CN100503520C - Method for preparing self-antifouling sanitation cement product - Google Patents
Method for preparing self-antifouling sanitation cement product Download PDFInfo
- Publication number
- CN100503520C CN100503520C CNB2007100711041A CN200710071104A CN100503520C CN 100503520 C CN100503520 C CN 100503520C CN B2007100711041 A CNB2007100711041 A CN B2007100711041A CN 200710071104 A CN200710071104 A CN 200710071104A CN 100503520 C CN100503520 C CN 100503520C
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- Prior art keywords
- cement product
- antifouling
- sanitation
- self
- titanium
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
Abstract
The present invention discloses making process of antifouling cement product. The making process includes: 1. painting resin onto the surface of cement product to form film and drying; and 2. painting anatase crystal type titania sol onto the surface of cement product with resin film to form one other film and drying. The present invention has resin film to close the micro pores in the surface of the cement product and to form smooth and compact isolating layer and anatase crystal type titania sol film with high antifouling performance.
Description
Technical field
The present invention relates to material science, relate to a kind of preparation method of self-antifouling sanitation cement product particularly.
Background technology
Titanium oxide sol is applied in pottery or glass surface, titanium oxide in the colloidal sol has superpower oxidation capacity under sunlight, fluorescent lamp or action of ultraviolet light, can destroy protein of bacteria, decomposing organic matter and obnoxious flavour, can be antifouling, sterilization, from clean and purify air.
The pure zirconia titanium must just can excite by ultraviolet light, and is lower to the utilization ratio of daily visible light.Many researchers increases the utilization of titanium oxide to visible light by modes such as ion doping, semi-conductor are compound, improving its antifouling and self-cleaning property, but need heat-treat technology.Therefore, prior preparation method is difficult to be applied to be difficult for the base materials such as cement product of heating.
Chinese patent 200510061118.6 discloses a kind of preparation method of titanium dioxide optical catalyst sol, may further comprise the steps: (1) adds titanium tetrachloride, titanium sulfate or butyl (tetra) titanate in the pure diluting solvent in wherein at least a under agitation condition; (2) under the water-bath, mixing solutions is dropwise added in the hydrolysising solvent, stir; (3) colloidal sol leaves standstill.
The colloidal sol of this patented method preparation can apply film forming by normal temperature, and when being used for porous cement products surface, its film forming and antifouling property are all not good.
Summary of the invention
The invention provides a kind of method for preparing self-antifouling sanitation cement product, this method has solved titanium oxide sol in cement product surface filming and the not good problem of antifouling property.
The preparation method of self-antifouling sanitation cement product provided by the invention may further comprise the steps:
(1) cold coating is coated in cement product surface filming, drying in advance;
(2) anatase crystal titanium colloidal sol is coated in the cement product surface filming that has applied resin, drying;
Described anatase crystal titanium colloidal sol prepares by the following method:
(a), regulate pH value to 0.1～5 of adjuvant water solution with the auxiliary agent adjuvant water solution that makes soluble in water;
(b) under the agitation condition, titanium salt is added alcohol solvent for dilution make titanium salt alcohol solution;
(c) under 5～95 ℃ of water-baths, titanium salt alcohol solution is dropwise joined in the adjuvant water solution, fully left standstill at least 1 hour after the reaction;
Described auxiliary agent is one or more in the soluble salt, tin tetrachloride, tetraethoxy, itrogenous organic substance of transition metal ion;
Described titanium salt is one or more in titanium tetrachloride, titanium sulfate and the butyl (tetra) titanate.
In the described auxiliary agent, metal ion can improve the antifouling property after the titanium colloidal sol film forming, and tetraethoxy can improve the film-forming properties of titanium colloidal sol on the cement products surface, and adding itrogenous organic substance all has improvement to didirtresistance and film-forming properties.
Described itrogenous organic substance comprises amine, nitro class, diazonium class and nitrogen heterocyclic ring class.
The soluble salt of described transition metal ion is the soluble salt of rare earth ion.
Auxiliary agent and water can be arbitrary proportions in the step (a), and preferred weight ratio is 1～500.
The used reagent of adjusting adjuvant water solution pH value is one or more in hydrochloric acid, sulfuric acid, nitric acid and the phosphoric acid in the step (a).
Titanium salt and alcoholic solvent can be arbitrary proportions in the step (b), and preferred weight ratio is 1～10.
Described alcoholic solvent is one or more in dehydrated alcohol, ethylene glycol and the Virahol.
Adjuvant water solution and titanium salt alcohol solution can be arbitrary proportions in the step (c), and preferred weight ratio is 50～500.
Described cold coating is the composition of resin, oxygenant, promotor etc., and described resin is one or more in acrylic resin, urethane resin, Resins, epoxy, the fluorocarbon resin.
Described coating method is spraying, spin coating, dip-coating, curtain coating, roller coat or brushing.
The preparation method of self-antifouling sanitation cement product provided by the invention, by earlier in cement product surface precoating one deck resin, sealed the micropore hole on cement product surface, form level and smooth compact isolating layer, solve titanium oxide and be used for the not good defective of cement product when surface performance, anatase crystal titanium colloidal sol of the present invention can be on the cement product surface normal temperature or 120 ℃ of following film forming, saved traditional heat treatment process.
Embodiment
Below further the present invention is further described by example.
Embodiment 1
(1) iron nitrate and lanthanum nitrate (weight ratio 1:1) are dissolved in the distilled water, the pH value to 0.1 with the nitric acid regulator solution makes iron nitrate and lanthanum nitrate hexahydrate, and the weight ratio of distilled water and iron nitrate and lanthanum nitrate is 1;
(2) under the agitation condition, butyl (tetra) titanate added in the dehydrated alcohol dilute, the mass ratio of dehydrated alcohol and titanium salt is 1, stirs to make the butyl (tetra) titanate ethanolic soln;
(3) under 5 ℃ of water-baths, the butyl (tetra) titanate ethanolic soln dropwise is added in iron nitrate and the lanthanum nitrate hexahydrate, the mass ratio of iron nitrate and lanthanum nitrate hexahydrate and butyl (tetra) titanate ethanolic soln is 50, fully after the reaction, leaves standstill 5 hours, makes anatase crystal titanium colloidal sol;
(4) get benzene emulsion, in cement plate surface precoating, film forming, drying forms sealing coat;
(5) get anatase crystal titanium colloidal sol, roller coat is applying the cement plate surface filming of phenylpropyl alcohol sealing coat, and 120 ℃ of dryings make the self-antifouling sanitation cement plate.
Embodiment 2
(1) triethylamine is dissolved in the deionized water, the pH value to 5 with hydrochloric acid conditioning solution makes triethylamine solution, and the mass ratio of deionized water and triethylamine is 500;
(2) under the agitation condition, titanium tetrachloride added in the ethylene glycol dilute, the mass ratio of ethylene glycol and titanium tetrachloride is 10, stirs to make the titanium tetrachloride ethylene glycol solution;
(3) under 95 ℃ of water-baths, the titanium tetrachloride ethylene glycol solution dropwise is added in the triethylamine solution, the mass ratio of triethylamine solution and titanium tetrachloride ethylene glycol solution is 500, fully after the reaction, leaves standstill 1 hour again, makes anatase crystal titanium colloidal sol;
(4) get acrylic resin paint, in the cement pavement precoating, film forming, drying forms sealing coat;
(5) get anatase crystal titanium colloidal sol, be sprayed on film forming on the cement pavement that has applied the vinylformic acid sealing coat, dry naturally under the room temperature, make the self-antifouling sanitation cement road surface.
Embodiment 3
(1) tetraethoxy is dissolved in the deionized water, with the pH value to 2.5 of sulfuric acid regulation solution, the weight ratio of deionized water and tetraethoxy is 1～80 simultaneously;
(2) under the agitation condition, butyl (tetra) titanate added in the Virahol dilute, the mass ratio of Virahol and butyl (tetra) titanate is 3, stirs to make the butyl (tetra) titanate aqueous isopropanol;
(3) the butyl (tetra) titanate aqueous isopropanol dropwise is added in step (1) the gained solution, the mass ratio of step (1) gained solution and butyl (tetra) titanate aqueous isopropanol is 100, after fully reacting under 35 ℃ of bath temperatures, left standstill again 20 hours, make anatase crystal titanium colloidal sol;
(4) get fluorocarbon resin coating, in cement brick surface precoating, film forming, drying forms sealing coat;
(5) get anatase crystal titanium colloidal sol, curtain coating is applying the cement road brick surface filming of fluorine carbon sealing coat, and 50 ℃ of dryings make the self-antifouling sanitation cement brick.
Embodiment 4
(1) tin tetrachloride being dissolved in the deionized water, is 3 with the pH value of phosphoric acid regulator solution, makes the tin tetrachloride aqueous solution, and the weight ratio of deionized water and tin tetrachloride is 230;
(2) under the agitation condition, titanium sulfate is added the alcohol solvent for dilution that dehydrated alcohol, ethylene glycol and Virahol are formed (weight ratio of dehydrated alcohol, ethylene glycol and Virahol is 5:2:3), the mass ratio of alcoholic solvent and titanium sulfate is 5, stirs to make the titanium sulfate alcoholic solution;
(3) under 55 ℃ of water-baths, the titanium sulfate alcoholic solution dropwise is added in the tin tetrachloride aqueous solution, the weight ratio of the tin tetrachloride aqueous solution and titanium sulfate alcoholic solution is 300, fully after the reaction, leaves standstill 15 hours again, makes anatase crystal titanium colloidal sol;
(4) get polyurethane resin coating, in cement tub surface precoating, film forming, drying forms sealing coat;
(5) get anatase crystal titanium colloidal sol, brush and to apply the cement tub surface-coated film forming of urethane sealing coat, 75 ℃ of dryings make the self-antifouling sanitation cement groove.
Embodiment 5
(1) lanthanum nitrate and tetraethoxy (weight ratio 1:25) are dissolved in the deionized water, the pH value to 3.8 with hydrochloric acid conditioning solution makes and mixes the lanthanum silicon sol, and the mass ratio of deionized water and lanthanum nitrate and tetraethoxy is 400;
(2) under the agitation condition, butyl (tetra) titanate is added the alcohol solvent for dilution that ethylene glycol and Virahol are formed (mass ratio of ethylene glycol and Virahol is 1:1), the mass ratio of alcoholic solvent and butyl (tetra) titanate is 7, stirs to make the butyl (tetra) titanate alcoholic solution;
(3) under 75 ℃ of water-baths, the butyl (tetra) titanate alcoholic solution dropwise is added to mixes in the lanthanum silicon sol, the mass ratio of mixing lanthanum silicon sol and butyl (tetra) titanate alcoholic solution is 410, fully after the reaction, leaves standstill 8 hours again, makes anatase crystal titanium colloidal sol;
(4) get benzene emulsion, in cement tile surface precoating, film forming, drying forms sealing coat;
(5) get anatase crystal titanium colloidal sol, brush and to apply the cement tile surface filming of phenylpropyl alcohol sealing coat, 105 ℃ of dryings make self-antifouling sanitation cement watt.
Embodiment 6
(1) auxiliary agent iron nitrate, lanthanum nitrate, tin tetrachloride, tetraethoxy, 3-dimethylamino propylamine (mass ratio of iron nitrate, lanthanum nitrate, tin tetrachloride, tetraethoxy, 3-dimethylamino propylamine is 1:1:10:30:1) are dissolved in the deionized water, pH value with hydrochloric acid conditioning solution is 4.5, make adjuvant water solution, the mass ratio of deionized water and auxiliary agent is 400;
(2) under the agitation condition, butyl (tetra) titanate added in the dehydrated alcohol dilute, the mass ratio of dehydrated alcohol and butyl (tetra) titanate is 8, stirs to make the butyl (tetra) titanate ethanolic soln;
(3) under 85 ℃ of water-baths, the butyl (tetra) titanate ethanolic soln dropwise is added in the adjuvant water solution, the mass ratio of adjuvant water solution and butyl (tetra) titanate ethanolic soln is 410, fully after the reaction, leaves standstill 6 hours again, makes anatase crystal titanium colloidal sol;
(4) get benzene emulsion, in cement pipe surface precoating, film forming, drying forms sealing coat;
(5) get anatase crystal titanium colloidal sol, applying the cement pipe surface dip-coating film forming of phenylpropyl alcohol sealing coat, 85 ℃ of dryings make self-antifouling sanitation cement goods pipe.
Detect the automatic antifouling of cement product and the result of the performance that keeps clean according to GB GB9780-88 coating contamination resistance experimental technique.In the test, adopt flyash as source of pollution, with the cement product surface that its brushing makes in each embodiment, water flushing again, the residual degree of observing flyash is calculated its anti-contamination rate x%.Flyash residual many more, the model surface reflectance reduces big more, and the x value is also big more, and the contamination resistance of model is poor more.
The x value of model is as shown in the table among each embodiment, in addition with the model that only applies corresponding cold coating among each embodiment plate as a comparison.As seen the best 6# plate of anti-fouling effect almost can be kept original surperficial whiteness and smooth finish.
Claims (8)
1. the preparation method of a self-antifouling sanitation cement product may further comprise the steps:
(1) cold coating is coated in cement product surface filming, drying in advance;
(2) anatase crystal titanium colloidal sol is coated in the cement product surface filming that has applied cold coating, drying;
Described anatase crystal titanium colloidal sol prepares by the following method:
(a), regulate pH value to 0.1～5 of adjuvant water solution with the auxiliary agent adjuvant water solution that makes soluble in water;
(b) under the agitation condition, titanium salt is added alcohol solvent for dilution make titanium salt alcohol solution;
(c) under 5～95 ℃ of water-baths, titanium salt alcohol solution is dropwise joined in the adjuvant water solution, fully left standstill at least 1 hour after the reaction;
Described auxiliary agent is amine, nitro class, diazonium class, nitrogen heterocyclic ring class itrogenous organic substance, the soluble salt of rare earth ion, one or more in tin tetrachloride and the tetraethoxy;
Described titanium salt is one or more in titanium tetrachloride, titanium sulfate and the butyl (tetra) titanate.
2. the preparation method of self-antifouling sanitation cement product according to claim 1 is characterized in that: water and auxiliary agent weight ratio are 1～500 in the step (a).
3. the preparation method of self-antifouling sanitation cement product according to claim 1 is characterized in that: regulate the used reagent of adjuvant water solution pH value in the step (a) and be in hydrochloric acid, sulfuric acid, nitric acid and the phosphoric acid one or more.
4. according to the preparation method of the described self-antifouling sanitation cement product of claim 1, it is characterized in that: alcoholic solvent and titanium salt weight ratio are 1～10 in the step (b).
5. the preparation method of self-antifouling sanitation cement product according to claim 1, it is characterized in that: described alcoholic solvent is one or more in dehydrated alcohol, ethylene glycol and the Virahol.
6. the preparation method of self-antifouling sanitation cement product according to claim 1 is characterized in that: adjuvant water solution and titanium salt alcohol solution weight ratio are 50～500 in the step (c).
7. the preparation method of self-antifouling sanitation cement product according to claim 1, it is characterized in that: the resin of described cold coating is one or more in acrylic resin, urethane resin, Resins, epoxy, the fluorocarbon resin.
8. the preparation method of self-antifouling sanitation cement product according to claim 1, it is characterized in that: described coating method is spraying, spin coating, dip-coating, curtain coating, roller coat or brushing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100711041A CN100503520C (en) | 2007-09-05 | 2007-09-05 | Method for preparing self-antifouling sanitation cement product |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100711041A CN100503520C (en) | 2007-09-05 | 2007-09-05 | Method for preparing self-antifouling sanitation cement product |
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| CN101148367A CN101148367A (en) | 2008-03-26 |
| CN100503520C true CN100503520C (en) | 2009-06-24 |
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| CN105366986A (en) * | 2015-11-25 | 2016-03-02 | 浙江大学自贡创新中心 | Preparation method of water repellent agent for foam concrete |
| CN108017308B (en) * | 2017-10-26 | 2020-11-13 | 连云港职业技术学院 | Additive for improving strength of building material and preparation method thereof |
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Granted publication date: 20090624 Termination date: 20120905 |