CN102676023B - 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 anti-corrosion coating, particularly relate to a kind of preparation method of nano meso-porous titanium dioxide/organo montmorillonite protective system.Used a kind of preparation method with the nano level mesoporous TiO 2 particle (it has dual nanostructure, i.e. nano-scale particle sizes and nano level meso-hole structure) of special construction and the protective system of nano lamellar material (organo montmorillonite).
Background technology
The use of metallic substance is more and more extensive, and the etching problem of metal and member thereof has spreaded all over and the every field of national economy, to human society, has caused massive losses.In order to reduce the loss of corrosion, people have taked a lot of safeguard procedures, but common, most economical, the most practical sfgd. or coating protection up to now.
Along with the continuous progress of nanometer material science, the excellent specific property of nano composite dope causes people's attention day by day.The nanometer size effect having according to nanoparticle and huge specific surface area characteristic, be dispersed in nanoparticle in traditional protective system and make nano composite dope, can greatly improve the excellent properties of protective system.
Because nano titanium oxide has special photocatalysis performance, Superhydrophilic, shielding ultraviolet rays performance, apply it to coating and make it in coating, keep nano level state, can improve the shortcomings such as existing coating weathering resistance is poor, easy contamination.As added nano-TiO in acrylic coating
2or nano-ZnO thickened pulp, when both having made coating machine improved performance, maskable 99% ultraviolet ray again.Utilize high temperature, high pressure to grind and make Ti nanometer polymer, as filler, add in resin and make anti-corrosion anti-scale coating, in units such as Shengli Oil Fields, be applied, effectively protected production unit.As what announce in granted patent ZL 200410027622.X, be to use nano titanium oxide/nanometer silver coating and preparation method thereof.
Polynite is bentonitic main component, and because it has surprising swelling capacity and thixotropic effect in solvent, therefore it has the thickening material being used as in coating.As disclosed a kind of wilkinite of using at U.S. Pat P4473407 as rheology modifier.
It is all to add separately the solid titanium dioxide of nano-scale particle sizes or the organo montmorillonite of laminate structure that great majority are declared what in patent and published domestic and foreign literature data, use, but because nano material is very tiny, its specific surface area is large, surface free energy is high, intermolecular attraction and electrostatic attraction are also quite high, therefore nanoparticle is very easily reunited, even if utilize sand milling, the methods such as high-speed stirring are dispersed in coating nanoparticle, also can there is agglomeration, lose the due effect of nano material, how to be distributed among base-material, it is the gordian technique that nano material is applied 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, obtain dispersed and improve consistency between inorganic nano-particle and organic matrix, improve antiseptic property.
The object of the invention is to be achieved through the following technical solutions:
A kind of preparation method of nano meso-porous titanium dioxide/organo montmorillonite protective system, described nano meso-porous titanium dioxide, take tensio-active agent as template, utilize sol-gel emulsification or microemulsified process, by the interface interaction between organism and inorganics, synthesize; Shape is take regular spherical as main, and median size is 60～100nm; Duct is that rule has duct or randomly has a pore passage structure, and aperture is 10～50nm; Its preparation process is as follows:
A gets 100-200 part water and 100-200 part aqueous epoxy resins, adds 0.3-1 part defoamer, 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 above resin system, disperses 1-2h in ball mill, obtains the mother liquor of protective system;
C gets 25-50 part waterborne curing agent and mixes with 50-100 part water;
D mixes with the waterborne curing agent having diluted the mother liquor of protective system in the ratio of 3-4:1.
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 defoamer 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 dibutyl phthalate or octyl phthalate.
A preparation method for nano meso-porous titanium dioxide/organo montmorillonite protective system, the method also comprises following process: gets 100 parts of water and 200 parts of aqueous epoxy resins, adds 1 part of defoamer, 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 above resin system, disperse 2h in ball mill, obtain the mother liquor of protective system; Getting 50 parts of waterborne curing agents mixes with 100 parts of water; The mother liquor of protective system is mixed and gets final product to obtain high rot-resistant coating in the ratio of 3.5:1 with the waterborne curing agent having diluted.
Advantage of the present invention and effect are:
1 the invention provides the preparation method of nano meso-porous titanium dioxide that a kind of addition is little and the rotten coating of organo montmorillonite, and its preparation process is to carry out under normal temperature, normal pressure, does not need to add new equipment, and technique is simple, and production cost is low.
In the preparation process of 2 corrosion protection coatings of the present invention, water-based anticorrosive paint formula 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.
Accompanying drawing explanation
The model schematic diagram of Fig. 1 nanometer network structure;
The N of Fig. 2 nano meso-porous titanium dioxide
2adsorption-desorption graphic representation;
Photo after the processing of Fig. 3 A stainless material nanometer anticorrosive coating after salt-fog test 500h;
Fig. 3 B adds separately the photo of nano meso-porous titanium dioxide particle corrosion protection coating after salt-fog test 500h;
Fig. 3 C adds separately the photo of organo montmorillonite corrosion protection coating after salt-fog test 500h;
Fig. 3 D adds organo montmorillonite and the photo of nano meso-porous titanium dioxide corrosion protection coating after salt-fog test 500h simultaneously.
Note: accompanying drawing of the present invention is state analysis schematic diagram or photo, the understanding of the unintelligible not image of figure Chinese word or image to technical solution of the present invention.
Specific embodiments
Below in conjunction with drawings and Examples, further illustrate the present invention.
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 document be differentiated.The object of the invention is to the properties-correcting agent using polynite as nanoparticle, interparticle autohemagglutination effect is reduced, and be evenly dispersed in coating with the form of nano particle, produce synergistic effect with nanometer porous titanium dioxide.Give full play to nano effect, make the coating and the ground that make have better sticking power, improve antiseptic property simultaneously.
Mesoporous TiO 2, take tensio-active agent as template, utilizes the chemical processes such as sol-gel emulsification or microemulsified, by the interface interaction between organism and inorganics, synthesizes.
For the mono-dispersed nano level mesoporous TiO 2 that has duct, replace the nanoparticle of solid construction as mineral filler, it has dual nanostructure, be nano-scale particle sizes and nano level meso-hole structure, owing to thering is unique pore passage structure, polymer molecular chain can enter into 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 spherical mesoporous TiO 2 particle produce synergistic effect to matrix resin, form nanometer network structure (as Fig. 1) simultaneously.
The synthetic employing sol-gel method of nano meso-porous titanium dioxide, from Fig. 2 (a), (b) the most probable aperture that shows mesoporous TiO2 is 13.3 nm, and specific surface area is 165m2/g, and pore volume is that 0. 4 ml.g-1(are 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 dibutyl phthalates, mechanical stirring is even;
2) getting 50 parts of waterborne curing agents mixes with 100 parts of water; The mother liquor of protective system is mixed and is coated on treated good steel plate in the ratio of 4:1 with the waterborne curing agent having diluted, control thickness at 35-200um, self-vulcanizing.
Smear surrounding wax sealing after solidifying is put into salt fog cabinet after processing, and after 500h, takes out, and takes a picture.By salt fog photo, can find out that pure epoxy resin coating is through 500h, there is corrosion point in coatingsurface, seriously corroded (Fig. 3 A).
Embodiment 3(by weight percentage, adds separately nano meso-porous titanium dioxide particle)
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 above resin system, in ball mill, disperse 1.5h.Getting 35 parts of waterborne curing agents mixes with 75 parts of water; The mother liquor of protective system is mixed and is coated on treated good steel plate in the ratio of 3.5:1 with the waterborne curing agent having diluted, control thickness at 35-200um, self-vulcanizing.
Smear surrounding wax sealing after solidifying is put into salt fog cabinet after processing, and after 500h, takes out, and takes a picture.By salt fog photo (Fig. 3 B), can be found out and be added separately the epoxy coating of nano meso-porous titanium dioxide through 500h, coatingsurface will be significantly better than the coating that does not add any Nano filling, and a small amount of corrosion pit only appears in surface.
Embodiment 4(by weight percentage, adds separately organo montmorillonite)
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 above resin system, in ball mill, disperse 1.5h.Getting 35 parts of waterborne curing agents mixes with 75 parts of water; The mother liquor of protective system is mixed and is coated on treated good steel plate in the ratio of 3.5:1 with the waterborne curing agent having diluted, control thickness at 35-200um, self-vulcanizing.
By salt fog photo (Fig. 3 C), can be found out and be added separately the epoxy coating of organo montmorillonite through 500h, coatingsurface will be better than the coating that does not add any Nano filling a little, but the corrosion pit of part appears in surface.
Embodiment 5(by weight percentage, adds 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 dibutyl phthalates, mechanical stirring is even;
2) get 5 parts of nano meso-porous titanium dioxide molecular sieves, 8 parts of organo montmorillonite fillers, add in above resin system, disperse 1h in ball mill.Getting 50 parts of waterborne curing agents mixes with 100 parts of water; The mother liquor of protective system is mixed and is coated on treated good steel plate in the ratio of 4:1 with the waterborne curing agent having diluted, control thickness at 35-200um, self-vulcanizing.
By salt fog photo (Fig. 3 D), can find out and add the epoxy coating of organo montmorillonite and nano meso-porous titanium dioxide through 500h simultaneously, coatingsurface also will be significantly better than adding separately organo montmorillonite, add separately the coating of nano meso-porous titanium dioxide, there is not any corrosion pit in surface, shows fully the synergy that two kinds of different shapes nanoparticles show epoxy coating.
Claims (6)
1. the preparation method of nano meso-porous titanium dioxide/organo montmorillonite protective system, it is characterized in that described nano meso-porous titanium dioxide, take tensio-active agent as template, utilize sol-gel emulsification or microemulsified process, by the interface interaction between organism and inorganics, synthesize; Shape is take regular spherical as main, and median size is 60～100nm; Duct is that rule has duct or randomly has a pore passage structure, and aperture is 10～50nm; Its preparation process is as follows:
A gets 100-200 part water and 100-200 part aqueous epoxy resins, adds 0.3-1 part defoamer, 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 above resin system, disperses 1-2h in ball mill, obtains the mother liquor of protective system;
C gets 25-50 part waterborne curing agent and mixes with 50-100 part water;
D mixes with the waterborne curing agent having diluted the mother liquor of protective system in the ratio of 3-4:1.
2. by the preparation method of a kind of nano meso-porous titanium dioxide/organo montmorillonite protective system claimed in claim 1, 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 a kind of nano meso-porous titanium dioxide/organo montmorillonite protective system claimed in claim 1, it is characterized in that described waterborne curing agent is W651, W650.
4. by the preparation method of a kind of nano meso-porous titanium dioxide/organo montmorillonite protective system claimed in claim 1, it is characterized in that described defoamer is ethylene oxide oligopolymer or methyl-silicone oil.
5. the preparation method of a kind of nano meso-porous titanium dioxide/organo montmorillonite protective system according to claim 1, is characterized in that described softening agent is dibutyl phthalate or octyl phthalate.
6. a preparation method for nano meso-porous titanium dioxide/organo montmorillonite protective system, is characterized in that the method also comprises following process: gets 100 parts of water and 200 parts of aqueous epoxy resins, adds 1 part of defoamer, 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 above resin system, disperse 2h in ball mill, obtain the mother liquor of protective system; Getting 50 parts of waterborne curing agents mixes with 100 parts of water; The mother liquor of protective system is mixed and gets final product to obtain high rot-resistant coating in the ratio of 3.5:1 with the waterborne curing agent having diluted.
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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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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. |