CN102199390A - Protective agent for bridge with steel structure, preparation method thereof and application thereof - Google Patents
Protective agent for bridge with steel structure, preparation method thereof and application thereof Download PDFInfo
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- CN102199390A CN102199390A CN 201110083287 CN201110083287A CN102199390A CN 102199390 A CN102199390 A CN 102199390A CN 201110083287 CN201110083287 CN 201110083287 CN 201110083287 A CN201110083287 A CN 201110083287A CN 102199390 A CN102199390 A CN 102199390A
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Abstract
The invention discloses a protective agent for a bridge with a steel structure, a preparation method thereof and application thereof. The protective agent comprises the following components: an organic/inorganic composite fluorosilicone styrene polymer, lithium silicate, sodium molybdate, benzotriazole, nanometer titanium dioxide, sodium gluconate, ethanolamine, absolute ethanol and distilled water. Corrosion inhibiting ingredients contained in the protective agent can be attached to the metal surface of the bridge with the steel structure, so that a compact protective film is formed on the metal surface due to a passivating reaction for corrosion inhibition and corrosion prevention; a low-surface energy fluorosilicone styrene polymer component contained in the protective agent can be cured to form a film for playing the hydrophobic and protective roles; a nanometer component can improve the performance of ultraviolet aging resistance of a film layer, improve the performance of the polymer and provide the excellent self-cleaning performance and the like for the cured film; and hydroxyl generated by hydrolyzing siloxane groups can perform a condensation reaction with hydroxyl on the surface of the bridge with the steel structure to generate a chemical bond so as to improve adhesive power between the film layer and a matrix material and improve interface bonding. The protective agent is high in stability, non-toxic, environment-friendly, multiple in functions and easy to construct, can be widely used for the protection of the structural engineering of various bridges with the steel structures, and is favorable for improving the service life of the bridge with the steel structure.
Description
Technical field
The present invention relates to a kind of steel structure bridge protective agent, relate in particular to and a kind ofly can improve steel structure bridge the water-based protective agent and the methods for making and using same thereof in work-ing life.
Background technology
Steel structure bridge is widely adopted because of having advantages such as stride that the footpath is big, supporting capacity is strong and the construction time is short.Bridge is mainly built in crossing over high humidity environments such as rivers and bay, extraneous corrosives (as villaumite, acid rain and vitriol etc.) very easily with steam in the surface condensation of steel structure bridge, enrichment, easily cause steel structure bridge corrosion and destruction.Simultaneously, under the materialization factor interaction such as the salt fog of steel structure bridge in physical environment, acid rain, freezing, sleet and illumination, easily performance degradation takes place and destroy.How reducing the destruction of extraneous materialization factor to steel structure bridge, is one of important measures that improve bridge work-ing life.At present, adopt the surfacecti proteon measure to reduce of the influence of external environment factor to steel structure bridge both at home and abroad to bridge structure more.The extraneous load of top layer protection available buffer, temperature field and moisture field etc. effectively reduce the intrusion of materials such as extraneous water, carbonic acid gas and chlorion, thereby reduce the erosion damage of various etching effects function served as bridge.Big quantity research and engineering practice show, one of the most frequently used and safeguard procedures that effect is preferable are to adopt the top layer protective agent.
The top layer protective agent is many to be composited by mineral-type materials, organic class material and both.Be coated on steel structure bridge surface after mineral-type materials commonly used mostly is component (as nitrite, phosphoric acid salt and dichromate etc.) with rust prevention function and reactive metal powder (as zinc powder and aluminium powder etc.) and a certain amount of gelling material or organism mix, reach and completely cut off the external world and corrosion mitigating effect; And organic class material mostly is resin (as urethane and Resins, epoxy etc.), pitch, organic coating, paint and polyol ester etc. and directly is coated on steel structure bridge surface, plays protection and the effect of resistance rust.Advantages such as that mineral-type materials has is anti-aging, stable, lasting and environmental protection, but often face problems such as function singleness and cohesive force difference; In addition, although the part mineral-type materials has preferable rust prevention function, because of having than overall situation negative effect be under an embargo (as nitrite etc.).Organic class material has many, the efficient and easy advantage such as construction of function, but easily wear out, be full of cracks, efflorescence and weathering resistance difference and environment negative effect be bigger.The deficiency of this two classes material self, it is required to make the single kind protective agent of its preparation be difficult to satisfy engineering.How giving full play to inorganic and organic materials advantage separately, is the focus and the difficult point of current metal protection area research.Wherein, the agent of exploitation organic/inorganic composite protective is a kind of effective way.
Yan Jiukaifa some metal protectors lay particular emphasis on single performance protection (as protection against corrosion, protection etc.) more now, and have easily ignored in the metal protection polyfunctional requirement.Patent of invention as a kind of " ferrous metal permanent protective agent and production method thereof " (Granted publication CN 101139496B) by name, it is characterized in that adopting resol, polyvinyl butyral acetal and polyvinylformal etc. is main body film forming liquid, generates the translucent liquid product with the aluminum napthenate reaction in reactor.This invention mechanism of action is to rely on to block external substance and metallic contact and play protection effect; If the protection rete suffers breakage, extraneous water and corrosives etc. are contacting metal and corrosion reaction takes place easily, thereby reduces protection effect.A kind of patent of invention of " a kind of composition of protective agent " (patent No. 93103720.4) by name, it is characterized in that benzotriazole, trolamine and Sodium orthomolybdate etc. are main, its mechanism of action is the passive film that generates one deck densification in the metallic surface, reduce extraneous corrosive medium and metallic contact, thereby improve the anticorrosive metal performance.From existing protective agent and result of use thereof as can be known, adopt protective agent to be difficult to guarantee that corrosion failure does not take place steel structure bridge with single performance.Therefore, developing a kind of composite protective agent that has isolated protection and rust prevention function concurrently, can to satisfy engineering to a certain extent required, has good economy and environmental benefit.
Summary of the invention
The objective of the invention is in order to remedy above-mentioned the deficiencies in the prior art, provide a kind of protection and protective agent of rust prevention function of having concurrently to improve steel structure bridge work-ing life.
Another object of the present invention provides the methods for making and using same of this protective agent.
The present invention has synthetic/inorganic compounding fluorine silicon styrene-acrylic polymer and resistance become rusty become to grade composite mutually and make a kind of the inorganic composite type protective agent arranged.Utilization of the present invention has hydrophobic and the organic polymer film-forming of protective effect and completely cuts off steel structure bridge and contact with extraneous, reduces the erosion of extraneous medium to steel structure bridge; Utilize resistance rust component easily by metal adsorption in the surface, make metal generation passivation reaction generate the resistant to tarnishing ability that fine and close oxidation film layer improves metal; Nano-component that contains and photostabilizer are given good resistance of aging of protective agent and stability.In addition, contained siloxane groups hydrolysis generates hydroxyl can generate chemical bond with steel structure bridge surface hydroxyl generation condensation reaction, improves the adhesive power between rete and the steel structure bridge.
The present invention mainly is achieved by following technical proposals:
A kind of steel structure bridge protective agent, it is prepared from by following component by weight:
Solid content 20-40% has/inorganic compounding fluorine silicon cinepazid polymer emulsion 40-100;
Benzotriazole 0.3-0.9; Lithium silicate 0.6-1.2;
Sodium orthomolybdate 0.03-0.3; Sunmorl N 60S 0.05-0.8;
Thanomin 1.5-8; Sodium tetraborate 0.02-0.1;
Nano titanium oxide 0.01-0.08; Dehydrated alcohol 0.5-4;
Distilled water 0-60.
Preparing preferred ratio range by weight of the present invention is:
Solid content 20-40% has/inorganic compounding fluorine silicon cinepazid polymer emulsion 60-90;
Benzotriazole 0.5-0.9; Lithium silicate 0.6-1;
Sodium orthomolybdate 0.05-0.2; Sunmorl N 60S 0.2-0.8;
Thanomin 2-6; Sodium tetraborate 0.05-0.08;
Nano titanium oxide 0.03-0.06; Dehydrated alcohol 1-3;
Distilled water 10-40.
The best of the present invention proportioning by weight is:
Having/inorganic compounding fluorine silicon cinepazid polymer emulsion 80 of solid content 25%;
Benzotriazole 0.7; Lithium silicate 0.8;
Sodium orthomolybdate 0.1; Sunmorl N 60S 0.6;
Thanomin 5; Sodium tetraborate 0.06;
Nano titanium oxide 0.04; Dehydrated alcohol 1;
Distilled water 20.
Described thanomin comprises a kind of or both mixtures in diethanolamine and the trolamine.
Described nano titanium oxide is an anatase octahedrite or based on the nano titanium oxide mixed crystal of anatase octahedrite.
Describedly have/inorganic compounding fluorine silicon cinepazid polymer emulsion adopts the semi-continuous emulsion polymerizing method to make the raw materials used following component that comprises by weight:
Fluorochemical monomer 20-60;
Siloxanyl monomers 3-12;
The water-sol 15-35 of the inorganic nano material of the surface modification of mass content 15-30%;
Methyl methacrylate 10-30;
Vinylbenzene 10-30;
Butyl acrylate 10-55;
Hydroxyethyl methylacrylate 2-10;
Methacrylic acid 2-10;
Emulsifying agent 2.5-8;
Initiator 0.5-2;
Distilled water 270-290.
Describedly have/when inorganic compounding fluorine silicon cinepazid polymer emulsion has optimum performance, the raw materials used following component that comprises by weight:
Fluorochemical monomer 35; Siloxanyl monomers 8
The inorganic nano material water-sol 30 of mass content 20% surface modification;
Methyl methacrylate 15; Vinylbenzene 15
Emulsifying agent 3.6; Butyl acrylate 18;
Methacrylic acid 5; Hydroxyethyl methylacrylate 5;
Initiator 1; Distilled water 280.
Inorganic nano material in the inorganic nano material water-sol of described surface modification comprises SiO
2, Al
2O
3And TiO
2One or more mixtures in three kinds of oxide compounds.
Described fluorochemical monomer comprises methacrylic acid hexafluoro butyl ester; Dodecafluorhe-ptylacrylate; The mixture of one or more in the vinylformic acid ten trifluoro monooctyl esters; Described siloxanyl monomers comprises one or more the mixture in methacryloxypropyl trimethoxy silane, aminopropyl triethoxysilane and the glycidoxy methyltrimethoxy silane.
Described initiator is a kind of or both mixtures in Potassium Persulphate and the ammonium persulfate; Described emulsifying agent is a kind of or both mixtures in octylphenol polyethylene oxidative ethane (10) ether and the allyl group Nonyl pheno sulfonic acid ammonia.
The water-sol of the inorganic nano material of described surface modification is to adopt sol-gel method, by organic alkoxide, dehydrated alcohol, distilled water and ammoniacal liquor is 1 in molar ratio: (15-50): (1-3): (0.06-0.15) reaction, obtain the alcosol of inorganic nano material, again through the siloxanyl monomers surface modification, and replace with water that alcoholic solvent obtains.Described organic alkoxide comprises one or more the mixture in tetraethyl orthosilicate, butyl (tetra) titanate and the aluminum isopropylate.Described siloxanyl monomers comprises one or more the mixture in methacryloxypropyl trimethoxy silane, aminopropyl triethoxysilane and the glycidoxy methyltrimethoxy silane, and its consumption is the 10-40% of nano-oxide gross weight in the alcoholic solution of inorganic nano material.
Describedly have/effective constituent of inorganic compounding fluorine siloxane-acrylate copolymer emulsion is to have inorganic nano material by surface modification to constitute the latex particle that nuclear and organic polymer constitute shell.
The inorganic nano material of the surface modification of described formation nuclear comprises SiO
2, Al
2O
3And TiO
2The mixture of one or more in three kinds of oxide compounds, and invest the siloxanyl monomers that is used for modification on its surface.
The organic polymer of described formation shell comprises: fluorochemical monomer, siloxanyl monomers, methyl methacrylate, butyl acrylate, vinylbenzene, methacrylic acid and hydroxyethyl methylacrylate.
The water-sol of the inorganic nano material of described surface modification is that the alcosol of the inorganic nano material that contains surface modification that above-mentioned employing sol-gel method is made adopts vacuum concentration, for continuous polyreaction after an action of the bowels use the alternative dehydrated alcohol of a small amount of distilled water to obtain; The inorganic nano material that its mass content 15-30% also is meant surface modification shared mass percent in the water-sol.
The preparation method of described steel structure bridge protective agent may further comprise the steps:
1) has/preparation of inorganic compounding fluorine silicon cinepazid polymer emulsion
Utilize the water-sol of the inorganic nano material of fluorochemical monomer, siloxanyl monomers, methyl methacrylate, vinylbenzene, butyl acrylate, methacrylic acid, methacrylic acid hydroxyl ethyl ester, emulsifying agent, initiator, surface modification, adopt the preparation of semi-continuous emulsion polymerizing method;
2) benzotriazole is dissolved in the dehydrated alcohol, is made into alcoholic solution;
3) with step 1) and 2) each solution, lithium silicate, Sodium orthomolybdate, Sunmorl N 60S, nano titanium oxide, sodium tetraborate and the thanomin that obtain add the water stirring and evenly mixing, promptly gets steel structure bridge protective agent.
Above-mentioned steel structure bridge protective agent preparation method is specific as follows:
The first step: organic alkoxide hydrolysis prepares inorganic nano material and surface modification thereof, and its preparation method is as follows:
A, organic alkoxide is dissolved in a certain amount of dehydrated alcohol, stand-by in the separating funnel of packing into after mixing;
B, dehydrated alcohol, distilled water and ammoniacal liquor are joined in the four-hole boiling flask that reflux condensate device and electric mixer are housed by certain ratio, stirred 1-4 hour, mix the back and slowly heat up with 100-300 rev/min speed;
C, when temperature rises to 45-60 ℃, the mixture in the separating funnel is added dropwise in the four-hole boiling flask, stir fast with 150-300 rev/min speed, reacted 1-6 hour;
Stir ageing 12-48 hour under D, the room temperature, obtain the alcosol of required inorganic nano material;
Under E, the stirring at low speed condition, a certain amount of siloxanyl monomers is added dropwise in the alcosol of inorganic nano material, reaction was warmed up to 40-60 ℃ and isothermal reaction 1-5 hour after 12-24 hour under the room temperature, promptly got the alcosol of the inorganic nano material of surface modification;
F, employing vacuumize the alcosol that drying mode concentrates the inorganic nano material of surface modification, and replace with a certain amount of water, get the water-sol of the inorganic nano material of surface modification.
Second step: adopting emulsion polymerization to synthesize has inorganic composite polymer, and its preparation method is as follows:
A, with the emulsifying agent that accounts for monomer mass 1-4% and with the water of quality such as monomer, prepare stable monomer pre-emulsion; Each monomer comprises: methyl methacrylate, vinylbenzene, butyl acrylate, methacrylic acid hydroxyl ethyl ester, methacrylic acid, fluorochemical monomer, siloxanyl monomers.
B, in the four-hole bottle that stirring, reflux condensing tube, thermometer are housed, add the water alcosol of the inorganic nano material of surface modification, and adding partial emulsifier, distilled water and sodium bicarbonate, speed with 200-300 rev/min stirs fast, mixes and heats up;
C, when temperature rises to 70-85 ℃, part methyl methyl acrylate and two kinds of monomeric pre-aqueous emulsions of small amounts of styrene are splashed into flask, and drip the part initiator solution synchronously, reacted 0.5-2 hour; Be warming up to 75-90 ℃, drip five kinds of pre-aqueous emulsions of monomer of methacrylic acid hydroxyl ethyl ester, remaining methyl methacrylate, part propylene acid butyl ester, remaining vinylbenzene and methacrylic acid, and drip the part initiator solution synchronously, isothermal reaction 0.5-1 hour; Drip fluorochemical monomer, siloxanyl monomers and three kinds of monomeric pre-aqueous emulsions of remaining butyl acrylate continuously, and drip the residue initiator solution synchronously, isothermal reaction 4-12 hour, be cooled to below 40 ℃, regulate the pH value to neutral, had/inorganic compounding fluorine silicon cinepazid polymer emulsion; Getting 5g left and right sides emulsion, to put into weight be m
0Culture dish in, be weighed as m
1It is dried to constant weight in 105 ± 5 ℃ of baking ovens, put into moisture eliminator after the taking-up and be cooled to room temperature and be weighed as m
2The solid content W of institute's synthetic polymer emulsion calculates according to following formula:
The 3rd step: benzotriazole is dissolved in a small amount of dehydrated alcohol, is made into alcoholic solution;
The 4th step: each solution, lithium silicate, nano titanium oxide, Sodium orthomolybdate, Sunmorl N 60S, thanomin and sodium tetraborate that second step, the 3rd step are obtained add in the reactor that contains a certain amount of distilled water in proportion, at room temperature mix, promptly get steel structure bridge protective agent with 100-150 rev/min speed.
Among the present invention, have/inorganic compounding fluorine silicon styrene-acrylic polymer can be in steel structure bridge surface cure film forming, and this rete has good mechanical properties and density, can effectively reduce the influence to steel structure bridge of outside temperature field and factors such as moisture field and illumination thereof.In the silicon fluoride component solidification process of contained low surface energy, can give rete good hydrophobic performance, inorganic nano material not only can improve polymer performance and increase the good roughness of film, and can give the rete anti-ultraviolet aging and from performances such as cleanings.In addition, contained siloxane groups hydrolysis generates hydroxyl can generate chemical bond with steel structure bridge surface hydroxyl generation condensation reaction, improves the adhesive power between rete and the steel structure bridge.
Benzotriazole is a kind of organic polymer photostabilizer, metal antirusting agent and inhibiter of excellent property.It has good uv absorption capacity, can give polymkeric substance good ageing resistance; Can form covalent linkage and coordinate bond with atoms metal, replace into chain polymer mutually and form protective membrane, the corrosion that stops redox reaction to cause in the metallic surface.In addition, when itself and multiple inhibiter were used, corrosion mitigating effect was better.
Lithium silicate can react with metal and surface hydroxyl thereof and generate Fe as surface treatment agent and rust-preventive agent
2(SiO
3)
3With the rete of other silicates, have heat-resisting, do not fire, radiation hardness, guarantor's look, nontoxic, do certainly and performance such as anti-alternation of wetting and drying.In addition, the part lithium ion is adsorbed on rebar surface, plays passivation and the effect of protection iron and steel.
Sodium orthomolybdate is a kind of effective pitting inhibiter, can significantly strengthen the metal corrosion resistance, generates Fe (MoO with the iron reaction
3)
3, can make pitting passivation and sealing again.During with composite uses such as poly-phosphate, gluconate, zinc salt and benzotriazoles, not only can reduce the rust inhibitor usage quantity, but also can play better corrosion mitigating effect.
Sunmorl N 60S is a kind of inhibiter and sequestrant.Have tangible coordinating effect, be applicable to molybdenum, silicon, phosphorus, tungsten and nitrite etc. when composite, can play the raising corrosion mitigating effect; Compare with general inhibiter, corrosion inhibition rate raises with temperature to be increased; It has extremely strong complex ability to calcium, magnesium and molysite etc., especially to Fe
3+Fabulous sequestering action is arranged, thereby effectively reduce the corrosion of outer bound pair iron.
Thanomin has inhibition and sequestering action.Can generate 2-4 coordinate stable chelate with the various heavy chelating, be good sequestrant; Can prevent oxidation on metal surface as inhibiter, thereby improve steel structure bridge metal corrosion-resisting.
Sodium tetraborate has certain corrosion inhibitive function, can coordinate to use with molybdate, silicate and gluconate etc., has good corrosion mitigating effect.
Water plays the homodisperse effect as solvent, helps construction and does not have the environment negative effect.
Steel structure bridge protective agent of the present invention is a liquid, is coated on steel structure bridge surface and gets final product.
The invention has the beneficial effects as follows:
1, adopt surface modification and emulsion polymerization way that organic and inorganic material is combined into one with the chemical bond form, thereby modified organic polymers, effectively reduced between the organic and peeled off, excessive contraction takes place when suppressing the polymer cure film forming, the shakiness and the phase-splitting that cause because of material is different have been overcome, give full play to inorganic and advantage organic materials self, realized the mutual supplement with each other's advantages between unlike material.
2, have/the contained silicon fluoride component of inorganic compounding fluorine silicon styrene-acrylic polymer itself has excellent hydrophobic property and ageing resistance, and film-forming can reduce extraneous water and hazardous medium contacting metal; Inorganic nano material has good synergy, can effectively improve the roughness of cured film and increases the rete hydrophobicity; Photostabilizer and nano-component can be given the good anti-ultraviolet aging of cured film and from performances such as cleanings; Contained resistance rust composition is to be composited by nontoxic, efficient and good multiple organic/inorganic rust inhibitor and the inhibiter of weathering resistance, has good coordinating effect each other, easily is adsorbed on the metallic surface and makes its passivation, thereby reduce the corrosion of metal rate.
3, the siloxane groups hydrolysis that contains generates hydroxyl can generate chemical bond with the hydroxyl generation condensation reaction on steel structure bridge surface, improves the adhesive power between protective agent and the matrix, avoids occurring in the use coming off and playing phenomenons such as bulging.
4, synthetic is solvent with water and small amount of ethanol, the lower and toxicological harmless byproduct generation of its cost; In the use, rely on each component self-characteristic of protective agent to give its multifunctionality, have good benefits in environment.
Description of drawings
Fig. 1 is embodiment 1,2 and the compound fluorine silicon of 3 synthetic organic/inorganics styrene-acrylic polymer microballoon TEM figure.
Embodiment
Following embodiment is to the further specifying of the technology of the present invention content, but is not the restriction to flesh and blood of the present invention.
Embodiment 1:
With 6 kilograms of 0.1 kilogram of aluminum isopropylate, 0.3 kilogram of butyl (tetra) titanate, 1.7 kilograms of tetraethyl orthosilicates and dehydrated alcohols, it is stand-by to mix the back; 10 kilograms of dehydrated alcohols, 0.4 kilogram of distilled water and ammoniacal liquor 0.1 kilogram (massfraction is 25%) are joined in the reactor that reflux condensate device and electric mixer are housed, stirred 1-2 hour, mix the back and slowly heat up with 150 rev/mins of speed; When temperature rises to 45-60 ℃, organic alkoxide and alcohol mixture are added dropwise in the reactor, stir fast with 200 rev/mins speed, reacted 2-4 hour; Stir ageing 24 hours under the room temperature, obtain the alcosol of required inorganic nano material.Under the stirring at low speed condition, 0.18 kilogram of methacryloxypropyl trimethoxy silane is added dropwise in the alcosol of inorganic nano material, reaction is 22 hours under the room temperature, is warmed up to 50 ℃ and isothermal reaction 2 hours, promptly gets the alcosol of the inorganic nano material of surface modification; Employing vacuumizes drying mode and concentrates, and adds 2 kg water instead of ethanol, obtains the water-sol of the inorganic nano material of surface modification.
3 kilograms of the water-sols (massfraction is about 20%) that in the reactor that stirring, reflux condensing tube, thermometer are housed, add the inorganic nano material of surface modification, and 0.01 kilogram in adding octylphenol polyethylene oxidative ethane (10) ether, 0.01 kilogram of allyl group Nonyl pheno sulfonic acid ammonia, 16 kilograms of distilled water and pH value are regulated 0.012 kilogram of buffer reagent sodium bicarbonate, 1 hour excluding air of feeding nitrogen; Then, stir and heat up with 200 rev/mins speed; When temperature rises to 75 ℃, 0.6 kilogram of methyl methacrylate, 0.7 kilogram of vinylbenzene, 1.3 kilograms in water, 0.015 kilogram in octylphenol polyethylene oxidative ethane (10) ether and 0.015 kilogram of pre-emulsion of making of allyl group Nonyl pheno sulfonic acid ammonia are added in the reactor, and be added dropwise to 0.26 kilogram of potassium persulfate solution (massfraction is 5%) synchronously, reacted 0.5 hour; Be warming up to 80 ℃, 1.2 kilograms of butyl acrylates, 0.5 kilogram of methacrylic acid hydroxyl ethyl ester, 0.5 kilogram of methacrylic acid, 0.9 kilogram of methyl methacrylate, 0.8 kilogram of vinylbenzene, 3.9 kilograms in water, 0.065 kilogram in octylphenol polyethylene oxidative ethane (10) ether and 0.065 kilogram of pre-emulsion of making of allyl group Nonyl pheno sulfonic acid ammonia are added in the reactor, and drip 0.76 kilogram of potassium persulfate solution (massfraction is 5%), isothermal reaction 0.5 hour synchronously; With 0.6 kilogram of butyl acrylate, 1.75 kilograms of methacrylic acid hexafluoro butyl esters, 1.75 kilograms of dodecafluorhe-ptylacrylates, 0.8 kilogram of methacryloxypropyl trimethoxy silane, 4.9 kilograms in water, 0.09 kilogram of pre-emulsion of making of 0.09 kilogram in octylphenol polyethylene oxidative ethane (10) ether and allyl group Nonyl pheno sulfonic acid ammonia adds in the reactor, and drip 0.98 kilogram of potassium persulfate solution (massfraction is 5%) synchronously, isothermal reaction 5 hours, be cooled to below 40 ℃, regulate the pH value to neutral with ammoniacal liquor (massfraction is 25%), promptly obtain stable having/inorganic compounding fluorine silicon cinepazid polymer emulsion (solid content is about 25%).
To have/60 kilograms of inorganic compounding fluorine silicon cinepazid polymer emulsions and distilled water joins in the mixing tank that has agitator for 40 kilograms, mixes with 100 rev/mins speed; Be warming up to 40 ± 5 ℃, slowly add in the agitator successively 1.5 kilograms of 0.2 kilogram of mixed solution, Sunmorl N 60S, nano titanium oxide 0.03, thanomins and the sodium tetraborate of 0.6 kilogram of lithium silicate, 0.1 kilogram, 0.3 kilogram benzotriazole of Sodium orthomolybdate and 0.6 kilogram of dehydrated alcohol for 0.05 kilogram, stirred 2-6 hour, and promptly got steel structure bridge protective agent.
Embodiment 2:
Have/inorganic compounding fluorine silicon cinepazid polymer emulsion prepares as embodiment 1.
To have/80 kilograms of inorganic compounding fluorine silicon cinepazid polymer emulsions and distilled water joins in the mixing tank that has agitator for 20 kilograms, mixes with 100 rev/mins speed; Be warming up to 40 ± 5 ℃, slowly add in the agitator successively 5 kilograms of 0.6 kilogram of mixed solution, Sunmorl N 60S, nano titanium oxide 0.04, thanomins and the sodium tetraborate of 0.8 kilogram of lithium silicate, 0.1 kilogram, 0.7 kilogram benzotriazole of Sodium orthomolybdate and 1 kilogram of dehydrated alcohol for 0.06 kilogram, stirred 2-6 hour, and promptly got steel structure bridge protective agent.
Embodiment 3:
Have/inorganic compounding fluorine silicon cinepazid polymer emulsion prepares as embodiment 1.
To have/70 kilograms of inorganic compounding fluorine silicon cinepazid polymer emulsions and water joins in the mixing tank that has agitator for 30 kilograms, mixes with 100 rev/mins speed; Be warming up to 40 ± 5 ℃, slowly add in the agitator successively 3 kilograms of 0.5 kilogram of mixed solution, Sunmorl N 60S, nano titanium oxide 0.05, thanomins and the sodium tetraborate of 0.8 kilogram of lithium silicate, 0.12 kilogram, 0.6 kilogram benzotriazole of Sodium orthomolybdate and 1 kilogram of dehydrated alcohol for 0.06 kilogram, stirred 2-6 hour, and promptly got steel structure bridge protective agent.
Embodiment 4:
The synthetic preparation of steel structure bridge protective agent is identical with embodiment 2, but synthesize solid content be about 20% have/inorganic compounding fluorine silicon cinepazid polymer emulsion is raw materials used as follows:
Fluorochemical monomer 22; Siloxanyl monomers 4;
The inorganic nano material of surface modification (massfraction is 20%) 10;
Emulsifying agent 2.5; Vinylbenzene 11;
Methyl methacrylate 11; Butyl acrylate 18;
Methacrylic acid 2; Hydroxyethyl methylacrylate 2;
Initiator 1; Distilled water 270.
Embodiment 5:
The synthetic preparation of steel structure bridge protective agent is identical with embodiment 2, but synthesize solid content be about 35% have/inorganic compounding fluorine siloxane-acrylate copolymer emulsion is raw materials used as follows:
Fluorochemical monomer 55; Siloxanyl monomers 10;
The inorganic nano material of surface modification (massfraction is 20%) 30;
Emulsifying agent 4.5; Vinylbenzene 22;
Methyl methacrylate 22; Butyl acrylate 38;
Methacrylic acid 6; Hydroxyethyl methylacrylate 6;
Initiator 1.3; Distilled water 270.
Embodiment 6:
The synthetic preparation of steel structure bridge protective agent is identical with embodiment 2, but synthesize solid content be about 30% have/inorganic compounding fluorine siloxane-acrylate copolymer emulsion is raw materials used as follows:
Fluorochemical monomer 25; Siloxanyl monomers 5;
The inorganic nano material of surface modification (massfraction is 20%) 20;
Emulsifying agent 3; Vinylbenzene 27;
Methyl methacrylate 28; Butyl acrylate 35;
Methacrylic acid 5; Hydroxyethyl methylacrylate 5;
Initiator 1.2; Distilled water 280.
Above-mentioned has/inorganic compounding fluorine silicon styrene-acrylic polymer microballoon TEM figure, as shown in Figure 1.As can be seen from the figure, the synthetic microsphere particle has the shell structure of the nuclear that is made of inorganic nano material and organic polymer structure, and this structure can be given the better weathering resistance of organic polymer emulsion particle, thermotolerance, anti-aging and other mechanical properties etc.
Prepared steel structure bridge protective agent performance test is as shown in the table:
Claims (9)
1. steel structure bridge protective agent is characterized in that comprising that following component by weight is prepared from:
Solid content 20-40% has/inorganic compounding fluorine silicon cinepazid polymer emulsion 40-100;
Benzotriazole 0.3-0.9;
Lithium silicate 0.6-1.2;
Sodium orthomolybdate 0.03-0.3;
Sunmorl N 60S 0.05-0.8;
Thanomin 1.5-8;
Sodium tetraborate 0.02-0.1;
Nano titanium oxide 0.01-0.08;
Dehydrated alcohol 0.5-4;
Distilled water 0-60.
2. steel structure bridge protective agent according to claim 1, it is characterized in that describedly having/inorganic compounding fluorine silicon styrene-acrylic polymer adopts the semi-continuous emulsion polymerizing method to make the raw materials used following component that comprises by weight:
Fluorochemical monomer 20-60;
Siloxanyl monomers 3-12;
The water-sol 15-35 of the inorganic nano material of the surface modification of mass content 15-30%;
Methyl methacrylate 10-30;
Vinylbenzene 10-30;
Butyl acrylate 10-55;
Hydroxyethyl methylacrylate 2-10;
Methacrylic acid 2-10;
Emulsifying agent 2.5-8;
Initiator 0.5-2;
Distilled water 270-290;
The inorganic nano material of described surface modification comprises SiO
2, Al
2O
3And TiO
2The mixture of one or more of three kinds of oxide compounds.
3. steel structure bridge protective agent according to claim 2 is characterized in that described fluorochemical monomer comprises methacrylic acid hexafluoro butyl ester; Dodecafluorhe-ptylacrylate; The mixture of one or more in the vinylformic acid ten trifluoro monooctyl esters; Described siloxanyl monomers comprises one or more the mixture in methacryloxypropyl trimethoxy silane, aminopropyl triethoxysilane and the glycidoxy methyltrimethoxy silane.
4. steel structure bridge protective agent according to claim 2 is characterized in that described initiator is a kind of or both mixtures in Potassium Persulphate and the ammonium persulfate; Described emulsifying agent is a kind of or both mixtures in octylphenol polyethylene oxidative ethane (10) ether and the allyl group Nonyl pheno sulfonic acid ammonia.
5. steel structure bridge protective agent according to claim 2, the water-sol that it is characterized in that the inorganic nano material of described surface modification is to adopt sol-gel method, by organic alkoxide, dehydrated alcohol, distilled water and ammoniacal liquor is 1 in molar ratio: (15-50): (1-3): (0.06-0.15) reaction, obtain the alcosol of inorganic nano material, again through the siloxanyl monomers surface modification, and replace with water that alcoholic solvent obtains.
6. steel structure bridge protective agent according to claim 5 is characterized in that described organic alkoxide comprises one or more the mixture in tetraethyl orthosilicate, butyl (tetra) titanate and the aluminum isopropylate.
7. steel structure bridge protective agent according to claim 5, it is characterized in that described siloxanyl monomers comprises one or more the mixture in methacryloxypropyl trimethoxy silane, aminopropyl triethoxysilane and the glycidoxy methyltrimethoxy silane, its consumption is the 10-40% of nano-oxide gross weight in the alcoholic solution of inorganic nano material.
8. the preparation method of any described steel structure bridge protective agent of claim 1-7 is characterized in that may further comprise the steps:
1) has/preparation of inorganic compounding fluorine silicon cinepazid polymer emulsion
Utilize the water-sol of the inorganic nano material of fluorochemical monomer, siloxanyl monomers, methyl methacrylate, vinylbenzene, butyl acrylate, methacrylic acid, methacrylic acid hydroxyl ethyl ester, emulsifying agent, initiator, surface modification, adopt the preparation of semi-continuous emulsion polymerizing method;
2) benzotriazole is dissolved in the dehydrated alcohol, is made into alcoholic solution;
3) with step 1) and 2) each solution, lithium silicate, Sodium orthomolybdate, Sunmorl N 60S, nano titanium oxide, sodium tetraborate and the thanomin that obtain add the water stirring and evenly mixing, promptly gets steel structure bridge protective agent.
9. any described steel structure bridge protective agent of claim 1-7 adopts mechanically spraying or artificial coating method to be applied to steel structure bridge surface.
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| CN110698986A (en) * | 2019-09-20 | 2020-01-17 | 江西省交通科学研究院 | Snow-melting and deicing emulsion coating and construction method thereof |
| CN110615632A (en) * | 2019-10-28 | 2019-12-27 | 山东交通职业学院 | Composite steel bar corrosion inhibitor for marine environment and application thereof |
| CN110615632B (en) * | 2019-10-28 | 2021-08-20 | 山东交通职业学院 | Composite steel bar corrosion inhibitor for marine environment and application thereof |
| CN111944335A (en) * | 2020-07-24 | 2020-11-17 | 苏州波菲特新材料科技有限公司 | Vitrification agent, preparation method thereof and stirring device |
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