The preparation method of anti-ultraviolet nano zinc oxide composite powderTechnical field
The present invention relates to a kind of preparation method of anti-ultraviolet nano zinc oxide composite powder, belong to uvioresistant inorganic-organic composite powder material fabricating technology field.
Background technology
As everyone knows, nano zine oxide, titanium dioxide, red iron oxide all can be used as the mineral compound of ultraviolet screening agent; Nano zine oxide particularly, because of itself being white, painted simple, and it is strong to absorb ultraviolet ability, UVA, UB and UVC is all had shielding effect, thereby be used widely.Nano zine oxide still is the good anti-ageing ageing-resistant performance that is made in obvious raising coating, paint, fiber, film in addition, is a kind of anti-ultraviolet ageing agent that has potentiality.
But nano zinc oxide particles surface energy height is in the thermodynamics unsteady state, very easily reunites; And the hydrophilic oleophobic of particle surface, poor with organic matrix consistency in the materials such as makeup, coating, paint, fiber, film, therefore, must carry out surface modification to it, bring into play the anti-aging uvioresistant effect of nano zine oxide in materials such as makeup, coating, paint, fiber, film better.
About the preparation of nano zinc oxide composite powder, once there were some Patent document datas to make report, for example:
U.S. Pat 5486631, the poly-method to the property nano zine oxide of a kind of organosilicon is disclosed, stable, oil loving composite granule have been obtained, but this method adopts one matter to coat, its photocatalysis performance of the composite granule that makes is stronger, limited its use range, this technology is also complicated in addition.
Chinese patent CN1398923, this patent disclosure a kind of super fine zinc oxide and preparation method thereof of modification, wherein the super fine zinc oxide of modification is in the ammonia still process process of alkaline process production or makes the super fine zinc oxide that zinc oxide adds the coupling agent acquisition modification of surface-modifying agent or new polymers dispersion agent or both sexes structure afterwards, but it adopts one matter to coat, and has limited the practical application effect of zinc oxide.
Chinese patent CN1260366, this patent report adopt ultrasonic micro-emulsion method for preparing nano zinc oxide UV ray shielding material, by making through the modification of the adulterated nano oxidized zinc surface coated non-ionic surfactant of magnesium oxide, this method adopts ultrasonic microemulsion method, the cost height is difficult to scale operation.
Chinese patent CN1657415 has reported nano zine oxide crystal grain and surface-modifying agent, and organic solvent, dispersion agent carry out the modification of nano zine oxide again by the ball milling blending dispersion under microwave exposure, obtain nanometer Zinc oxide powder.This method adopts organic solvent, increases cost, and easily pollutes; The ball milling blending dispersion also is difficult to obtain uniformly, particle diameter controllable compound powder; Microwave exposure has also limited the large-scale industrialized production of this method.
Chinese patent CN1246443 discloses the nanometer Zinc oxide powder and the preparation method of a kind of surface clad titanium or aluminum compound, and its powder that makes has excellent ultraviolet radiation absorption characteristic, simultaneously the visible reflectance height.But it is difficult in homodisperse in the lipophilicity matrix.
Chinese patent CN1659223A, a kind of preparation method who comprises the zinc oxide fine granular powder that scribbles silicon-dioxide of surperficial Ceng Shui is disclosed, wherein the average original particle size of powder is 5～120nm, and size range is too broad, is difficult to determine best globule size during use; Select for use organic solvents such as tetramethoxy, tetraethoxysilane to produce silicic acid in addition, the cost height, and easily pollute.
Mostly cost is higher for above-mentioned all methods, is difficult to large-scale industrialization promotion; These methods adopt one matter to coat mostly, can not satisfy the oleaginous base of materials such as nano zine oxide and makeup, coating, paint, fiber, film and stablize compatible.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of anti-ultraviolet nano zinc oxide composite powder.Another purpose of the present invention provide a kind ofly have good hydrophobic performance, photocatalytic activity is low, the nano zinc oxide composite powder that has extensive excellent compatibility with the used oleaginous base segmentation of materials such as makeup, coating, paint, fiber, film; This composite granule has the function of effective shielding ultraviolet rays.
The preparation method of a kind of anti-ultraviolet nano zinc oxide composite powder of the present invention is characterized in that having following technological process and step:
(a) at first with nanometer Zinc oxide powder and dispersion agent in a certain amount of deionized water high speed dispersed with stirring, make slurry; The concentration of zinc oxide slurry is 5～20%; Dispersion agent is any in polyoxyethylene glycol, triethanol ammonium, polyvinyl alcohol, the Sodium hexametaphosphate 99, and the addition of dispersion agent is counted 1～6% of zinc oxide weight with zinc oxide weight; The rotating speed of high-speed stirring is 2000～7000rpm, and the dispersed with stirring time is 10～60 minutes;
(b) add water glass or potassium silicate solution subsequently in above-mentioned zinc oxide slurry, its concentration is 0.5～3.0mol/L; The consumption of water glass or potassium silicate counts 1～10% with the silicon-dioxide and the massfraction ratio of zinc oxide; Stir then, and be warming up to 40～80 ℃, slowly drip dilute sulphuric acid, the pH value of regulator solution is 8.0～12.0, keeps constant temperature 1～3 hour;
(c) and then with silicoorganic compound be incorporated in the above-mentioned solution, silicoorganic compound are selected from any in dimethyl siloxane, epoxy dimethyl siloxane, the dimethyl diphenyl polysiloxane; The consumption of silicoorganic compound serves as to calculate benchmark with the weight of zinc oxide, is 6～30% of zinc oxide weight; Carry out high-speed stirring then, mixing speed is 2000～7000rpm, and 40～80 ℃ of following constant temperature 0.5～2.5 hour; Washing then, washing is to there not being SO42-Exist; After under 60～120 ℃ dry 10～24 hours, pulverize, finally obtain nano zinc oxide composite powder.
The granularity of nanometer Zinc oxide powder recited above is 10～50nm; The concentration of the dilute sulphuric acid of described adjusting pH value is 10～15%.
In the processing method of the present invention,, make it have photocatalytic activity restraining effect preferably, reduce photocatalytic activity, prevent premature aging owing to contain the silica-coating layer in the nano zinc oxide composite powder; Later on further carry out organic-silicon-modified processing in the operation, then organosilicon is coated with the consistency that the rosy clouds layer can improve the used organic matrix of materials such as nano zine oxide and makeup, coating, paint, fiber, film.Prepared nano zinc oxide composite powder has the permanent stability and the low phototoxicity of remarkable excellence as the UV shielding material.
Technology of the present invention is simple, and is with low cost, be easy to amplify and enlarge produce, and the Nano-class zinc oxide composite granule of the present invention's preparation, its particle diameter is 10～50nm, specific surface area is 100～300m2/ g, activation index are 50～100%, and the ultraviolet shielded rate of UV is reached 85～99.5%.
Embodiment
After now embodiments of the invention specifically being described in.
Embodiment 1
Adding 2g polyoxyethylene glycol dispersion agent and 150g particle diameter in the 850ml deionized water is the zinc oxide of 10～20nm, and at room temperature high-speed stirring evenly and make dispersion is made slurry; The rotating speed of homogenizer is 5000rpm, and the dispersed with stirring time is 30 minutes.Subsequently above-mentioned slurry is placed the beaker of 2000ml, adding 250ml concentration is the sodium silicate solution of 1mol/L, stirs, and is warming up to 60 ℃; Slowly drip concentration then and be 10% dilute sulphuric acid, the pH value of regulator solution is 10, and keeps 60 ℃ of constant temperature 1 hour.And then add the 15g dimethyl silicone oil, and carry out high-speed stirring, under agitation kept constant temperature 30 minutes in 60 ℃; The stirrer rotating speed is 5000rpm; Wash then, with deionized water wash to there not being SO42-Ion exists; After under 120 ℃ of temperature dry 12 hours, pulverize, finally obtain nano zinc oxide composite powder.
Above-mentioned powder is made into 0.02% solution, and ultra-sonic dispersion 30 minutes is used its absorbancy of UV-Vis spectrophotometer measurement then, and test finds that its rate of ultraviolet shield to UVA, UVB, UVC wave band is 99.5%, and visible light almost completely sees through.
Embodiment 2
Adding 2g triethanol ammonium dispersion agent and 200g particle diameter in the 1000ml deionized water is the zinc oxide of 20～30nm, and at room temperature high-speed stirring evenly and make dispersion is made slurry; The rotating speed of homogenizer is 5000rpm, and the dispersed with stirring time is 1 hour.Subsequently above-mentioned slurry is placed the beaker of 2000ml, adding 300ml concentration is the sodium silicate solution of 1mol/L, stirs, and is warming up to 60 ℃; Slowly drip concentration then and be 10% dilute sulphuric acid, the pH value of regulator solution is 10, and keeps 60 ℃ of constant temperature 1 hour.And then add the 15g dimethyl silicone oil, and carry out high-speed stirring, under agitation kept constant temperature 1 hour in 60 ℃; The stirrer rotating speed is 5000rpm; Wash then, with deionized water wash to there not being SO42-Ion exists; After under 120 ℃ of temperature dry 24 hours, pulverize, finally obtain nano zinc oxide composite powder.
Above-mentioned powder is added in the coating by 0.02% solution (weight ratio), and with its absorbancy of UV-Vis spectrophotometer measurement, test finds that this coating is 98% to the rate of ultraviolet shield of UVA, UVB wave band, and visible light permeability is better.
Embodiment 3
Adding 5g polyvinyl alcohol dispersion agent and 200g particle diameter in the 1000ml deionized water is the zinc oxide of 20～40nm, and at room temperature high-speed stirring evenly and make dispersion is made slurry; The rotating speed of homogenizer is 5000rpm, and the dispersed with stirring time is 40 minutes.Subsequently above-mentioned slurry is placed the beaker of 2000ml, adding 300ml concentration is the potassium silicate solution of 0.5ml/L, stirs, and is warming up to 80 ℃; Slowly drip concentration then and be 15% dilute sulphuric acid, the pH value of regulator solution is 9.0, and keeps 80 ℃ of constant temperature 1.5 hours.And then add the 40g dimethyl silicone oil, and carry out high-speed stirring, under agitation kept constant temperature 1 hour in 80 ℃; The stirrer rotating speed is 3000rpm; Wash then, with deionized water wash to there not being SO42-Ion exists; After under 120 ℃ of temperature dry 12 hours, pulverize, finally obtain nano zinc oxide composite powder.
Above-mentioned powder is added in the used for cosmetic slurry by 0.01% (weight ratio), and with its absorbancy of UV-Vis spectrophotometer measurement, test finds that this makeup slurry is 97% to the rate of ultraviolet shield of UVA, UVB wave band, and visible light permeability is better.
Embodiment 4
Adding 10g Sodium hexametaphosphate 99 dispersion agent and 300g particle diameter in the 700ml deionized water is the zinc oxide of 30～50nm, and at room temperature high-speed stirring evenly and make dispersion is made slurry; The rotating speed of homogenizer is 7000rpm, and the dispersed with stirring time is 10 minutes.Subsequently above-mentioned slurry is placed the beaker of 2000ml, adding 300ml concentration is the sodium silicate solution of 2mol/L, stirs, and is warming up to 50 ℃; Slowly drip concentration then and be 15% dilute sulphuric acid, the pH value of regulator solution is 8.0, and keeps 50 ℃ of constant temperature 3 hours.And then add 40g dimethyl diphenyl polysiloxane, and carry out high-speed stirring, under agitation kept constant temperature 1 hour in 50 ℃, the stirrer rotating speed is 7000rpm; Wash then, with deionized water wash to there not being SO42-Ion exists; After under 120 ℃ of temperature dry 12 hours, pulverize, finally obtain nano zinc oxide composite powder.
Above-mentioned powder is added in the paint by 0.01% (weight ratio), and with its absorbancy of UV-Vis spectrophotometer measurement, test finds that this paint is 85% to the rate of ultraviolet shield of UVA, UVB wave band, and visible light permeability is relatively poor.
Embodiment 5
Adding 60g polyoxyethylene glycol dispersion agent and 100g particle diameter in the 900ml deionized water is the zinc oxide of 20～30nm, and at room temperature high-speed stirring evenly and make dispersion is made slurry; The rotating speed of homogenizer is 4000rpm, and the dispersed with stirring time is 60 minutes.Subsequently above-mentioned slurry is placed the beaker of 2000ml, adding 60ml concentration is the sodium silicate solution of 3mol/L, stirs, and is warming up to 60 ℃; Slowly drip concentration then and be 10% dilute sulphuric acid, the pH value of regulator solution is 10, and keeps 60 ℃ of constant temperature 2 hours.And then add 40g epoxy dimethyl siloxane, and carry out high-speed stirring, under agitation kept constant temperature 1 hour in 60 ℃, the stirrer rotating speed is 4000rpm; Wash then, with deionized water wash to there not being SO42-Ion exists; After under 60 ℃ of temperature dry 24 hours, pulverize, finally obtain nano zinc oxide composite powder.
Above-mentioned powder is added in the coating by 0.01% (weight ratio), and with its absorbancy of UV-Vis spectrophotometer measurement, test finds that this coating is 97% to the rate of ultraviolet shield of UVA, UVB wave band, and visible light permeability is better.
The detection and the test of the comprehensive prepared nano zine oxide complex body of the various embodiments described above, the transmission electron microscope photo by composite granule as can be known, its particle distribution is more even, particle diameter is in 10～50nm scope.Its specific surface area is 100～300m2/ g, activation index are 50～100%.To the UV rate of ultraviolet shield is 85～99.5%.
This composite granule good dispersity, photocatalytic activity is lower.It has good consistency to used organic base-materials such as makeup, coating, paint, and it is stable to be uniformly dispersed, and this nano zinc oxide composite powder can be used as uvioresistant material or ultraviolet screening agent.