CN115181495B - Super-amphiphobic super-weather-resistant organic silicon protective coating and preparation method thereof - Google Patents
Super-amphiphobic super-weather-resistant organic silicon protective coating and preparation method thereof Download PDFInfo
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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
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- C09D5/08—Anti-corrosive paints
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Abstract
The invention discloses a super-amphiphobic super-weather-resistant organic silicon protective coating and a preparation method thereof. According to the invention, after the organic silicon resin is modified by partial dealcoholization condensation reaction of fluorocarbon alcohol, a high bond energy fluorocarbon chain segment is introduced, so that the resin matrix has extremely low surface energy, and the high-activity phenolic hydroxyl contained on the surface of the polydopamine bionic modified nano particle can form a stable covalent bond with the modified organic silicon resin matrix and the surface layers of metal and concrete matrixes, so that the weather resistance, the water repellency and the oleophobicity of the protective coating are remarkably improved, and the bonding strength of the protective coating and the metal and concrete basal plane is effectively improved.
Description
Technical Field
The invention belongs to the technical field of protective coatings, and relates to a super-amphiphobic super-weather-resistant organic silicon protective coating and a preparation method thereof.
Background
In recent years, great engineering construction expands to regions such as highland, ocean, mountain land and the like, extreme environments (high ultraviolet, large temperature difference, high humidity, high salt, freeze thawing and the like) provide great challenges for the century life of engineering, and simultaneously provide higher and more demands for protective materials. Super-amphiphobic surfaces (contact angles to water and oil are more than 150 degrees, and rolling angles are less than 10 degrees) are widely focused by scientific researchers due to excellent performances of antifouling property, self-cleaning property, anti-icing property, corrosion resistance and the like. Because the water and the oil can not infiltrate on the surface of the super-amphiphobic protective coating, the problem that a single super-hydrophobic protective coating is easy to be polluted by external oily substances can be solved, and the coating has wider application prospect in the fields of oil fields, sea, transportation, industrial production and the like. However, since the surface energy of oily substances is much lower than that of water, this requires a protective coating with a lower surface energy and finer and more uniform micro-nano structure. Most of the existing super-hydrophobic or super-amphiphobic protective coatings are complex in preparation process, poor in adhesion between the coating and a substrate, and low in durability and service life, and are not wear-resistant, poor in weather resistance and super-hydrophobic or super-amphiphobic when used in outdoor extreme environments.
Patent CN112375244A provides a wear-resistant self-cleaning super-amphiphobic coating and a preparation method thereof, and the operation steps are as follows: coating polystyrene microspheres on a transparent substrate in a lifting coating mode; plating a layer of metal film by magnetron sputtering; then removing polystyrene microspheres by water bath ultrasonic to obtain a metal film with a groove microstructure, and growing a layer of metal oxide on the surface of the metal film by an anodic oxidation method; then continuing to grow nanoparticles on the metal oxide; and finally, carrying out low-surface energy modification on the coating to obtain the coating attached to the transparent substrate. Although the super-amphiphobic coating prepared by the scheme has good wear resistance, the operation flow is numerous, the preparation process is complex, in addition, the low surface energy modification of the nano particles on the surface of the coating can cause the reduction of the super-amphiphobic effect after a period of service due to wear and oxidative degradation reaction, and the protection effect of the coating is directly influenced.
Patent CN112812676A provides a super-amphiphobic acid-resistant coating and a preparation method thereof, and the operation steps are as follows: firstly, immersing nano SiO2 particles into an ethanol solution of fluorosilane for modification at room temperature, drying, and grinding and dispersing to obtain modified nano SiO2 particles; and then coating polyurethane anti-corrosion coating on the surface of the pretreated substrate, drying, spraying the prepared modified nano SiO2 particles on the surface of the coating in the semi-cured state after the coating on the surface of the substrate enters the semi-cured state, and curing to obtain the super-amphiphobic acid-resistant coating. The scheme solves the problems of complex preparation process, expensive instrument and equipment, high preparation cost and severe preparation conditions in the prior art. However, the semi-cured state of the polyurethane coating is difficult to control in the preparation process, modified nano SiO2 particles are too early in spraying and easily completely sink into the polyurethane coating, so that the polyurethane coating cannot have the effect, and the modified nano SiO2 particles are too late in spraying and easily adhere with the coating and are not firm and fall off. In addition, because the ageing resistance of polyurethane is poor, the ultraviolet irradiation coating is easy to generate photooxidation degradation reaction in the outdoor use process, the polymer is decomposed, and modified nano SiO2 particles fall off from the surface of the coating to form pulverization.
Patent CN112940585a provides a method for preparing a self-cleaning amphiphobic coating for degrading NO, in which nano silicon dioxide is introduced to avoid direct degradation of epoxy resin by strong oxidative groups generated by titanium dioxide nanotubes, thereby improving ultraviolet stability of the coating. However, in the scheme, the mass parts of the epoxy resin and the curing agent are 3-4 times of that of the fluorosilane, the main resin of the whole coating is still epoxy resin, the nano silicon dioxide can slow down the strong oxidative degradation reaction of the titanium dioxide nanotube on the epoxy resin to a certain extent, but the coating inevitably receives the ultraviolet light to generate the photo-oxidative degradation reaction in the outdoor service process for a long time, the main epoxy resin is oxidatively degraded, nano particles are pulverized and fall off, the coating fails, and the service life of the coating is seriously reduced.
Disclosure of Invention
The invention provides a super-amphiphobic super-weather-resistant organic silicon protective coating and a preparation method thereof, and solves the problems of complex preparation process, harsh synthesis conditions, expensive instrument and equipment and the like in the prior art.
The invention provides a super-amphiphobic super-weather-resistant organic silicon protective coating which comprises the following raw material components in parts by weight:
30-60 parts of organic silicon resin,
20-30 parts of fluorocarbon alcohol,
15-25 parts of polydopamine bionic modified nano particles;
the organic silicon resin is trimethoxy or triethoxy silane containing long-chain alkyl, wherein the carbon number of the long-chain alkyl is 6-18;
the fluorocarbon alcohol is straight-chain fluorocarbon alcohol with the carbon number of 5-10 and no fluorine group on the carbon atom directly connected with the hydroxyl;
the nano particles in the polydopamine bionic modified nano particles are of fiber rod-shaped or wire-shaped structures and are selected from one or more of carbon nano tubes, carbon nano fibers, palygorskite, titanium dioxide whiskers and potassium titanate whiskers.
The super-amphiphobic super-weather-resistant organic silicon protective coating comprises the following raw material components in parts by weight:
the catalyst is any one of naphthenate or carboxylate, phosphonitrile chloride and phthalate ester complex of Pb, fe, zn, sn, co and the like.
Further preferably, the mass ratio of the organic silicon resin to the fluorocarbon alcohol is (1.5-2): 1, the mass sum of the organic silicon resin, the fluorocarbon alcohol and the polydopamine bionic modified nano particles accounts for 65-85% of the total mass.
Further preferably, the fluorocarbon alcohol is selected from any one of 1H, 1H-nonafluoro-1-pentanol, 1H-undecfluoro-1-hexanol, 1H-tridecafluoro-1-heptanol, 1H-pentadecafluoro-1-octanol, 1H-heptadecafluoro-1-nonanol, 1H-nonadecafluoro-1-decanol.
The poly-dopamine bionic modified nano particles are prepared by oxidizing and self-polymerizing dopamine hydrochloride on the surfaces of the nano particles, and the preparation method is well known to those skilled in the industry field. The particle size of the nano particles is 25-100nm.
Further preferably, the catalyst is any one of lead naphthenate, iron naphthenate, zinc naphthenate, tin naphthenate, cobalt naphthenate, dibutyl tin dilaurate, stannous octoate, hexachlorocyclotriphosphazene and titanate complex.
The organosilicon leveling agent, the dispersing agent and the organosilicon defoaming agent are common products which are suitable for organosilicon resin coating and are widely known by the technicians in the field of the industry; preferably, the organosilicon leveling agent can be selected from one or more of the models BYK-325N, BYK-333, BYK-306 and the like of the commercial Pick chemical company; preferably, the dispersant may be selected from one or more of the commercially available types BYK-110, BYK-111, BYK-161, BYK-163, etc. of the Pick chemical company; preferably, the silicone defoamer may be selected from one or more of the commercially available types BYK-088, BYK-085, AFE-0120, ACP-0544, 1430, DC-7, etc. from Pick chemical company.
The organic solvent is one or a mixture of more of toluene, xylene, cyclohexane, ethyl acetate, butyl acetate and butanol.
The invention also provides a preparation method of the super-amphiphobic super-weather-resistant organic silicon protective coating, which comprises the following specific steps:
(1) Preparation of modified organic silicon resin: adding the organic silicon resin and fluorocarbon alcohol into a reaction container, stirring and heating to 60-80 ℃, and continuously reacting for 1-2h at the temperature to obtain the modified organic silicon resin.
(2) The modified organic silicon resin, the poly dopamine bionic modified nano particles, the catalyst, the organic silicon leveling agent, the dispersing agent, the organic silicon defoaming agent and the solvent are respectively added into a paint mixing tank, and the mixture is stirred and mixed uniformly at a high speed under the normal temperature condition to obtain the super-amphiphobic super-weather-resistant organic silicon protective coating.
(3) Spraying the protective coating obtained in the step (2) on the surface of the substrate after surface treatment, and curing and drying under the normal temperature condition to obtain the organic silicon protective coating with super-amphiphobic and super-weather-resistant properties.
Compared with the prior art, the invention has the advantages that:
(a) The organic silicon resin is long-chain alkyl silicon resin, and has good hydrophobicity; and then, after the fluorocarbon alcohol is subjected to partial dealcoholization condensation reaction modification, a fluorocarbon chain segment with high bond energy is introduced, so that the resin matrix has extremely low surface energy, and the weather resistance, the water repellency and the oil repellency of the protective coating are obviously improved.
(b) On one hand, the high-activity phenolic hydroxyl groups contained on the surfaces of the polydopamine bionic modified nano particles can form stable covalent bonds with the modified organic silicon resin matrix, the metal and concrete matrix surface layers, so that the crosslinking degree of the resin matrix is effectively improved, and the nano particles and the resin matrix are integrated; in addition, the bonding strength of the protective coating and the metal and concrete basal planes is effectively improved, and the bonding strength of the protective coating and the metal and concrete basal planes respectively exceeds 10MPa and 4MPa; on the other hand, the introduction of the polydopamine bionic modified nano particles with uniform particle size increases the fine roughness of the surface of the protective coating, further improves the super-amphiphobic effect of the protective coating, and the actual test shows that the contact angles of water, glycol, hexadecane and other liquid drops on the surface of the protective coating can reach 165-170 degrees, 158-165 degrees and 155-160 degrees respectively.
(c) In addition, the polydopamine has excellent ultraviolet light absorption capability and photo-thermal conversion performance, high chemical and mechanical stability, and can further improve the weather resistance of the protective coating, and the ageing resistance duration of the protective coating can reach 7000 hours through an actual artificial accelerated ultraviolet ageing test. Meanwhile, the protective coating has excellent wear resistance, corrosion resistance and anti-icing performance after being formed into a film.
(d) The preparation flow and process of the super-amphiphobic super-weather-resistant organic silicon protective coating provided by the invention are simple, the synthesis conditions are mild, the requirements on instruments and equipment are low, and the preparation method has obvious advantages compared with a complex etching method, a chemical vapor deposition method, an electrostatic spinning method and the like.
Drawings
FIG. 1 is a schematic structural diagram of a super-amphiphobic super-weather-resistant organic silicon protective coating provided in example 1 of the invention;
Detailed Description
In order to make the technical solution, advantages and achieved objects of the present invention more clear and clear, the present invention is described in detail by the following specific examples, which are only illustrative and not intended to limit the scope of the present invention, but all non-essential equivalent changes or modifications made according to the above-described summary and spirit are within the scope of the present invention.
1. Synthetic examples:
example 1
(1) Preparation of modified organic silicon resin:
at room temperature, hexyl triethoxysilane and 1H, 1H-nonafluoro-1-amyl alcohol are mixed according to the mass part ratio of 2:1 into a three-mouth bottle, stirring and heating to 60 ℃ and reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparation of protective coating:
60 parts by mass of modified organic silicon resin, 20 parts by mass of poly dopamine bionic modified palygorskite nano particles, 2.5 parts of cobalt naphthenate catalyst, 2 parts of organic silicon leveling agent, 1 part of dispersing agent, 2 parts of organic silicon defoaming agent and 20 parts of butyl acetate solvent are respectively added into a paint mixing tank, and the mixture is stirred and mixed uniformly at a high speed under the normal temperature condition to obtain the mixed paint. And then spraying the mixed coating on the surfaces of the steel plate and the concrete matrix after surface treatment, and drying and curing at room temperature to obtain the organosilicon protective coating with super amphiphobic and super weather resistance.
Example 2
(1) Preparation of modified organic silicon resin:
octyl trimethoxy silane and 1H, 1H-tridecyl-fluoro-1-heptanol are mixed according to the mass ratio of 1.5:1 into a three-mouth bottle, stirring and heating to 65 ℃ and reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparation of protective coating:
76 parts by mass of modified organosilicon resin, 18 parts by mass of polydopamine bionic modified carbon nano tube nano particles, 0.2 part of dibutyltin dilaurate catalyst, 1.5 parts of organosilicon leveling agent, 1.5 parts of dispersing agent, 2.5 parts of organosilicon defoaming agent and 22 parts of cyclohexane solvent are respectively added into a paint mixing tank, and the mixture is stirred and mixed uniformly at a high speed under normal temperature to obtain the mixed paint. And then spraying the mixed coating on the surfaces of the steel plate and the concrete matrix after surface treatment, and drying and curing at room temperature to obtain the organosilicon protective coating with super amphiphobic and super weather resistance.
Example 3
(1) Preparation of modified organic silicon resin:
decyl triethoxysilane and 1H, 1H-undec-fluoro-1-hexanol are mixed according to the mass part ratio of 2: 1. adding the mixture into a three-mouth bottle, stirring and heating to 70 ℃, reacting for 1.5h, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparation of protective coating:
55 parts by mass of modified organic silicon resin, 24 parts by mass of poly dopamine bionic modified titanium dioxide whisker nano particles, 2 parts of phthalate ester complex catalyst, 2.5 parts of organic silicon flatting agent, 2 parts of dispersing agent, 2.5 parts of organic silicon defoamer and 24 parts of butyl acetate solvent are respectively added into a paint mixing tank, and the mixture is stirred and mixed uniformly at a high speed under normal temperature to obtain the mixed paint. And then spraying the mixed coating on the surfaces of the steel plate and the concrete matrix after surface treatment, and drying and curing at room temperature to obtain the organosilicon protective coating with super amphiphobic and super weather resistance.
Example 4
(1) Preparation of modified organic silicon resin:
dodecyl trimethoxy silane and 1H, 1H-pentadecafluoro-1-octanol are mixed according to the mass ratio of 1.9:1 into a three-mouth bottle, stirring and heating to 70 ℃ and reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparation of protective coating:
68 parts by mass of modified organic silicon resin, 25 parts by mass of poly dopamine bionic modified carbon nanofiber nano particles, 0.5 part of stannous octoate, 2 parts of organic silicon flatting agent, 2 parts of dispersing agent, 2.5 parts of organic silicon defoamer and 28 parts of butanol solvent are respectively added into a paint mixing tank, and the mixture is stirred and mixed uniformly at a high speed under normal temperature to obtain the mixed paint. And then spraying the mixed coating on the surfaces of the steel plate and the concrete matrix after surface treatment, and drying and curing at room temperature to obtain the organosilicon protective coating with super amphiphobic and super weather resistance.
Example 5
(1) Preparation of modified organic silicon resin:
tetradecyltriethoxysilane and 1H, 1H-nonafluoro-1-decanol are mixed according to the mass part ratio of 1.6:1 into a three-mouth bottle, stirring and heating to 75 ℃ and reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparation of protective coating:
71 parts by mass of modified organic silicon resin, 20 parts by mass of poly-dopamine bionic modified carbon nanofiber nano particles, 1 part of tin naphthenate, 2 parts of organic silicon flatting agent, 1.5 parts of dispersing agent, 2.5 parts of organic silicon defoaming agent and 25 parts of ethyl acetate solvent are respectively added into a paint mixing tank, and the mixture is stirred and mixed uniformly at a high speed under the normal temperature condition to obtain the mixed paint. And then spraying the mixed coating on the surfaces of the steel plate and the concrete matrix after surface treatment, and drying and curing at room temperature to obtain the organosilicon protective coating with super amphiphobic and super weather resistance.
Example 6
(1) Preparation of modified organic silicon resin:
at room temperature, hexadecyltrimethoxysilane and 1H, 1H-heptadecafluoro-1-nonanol are mixed according to the mass ratio of 2:1 into a three-mouth bottle, stirring and heating to 75 ℃ and reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparation of protective coating:
89 parts by mass of modified organic silicon resin, 15 parts by mass of poly-dopamine bionic modified potassium titanate whisker nano particles, 2 parts of zinc naphthenate, 2 parts of organic silicon flatting agent, 1.5 parts of dispersing agent, 2.5 parts of organic silicon defoamer and 15 parts of xylene solvent are respectively added into a paint mixing tank, and the mixture is stirred and mixed uniformly at a high speed under the normal temperature condition to obtain the mixed paint. And then spraying the mixed coating on the surfaces of the steel plate and the concrete matrix after surface treatment, and drying and curing at room temperature to obtain the organosilicon protective coating with super amphiphobic and super weather resistance.
Example 7
(1) Preparation of modified organic silicon resin:
octadecyltriethoxysilane and 1H, 1H-undecane-1-hexanol are mixed according to the mass ratio of 1.8:1 into a three-mouth bottle, stirring and heating to 80 ℃ and reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparation of protective coating:
52 parts by mass of modified organosilicon resin, 25 parts by mass of polydopamine bionic modified carbon nano tube nano particles, 0.5 part by mass of hexachlorocyclotriphosphazene, 2.5 parts by mass of organosilicon leveling agent, 2 parts by mass of dispersing agent, 2.5 parts by mass of organosilicon defoaming agent and 30 parts by mass of butyl acetate solvent are respectively added into a paint mixing tank, and the mixture is stirred and mixed uniformly at a high speed under normal temperature to obtain the mixed paint. And then spraying the mixed coating on the surfaces of the steel plate and the concrete matrix after surface treatment, and drying and curing at room temperature to obtain the organosilicon protective coating with super amphiphobic and super weather resistance.
Example 8
(1) Preparation of modified organic silicon resin:
pentadecyl trimethoxy silane and 1H, 1H-pentadecafluoro-1-octanol are mixed according to the mass part ratio of 1.7:1 into a three-mouth bottle, stirring and heating to 65 ℃ and reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparation of protective coating:
57 parts by mass of modified organic silicon resin, 16 parts by mass of poly dopamine bionic modified palygorskite nano particles, 0.05 part by mass of lead naphthenate, 2.5 parts by mass of organic silicon flatting agent, 2.5 parts by mass of dispersing agent, 2.5 parts by mass of organic silicon defoamer and 18 parts by mass of toluene solvent are respectively added into a paint mixing tank, and the mixture is stirred and mixed uniformly at a high speed under normal temperature to obtain the mixed paint. And then spraying the mixed coating on the surfaces of the steel plate and the concrete matrix after surface treatment, and drying and curing at room temperature to obtain the organosilicon protective coating with super amphiphobic and super weather resistance.
Comparative example 1
(1) Preparation of modified organic silicon resin:
at room temperature, hexyl triethoxysilane and 1H, 1H-nonafluoro-1-amyl alcohol are mixed according to the mass part ratio of 2:1 into a three-mouth bottle, stirring and heating to 60 ℃ and reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparation of protective coating:
60 parts by mass of modified organic silicon resin, 20 parts by mass of palygorskite nano particles, 2.5 parts of cobalt naphthenate catalyst, 2 parts of organic silicon flatting agent, 1 part of dispersing agent, 2 parts of organic silicon defoamer and 20 parts of butyl acetate solvent are respectively added into a paint mixing tank, and the mixture is stirred and mixed uniformly at a high speed under normal temperature to obtain the mixed paint. And then spraying the mixed paint on the surfaces of the steel plate and the concrete matrix after the surface treatment, and drying and curing at room temperature to obtain the corresponding organic silicon protective coating.
Comparative example 2
(1) Preparation of modified organic silicon resin:
octyl trimethoxy silane and 1H, 1H-tridecyl-fluoro-1-heptanol are mixed according to the mass ratio of 1.5: 1. adding the mixture into a three-mouth bottle, stirring and heating to 65 ℃ for 2h, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparation of protective coating:
76 parts by mass of modified organic silicon resin, 18 parts by mass of polydopamine formed by self-polymerization of pure dopamine hydrochloride, 0.2 part of dibutyl tin dilaurate catalyst, 1.5 parts of organic silicon leveling agent, 1.5 parts of dispersing agent, 2.5 parts of organic silicon defoaming agent and 22 parts of cyclohexane solvent are respectively added into a paint mixing tank, and the mixture is stirred and mixed uniformly at a high speed under normal temperature to obtain the mixed paint. And then spraying the mixed paint on the surfaces of the steel plate and the concrete matrix after the surface treatment, and drying and curing at room temperature to obtain the corresponding organic silicon protective coating.
Comparative example 3
(1) Preparation of modified organic silicon resin:
decyl triethoxysilane and 1H, 1H-undec-fluoro-1-hexanol are mixed according to the mass part ratio of 3: 1. adding the mixture into a three-mouth bottle, stirring and heating to 70 ℃, reacting for 1.5h, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparation of protective coating:
55 parts by mass of modified organic silicon resin, 24 parts by mass of poly dopamine bionic modified titanium dioxide whisker nano particles, 2 parts of phthalate ester complex catalyst, 2.5 parts of organic silicon flatting agent, 2 parts of dispersing agent, 2.5 parts of organic silicon defoamer and 24 parts of butyl acetate solvent are respectively added into a paint mixing tank, and the mixture is stirred and mixed uniformly at a high speed under normal temperature to obtain the mixed paint. And then spraying the mixed coating on the surfaces of the steel plate and the concrete matrix after surface treatment, and drying and curing at room temperature to obtain the organosilicon protective coating with super amphiphobic and super weather resistance.
Comparative example 4
(1) Preparation of modified organic silicon resin:
decyl triethoxysilane and 1H, 1H-undec-fluoro-1-hexanol are mixed according to the mass part ratio of 1: 1. adding the mixture into a three-mouth bottle, stirring and heating to 70 ℃, reacting for 1.5h, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparation of protective coating:
55 parts by mass of modified organic silicon resin, 24 parts by mass of poly dopamine bionic modified titanium dioxide whisker nano particles, 2 parts of phthalate ester complex catalyst, 2.5 parts of organic silicon flatting agent, 2 parts of dispersing agent, 2.5 parts of organic silicon defoamer and 24 parts of butyl acetate solvent are respectively added into a paint mixing tank, and the mixture is stirred and mixed uniformly at a high speed under normal temperature to obtain the mixed paint. And then spraying the mixed coating on the surfaces of the steel plate and the concrete matrix after surface treatment, and drying and curing at room temperature to obtain the organosilicon protective coating with super amphiphobic and super weather resistance.
Comparative example 5
At room temperature, 44.55 parts by mass of dodecyl trimethoxy silane, 23.45 parts by mass of 1H, 1H-pentadecafluoro-1-octanol (the weight ratio of the dodecyl trimethoxy silane to the 1H, 1H-pentadecafluoro-1-octanol is 1.9:1), 25 parts by mass of poly dopamine bionic modified carbon nanofiber nano particles, 0.5 part of stannous octoate, 2 parts of organosilicon leveling agent, 2 parts of dispersing agent, 2.5 parts of organosilicon defoaming agent and 28 parts of butanol solvent are respectively added into a paint mixing tank, and the mixture is stirred and mixed uniformly at a high speed under normal temperature to obtain the mixed paint. And then spraying the mixed paint on the surfaces of the steel plate and the concrete matrix after the surface treatment, and drying and curing at room temperature to obtain the corresponding organic silicon protective coating.
Comparative example 6
71 parts by mass of tetradecyltriethoxysilane (1H, 1H-nineteen-fluorine-1-decanol is removed), 20 parts by mass of polydopamine bionic modified carbon nanofiber nano particles, 1 part of tin naphthenate, 2 parts of an organosilicon leveling agent, 1.5 parts of a dispersing agent, 2.5 parts of an organosilicon defoaming agent and 25 parts of an ethyl acetate solvent are respectively added into a paint mixing tank at room temperature, and the mixture is stirred and mixed uniformly at a high speed under the normal temperature condition to obtain the mixed paint. And then spraying the mixed paint on the surfaces of the steel plate and the concrete matrix after the surface treatment, and drying and curing at room temperature to obtain the corresponding organic silicon protective coating.
2. Performance measurement of protective coating:
(1) Superhydrophobic and superoleophobic properties:
a20 μl syringe was used to drop a drop of deionized water, ethylene glycol, and hexadecane onto the surfaces of the protective coatings prepared in examples and comparative examples, respectively, and the contact angles of each protective coating to water, ethylene glycol, and hexadecane were measured using a static hydrophobic angle meter.
(2) Artificial accelerated aging resistance:
the protective coatings prepared in the examples and the comparative examples are respectively placed in an accelerated aging tester (QUVTM), and the surface morphology of the coating is observed after continuous 3000h, 5000h and 7000h tests are respectively carried out by adopting Sup>A UV-A bulb (the experimental conditions are that the ultraviolet lamp radiates for 8h, the rain is 4h and the temperature is circulated within the range of 35-80 ℃), and meanwhile, the contact angles of the protective coating to water, ethylene glycol and hexadecane after 7000h aging are tested.
(3) Wear resistance:
the abrasion resistance test is carried out on the protective coatings prepared in the examples and the comparative examples by sticking 800-mesh sand paper on the surface of the grinding wheel of an abrasion tester, the load mass of each rubber grinding wheel is 1kg, after the continuous 5000-rotation abrasion test is carried out under the condition, the abrasion condition of the surface of the protective coating is observed, and the contact angles of the worn protective coating to water, ethylene glycol and hexadecane are tested.
(4) Adhesive properties:
the protective coatings prepared in the examples and the comparative examples are respectively sprayed on the surfaces of the ultra-high performance concrete test block and the steel plate after surface treatment, and after drying, the protective coatings are cured for 7 days under standard conditions, and finally the bonding strength of the protective coatings on the concrete base surface and the steel plate base surface is respectively tested according to the GB/T5210-2006 standard and compared with the bonding strength of protective coatings such as acrylic acid, polyurethane, polyurea, alkyd resin, organic silicon resin and the like which are commonly used in the market.
(5) Corrosion resistance:
the protective coatings prepared in the examples and the comparative examples are respectively immersed in 3.5% sodium chloride solution by mass for immersion corrosion test, the surface appearance of the coating is observed after the coating is respectively tested for 7 days, 14 days, 28 days and 56 days, and the contact angles of the protective coating to water, ethylene glycol and hexadecane after the protective coating is immersed for 56 days are tested.
The results of the performance tests of the examples and comparative examples of the present invention are as follows:
the protective coatings prepared in examples 1 to 8 have excellent super-amphiphobic performance, ageing resistance (the paint film does not have the phenomena of pulverization, foaming, cracking, peeling and the like after 7000h manual accelerated ageing test, the coating still has super-hydrophobic and certain oleophobic performance), wear resistance (after continuous 5000-rotation abrasion test, the surface of the protective coating does not have obvious abrasion phenomenon, the coating still has super-hydrophobic and certain oleophobic performance), high adhesive property (the adhesive strength of a metal base surface and a concrete base surface is respectively more than 10MPa and 4 MPa), and corrosion resistance (the surface of the coating is found to have no obvious phenomena of swelling, pulverization, cracking and the like after continuous 7 days, 14 days, 28 days and 56 days of test, and the coating still has super-amphiphobic performance after 56 days of test). In the comparative example 1, the nano particles are not modified, so that the bonding strength between the coating and the surface of the substrate and the crosslinking degree of the coating are obviously reduced, and the wear resistance, bonding strength and corrosion resistance of the coating are obviously reduced compared with those of the example 1; the comparative example 2 does not contain fibrous or filamentous nano particles, only contains polydopamine formed by self-polymerization of pure dopamine hydrochloride, and the prepared coating does not have super amphiphobic function; in comparative examples 3 and 4, the mass part ratio of the organic silicon resin to the fluorocarbon alcohol exceeds the specified range, and each performance of the prepared coating is different to a certain extent from that of the examples; in comparative example 5, after fluorocarbon alcohol is directly blended, the film forming property of the coating is poor, the coating does not have super oleophobic function, and the durability and the bonding property are poor; after fluorocarbon alcohol is removed in comparative example 6, the coating does not have super oleophobic function, and the ageing resistance is obviously reduced.
Claims (8)
1. The super-amphiphobic super-weather-resistant organic silicon protective coating is characterized by comprising the following raw material components in parts by weight:
30-60 parts of organic silicon resin,
20-30 parts of fluorocarbon alcohol,
15-25 parts of polydopamine bionic modified nano particles;
the organic silicon resin is trimethoxy or triethoxy silane containing long-chain alkyl, wherein the carbon number of the long-chain alkyl is 6-18;
the fluorocarbon alcohol is straight-chain fluorocarbon alcohol with the carbon number of 5-10 and no fluorine group on the carbon atom directly connected with the hydroxyl;
the nano particles in the polydopamine bionic modified nano particles are of fiber rod-shaped or wire-shaped structures and are selected from one or more of carbon nano tubes, carbon nano fibers, palygorskite, titanium dioxide whiskers and potassium titanate whiskers;
the mass ratio of the organic silicon resin to the fluorocarbon alcohol is (1.5-2): 1.
2. the super-amphiphobic super-weather-resistant organic silicon protective coating according to claim 1 is characterized by further comprising the following raw material components in parts by weight:
0.01-2.5 parts of catalyst,
1-3 parts of organic silicon flatting agent,
0.5-2 parts of dispersing agent,
0.5-3 parts of organic silicon defoamer,
15-30 parts of an organic solvent;
the catalyst is any one of naphthenate or carboxylate, phosphonitrile chloride and phthalate ester complex of Pb, fe, zn, sn, co and the like.
3. The super-amphiphobic super-weather-resistant organic silicon protective coating according to claim 1 or 2, wherein the sum of the mass of the organic silicon resin, fluorocarbon alcohol and polydopamine bionic modified nano particles accounts for 65-85% of the total mass.
4. The super-amphiphobic super-weather resistant silicone protective coating of claim 1, wherein the fluorocarbon alcohol is selected from any one of 1H, 1H-nonafluoro-1-pentanol, 1H-undec-1-hexanol, 1H-tride-fluoro-1-heptanol, 1H-pentadecafluoro-1-octanol, 1H-heptadecafluoro-1-nonanol, 1H-nonadecafluoro-1-decanol.
5. The super-amphiphobic super-weather resistant silicone protective coating according to claim 1, wherein the nanoparticle has a particle size of 25-100nm.
6. The super-amphiphobic super-weather resistant organic silicon protective coating according to claim 2, wherein the catalyst is selected from any one of lead naphthenate, iron naphthenate, zinc naphthenate, tin naphthenate, cobalt naphthenate, dibutyl tin dilaurate, stannous octoate, hexachlorocyclotriphosphazene and titanate complex.
7. The super-amphiphobic super-weatherable silicone protective coating according to claim 2, wherein the organic solvent is a mixture of one or more of toluene, xylene, cyclohexane, ethyl acetate, butyl acetate, butanol.
8. The method for preparing the super-amphiphobic super-weather-resistant organic silicon protective coating according to any one of claims 1 to 7, which is characterized by comprising the following specific steps:
(1) Preparation of modified organic silicon resin: adding organic silicon resin and fluorocarbon alcohol into a reaction container, stirring and heating to 60-80 ℃, and continuously reacting at the temperature for 1-2h to obtain modified organic silicon resin;
(2) The modified organic silicon resin, the poly-dopamine bionic modified nano particles, the catalyst, the organic silicon leveling agent, the dispersing agent, the organic silicon defoaming agent and the solvent are respectively added into a paint mixing tank, and are stirred and mixed uniformly at a high speed under the normal temperature condition to obtain the super-amphiphobic super-weather-resistant organic silicon protective coating;
(3) Spraying the protective coating obtained in the step (2) on the surface of the substrate after surface treatment, and curing and drying under the normal temperature condition to obtain the organic silicon protective coating with super-amphiphobic and super-weather-resistant properties.
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| CN105585954A (en) * | 2015-12-04 | 2016-05-18 | 金湖县兴鹏机械制造有限公司 | Protective coating for inner wall of shell of machine for cutting straw and throwing straw back into field and preparation method thereof |
| EP4045569A1 (en) * | 2019-10-18 | 2022-08-24 | Momentive Performance Materials Inc. | Reactive poly(fluoroalkyl-functional siloxane) oligomers, process for forming the same, and compositions using the same |
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