CN115181495A - 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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Abstract
The invention discloses a super-amphiphobic super-weather-resistant organic silicon protective coating and a preparation method thereof. According to the invention, the organic silicon resin is modified by partial dealcoholization condensation reaction of fluorocarbon alcohol, and then 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 nanoparticles can form a stable covalent bond with the modified organic silicon resin matrix and the surfaces of metal and concrete matrix, thereby not only obviously improving the weather resistance and hydrophobic and oleophobic properties of the protective coating, but also effectively improving the bonding strength of the protective coating with the metal and concrete matrix.
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, the construction of major projects is expanded to regions such as plateaus, oceans, mountainous regions and the like, extreme environments (high ultraviolet, large temperature difference, high humidity, high salt, freezing and thawing and the like) provide great challenges for the hundred-year service life of the projects, and higher and more requirements for protective materials are provided. The super-amphiphobic surface (the contact angle to water and oil is more than 150 degrees, and the rolling angle is less than 10 degrees) attracts extensive attention of scientific researchers due to excellent performances of antifouling, self-cleaning, anti-icing, anti-corrosion and the like. As water and oil can not be infiltrated on the surface of the super-amphiphobic protective coating, the problem that a single super-hydrophobic protective coating is easily polluted by external oily substances can be solved, and the coating has wider application prospect in the fields of oil fields, oceans, transportation, industrial production and the like. However, the surface energy of oily substances is much lower than that of water, so that the surface energy of the protective coating is required to be lower, and the micro-nano structure is finer and more uniform. Most of the existing super-hydrophobic or super-amphiphobic protective coatings have complicated preparation processes, poor adhesion between the coatings and a base material, no wear resistance and poor weather resistance when used in outdoor extreme environments, and short service life because the super-hydrophobic or super-amphiphobic protective coatings do not have long-acting performance.
Patent CN112375244A provides a wear-resistant self-cleaning super-amphiphobic coating and a preparation method thereof, and the operation steps are as follows: plating the polystyrene microspheres on a transparent substrate in a pulling film plating mode; plating a layer of metal film by magnetron sputtering; removing the polystyrene microspheres by water bath ultrasound 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 nano particles on the metal oxide; finally, the coating is subjected to low surface energy modification 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 various and the preparation process is complex, and 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 abrasion and oxidative degradation reaction, so that the protection effect of the coating is directly influenced.
The patent CN112812676A provides a super-amphiphobic acid-resistant coating and a preparation method thereof, and the operation steps are as follows: firstly, soaking nano SiO2 particles into an ethanol solution of fluorosilane for modification at room temperature, drying, grinding and dispersing to obtain modified nano SiO2 particles; and then coating the polyurethane anticorrosive paint on the surface of the pretreated base material, drying, spraying the prepared modified nano SiO2 particles on the surface of the semi-cured paint after the paint on the surface of the base material enters a semi-cured state, and curing to obtain the super-amphiphobic acid-resistant paint. The scheme solves the problems of complex preparation process, expensive instruments and equipment, high preparation cost and harsh preparation conditions in the prior art. However, the semi-cured state of the polyurethane coating is difficult to control in the preparation process of the coating, the modified nano SiO2 particles are sprayed too early and are easy to be completely sunk into the polyurethane coating, so that the modified nano SiO2 particles cannot achieve the required effect, and the modified nano SiO2 particles are easy to be bonded with the coating too late and fall off. In addition, because the ageing resistance of polyurethane is poor, the ultraviolet irradiation coating is easy to generate a photooxidation degradation reaction in the outdoor use process, the polymer is decomposed, and the modified nano SiO2 particles fall off from the surface of the coating to form pulverization.
Patent CN112940585A provides a preparation method of a self-cleaning double-hydrophobic coating for degrading NO, and the coating is prevented from generating direct degradation of strong oxidizing groups to epoxy resin by introducing nano-silica, so that the ultraviolet stability of the coating is improved. 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 the epoxy resin, and although the nano-silica can slow down the strong oxidative degradation reaction of the titanium dioxide nano-tube to the epoxy resin to a certain extent, the coating inevitably receives the action of ultraviolet light to generate the photooxidative degradation reaction in the outdoor service process for a long time, the main epoxy resin is oxidized and degraded, the nano-particles are pulverized and fall off, the coating fails, and the service life of the coating is seriously reduced.
Disclosure of Invention
In order to overcome the defects that the existing protective coating has short weather-proof duration, the super-amphiphobic effect is not lasting, and the adhesion between the protective coating and the surface of the base material or between the nano particles and the coating is low, the invention provides the super-amphiphobic super-weather-proof organic silicon protective coating and the preparation method thereof, and simultaneously solves the problems of complicated preparation process, harsh synthesis conditions, expensive instruments 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 silane or triethoxy silane containing long-chain alkyl, wherein the carbon atom number of the long-chain alkyl is 6-18;
the fluorocarbon alcohol is a straight-chain fluorocarbon alcohol with 5-10 carbon atoms and no fluorine group on the carbon atom directly connected with the hydroxyl;
the nano particles in the poly-dopamine biomimetic modified nano particles are of fiber rod-shaped or filamentous structures and are selected from one or a mixture of 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 of Pb, fe, zn, sn, co, etc., phosphonitrile chloride and phthalate ester complex.
More preferably, the mass ratio of the organic silicon resin to the fluorocarbon alcohol is (1.5-2): 1, the sum of the mass 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 any one selected from 1H, 1H-nonafluoro-1-pentanol, 1H-undecafluoro-1-hexanol, 1H-tridecafluoro-1-heptanol, 1H-pentadecafluoro-1-octanol, 1H-heptadecafluoro-1-nonanol, and 1H, 1H-nonadecafluoro-1-decanol.
The poly-dopamine biomimetic modified nano particle is prepared by oxidizing and self-polymerizing dopamine hydrochloride on the surface of the nano particle, and the preparation method is well known to technical personnel in the field of industry. The particle size of the nano particles is 25-100nm.
More preferably, the catalyst is any one of lead naphthenate, iron naphthenate, zinc naphthenate, tin naphthenate, cobalt naphthenate, dibutyltin dilaurate, stannous octoate, hexachlorocyclotriphosphazene and titanate complex.
The organic silicon flatting agent, the dispersing agent and the organic silicon defoaming agent are related products which are commonly used in the industry and are suitable for organic silicon resin coatings, and are widely known by the technical personnel in the field; preferably, the silicone leveling agent can be selected from one or more of BYK-325N, BYK-333, BYK-306, and the like, which are commercially available from Bick chemical company; preferably, the dispersant may be selected from one or more of BYK-110, BYK-111, BYK-161, BYK-163, etc., available from Bik chemical; preferably, the silicone defoamer may be selected from one or more of BYK-088, BYK-085, AFE-0120, ACP-0544, 1430, DC-7, etc., commercially available from Bike chemical company.
The organic solvent is one or a mixture 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 silicone resin: adding 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) Respectively adding the modified organic silicon resin, the polydopamine bionic modified nano particles, the catalyst, the organic silicon flatting agent, the dispersing agent, the organic silicon defoaming agent and the solvent into a paint mixing tank, and uniformly stirring and mixing at a high speed under a normal temperature condition to obtain the super-amphiphobic super-weather-resistant organic silicon protective coating.
(3) And (3) spraying the protective coating obtained in the step (2) on the surface of the substrate after surface treatment, and curing and drying at normal temperature to obtain the organic silicon protective coating with the super-amphiphobic and super-weather-resistant properties.
Compared with the prior art, the invention has the advantages and beneficial effects that:
(a) The organic silicon resin is long-chain alkyl silicon resin which has good hydrophobicity; and secondly, a high-bond-energy fluorocarbon chain segment is introduced after partial dealcoholization condensation reaction modification is carried out on the fluorocarbon alcohol, so that the resin matrix has extremely low surface energy, and the weather resistance and the water and oil repellency of the protective coating are obviously improved.
(b) On one hand, the high-activity phenolic hydroxyl contained on the surface of the poly-dopamine biomimetic modified nano particle can form a stable covalent bond with the modified organic silicon resin matrix and the surface layers of metal and concrete matrix, so that the self-crosslinking degree of the resin matrix is effectively improved, and the nano particle and the resin matrix are integrated; in addition, the bonding strength of the protective coating with the metal and concrete basal planes is effectively improved, and the bonding strength on the metal and concrete basal planes respectively exceeds 10MPa and 4MPa; on the other hand, the introduction of the polydopamine biomimetic 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 finds that the contact angles of liquid drops of water, ethylene glycol, hexadecane and the like on the surface of the protective coating can reach 165-170 degrees, 158-165 degrees and 155-160 degrees respectively through practical tests.
(c) In addition, the polydopamine has excellent ultraviolet light absorption capacity and photo-thermal conversion performance, high chemical and mechanical stability and can further improve the weather resistance of the protective coating, and the aging resistance time of the protective coating can reach 7000h through actual artificial accelerated ultraviolet aging test tests. Meanwhile, the protective coating has excellent wear resistance, corrosion resistance and anti-icing performance after being formed into a film.
(d) The super-amphiphobic super-weather-resistant organic silicon protective coating provided by the invention is simple in preparation process and technology, mild in synthesis condition, low in requirements on instruments and equipment, and 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-weatherable silicone protective coating provided in example 1 of the present invention;
Detailed Description
In order to make the technical solution, advantages and objectives of the present invention more clear and more obvious, the present invention is described in detail by the following specific embodiments, which are merely illustrative and not meant to limit the scope of the present invention, and the non-essential equivalent changes or modifications made according to the above summary and spirit of the invention are included in the scope of the present invention.
1. Synthesis examples:
example 1
(1) Preparation of modified silicone resin:
and (2) mixing hexyltriethoxysilane and 1H, 1H-nonafluoro-1-pentanol at room temperature according to the mass part ratio of 2: adding the mixture into a three-necked bottle according to the proportion of 1, stirring, heating to 60 ℃, reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparing a protective coating:
60 parts of modified organic silicon resin, 20 parts of polydopamine bionic modified 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 defoaming agent and 20 parts of butyl acetate solvent are respectively added into a paint mixing tank and stirred at high speed and mixed uniformly at normal temperature to obtain the mixed coating. 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 organic silicon protective coating with the super-amphiphobic and super-weather-resistant properties.
Example 2
(1) Preparation of modified silicone resin:
octyl trimethoxy silane and 1H, 1H-tridecafluoro-1-heptanol are mixed at room temperature according to the mass part ratio of 1.5: 1. adding the components into a three-mouth bottle according to the proportion, stirring and heating to 65 ℃, reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparing a protective coating:
76 parts of modified organic silicon resin, 18 parts of polydopamine biomimetic modified carbon nano tube nano particles, 0.2 part of dibutyltin dilaurate catalyst, 1.5 parts of organic silicon flatting 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 stirred at high speed and mixed uniformly under the normal temperature condition to obtain the mixed coating. 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 organic silicon protective coating with the super-amphiphobic and super-weather-resistant properties.
Example 3
(1) Preparation of modified silicone resin:
decyl triethoxysilane and 1H, 1H-undecafluoro-1-hexanol are mixed according to the mass portion ratio of 2: 1. adding the components into a three-mouth bottle according to the proportion, stirring, heating to 70 ℃, reacting for 1.5h, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparing a protective coating:
55 parts by mass of modified organic silicon resin, 24 parts by mass of polydopamine biomimetic modified titanium dioxide whisker nano particles, 2 parts by mass of phthalate complex catalyst, 2.5 parts by mass of organic silicon flatting agent, 2 parts by mass of dispersing agent, 2.5 parts by mass of organic silicon defoaming agent and 24 parts by mass of butyl acetate solvent are respectively added into a paint mixing tank and are stirred and mixed uniformly at high speed under the normal temperature condition to obtain the mixed coating. And then spraying the mixed coating on the surfaces of the steel plate and the concrete substrate after surface treatment, and drying and curing at room temperature to obtain the organic silicon protective coating with the super-amphiphobic and super-weather resistance.
Example 4
(1) Preparation of modified silicone resin:
dodecyl trimethoxy silane and 1H, 1H-pentadecafluoro-1-octanol are added at room temperature according to the mass part ratio of 1.9: adding the mixture into a three-mouth bottle according to the proportion of 1, stirring, heating to 70 ℃, reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparing a protective coating:
respectively adding 68 parts by mass of modified organic silicon resin, 25 parts by mass of polydopamine biomimetic modified carbon nanofiber nano particles, 0.5 part by mass of stannous octoate, 2 parts by mass of an organic silicon leveling agent, 2 parts by mass of a dispersing agent, 2.5 parts by mass of an organic silicon defoaming agent and 28 parts by mass of a butanol solvent into a paint mixing tank, and stirring and mixing uniformly at a high speed under a normal temperature condition to obtain a mixed coating. 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 organic silicon protective coating with the super-amphiphobic and super-weather-resistant properties.
Example 5
(1) Preparation of modified silicone resin:
tetradecyl triethoxysilane and 1H, 1H-nonadecafluoro-1-decanol are mixed at room temperature according to the mass portion ratio of 1.6: adding the mixture into a three-necked bottle according to the proportion of 1, stirring, heating to 75 ℃, reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparing a protective coating:
71 parts by weight of modified organic silicon resin, 20 parts by weight of polydopamine biomimetic modified carbon nanofiber nano-particles, 1 part by weight of tin naphthenate, 2 parts by weight of organic silicon flatting agent, 1.5 parts by weight of dispersing agent, 2.5 parts by weight of organic silicon defoaming agent and 25 parts by weight of ethyl acetate solvent are respectively added into a paint mixing tank and are stirred at high speed and mixed uniformly under the condition of normal temperature to obtain the mixed coating. 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 organic silicon protective coating with the super-amphiphobic and super-weather-resistant properties.
Example 6
(1) Preparation of modified silicone resin:
hexadecyl trimethoxy silane and 1H, 1H-heptadecafluoro-1-nonanol are mixed at room temperature according to the mass part ratio of 2: adding the mixture into a three-necked bottle according to the proportion of 1, stirring, heating to 75 ℃, reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparing a protective coating:
respectively adding 89 parts by mass of modified organic silicon resin, 15 parts by mass of polydopamine bionic modified potassium titanate whisker nano particles, 2 parts by mass of zinc naphthenate, 2 parts by mass of an organic silicon leveling agent, 1.5 parts by mass of a dispersing agent, 2.5 parts by mass of an organic silicon defoaming agent and 15 parts by mass of a xylene solvent into a paint mixing tank, and stirring and mixing uniformly at a high speed under a normal temperature condition to obtain the mixed coating. 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 organic silicon protective coating with the super-amphiphobic and super-weather-resistant properties.
Example 7
(1) Preparation of modified silicone resin:
at room temperature, mixing octadecyl triethoxy silane and 1H, 1H-undecafluoro-1-hexanol according to the mass portion ratio of 1.8: adding the mixture into a three-mouth bottle according to the proportion of 1, stirring, heating to 80 ℃, reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparing a protective coating:
respectively adding 52 parts by mass of modified organic silicon resin, 25 parts by mass of poly dopamine biomimetic modified carbon nano tube nano particles, 0.5 part by mass of hexachlorocyclotriphosphazene, 2.5 parts by mass of organic silicon flatting agent, 2 parts by mass of dispersing agent, 2.5 parts by mass of organic silicon defoaming agent and 30 parts by mass of butyl acetate solvent into a paint mixing tank, and stirring and mixing uniformly at high speed under the normal temperature condition to obtain the mixed coating. 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 organic silicon protective coating with the super-amphiphobic and super-weather-resistant properties.
Example 8
(1) Preparation of modified silicone resin:
pentadecyltrimethoxysilane and 1H, 1H-pentadecafluoro-1-octanol are added at room temperature according to the mass part ratio of 1.7: adding the mixture into a three-necked bottle according to the proportion of 1, stirring and heating to 65 ℃, reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparing a protective coating:
57 parts by mass of modified organic silicon resin, 16 parts by mass of polydopamine bionic modified palygorskite nano particles, 0.05 part by mass of lead naphthenate, 2.5 parts by mass of an organic silicon leveling agent, 2.5 parts by mass of a dispersing agent, 2.5 parts by mass of an organic silicon defoaming agent and 18 parts by mass of a toluene 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 mixed coating. 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 organic silicon protective coating with the super-amphiphobic and super-weather-resistant properties.
Comparative example 1
(1) Preparation of modified silicone resin:
and (2) mixing hexyltriethoxysilane and 1H, 1H-nonafluoro-1-pentanol at room temperature according to the mass part ratio of 2: adding the mixture into a three-necked bottle according to the proportion of 1, stirring, heating to 60 ℃, reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparing a protective coating:
60 parts of modified organic silicon resin, 20 parts 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 defoaming agent and 20 parts of butyl acetate solvent are respectively added into a paint mixing tank and are stirred and mixed uniformly at high speed under normal temperature to obtain the mixed coating. 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 prepare the corresponding organic silicon protective coating.
Comparative example 2
(1) Preparation of modified silicone resin:
octyl trimethoxy silane and 1H, 1H-tridecafluoro-1-heptanol are mixed at room temperature according to the mass part ratio of 1.5: 1. adding the components into a three-mouth bottle according to the proportion, stirring and heating to 65 ℃, reacting for 2 hours, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparing a protective coating:
76 parts of modified organic silicon resin, 18 parts of polydopamine formed by self-polymerization of pure dopamine hydrochloride, 0.2 part of dibutyltin dilaurate catalyst, 1.5 parts of organic silicon flatting 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 stirred at high speed and mixed uniformly at normal temperature to obtain the mixed coating. 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 prepare the corresponding organic silicon protective coating.
Comparative example 3
(1) Preparation of modified silicone resin:
decyl triethoxysilane and 1H, 1H-undecafluoro-1-hexanol are mixed according to the mass portion ratio of 3: 1. adding the components into a three-mouth bottle according to the proportion, stirring, heating to 70 ℃, reacting for 1.5h, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparing a protective coating:
55 parts by mass of modified organic silicon resin, 24 parts by mass of polydopamine biomimetic modified titanium dioxide whisker nano particles, 2 parts by mass of phthalate complex catalyst, 2.5 parts by mass of organic silicon flatting agent, 2 parts by mass of dispersing agent, 2.5 parts by mass of organic silicon defoaming agent and 24 parts by mass of butyl acetate solvent are respectively added into a paint mixing tank and are stirred and mixed uniformly at high speed under the normal temperature condition to obtain the mixed coating. 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 organic silicon protective coating with the super-amphiphobic and super-weather-resistant properties.
Comparative example 4
(1) Preparation of modified silicone resin:
decyl triethoxysilane and 1H, 1H-undecafluoro-1-hexanol are mixed according to the mass portion ratio of 1: 1. adding the components into a three-mouth bottle according to the proportion, stirring, heating to 70 ℃, reacting for 1.5h, and then cooling and discharging to obtain the modified organic silicon resin.
(2) Preparing a protective coating:
55 parts by mass of modified organic silicon resin, 24 parts by mass of polydopamine biomimetic modified titanium dioxide whisker nano particles, 2 parts by mass of phthalate complex catalyst, 2.5 parts by mass of organic silicon flatting agent, 2 parts by mass of dispersing agent, 2.5 parts by mass of organic silicon defoaming agent and 24 parts by mass of butyl acetate solvent are respectively added into a paint mixing tank and are stirred and mixed uniformly at high speed under the normal temperature condition to obtain the mixed coating. 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 organic silicon protective coating with the super-amphiphobic and super-weather-resistant properties.
Comparative example 5
Adding 44.55 parts by mass of dodecyl trimethoxy silane, 23.45 parts by mass of 1H, 1H-pentadecafluoro-1-octanol (the mass part ratio of the dodecyl trimethoxy silane to the 1H, 1H-pentadecafluoro-1-octanol is 1.9: 1), 25 parts by mass of polydopamine bionic modified carbon nanofiber nano particles, 0.5 part of stannous octoate, 2 parts of organic silicon leveling agent, 2 parts of dispersing agent, 2.5 parts of organic silicon defoaming agent and 28 parts of butanol solvent into a paint mixing tank at room temperature, and stirring at high speed and mixing uniformly 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 prepare the corresponding organic silicon protective coating.
Comparative example 6
Adding 71 parts by mass of tetradecyl triethoxysilane (1H removed, 1H-nonadecafluoro-1-decanol), 20 parts by mass of polydopamine biomimetic modified carbon nanofiber nanoparticles, 1 part by mass of stannic naphthenate, 2 parts by mass of an organic silicon flatting agent, 1.5 parts by mass of a dispersing agent, 2.5 parts by mass of an organic silicon defoaming agent and 25 parts by mass of an ethyl acetate solvent into a paint mixing tank respectively at room temperature, and stirring and mixing uniformly at high speed under normal temperature to obtain the mixed coating. And then spraying the mixed coating on the surfaces of the steel plate and the concrete substrate after surface treatment, and drying and curing at room temperature to prepare the corresponding organic silicon protective coating.
2. Performance measurement of protective coating:
(1) Super-hydrophobic and super-oleophobic properties:
a20-microliter syringe is used for respectively dropping a drop of deionized water, ethylene glycol and hexadecane on the surfaces of the protective coatings prepared in the examples and the comparative examples, and a static hydrophobic angle measuring instrument is adopted to respectively measure the contact angles of the protective coatings to the water, the ethylene glycol and the hexadecane.
(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 appearance of the coating is observed after continuous 3000h, 5000h and 7000h tests by using UV-A bulbs (the experimental conditions are that the radiation is carried out for 8h under an ultraviolet lamp, the rain is carried out for 4h, and the temperature is cycled within the range of 35-80 ℃), and meanwhile, the contact angles of the protective coating to water, glycol and hexadecane after 7000h aging are tested.
(3) Wear resistance:
the wear resistance of the protective coatings prepared in the examples and the comparative examples was tested by adhering 800-mesh sandpaper to the surface of a grinding wheel of a wear tester, the load mass of each rubber grinding wheel was 1kg, and after a continuous 5000-revolution wear test under the conditions, the surface wear condition of the protective coating was observed and the contact angles of the worn protective coating to water, ethylene glycol and hexadecane were tested.
(4) Adhesive property:
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, the concrete test block and the steel plate are cured for 7 days under standard conditions after drying, and finally, the bonding strength of each protective coating to the concrete base surface and the steel plate base surface is respectively tested according to the GB/T5210-2006 standard, and the bonding strength is compared with the bonding strength of the protective coatings commonly used in the market, such as acrylic acid, polyurethane, polyurea, alkyd resin, organic silicon resin and the like.
(5) The corrosion resistance is as follows:
the protective coatings prepared in the examples and the comparative examples are respectively immersed in sodium chloride solution with the mass fraction of 3.5% for immersion corrosion test, the surface appearance of the coatings is observed after the coatings are continuously tested for 7 days, 14 days, 28 days and 56 days, and the contact angles of the protective coatings to water, ethylene glycol and hexadecane after the coatings are 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 1-8 have excellent super-amphiphobic performance, aging resistance (after 7000h artificial accelerated aging test, the paint film does not have the phenomena of pulverization, bubbling, cracking, peeling and the like, and the coating still has super-hydrophobic and certain oleophobic performance), wear resistance (after continuous 5000-turn abrasion test, the surface of the protective coating is not obviously worn and the coating still has super-hydrophobic and certain oleophobic performance), high adhesion performance (the adhesion strength of the metal base surface and the concrete base surface is respectively greater than 10MPa and 4 MPa) and corrosion resistance (after the coating is tested for 7 days, 14 days, 28 days and 56 days, the surface of the coating is not obviously subjected to the phenomena of swelling, pulverization, cracking and the like, and after the 56 days, the coating still has the super-amphiphobic performance). In the comparative example 1, the nano particles are not modified, so that the bonding strength between the coating and the surface of the matrix and the crosslinking degree of the coating are obviously reduced, and the wear resistance, the bonding strength and the corrosion resistance of the coating are obviously reduced compared with those of the coating in the example 1; comparative example 2 does not contain fibrous or filamentous nanoparticles, only contains polydopamine formed by pure dopamine hydrochloride self-polymerization, and the prepared coating does not have the function of super-amphiphobicity; in comparative examples 3 and 4, the mass part ratio of the organic silicon resin to the fluorocarbon alcohol exceeds the specified range, and the performances of the prepared coatings have certain difference compared with those of the examples; in the comparative example 5, after the fluorocarbon alcohol is directly blended, the coating has poor film forming property, does not have the super-oleophobic function, and has poor durability and bonding property; in comparative example 6, after the fluorocarbon alcohol is removed, the coating does not have the super oleophobic function, and the aging 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 silane or triethoxy silane containing long-chain alkyl, wherein the carbon atom number of the long-chain alkyl is 6-18;
the fluorocarbon alcohol is a straight-chain fluorocarbon alcohol with 5-10 carbon atoms and no fluorine group on the carbon atom directly connected with the hydroxyl;
the nano particles in the poly-dopamine biomimetic modified nano particles are of fiber rod-shaped or filamentous structures and are selected from one or a mixture of more of carbon nano tubes, carbon nano fibers, palygorskite, titanium dioxide whiskers and potassium titanate whiskers.
2. The super-amphiphobic super-weather-resistant organic silicon protective coating as claimed in claim 1, which is characterized by further comprising the following raw material components in parts by weight:
the catalyst is any one of naphthenate or carboxylate of Pb, fe, zn, sn, co, etc., phosphonitrile chloride and phthalate ester complex.
3. The super-amphiphobic super-weatherable silicone protective coating according to claim 1 or 2, wherein the mass ratio of the silicone resin to the fluorocarbon alcohol is (1.5-2): 1, the sum of the mass of the organic silicon resin, the fluorocarbon alcohol and the polydopamine bionic modified nano particles accounts for 65-85% of the total mass.
4. The super-amphiphobic super-weatherable silicone protective coating of claim 1, wherein said fluorocarbon alcohol is selected from any one of 1H, 1H-nonafluoro-1-pentanol, 1H-undecafluoro-1-hexanol, 1H-tridecafluoro-1-heptanol, 1H-pentadecafluoro-1-octanol, 1H-heptadecafluoro-1-nonanol, and 1H, 1H-nonadecafluoro-1-decanol.
5. The super-amphiphobic super-weatherable silicone protective coating of claim 1, wherein the nanoparticles have a particle size of 25-100nm.
6. The super-amphiphobic super-weatherable silicone protective coating of claim 2, wherein the catalyst is selected from any one of lead naphthenate, iron naphthenate, zinc naphthenate, tin naphthenate, cobalt naphthenate, dibutyltin dilaurate, stannous octoate, hexachlorocyclotriphosphazene, titanate complex.
7. The super-amphiphobic super-weatherable silicone protective coating of claim 1, wherein the organic solvent is a mixture of one or more of toluene, xylene, cyclohexane, ethyl acetate, butyl acetate, butanol.
8. The preparation method of the super-amphiphobic super-weatherable organic silicon protective coating disclosed by any one of claims 1 to 7 is characterized by comprising the following specific steps of:
(1) Preparation of modified silicone resin: adding 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 modified organic silicon resin;
(2) Respectively adding modified organic silicon resin, polydopamine bionic modified nano particles, a catalyst, an organic silicon flatting agent, a dispersing agent, an organic silicon defoaming agent and a solvent into a paint mixing tank, and stirring and mixing uniformly at a high speed under a normal temperature condition to obtain the super-amphiphobic super-weather-resistant organic silicon protective coating;
(3) And (3) spraying the protective coating obtained in the step (2) on the surface of the substrate after surface treatment, and curing and drying at normal temperature to obtain the organic silicon protective coating with the super-amphiphobic and super-weather-resistant properties.
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