CN102676023A - Method for preparing nano mesoporous titanium dioxide/organic montmorillonite anticorrosion paint - Google Patents
Method for preparing nano mesoporous titanium dioxide/organic montmorillonite anticorrosion paint Download PDFInfo
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Abstract
The invention relates to a method for preparing organic nano anticorrosion paint, in particular to a method for preparing nano mesoporous titanium dioxide/organic montmorillonite anticorrosion paint. Nano mesoporous titanium dioxide adopts surfactant as template agent and is synthesized in a sol-gel emulsification or microemulsion process under the interface action between organic matters and inorganic matters, the nano mesoporous titanium dioxide is mainly regular spherical, the average particle size ranges from 60nm to 100nm, pore passages are regular or irregular, and the pore diameter ranges from 10nm to 50nm. The nano mesoporous titanium dioxide particles with special duplex nano structures and nano hybrid materials are introduced into an anticorrosion paint system, the defects of difficulty in dispersion of existing nano filler in organic matrix and poor compatibility of the nano filler to the organic matrix can be overcome to enable the nano filler and the organic matrix to have synergistic effect, the common problem of short anticorrosion period of current nano anticorrosion paint is solved, and performances of the anticorrosion paint can be greatly improved.
Description
Technical field
The present invention relates to the preparation method of organic nano protective system, particularly relate to the preparation method of a kind of nano meso-porous titanium dioxide/organo montmorillonite protective system.Used a kind of preparation method with nano level mesoporous TiO 2 particle (it has dual nanostructure, i.e. nano-scale particle sizes and nano level meso-hole structure) with protective system of nano lamellar material (organo montmorillonite) of special construction.
Background technology
The use of metallic substance more and more widely, the etching problem of metal and member thereof has spreaded all over and the every field of national economy, has caused massive losses to human society.In order to reduce the corrosive loss, people have taked a lot of safeguard procedures, but the most common, most economical up to now, the most practical sfgd. or coating protection.
Along with the continuous progress of nanometer material science, the excellent specific property paid more and more attention of nano composite dope.According to nanometer size effect that nanoparticle had and huge specific surface area characteristic, nanoparticle is dispersed in traditional protective system processes nano composite dope, can improve the excellent properties of protective system greatly.
Because nano titanium oxide has special photocatalysis performance, Superhydrophilic, shielding ultraviolet rays performance, applies it to coating and makes it in coating, keep the nano level state, can improve shortcomings such as poor, the easy contamination of existing coating weathering resistance.As in acrylic coating, adding nano-TiO
2Or the nano-ZnO thickened pulp, when then both having made the coating machine improved performance, maskable 99% ultraviolet ray again.Utilize high temperature, high pressure to grind and process the Ti nanometer polymer, add in the resin as filler and process anti-corrosion anti-scale coating, be applied, effectively protected production unit in units such as Shengli Oil Fields.Be to use nano titanium oxide/nanometer silver coating and preparation method thereof like what announce among the granted patent ZL 200410027622.X.
Polynite is bentonitic staple, because it has surprising swelling capacity and thixotropic effect in solvent, so it has the thickening material that is used as in the coating.As disclose at U.S. Pat P4473407 a kind of with wilkinite as rheology modifier.
It all is to add the solid titanium oxide of nano-scale particle sizes or the organo montmorillonite of laminate structure separately that great majority are declared what use in patent and the disclosed domestic and foreign literature data, but because nano material is very tiny, its specific surface area is big; Surface free energy is high; Intermolecular attraction and electrostatic attraction are also quite high, so nanoparticle very easily reunites, even utilize methods such as sand milling, high-speed stirring that nanoparticle is dispersed in the coating; Also agglomeration can take place; Losing the due effect of nano material, how it is distributed among the base-material, is nano material key technologies for application in coating.
Summary of the invention
The object of the present invention is to provide a kind of nano meso-porous titanium dioxide/organo montmorillonite protective system and preparation method thereof, can effectively improve nanoparticle and in coating, get consistency between dispersed and raising inorganic nano-particle and organic matrix, improve antiseptic property.
The objective of the invention is to realize through following technical scheme:
The preparation method of a kind of nano meso-porous titanium dioxide/organo montmorillonite protective system; Said nano meso-porous titanium dioxide; With the tensio-active agent is template, utilizes sol-gel emulsification or microemulsified process, synthesizes through the interface interaction between organism and the inorganics; Shape is main with regular spherical, and median size is 60～100nm; The duct is that rule has duct or random that pore passage structure is arranged, and the aperture is 10～50nm; Its preparation process is following:
A gets 100-200 part water and 100-200 part aqueous epoxy resins, adds 0.3-1 part skimmer, 50-100 part softening agent, and mechanical stirring is even;
B gets 5-10 part nano meso-porous titanium dioxide filler, and 5-10 part organo montmorillonite adds in the above resin system, in ball mill, disperses 1-2h, promptly gets the mother liquor of protective system;
C gets 25-50 part waterborne curing agent and 50-100 part water mixes;
The mixed that d presses 3-4:1 with the mother liquor and the good waterborne curing agent of dilution of protective system gets final product.
The preparation method of described a kind of nano meso-porous titanium dioxide/organo montmorillonite protective system, described aqueous epoxy resins is E44 epoxy emulsion, E51 epoxy emulsion, E20 epoxy emulsion.
The preparation method of described a kind of nano meso-porous titanium dioxide/organo montmorillonite protective system, described waterborne curing agent is W651, W650.
The preparation method of described a kind of nano meso-porous titanium dioxide/organo montmorillonite protective system, described skimmer is ethylene oxide oligopolymer or methyl-silicone oil.
The preparation method of described a kind of nano meso-porous titanium dioxide/organo montmorillonite protective system, described softening agent is Witcizer 300 or octyl phthalate.
The preparation method of a kind of nano meso-porous titanium dioxide/organo montmorillonite protective system, this method also comprises following process: gets 100 parts of water and 200 parts of aqueous epoxy resins, adds 1 part of skimmer, 50 parts of softening agent, mechanical stirring is even; Get 5 parts of nano meso-porous titanium dioxide fillers, 5 parts of organo montmorillonite fillers add in the above resin system, in ball mill, disperse 2h, promptly get the mother liquor of protective system; Get 50 parts of waterborne curing agents and 100 parts of water mix; The waterborne curing agent that the mother liquor of protective system and dilution is good by the mixed of 3.5:1 get final product high rot-resistant coating.
Advantage of the present invention and effect are:
1 the present invention provides the preparation method of little nano meso-porous titanium dioxide of a kind of addition and the rotten coating of organo montmorillonite, and its preparation process is under normal temperature, normal pressure, to carry out, and need not add new equipment, and technology is simple, and production cost is low.
In the preparation process of 2 corrosion protection coatings of the present invention, the water-based anticorrosive paint prescription does not pollute environment, belongs to green environmental friendly coatings.
3 nano composite dopes of the present invention can ambient cure, and easy construction can spray, brushing, roller coating, coat-thickness can adjust arbitrarily as required.
Description of drawings
The model synoptic diagram of Fig. 1 nanometer network structure;
The N of Fig. 2 nano meso-porous titanium dioxide
2The adsorption-desorption graphic representation;
Fig. 3 A stainless material nanometer anticorrosive coating is handled after the photo behind the salt-fog test 500h;
Fig. 3 B adds the photo of nano meso-porous titanium dioxide particle corrosion protection coating behind salt-fog test 500h separately;
Fig. 3 C adds the photo of organo montmorillonite corrosion protection coating behind salt-fog test 500h separately;
Fig. 3 D adds organo montmorillonite and the photo of nano meso-porous titanium dioxide corrosion protection coating behind salt-fog test 500h simultaneously.
Annotate: accompanying drawing of the present invention is state analysis synoptic diagram or photo, and figure Chinese words or the unintelligible not image of image are to the understanding of technical scheme of the present invention.
Specific embodiments
Further specify the present invention below in conjunction with accompanying drawing and embodiment.
The use nano meso-porous titanium dioxide that the present invention proposes is that (it has dual nanostructure to a kind of titanium dioxide granule with special construction; Be nano-scale particle sizes and nano level meso-hole structure), with the solid nano titanium oxide of reporting in conventional patents and the document be differentiated.The objective of the invention is to the properties-correcting agent of polynite, make interparticle autohemagglutination effect reduce, and be evenly dispersed in the coating, produce synergistic effect with nanometer porous titanium oxide with the form of nano particle as nanoparticle.Give full play to nano effect, make the coating and the ground that make that better sticking power arranged, improve antiseptic property simultaneously.
Mesoporous TiO 2 is a template with the tensio-active agent, utilizes chemical processes such as sol-gel emulsification or microemulsified, synthesizes through the interface interaction between organism and the inorganics.
For the mono-dispersed nano level mesoporous TiO 2 that the duct is arranged; The nanoparticle that replaces solid construction is as mineral filler, and it has dual nanostructure, i.e. nano-scale particle sizes and nano level meso-hole structure; Owing to have unique pore passage structure; Polymer molecular chain can enter into the duct and go, and the organic polymer chain that extends to place, mesoporous aperture can produce stronger interfacial interaction with polymeric matrix, increases both consistencies and prevents the reunion of nanoparticle in resin matrix.Laminar structured polynite and spheric mesoporous TiO 2 particle produce synergistic effect to matrix resin, form nanometer network structure (like Fig. 1) simultaneously.
The synthetic employing sol-gel method of nano meso-porous titanium dioxide, from Fig. 2 (a), (b) the most probable aperture of the mesoporous TiO2 of demonstration is 13.3 nm, and specific surface area is 165m2/g, and pore volume is 0. 4 ml.g-1 (being provided by the test of N2 adsorption-desorption).
Embodiment 2 (not adding any Nano filling)
The preparation of protective system
1) get 100 parts of aqueous epoxy resins and 100 parts of water, add 0.6 part of ethylene oxide oligopolymer, 70 parts of Witcizer 300s, mechanical stirring is even;
2) get 50 parts of waterborne curing agents and 100 parts of water mix; The waterborne curing agent that the mother liquor of protective system and dilution is good is coated on the treated good steel plate by the mixed of 4:1, and control thickness is at 35-200um, self-vulcanizing.
After wax sealing is handled around the smear after the curing, put into salt fog cabinet, take out behind the 500h, take a picture.Can find out the pure epoxy resin coating through 500h by the salt fog photo, the corrosion point has appearred in coatingsurface, seriously corroded (Fig. 3 A).
Embodiment 3 (by weight percentage, adding the nano meso-porous titanium dioxide particle separately)
1) get 150 parts of aqueous epoxy resins and 150 parts of water, add 0.3 part of methyl-silicone oil, 60 parts of octyl phthalates, mechanical stirring is even;
2) get 10 parts of nano meso-porous titanium dioxide molecular sieve fillings, add in the above resin system, in ball mill, disperse 1.5h.Get 35 parts of waterborne curing agents and 75 parts of water mix; The mother liquor of protective system is coated on the treated good steel plate with the mixed of dilution waterborne curing agent well by 3.5:1, and control thickness is at 35-200um, and self-vulcanizing gets final product.
After wax sealing is handled around the smear after the curing, put into salt fog cabinet, take out behind the 500h, take a picture.The epoxy coating that can be found out independent adding nano meso-porous titanium dioxide by salt fog photo (Fig. 3 B) is through 500h, and coatingsurface will obviously be better than the coating that does not add any Nano filling, and a spot of corrosion pit only appears in the surface.
Embodiment 4 (by weight percentage, adding organo montmorillonite separately)
1) get 150 parts of aqueous epoxy resins and 150 parts of water, add 0.3 part of methyl-silicone oil, 60 parts of octyl phthalates, mechanical stirring is even;
2) get 10 parts of organo montmorillonite fillers, add in the above resin system, in ball mill, disperse 1.5h.Get 35 parts of waterborne curing agents and 75 parts of water mix; The mother liquor of protective system is coated on the treated good steel plate with the mixed of dilution waterborne curing agent well by 3.5:1, and control thickness is at 35-200um, and self-vulcanizing gets final product.
The epoxy coating that can be found out independent adding organo montmorillonite by salt fog photo (Fig. 3 C) is through 500h, and coatingsurface will be better than the coating that does not add any Nano filling a little, but the corrosion pit of part appears in the surface.
Embodiment 5 (by weight percentage, adding organo montmorillonite and nano meso-porous titanium dioxide simultaneously)
1) get 100 parts of aqueous epoxy resins and 100 parts of water, add 0.6 part of ethylene oxide oligopolymer, 70 parts of Witcizer 300s, mechanical stirring is even;
2) get 5 parts of nano meso-porous titanium dioxide molecular sieves, 8 parts of organo montmorillonite fillers add in the above resin system, in ball mill, disperse 1h.Get 50 parts of waterborne curing agents and 100 parts of water mix; The waterborne curing agent that the mother liquor of protective system and dilution is good is coated on the treated good steel plate by the mixed of 4:1, and control thickness is at 35-200um, self-vulcanizing.
Can find out the epoxy coating process 500h that adds organo montmorillonite and nano meso-porous titanium dioxide simultaneously by salt fog photo (Fig. 3 D); Coatingsurface also will obviously be better than independent adding organo montmorillonite; The coating that adds nano meso-porous titanium dioxide separately; Any corrosion pit does not appear in the surface, shows the synergy that two kinds of different shapes nanoparticles show epoxy coating fully.
Claims (6)
1. the preparation method of nano meso-porous titanium dioxide/organo montmorillonite protective system; It is characterized in that said nano meso-porous titanium dioxide; With the tensio-active agent is template, utilizes sol-gel emulsification or microemulsified process, synthesizes through the interface interaction between organism and the inorganics; Shape is main with regular spherical, and median size is 60～100nm; The duct is that rule has duct or random that pore passage structure is arranged, and the aperture is 10～50nm; Its preparation process is following:
A gets 100-200 part water and 100-200 part aqueous epoxy resins, adds 0.3-1 part skimmer, 50-100 part softening agent, and mechanical stirring is even;
B gets 5-10 part nano meso-porous titanium dioxide filler, and 5-10 part organo montmorillonite adds in the above resin system, in ball mill, disperses 1-2h, promptly gets the mother liquor of protective system;
C gets 25-50 part waterborne curing agent and 50-100 part water mixes;
The mixed that d presses 3-4:1 with the mother liquor and the good waterborne curing agent of dilution of protective system gets final product.
2. by the preparation method of the described a kind of nano meso-porous titanium dioxide of claim 1/organo montmorillonite protective system, it is characterized in that described aqueous epoxy resins is E44 epoxy emulsion, E51 epoxy emulsion, E20 epoxy emulsion.
3. by the preparation method of the described a kind of nano meso-porous titanium dioxide of claim 1/organo montmorillonite protective system, it is characterized in that described waterborne curing agent is W651, W650.
4. by the preparation method of the described a kind of nano meso-porous titanium dioxide of claim 1/organo montmorillonite protective system, it is characterized in that described skimmer is ethylene oxide oligopolymer or methyl-silicone oil.
5. the preparation method of a kind of nano meso-porous titanium dioxide according to claim 1/organo montmorillonite protective system is characterized in that described softening agent is Witcizer 300 or octyl phthalate.
6. the preparation method of nano meso-porous titanium dioxide/organo montmorillonite protective system is characterized in that this method also comprises following process: gets 100 parts of water and 200 parts of aqueous epoxy resins, adds 1 part of skimmer, and 50 parts of softening agent, mechanical stirring is even; Get 5 parts of nano meso-porous titanium dioxide fillers, 5 parts of organo montmorillonite fillers add in the above resin system, in ball mill, disperse 2h, promptly get the mother liquor of protective system; Get 50 parts of waterborne curing agents and 100 parts of water mix; The waterborne curing agent that the mother liquor of protective system and dilution is good by the mixed of 3.5:1 get final product high rot-resistant coating.
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Cited By (3)
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| CN104910753A (en) * | 2015-06-17 | 2015-09-16 | 牛无畏 | Nano-mesoporous titanium dioxide anticorrosive coating |
| CN105057572A (en) * | 2015-07-27 | 2015-11-18 | 明光市留香泵业有限公司 | Mesoporous-silica-contained high-adsorbability water-based paint for evaporative pattern casting and preparation method for mesoporous-silica-contained high-adsorbability water-based paint |
| CN113388311A (en) * | 2021-06-17 | 2021-09-14 | 沈阳化工大学 | Preparation method of nano titanium dioxide modified hexagonal boron nitride modified coating |
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| CN101984008A (en) * | 2010-10-29 | 2011-03-09 | 沈阳化工大学 | Organic nano anti-corrosion coating and preparation method thereof |
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| WO2011146811A2 (en) * | 2010-05-21 | 2011-11-24 | Inpore Technologies, Inc. | Mesoporous silicate fire retardant compositions |
| KR20120031608A (en) * | 2010-09-27 | 2012-04-04 | 건설화학공업주식회사 | Composition of heat-curable bisphenol f type epoxy powder coating for waterworks and its manufacturing method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910753A (en) * | 2015-06-17 | 2015-09-16 | 牛无畏 | Nano-mesoporous titanium dioxide anticorrosive coating |
| CN105057572A (en) * | 2015-07-27 | 2015-11-18 | 明光市留香泵业有限公司 | Mesoporous-silica-contained high-adsorbability water-based paint for evaporative pattern casting and preparation method for mesoporous-silica-contained high-adsorbability water-based paint |
| CN113388311A (en) * | 2021-06-17 | 2021-09-14 | 沈阳化工大学 | Preparation method of nano titanium dioxide modified hexagonal boron nitride modified coating |
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Application publication date: 20120919 Assignee: SHENYANG PAIER CHEMICAL Co.,Ltd. Assignor: Shenyang University of Chemical Technology Contract record no.: 2015210000039 Denomination of invention: Method for preparing nano mesoporous titanium dioxide/organic montmorillonite anticorrosion paint Granted publication date: 20140430 License type: Exclusive License Record date: 20150623 |
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Effective date of registration: 20160817 Address after: 110143 Liaoning province Shenyang Xihe economic and Technological Development Zone No. 28 North Street eight Patentee after: SHENYANG PAIER CHEMICAL Co.,Ltd. Address before: 110142 Shenyang economic and Technological Development Zone, Liaoning, No. 11 Patentee before: Shenyang University of Chemical Technology |
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Address after: No. 28 Xiheba North Street, Shenyang Economic and Technological Development Zone, Shenyang City, Liaoning Province, 110027 Patentee after: Liaoning Subote Shipboard Paint Co.,Ltd. Address before: No.28, Xihe babei street, Shenyang Economic and Technological Development Zone, Liaoning Province Patentee before: SHENYANG PAIER CHEMICAL Co.,Ltd. |