) * | 2021-06-18 | 2021-09-03 | 宁夏清研高分子新材料有限公司 | Polyphenylene sulfide coating with high corrosion resistance and preparation method thereof |
-
2022
- 2022-02-23 CN CN202210165854.XA patent/CN114410218A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3931421A (en) * | 1972-10-19 | 1976-01-06 | Phillips Petroleum Company | Coating with a dispersion of an arylene sulfide polymer containing high molecular weight fluorocarbon polymer |
| JPH0617475B1 (en) * | 1986-12-26 | 1994-03-09 | Idemitsu Petrochemical Co | |
| JPH0598158A (en) * | 1991-10-11 | 1993-04-20 | Dainippon Ink & Chem Inc | Slurry composition |
| JPH05295300A (en) * | 1992-04-20 | 1993-11-09 | Furukawa Electric Co Ltd:The | Powder-coating composition composed of polyphenylene sulfide resin |
| CN110194839A (en) * | 2019-06-25 | 2019-09-03 | 西北师范大学 | A kind of preparation and application of graphene quantum dot/polyphenyl thioether composite material |
| CN113308115A (en) * | 2021-06-11 | 2021-08-27 | 西北师范大学 | Preparation and application of modified zinc oxide-attapulgite/carboxylated polyphenylene sulfide composite material |
| CN113337205A (en) * | 2021-06-18 | 2021-09-03 | 宁夏清研高分子新材料有限公司 | Polyphenylene sulfide coating with high corrosion resistance and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 李国丽等: "氟树脂防腐蚀涂层涂装工艺的研究进展", 《四川化工》 * |
| 莫春燕等: "TiO2/聚二甲基硅氧烷超疏水涂层制备及其金属防腐性能研究", 《塑料工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114933712A (en) * | 2022-06-23 | 2022-08-23 | 西北师范大学 | Preparation and application of reduced graphene oxide grafted aminated polyphenylene sulfide composite material |
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