CN109354961B

CN109354961B - Organic fluorine-silicon polymer, rusty anti-corrosion protective coating agent thereof and preparation method thereof

Info

Publication number: CN109354961B
Application number: CN201810625457.XA
Authority: CN
Inventors: 高丽; 郝健; 崔永梅; 王辉; 李小伟
Original assignee: University of Shanghai for Science and Technology
Current assignee: University of Shanghai for Science and Technology
Priority date: 2018-06-18
Filing date: 2018-06-18
Publication date: 2021-01-12
Anticipated expiration: 2038-06-18
Also published as: CN109354961A

Abstract

The invention relates to an organic fluorine-silicon polymer, a rusty anti-corrosion protective coating agent and a preparation method thereof, wherein the structural formula of the polymer is as follows:

Description

Organic fluorine-silicon polymer, rusty anti-corrosion protective coating agent thereof and preparation method thereof

Technical Field

The invention relates to a coating agent and application thereof in the field of metallic cultural relic protection, in particular to an organic fluorine-silicon polymer, a rusty anti-corrosion protective coating agent thereof and a preparation method thereof.

Background

The representative technologies for the current rust corrosion protection are mainly rust paints, which form a wide variety of types, and the basic film-forming materials used at present include: polyethylene, polystyrene butylene, alkyd, epoxy, oily phenolic, epoxy-asphalt, polyacrylate, polyvinyl butyral, and the like. The mechanism of the rust-containing anticorrosion action of the coating is generally divided into: stable, conversion, permeation, water-based rusty paint and functional rusty anticorrosive paint. Active rust preventive pigments are often used for stable rust preventive coatings. Mainly comprises active antirust pigments such as chromate, phosphate, ferrite and the like. The conversion type rusty paint contains a conversion agent which can chemically react with rust, and the conversion agent mainly comprises inorganic acid, organic complex and the like with passivation complexing effect. The commonly used permeable paint is vacuum boiled oil with strong permeability, oxidized fish oil, linseed oil varnish and alkyd resin mixture, etc. The film forming matter of the water-based rust-bearing antirust paint mainly comprises epoxy resin, polyurethane resin, acrylic resin, styrene-acrylic emulsion and the like. Each single type of rust-bearing coating also has its own limitations. For example, in the case of the stable type, the acid radical ions generated mainly by hydrolysis of the active pigment react with rust to form a stable complex, so that a long time is required for achieving the stability of the rust layer, and the drying of the coating film has certain limitation on the exertion of the effect of the active pigment. The conversion is less suitable for substrates with uneven plate rust. The penetration type has a certain difficulty in coating a rust layer with harmful active impurities and large thickness, and is easy to generate rust return. The water-based rusty paint has far lower water resistance, hardness and other comprehensive properties than the oil-based rusty paint. The functional rusted antirust coating combines the common characteristics of stable, conversion and permeation coatings, and is a hotspot of current research.

The metal corrosion process generally proceeds by two routes: chemical etching and electrochemical etching. Electrochemical corrosion is the main cause of metal corrosion. The electrochemical corrosion is that the metal and the electrolyte form two electrodes to form a primary battery with corrosiveness^[7]. The corrosion of the battery is mainly caused by that the moisture in the air is adsorbed on the surface of the metal to form a water film and the CO in the air₂、SO₂、NO₂The metal is dissolved in the water film to form electrolyte solution, and the metal soaked in the electrolyte solution always has impurities, so that the electrolyte solution is formedThe corrosion cell of (1), the metal is an anode and the impurity is a cathode, plus the metal is in close contact with the impurity, so that corrosion is continuously carried out. The corrosion is characterized in that a plurality of small bulges with different diameters are formed on the surface subjected to corrosion, and the sublayer is similar to black powdery ulcer corrosion pits. The technical principle of the invention is as follows: the loose and porous rust layer is bonded into a continuous closed coating, so that the air and water are prevented from permeating again, and the active and harmful rust in the rust layer is passivated into stable and harmless filler by the coating film to form a closed metal protective barrier layer, so that the environment generated by rust is inhibited. The protected base material and the corrosion product (harmful rust) are effectively isolated from the external corrosion medium, so that the harmful rust loses activity, and meanwhile, the adhesive force among the rust layer, the coating and the metal base material is enhanced, so that the harmful rust with higher potential is prevented from further performing electrochemical reaction with the metal base material with lower potential to generate new rust, and the metal cultural relic does not rust any more. In addition, the surface volume resistance is as high as 4 multiplied by 10 measured by the volume surface resistance¹³Omega, has good insulating property, further prevents current conduction, and effectively reduces the electrochemical corrosion rate. The rusted anti-corrosion coating technology has excellent anti-rust performance, can be directly coated on the surface of rusted metal cultural relics, simplifies the rust removal process, improves the working efficiency and reduces the cost. Meanwhile, the technology is developing towards the multifunctional rusty direction integrating the functions of rust infiltration, rust stabilization and rust conversion, and the technology is not like the traditional single type and has small application scope. The technology of the invention can keep rust stable, prevent the rusted surface of the metal cultural relic from being further corroded, and achieve the purposes of rust removal and corrosion prevention. The technology has no obvious influence on the appearance of the metal cultural relic substrate (no brightening and no obvious change of the original appearance vision of the substrate), has the characteristics of ultra-thin property, quick drying, water resistance, corrosion resistance, weather resistance, strong adhesive force, insulation, convenient use and the like, and can play a good role in protecting the surfaces of various metals. The product of the coating technology has no chemical corrosion effect on various metal materials. The artificial accelerated aging test shows that the polymer coating generates ester group fracture and forms stability when being subjected to long-time photodegradationThe lactone with better performance can not cause secondary damage to the metallic cultural relics, and the coating can be removed in a simple and easy way without damaging the protective base material. The appearance and the aging performance of the coating film are tested and meet the corresponding national standard. Research results show that the technology has good application prospect in the field of metal on-rust corrosion protection. Can replace the traditional manual or mechanical polishing, sand blasting or acid pickling rust removal process, and belongs to an energy-saving and environment-friendly product.

Ancient people in China leave abundant cultural heritages for us. Unfortunately, over time, combined with the effects of the natural environment, historical cultural heritage is subject to varying degrees of damage and harm over the years. The variety of metallic cultural relics is many, and the ironware and the cuprum ware have the largest quantity and the most serious problems. The most easily rusted metal cultural relics are ironware, and then bronze, brass and the like, and unearthed copper and ironware cultural relics are easily corroded by oxygen, carbon dioxide and water vapor in the air. And due to the long-term burying underground and the limitation of storage conditions after unearthing, a series of problems of corrosion repair, subsequent corrosion prevention and the like are faced.

From the cultural relic protection unit and the literature inquiry, the existing metal cultural relic protection is understood to be respectively treated from different materials and damage reasons:

1) ironware cultural relics

The manual rust removal method mainly comprises the steps of removing rust manually, but has the disadvantages of low production efficiency, high labor intensity, poor protection of workers and poor rust removal effect, and cannot fundamentally solve the problem of long-term storage of ironware.

Secondly, chemical rust removal, wherein acid mist generated in the acid cleaning process can damage the respiratory system of constructors, and volatile gas and sewage can pollute the environment.

Bronze cultural relics

And (4) protecting the bronze metal cultural relics. The cause of bronze cultural relic corrosion: mainly because the harmful rust interacts with air and water, and the bronze ware is pulverized in a circulating corrosion process, so that the bronze ware is called bronze disease and is difficult to treat. The rust on the bronze ware can be removed mechanically or by electrolytic reduction, which is unstable in operation, uniform cleanliness of the bronze surface is difficult to obtain, and scale and rust firmly adhered to the bronze ware surface cannot be removed. Furthermore, the brass is corroded seriously and cannot be subjected to rust removal treatment. The bronze ware is protected by corrosion inhibitor, such as benzotriazole, but benzotriazole is easy to be sublimated by heat and loses protection effect. And the protection effect on the bronze ware with serious corrosion is not very ideal.

At present, most of metal cultural relics adopt the protection method, the metal cultural relic protection method has the defects, in addition, the metal cultural relic protection method is not long, or the appearance of the metal cultural relic is influenced to a certain extent by the protection means, and meanwhile, the problem that the cultural relic is subjected to color change or even invalidation after being placed for a period of time due to the insufficient protection capability of the cultural relic protection method can influence the appearance and even cause potential safety hazards. The cultural relic protection unit expects a novel metal cultural relic protection technology which is simple and effective in construction and does not influence the appearance of the cultural relic, and is a hotspot and a difficulty of current research.

Disclosure of Invention

An object of the present invention is to provide an organofluorosilicone polymer.

The invention also aims to provide a rust-bearing anti-corrosion protective coating agent.

The invention also aims to provide a preparation method of the film coating agent.

An organic fluorine-silicon polymer is characterized in that the structural formula of the polymer is as follows:

the anticorrosive protective film coating agent with rust adopts the organic fluorine-silicon polymer as a main component, and is characterized in that R is_FA C3 to C8 fluoroalkyl group; r is H or CH₃(ii) a R' is CzH_2z+1Z is 1-8; g is: c₆H₅(ii) a K is Si (OCzH)_2z+1)₃Z is 1-2; n is 30-100, m is 30-150, o is 5-10, and p is 5-10. The coating agent comprises the following components by weightThe parts are as follows:

a method for preparing the rusty anti-corrosion protective coating agent is characterized by comprising the following specific steps:

a. stirring 30-60 parts of fluorine-containing acrylate monomer, 5-10 parts of vinyl silicon monomer, 30-60 parts of (methyl) acrylate monomer, 5-10 parts of styrene, preferably 0.6-0.8 part of azobisisobutyronitrile at 65-80 ℃ for 1.5-4 hours, and adding 3-5 parts of cross-linking agent when the polymerized monomer is polymerized to have certain viscosity (glycerin shape); continuously stirring and reacting for 1.5-3 hours, and adding a solvent accounting for 30-50% of the total mass of the mixed monomers in the reaction to prevent the reaction from imploding; after the reaction is finished, adding a solvent accounting for 10-30% of the total mass of the mixed monomers for dilution;

b. and (b) adding the rest components into the solution obtained in the step (a), and dispersing at a high speed for 0.5-1 hour to obtain the rusty anticorrosive protective coating agent.

The fluorine-containing acrylate monomer is trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluorobutyl methacrylate, octafluoropentyl methacrylate or 2- (perfluorohexyl) ethyl methacrylate.

The vinyl silicon monomer is tetramethyl divinyl disiloxane, vinyl trimethoxy silane or vinyl triethoxy silane.

The particle size of the silicon dioxide is 14-16 nm; the titanium dioxide is rutile type and 800-1250 meshes; the particle size of the graphite fluoride is 3-8 um.

The auxiliary agents are thickening agents, delustering agents, coupling agents, rust stabilizers and antioxidants. The coupling agent is KH-570, KH-550 and KH-560.

The cross-linking agent is divinylbenzene, ethylene glycol dimethacrylate or neopentyl glycol diacrylate; the initiator is benzoyl peroxide, azobisisobutyronitrile and a peroxy-tert-butyl compound.

The solvent is one or a mixture of ester organic solvent or fluorine-containing organic solvent, alkane solvent or ether.

The ester organic solvent comprises one or more of methyl acetate, ethyl acetate, propyl acetate, butyl acetate, dimethyl carbonate or amyl acetate.

The fluorine-containing organic solvent comprises one or more of perfluoroheptane, perfluorohexane or tetrafluoroethyl tetrafluoropropyl ether.

The alkane solvent comprises mineral oil, liquid paraffin or ethanol, etc.

The ether solvent includes petroleum ether and the like.

The essence comprises one or more of green apple essence, lemon essence and orange essence.

The high-speed dispersion is preferably carried out using a disk high-speed disperser.

Adding the mixed polymer monomer and the initiator into a reaction vessel according to a certain weight ratio, heating and stirring. The polymerization time is different when the monomers are mixed according to different total mass, and the heating and stirring time is longer when the total mass of the reaction polymerization monomers is larger.

When the initiator is a thermal initiator such as dibenzoyl peroxide, azobisisobutyronitrile, the polymerization is carried out in the following manner: stirring for 1.5-5 hours at 70 ℃ (the stirring time is prolonged along with the increase of the amount of the reaction mixed monomers), then cooling to 50 ℃, and keeping for 30-60 minutes at 50 ℃. Naturally cooling to room temperature, diluting the polymer resin to a certain concentration, and then generally 10-30%, wherein the polymer resin can be used after being aged at room temperature at a low concentration, and the aging effect is better under the heating condition of high concentration. High-concentration high-temperature curing is favorable for quick drying of the coating, so that the time is saved.

When the initiator is a high temperature initiator such as a peroxy-tert-butyl compound, the polymerization mode is: stirring for 1.5-4 hours at 120 ℃, then cooling to 50 ℃, and keeping for 30-60 minutes at 50 ℃. Naturally cooling to room temperature, diluting the polymer resin to a certain concentration, and then generally 10-30%, aging at room temperature for use, and the aging effect under heating condition is better.

The polymer formed after the free radical initiation is a thermoplastic polymer, and is a solvent soluble polymer resin. The fluorine-containing monomer and the fluorine-containing solvent in the polymer coating liquid ensure the flame retardant property of the coating material.

Proper amount of nano silicon dioxide, titanium dioxide and graphite fluoride are added into the polymer coating liquid to increase the water repellency and corrosion resistance of the polymer. Graphite fluoride also increases lubricity.

The polymer coating has high water repellency, and has a large contact angle with water, which is more than 110 degrees, so that water drops are easy to roll off and difficult to adhere to the surface, and dust on the surface is easy to be taken away by the water drops, so that the polymer coating has good self-cleaning capability. On the other hand, the surface of the base material coated with the self-made fluorine-containing acrylic resin has lower surface energy, so that chemical medicines such as acid and alkali are difficult to spread and wet on the surface of the material, and the etching of the chemical medicines to the base material is further prevented or delayed, thereby playing a role in protecting the base material. The pretreatment requirement of the surface of the base material is as follows: the coated surface is simply cleaned and the greasy dirt and water on the surface are removed. And the coating technology is compared with manual rust removal, commercially available rusty paint, a citric acid rust remover and benzotriazole. The rusted anti-corrosion metal protective coating technology provided by the invention overcomes the defects in the technical field of the existing metal cultural relic protection, and has a wide market prospect.

Detailed Description

The sources of the raw materials used are shown in table 1.

TABLE 1

The first embodiment is as follows:

adding 30 g of hexafluorobutyl methacrylate, 5 g of vinyltrimethoxysilane, 12.5 g of (methyl) acrylates (4.5 g of methyl methacrylate, 3.5 g of glycidyl methacrylate, 2.5 g of n-butyl acrylate and 2 g of isooctyl acrylate) and 2.5 g of styrene into a container, then adding 0.3 g of azobisisobutyronitrile, stirring for 1.5 hours at 70 ℃ to completely dissolve the initiator, adding 1.5 g of a cross-linking agent to continue stirring for half an hour after the polymerized monomer is polymerized to have certain viscosity (in a glycerol state), and controlling the crosslinking degree of the monomer (the reaction polymer is in a viscous and threadlike shape). And adding a solvent accounting for 30 percent of the total mass ratio of the mixed monomers in the reaction to prevent the reaction from imploding. After the reaction is finished, adding a solvent to dilute the mixture to a certain concentration, wherein the concentration is usually 10-30%, the concentration is low for simple protection, and the concentration is high for high protection degree. 4 g of nano silicon dioxide, 0,5 g of titanium dioxide, 0.5 g of graphite fluoride, 4 g of flatting agent, 1 g of antioxidant and 3 g of coupling agent can be added, and a high-speed dispersion machine is used for dispersing for half an hour at 4000 revolutions per minute.

Firstly, simply cleaning and drying an iron plate, then uniformly coating or spraying the mixed coating liquid on the surface of the iron plate by using a spray gun, adjusting the concentration according to the requirement, aging for 30 minutes at room temperature when the concentration is low, drying better by using a hair drier, placing an iron sheet in a drying oven which is kept at a constant temperature of 25 ℃ for 60 minutes when the concentration is high, then raising the temperature to 100 ℃ by programming, and keeping for 30 minutes at 100 ℃. Naturally cooling to room temperature, aging at room temperature for 1 day, and making the polymer on the surface layer of the iron plate uniform, flat and smooth. The coating film can be quickly dried by heating and curing at high concentration, so that the time is saved.

The contact angle and the rolling angle were measured, and the results of the coating film correlation property test and the flame retardant property are shown in table 2.

TABLE 2

Example two:

adding 15 g of dodecafluoroheptyl methacrylate, 5 g of vinyl triethoxysilane, 25 g of (meth) acrylates (9 g of methyl methacrylate, 7 g of glycidyl methacrylate, 5 g of n-butyl acrylate and 4 g of isooctyl acrylate) and 5 g of styrene into a container, then adding 0.3 g of azobisisobutyronitrile, stirring for 1.5-3 hours to completely dissolve an initiator, adding 1.5 g of a crosslinking agent into the mixture after the polymerization monomer is polymerized to have a certain viscosity (in a glycerol state), and continuing stirring for half an hour to control the crosslinking degree of the monomer (the reaction polymer is viscous and threadlike). And adding a solvent accounting for 30 percent of the total mass ratio of the mixed monomers in the reaction to prevent the reaction from imploding. After the reaction is finished, adding a solvent to dilute the mixture to a certain concentration, wherein the concentration is usually 10-30%. The concentration is low for simple protection, and high for the requirement of the protection degree. 4 g of nano silicon dioxide, 0,5 g of titanium dioxide, 0.5 g of graphite fluoride, 4 g of flatting agent, 1 g of antioxidant and 3 g of coupling agent can be added, and a high-speed dispersion machine is used for dispersing for half an hour at 4000 revolutions per minute.

Preparing two rusted iron plates which are identical in shape, firstly simply cleaning and drying the rusted iron plates, then uniformly coating or spraying a mixed coating liquid on the surface of one rusted iron plate by using a spray gun, adjusting the concentration according to requirements, aging the rusted iron plates for 30 minutes at room temperature when the concentration is low, drying the rusted iron plates better under the assistance of a hair dryer, placing the rusted iron plates in an oven which is kept at a constant temperature of 25 ℃ for 60 minutes when the concentration is high, then heating the rusted iron plates to 100 ℃ by a program, and keeping the rusted iron plates for 30 minutes at 100 ℃. Naturally cooling to room temperature, aging at room temperature for 1 day, and making the polymer on the surface layer of the iron plate uniform, flat and smooth.

The contact angle and the rolling angle were measured, and the results of the performance test and the flame retardant property of the iron plate surface film layer are shown in table 3.

TABLE 3

And (4) manually and mechanically removing rust from the other rusted iron plate, and comparing the two iron plates after the iron plates are placed for half a month.

After half a month, the surface of the artificially-derusted iron plate is continuously corroded, the iron plate is pulverized, the other piece of the coated iron plate is not continuously corroded, and the coated film is intact. The result shows that the film coating technology of the invention is also suitable for rusted metal, can replace manual mechanical derusting, reduces labor intensity and improves efficiency.

Example three:

adding 35 g of dodecafluoroheptyl methacrylate, 5 g of vinyltrimethoxysilane, 7.5 g of (methyl) acrylates (1.5 g of methyl methacrylate, 3 g of glycidyl methacrylate, 2 g of n-butyl acrylate and 1 g of isooctyl acrylate) and 2.5 g of styrene into a container, then adding 0.3 g of azobisisobutyronitrile, stirring for 2.5 hours to completely dissolve an initiator, adding 1.5 g of a crosslinking agent into the mixture until the monomers are polymerized to have certain viscosity (in a glycerol shape), and continuously stirring for half an hour to control the crosslinking degree of the monomers (the reaction polymer is viscous and in a pulling-shaped shape). And adding a solvent accounting for 30 percent of the total mass ratio of the mixed monomers in the reaction to prevent the reaction from imploding. After the reaction is finished, adding a solvent for dilution (different concentrations can be prepared according to requirements), wherein the dilution is usually 10-30%, the concentration is low for simple protection, and the requirement on the protection degree is high and the required concentration is high. 4 g of nano silicon dioxide, 0.5 g of titanium dioxide, 0.5 g of graphite fluoride, 4 g of flatting agent, 1 g of antioxidant and 3 g of coupling agent can be added, and a high-speed dispersion machine is used for dispersing for half an hour at 4000 revolutions per minute.

Firstly, simply cleaning and drying an iron plate, then uniformly coating the mixed coating liquid on the half-edge surface of the iron plate or spraying the mixed coating liquid by using a spray gun for coating, adjusting the concentration according to the requirement, aging for 30 minutes at room temperature when the concentration is low, drying better by using a hair drier, baking the iron plate for 60 minutes in an oven which has the constant temperature of 25 ℃ when the solid content concentration is high, then programming the temperature to 100 ℃, and keeping the temperature for 30 minutes at 100 ℃. Naturally cooling to room temperature, aging at room temperature for 1 day, and making the polymer on the surface layer of the iron plate uniform, flat and smooth. After the iron plate is normally placed in an external environment for three months, the iron plate still shows water repellency after being coated, the appearance of the iron plate has no obvious change, and the iron plate which is not coated is spread by water flow and has no water repellency, and obvious rusts appear on the surface of the iron plate which is not coated.

Example four:

300 g of dodecafluoroheptyl methacrylate, 50 g of vinyl triethoxysilane, 125 g of (meth) acrylates (wherein 35 g of methyl methacrylate, 45 g of glycidyl methacrylate, 25 g of n-butyl acrylate and 20 g of isooctyl acrylate) and 25 g of styrene are added into a container, then 3 g of azobisisobutyronitrile is added, stirring is carried out for 3 hours to completely dissolve the initiator, when the polymerization monomer is polymerized to have certain viscosity (in a glycerol shape), 15 g of crosslinking agent is added, stirring is continued for half an hour, and the crosslinking degree of the monomer is controlled (the reaction polymer is in a viscous and pull-thread shape). And adding a solvent accounting for 30 percent of the total mass ratio of the mixed monomers in the reaction to prevent the reaction from imploding. After the reaction is finished, adding a solvent for dilution (different concentrations can be prepared according to requirements), wherein the dilution is usually 10-30%, the concentration is low for simple protection, and the concentration is high for high protection degree. 4 g of nano silicon dioxide, 0,5 g of titanium dioxide, 0.5 g of graphite fluoride, 4 g of flatting agent, 1 g of antioxidant and 3 g of coupling agent can be added, and a high-speed dispersion machine is used for dispersing for half an hour at 4000 revolutions per minute.

Firstly, cleaning and drying the surface of a certain museum ironware cultural relic, then uniformly coating or spraying the mixed coating liquid on the surface of the certain museum ironware cultural relic by using a spray gun, wherein one half of the certain museum ironware cultural relic is coated by the coating liquid, the coating method is the same as the third embodiment, the other half of the certain museum ironware cultural relic is coated by using the commercial product rusty paint, the museum ironware cultural relic is placed in a drying oven which is kept at the constant temperature of 25 ℃ for baking for 60 minutes, then the temperature is programmed to 100 ℃, and the temperature is kept at 100 ℃ for 30 minutes. Naturally cooling to room temperature, and aging for 1 day at room temperature.

The contact angle and the rolling angle of two sides of the ironware cultural relic in a certain museum are measured, and the related performance test and the flame retardant performance of two sides of the ironware cultural relic in a certain museum are shown in the table 4.

TABLE 4

From the test results in the table, the commercial rusty paint changes the luster of the surface of ironware, which obviously does not conform to the cultural relic protection principle, the commercial rusty paint has longer surface drying time and is time-consuming, the wear resistance of the commercial rusty paint is poorer than that of the sample, the volume resistance of the commercial rusty paint is far smaller than that of the self-made rusty anti-corrosion coating liquid, the insulation property is poor, and in addition, the water resistance and the chemical corrosion resistance of the commercial rusty paint lose effectiveness with the passage of time. In addition, most of the commercially available rusty paint is a double-component product, and the rusty paint is a single component, can be directly sprayed or brushed without adding any matched product, and is convenient to use. The comparison result shows that the coating technology has excellent water-repellent anticorrosion protection effect and is easy to remove.

Example five:

300 g of dodecafluoroheptyl methacrylate, 50 g of vinyl triethoxysilane, 125 g of (meth) acrylates (wherein 35 g of methyl methacrylate, 45 g of glycidyl methacrylate, 25 g of n-butyl acrylate and 20 g of isooctyl acrylate) and 25 g of styrene are added into a container, then 3 g of azobisisobutyronitrile is added, stirring is carried out for 3 hours to completely dissolve the initiator, when the polymerization monomer is polymerized to have certain viscosity (in a glycerol shape), 15 g of crosslinking agent is added, stirring is continued for half an hour, and the crosslinking degree of the monomer is controlled (the reaction polymer is in a viscous and pull-thread shape). And adding 50% of solvent of the total mass ratio of the mixed monomers in the reaction to prevent the reaction from imploding. After the reaction is finished, adding a solvent for dilution (different concentrations can be prepared according to requirements), wherein the dilution is usually 10-30%, the concentration is low for simple protection, and the concentration is high for high protection degree. 4 g of nano silicon dioxide, 0,5 g of titanium dioxide, 0.5 g of graphite fluoride, 4 g of flatting agent, 1 g of antioxidant and 3 g of coupling agent can be added, and a high-speed dispersion machine is used for dispersing for half an hour at 4000 revolutions per minute.

The museum copper cultural relics are cleaned simply, dedusted, degreased, washed by ethanol and dried to be dry. The construction is carried out region by region. Coating the coating liquid on the surface of the copper cultural relics by using a brush, or spraying the coating liquid on the copper cultural relics of a museum by using a spray gun, standing and airing the copper cultural relics of the museum, or drying the copper cultural relics of the museum by using electric blowing for assistance. After the film coating is finished, the copper cultural relics in a certain museum are placed for 3 hours in a static mode and then are placed normally. After 1 day of further curing, the effect was tested. Scratches on the surface of the copper cultural relics in a certain museum are reduced, and the polymer coating on the surface layer is uniform, flat and smooth in texture. The paint film simultaneously shows good water-repellent and anti-corrosion characteristics.

The contact angle and the rolling angle, the film layer-related property test and the flame retardant property were measured, and the results are shown in table 5.

TABLE 5

Example six:

15 kg of dodecafluoroheptyl methacrylate, 5 kg of vinyl trimethoxy silane, 22.5 kg of (meth) acrylates (8.5 kg of methyl methacrylate, 5.5 kg of glycidyl methacrylate, 4.5 kg of n-butyl acrylate and 4 kg of isooctyl acrylate) and 2.5 kg of styrene are added into a container, then 0.3 kg of azobisisobutyronitrile is added, stirring is carried out for 4 hours to completely dissolve the initiator, 1.5 kg of a cross-linking agent is added to continue stirring for half an hour after the polymerization monomer has a certain viscosity (in a glycerol state), and the degree of cross-linking of the monomer (the reaction polymer is viscous and pulled) is controlled. And adding a solvent accounting for 80 percent of the total mass ratio of the mixed monomers in the reaction to prevent the reaction from imploding. After the reaction is finished, adding a solvent for dilution (different concentrations can be prepared according to requirements), wherein the dilution is usually 10-30% for simple protection and low concentration, and the requirement on the protection degree is high and the required concentration is high. 40 g of nano silicon dioxide, 5 g of titanium dioxide, 5 g of graphite fluoride, 40 g of flatting agent, 40 g of antioxidant and 30 g of coupling agent can be added, and a high-speed dispersion machine is used for dispersing for 1 and half hours at 4000 revolutions per minute.

After being cleaned, dedusted and degreased simply, certain waste bronze is cleaned by ethanol and then dried to be in a dry state. And one half of the waste bronze is coated by using coating liquid, the coating method is the same as that of the fifth embodiment, and the other half of the waste bronze is coated by using a commercial product citric acid rust remover. After the waste bronze is solidified for 1 day, the waste bronze is normally placed for half a year and then subjected to a water splashing experiment. The waste bronze after coating obviously shows the water repellency and the appearance of the cultural relic is not changed, and the surface of the waste bronze which is not coated with the citric acid rust remover only spreads in a water flow manner, so that the waste bronze has no water repellency and the surface is heavily rusted.

Therefore, the rust on the surface of bronze can be removed only in a short time by coating the citric acid rust remover, and the bronze ware can be continuously rusted after being placed for a long time, so that the protection effect is lost. The coating technology of the invention has long-term effect.

Example seven:

adding 35 kg of dodecafluoroheptyl methacrylate, 5 kg of vinyltrimethoxysilane, 7.5 kg of (meth) acrylates (wherein 2 kg of methyl methacrylate, 2.5 kg of glycidyl methacrylate, 1.5 kg of n-butyl acrylate and 1.5 kg of isooctyl acrylate) and 2.5 kg of styrene into a container, then adding 0.3 kg of azobisisobutyronitrile, stirring for 5 hours to completely dissolve an initiator, adding 1.5 kg of a crosslinking agent into the mixture until the monomer is polymerized to have certain viscosity (in a glycerol state), and continuously stirring for half an hour to control the crosslinking degree of the monomer (the reaction polymer is in a viscous zipper shape). And adding 50% of solvent of the total mass ratio of the mixed monomers in the reaction to prevent the reaction from imploding. After the reaction is finished, adding a solvent for dilution (different concentrations can be prepared according to requirements), wherein the dilution is usually 10-30%, the concentration is low for simple protection, and the requirement on the protection degree is high and the required concentration is high. 4 g of nano silicon dioxide, 1 g of titanium dioxide, 4 g of graphite fluoride, 4 g of a leveling agent, 4 g of an antioxidant and 10 g of a coupling agent can be added, and a high-speed dispersion machine is used for dispersing for one hour at 4000 revolutions per minute.

After being cleaned, dedusted and degreased simply, certain waste bronze is cleaned by ethanol and then dried to be in a dry state. And one half of the waste bronze is coated by using the coating liquid, the coating method is the same as that of the fifth embodiment, and the other half of the waste bronze is coated by using the benzotriazole which is a commercially available product. After the waste bronze is solidified for 1 day, the waste bronze is normally placed for half a year and then subjected to a water splashing experiment. The waste bronze after coating obviously shows water repellency and the cultural relics are not changed in appearance, and the surface of the waste bronze which is not coated with the benzotriazole only spreads in a water flow manner, so that the waste bronze has no water repellency and is aggravated in surface corrosion.

The contact angle and the rolling angle were measured, and the bronze surface film layer-related property tests and flame retardancy were performed, and the results are shown in table 6.

TABLE 6

The commercially available benzotriazole is slightly soluble in water, has poor water repellency, poor acid corrosion resistance, easy combustion, easy failure under high temperature conditions, poor neutral salt spray resistance and poor ultraviolet aging resistance. The coating technology of the invention obviously improves the technical defects of the benzotriazole on the market.

Example eight:

30 kg of dodecafluoroheptyl methacrylate, 2.5 kg of vinyl trimethoxy silane, 15 kg of (meth) acrylates (wherein the methyl methacrylate is 5 kg, the glycidyl methacrylate is 4 kg, the n-butyl acrylate is 3 kg, and the isooctyl acrylate is 3 kg) and 2.5 kg of styrene are added into a reaction kettle, then 0.3 kg of azobisisobutyronitrile is added, stirring is carried out for 6 hours to completely dissolve the initiator, 1.5 kg of a cross-linking agent is added to continue stirring for half an hour after the polymerization monomer is polymerized to have certain viscosity (in a glycerol shape), and the cross-linking degree of the monomer is controlled (the reaction polymer is in a viscous pull-thread shape). And adding 50% of solvent of the total mass ratio of the mixed monomers in the reaction to prevent the reaction from imploding. After the reaction is finished, adding a solvent for dilution (different concentrations can be prepared according to requirements), wherein the dilution is usually 10-30%, the concentration is low for simple protection, and the concentration is high for high protection degree. 40 g of nano silicon dioxide, 10 g of titanium dioxide, 10 g of graphite fluoride, 40 g of flatting agent, 40 g of antioxidant and 30 g of coupling agent can be added, and a high-speed dispersion machine is used for dispersing for one hour at 4000 revolutions per minute.

The bronze cultural relics in a certain museum are cleaned simply, dedusted, degreased, washed by ethanol and dried to be in a dry state. And (3) coating one half of the bronze ware of a certain museum by using the coating liquid, wherein the coating method is the same as that of the sixth embodiment, and the other half of the bronze ware keeps the original appearance. After being normally placed for three months, a water splashing experiment is carried out. The bronze relic after being coated obviously shows the water-repellent characteristic, and obvious rust stains do not appear on the surface of the coated bronze relic, while the bronze relic which is not coated spreads by water flow, has no water-repellent characteristic, and obviously aggravates the surface rust stains.

The contact and rolling angles, the coating related performance tests and the flame retardant properties were measured and the results are given in table 7.

TABLE 7

The technical scheme and the technical effect of the invention can be realized by changing fluorine-containing acrylate into dodecafluoroheptyl methacrylate, hexafluorobutyl methacrylate, trifluoroethyl methacrylate, octafluoropentyl methacrylate, tetrafluoropropyl methacrylate and 2- (perfluorohexyl) ethyl methacrylate and changing vinyl silicon monomer into tetramethyl divinyl disiloxane, vinyl trimethoxy silane or vinyl triethoxy silane.

The single-component rusty anti-corrosion coating liquid is prepared by adopting self-made fluorine-containing silicon acrylic resin as a main film forming substance and adding a certain proportion of auxiliary agent and inorganic pigment, has the advantages of no toxicity, no combustion, no explosion and low VOC, can be directly coated on the rustless metal surface by the coating technology, can be coated by slightly cleaning the rusted metal surface and removing surface grease and other impurities, and has a more prominent protective effect.

In conclusion, the invention effectively overcomes the defects in the prior art and simultaneously shows high industrialized market value and practical use value.

Claims

1. The anticorrosive protective film coating agent with rust adopts organic fluorine-silicon polymer as a main component, and is characterized in that the film coating agent comprises the following components in parts by weight:

the structural formula of the organic fluorine-silicon polymer is as follows:

wherein R is_FA C7 to C8 fluoroalkyl group; r is CH₃(ii) a R' is C_zH_2z+1Z is 5-8; g is: c₆H₅(ii) a K is Si (OC)_xH_2x+1)₃，x＝1-2；n＝30-100，m＝30-150，o＝5-10，p＝5-10。

2. The method for preparing the rusty anti-corrosion protective coating agent according to claim 1 is characterized by comprising the following specific steps:

a. stirring 30-60 parts of fluorine-containing acrylate monomer, 5-10 parts of vinyl silicon monomer, 30-60 parts of (methyl) acrylate monomer, 5-10 parts of styrene and 0.6-0.8 part of azodiisobutyronitrile at 70 ℃ for 1.5-4 hours, and adding 3-5 parts of cross-linking agent; continuously stirring and reacting for 1.5-3 hours, and adding a solvent accounting for 30% of the total mass of the mixed monomers in the reaction to prevent the reaction from imploding; after the reaction is finished, adding a solvent accounting for 10-30% of the total mass of the mixed monomers for dilution; the cross-linking agent is divinylbenzene, ethylene glycol dimethacrylate or neopentyl glycol diacrylate;

b. and (b) adding the rest components into the solution obtained in the step a, and dispersing at a high speed of 4000r/min for 0.5-1 hour to obtain the rusty anticorrosive protective coating agent.

3. The method of claim 2, wherein the fluoroacrylate monomer is dodecafluoroheptyl methacrylate or 2- (perfluorohexyl) ethylmethacrylate.

4. The method of claim 2, wherein the vinyl silicon monomer is tetramethyldivinyldisiloxane, vinyltrimethoxysilane, or vinyltriethoxysilane.

5. The method according to claim 2, wherein the silica has a particle size of 14 to 16 μm; the titanium dioxide is rutile type and 800-1250 meshes; the particle size of the graphite fluoride is 3-8 mu m.

6. The method according to claim 2, characterized in that the auxiliaries are thickeners, coupling agents, matting agents, rust stabilizers and antioxidants; the coupling agent is KH-570, KH-550 or KH-560.

7. The process according to claim 2, characterized in that the initiator is benzoyl peroxide, azobisisobutyronitrile or a peroxy tert-butyl compound.

8. The method according to claim 2, wherein the solvent is one or a mixture of an ester organic solvent or a fluorine-containing organic solvent, an alkane solvent or an ether.