CN101173121B - Anti-ultraviolet organic-inorganic nano composite transparent coating and method for producing the same - Google Patents
Anti-ultraviolet organic-inorganic nano composite transparent coating and method for producing the same Download PDFInfo
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- CN101173121B CN101173121B CN2007100469014A CN200710046901A CN101173121B CN 101173121 B CN101173121 B CN 101173121B CN 2007100469014 A CN2007100469014 A CN 2007100469014A CN 200710046901 A CN200710046901 A CN 200710046901A CN 101173121 B CN101173121 B CN 101173121B
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Abstract
The invention belongs to the technical field of the coating composite, in particular to ultraviolet radiation-resistant organic-inorganic compound transparent coating and the preparative method thereof. The invention comprises the steps as follows: amphoteric ion multipolymer is adopted as the surface activator and the stabilizing agent to conduct surface modification for the organic nm grain; effective blending physical compounding of the inorganic nm grain and the polymer basal body is carried out for the aim of producing the organic-inorganic compound transparent coating. The invention overcomes the disadvantages of uneven reuniting and dispersion, weak heat stability and bad function durability of ultraviolet absorbent in the traditional blending fusion composite algorithm in the polymer, as well as rejects the shortcomings such as complicate preparative technique, high cost and so on of the prior chemical compounding method. The film made of the compound transparent coating has an ultraviolet screening factor of higher than 99.9 percent and the permeability of visible beam region of more than 90 percent. Moreover, the invention is applicable for the production of the ultraviolet radiation-resistant film and various anti-aging plastic products requiring high light permeability, and the fields of automobile, preservation of cultural relics and environment protection.
Description
Technical field
The invention belongs to the coating composition technical field, be specifically related to a kind of anti-ultraviolet organic-inorganic nano composite transparent coating and preparation method thereof.
Background technology
Ultraviolet ray is the hertzian wave between 200～400 nanometers, be divided into shortwave (200～280nm), medium wave (280～320nm) and long wave (320～400nm), ultraviolet wavelength is short more, and is big more to the damage of human body skin.Simultaneously, the energy that ultraviolet ray has is about 314～419KJ/mol, is enough to destroy the chemical bond of polymkeric substance, causes the autoxidation reaction, causes the degradation with aging of polymkeric substance such as plastics, rubber, coating resin, and the loss that therefore cause every year is huge.
At present, the polymkeric substance with the ageing-resistant function of uvioresistant mainly adopts interpolation uvioresistant additive to carry out the preparation of blended melting method.The uvioresistant additive is divided into inorganic and organic two big classes, and wherein, particularly inorganic ultraviolet binder component becomes research and application focus with characteristics such as the chemistry of its brilliance and stability, non-migrating, tasteless, nontoxic, nonirritants.But traditional organic/inorganic blended melting method exists uv-absorbing agent and reunites in polymkeric substance and disperse disadvantage such as the low and heat resistance difference of mechanical strength uneven, material.
Xu Yanli and Chen Shanyun etc. (publication number CN 1715349A) have proposed a kind of preparation method with water polyurethane/hydrotalcite composite paint of anti-ultraviolet property.Its this coating has good anti-ultraviolet property and mechanical property, and coating is in the ultraviolet ray of wavelength 200～300 nanometer ultraviolet ray scope maskables 86%.This preparation technology is simple and convenient, and cost is lower, but this invention does not still break away from traditional blend physics complex method, and the stability of this organic/inorganic nano composite coating and uvioresistant effect still remain further to be improved.Xu Hong and Cheng Cunkang etc. (Granted publication CN 1224640C) utilize a kind of ultra-violet radiation resisting nano titanium oxide/polyester composite of nano titanium oxide in-situ preparing, in-situ polymerization is adopted in this invention, by inorganic nanoparticles and polymkeric substance are carried out chemical bonding, realize the homodisperse of inorganic nanoparticles in polymeric matrix, solved the agglomeration traits of nano titania particle in matrix, the uvioresistant Organic that this inventive method makes has good mechanics, thermal property and uvioresistant effect, but this preparation process has adopted the chemical method preparation method, complex process and loaded down with trivial details, cost is higher, lack ubiquity, the more important thing is that organic/inorganic original position compounding efficiency is lower.
Summary of the invention
The object of the present invention is to provide that a kind of technology is simple, lower-cost anti-ultraviolet organic-inorganic nano composite transparent coating and preparation method thereof.
Uvioresistant organic-inorganic nano composite transparent coating provided by the invention is prepared by following method: the amphoteric ion copolymer by a kind of easy preparation carries out the physical surface modification as tensio-active agent and stablizer to inorganic nanoparticles.Again should oil loving inorganic nanoparticles and polymeric matrix (such as polymethylmethacrylate, polycarbonate and polyvinyl butyral etc.) to carry out effective blend physics compound, prepare the uvioresistant organic/inorganic nano composite transparent coating of high stability and dispersing uniformity.Thus anti-ultraviolet organic-inorganic nano composite transparent coating make film rate of ultraviolet shield greater than 99.9%, and reach more than 90% in the transmitance of visible region.Having overcome traditional blended melting composite algorithm fully exists uv-absorbing agent and reunites in polymkeric substance and disperse shortcomings such as the thermal stability difference of inhomogeneous, composite product and function weather resistance be not good, complicated process of preparation and the more high drawback of cost of also having avoided chemically composited method to exist.
The preparation method of the anti-ultraviolet organic-inorganic nano composite transparent coating that the present invention proposes is as follows:
(1) the polyacrylamide amphoteric ion copolymer of 100～1000mg is put into 200～2000mL toluene solution, multipolymer is fully dissolved, and will not dissolve multipolymer and filter out, make solution transparent, repeatedly several times, finally standby in duplicate;
(2) 0.1～1.0g metal-salt (inorganics) is dissolved in 1～10mL ethanol, dissolves under ultrasonoscope, join then in above-mentioned first part of stock solution, ultra-sonic dispersion is even;
(3) 0.05～0.5g alkaline matter is added in 0.5～5.0mL ethanol, dissolving back (can add small amount of deionized water, so that dissolving) joins in above-mentioned second part of stock solution fully;
(4) under the high-speed stirring condition, second part of solution dropwise is added dropwise in first part of solution, continue reaction 10～60 minutes after the mixing again, organic solvent and water are removed in underpressure distillation under 55-65 ℃ of condition again; Resulting solid is repeatedly washed purifying with ethanol, obtain oil loving inorganic nanoparticles after the last vacuum-drying.
(5) above-mentioned a certain amount of oil loving inorganic nanoparticles and organic polymer are dissolved in the organic solvent together, ultra-sonic dispersion is even, obtains inorganic nanoparticles content at 1～20% organic-inorganic nano composite transparent solution, leaves standstill 12～72 hours.At last this clear solution is applied to carrier surface, obtains transparent film after the film forming, its thickness is in 10 nanometers～100 micron.
Among the present invention, used polyacrylamide amphoteric ion copolymer is to be formed by cationic monomer, acrylamide monomer, hydrolytic reagent terpolymer.This product is existing positive charge on the molecular chain, again the zwitter-ion irregular polymer of anionic charge is arranged.
Among the present invention, used metal-salt, be copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the acetate of silicon, copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the formate of silicon, copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the carbonate of silicon, copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the nitrate of silicon, copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the vitriol of silicon, copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the fluorochemical of silicon, copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the iodide of silicon, copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the muriate of silicon, copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the bromide of silicon, and at least two kinds mixture in these metal-salts.
Among the present invention, used alkaline matter can be the oxyhydroxide of sodium, potassium, ammonia, the sulphide salt of sodium, potassium, amine, the carbonate of sodium, potassium, ammonium, the supercarbonate of sodium, potassium, ammonium etc.
Among the present invention, used organic solvent in the step (5) is benzene,toluene,xylene, tetrahydrofuran (THF), dioxane, trichloromethane, methylene dichloride, vinyl acetic monomer, N-BUTYL ACETATE, dimethyl formamide, N,N-DIMETHYLACETAMIDE or N-N-methyl-2-2-pyrrolidone N-etc.
Among the present invention, used organic polymer in the step (5) can be polymethylmethacrylate or polycarbonate and polyvinyl butyral etc.
Among the present invention, said film forming in the step (5) is to remove solvent, obtains the transparent organic/inorganic nano laminated film of exsiccant, and its bake out temperature is 45-120 ℃, and drying time is 0.5-8 hour, and the exsiccant film thickness is 10 nanometers～100 micron.
Advantage of the present invention is: 1. this method at first adopt a kind of easy preparation amphoteric ion copolymer as tensio-active agent and stablizer, inorganic nanoparticles (for example zinc oxide, titanium dioxide, tungstic oxide and Cadmium Sulfide etc.) is carried out surface modification makes a kind of oil loving inorganic nanoparticles.This amphoteric ion copolymer on the one hand can stable emulsion and the diameter of control drop; On the other hand, they are retained in the inorganic nanoparticles surface all the time, by physisorption modification are carried out on the inorganic particle surface, become a kind of good compatilizer between inorganic nanoparticles and the polymeric matrix.Carry out oil loving inorganic nanoparticles and polymkeric substance (polymethylmethacrylate, polycarbonate and polyvinyl butyral etc.) matrix fully effectively that physics is compound more again, last film forming makes a kind of novel organic/inorganic nano composite transparent uv-absorbing coating.It has overcome and traditional overcome traditional blended melting composite algorithm and exist uv-absorbing agent and reunite in polymkeric substance and disperse disadvantages such as intensity uneven, material is low, heat resistance difference, overcome complicated process of preparation and the more high drawback of cost that chemically composited method exists, also overcome difficult problems such as the thermal stability difference of Organic goods and function weather resistance be not good; 2. preparation method of the present invention has that technology is simple and convenient, pollution-free, film quality is high, is easy to mass production, with low cost, advantage such as input-output ratio is high and application prospect is extensive, is high-performance organic/inorganic nano composite coating product of new generation; 3. this organic/inorganic nano composite transparent uv-absorbing coating has good anti-ultraviolet property, thermostability, film forming properties, mechanical property and resistance to elevated temperatures etc.; have boundless application prospect, can be applicable to fields such as automobile, historical relic's protection, environment protection.This organic/inorganic nano composite transparent uv-absorbing coating is utilized unique nano-powder dispersing technology and polymer-based carbon volume recombination technology of preparing, make film not only have good ultraviolet shielding function, and have the good transparency, weathering resistance and chemical stability, also can be used for preparing to demanding uvioresistant film of visible transparent and various ageing-resistant plastics etc.
Description of drawings
Fig. 1 is the X-ray diffractogram of organic modified nano oxide compound.
Fig. 2 is the uv-visible absorption spectroscopy of the organic-inorganic nano composite transparent coating of different inorganic nanometer oxide content.
Table 1 is the anti-uv-ray test of the organic-inorganic nano composite transparent coating of different inorganic nanometer oxide content.
Embodiment
Embodiment 1
The polyacrylamide amphoteric ion copolymer of 300mg fully is dissolved in the 25mL toluene solution, obtains a kind of clear solution, duplicate.With 0.4gZn (Ac)
22H
2After O is dissolved in 5mL ethanol (can add small amount of deionized water) fully, join in above-mentioned first part of solution.After 0.15g NaOH is dissolved in 5mL ethanol (can add small amount of deionized water) fully, join in above-mentioned second part of solution.Under the high-speed stirring condition, above-mentioned second part of solution dropwise is added dropwise in first part of solution, continue reaction 30 minutes after mixing again.After reaction finishes with solvent and water 60 ℃ of underpressure distillation, the solid particulate that obtains is used ethanol repetitive scrubbing and purifying again.Zinc oxide nanoparticle with the oleophylic modification after the vacuum-drying is back in the toluene once more at last, leaves standstill two days.Oil loving Zinc oxide nanoparticle and the polymethylmethacrylate ratio with 5: 95 is dissolved in the toluene together, ultra-sonic dispersion evenly after, obtain Zinc oxide nanoparticle content at 5% organic/inorganic nano composite transparent solution, left standstill 24 hours.At last this clear solution is applied to glass surface, dried 2 hours for 60 ℃, obtain the compound uvioresistant Clear coating of organic/inorganic nano, its thickness is approximately 20 microns.
The X ray diffracting spectrum of lipophilicity Zinc oxide nanoparticle is seen Fig. 1.The uv-visible absorption spectroscopy of this organic/inorganic nano composite transparent uv-absorbing coating as shown in Figure 2, its anti-uv-ray test performance is as shown in table 1.
Identical with embodiment 1, but the blending ratio of oil loving Zinc oxide nanoparticle and polymethylmethacrylate becomes 10: 90.
Embodiment 3
Identical with embodiment 1, but the blending ratio of oil loving Zinc oxide nanoparticle and polymethylmethacrylate becomes 15: 85.
Embodiment 4
Identical with embodiment 1, but the blending ratio of oil loving Zinc oxide nanoparticle and polymethylmethacrylate becomes 0: 100.
Embodiment 5
Identical with embodiment 1, but zinc oxide becomes titanium dioxide, and its content is constant.
Embodiment 6
Identical with embodiment 1, but zinc oxide becomes titanium dioxide, and its content becomes 10%.
Embodiment 7
Identical with embodiment 1, but zinc oxide becomes titanium dioxide, and its content becomes 20%.
Embodiment 8
Identical with embodiment 1, but the polymethyl methacrylate base body becomes polycarbonate.
Identical with embodiment 1, but the polymethyl methacrylate base body becomes polyvinyl butyral.
The material of organic-inorganic nano composite transparent coating that obtains among the embodiment 2-9 and embodiment 1 has similar performance.
Table 1
Claims (8)
1. anti-ultraviolet organic-inorganic nano composite transparent coating, it is characterized in that being prepared by following method: the polyacrylamide amphoteric ion copolymer carries out the physical surface modification as tensio-active agent and stablizer to the lipophilicity inorganic nanoparticles; Again should oil loving inorganic nanoparticles and polymeric matrix to carry out blend physics compound, prepare the anti-ultraviolet organic-inorganic nano composite transparent coating of a kind of high stability and dispersing uniformity.
2. the preparation method of an anti-ultraviolet organic-inorganic nano composite transparent coating as claimed in claim 1 is characterized in that concrete steps are:
(1) the polyacrylamide amphoteric ion copolymer of 100～1000mg is put into 200～2000mL toluene solution, multipolymer is fully dissolved, and will not dissolve multipolymer and filter out, make solution transparent, repeatedly several times, finally standby in duplicate;
(2) 0.1～1.0g inorganics metal-salt is dissolved in 1～10mL ethanol, dissolves under ultrasonoscope, join then in above-mentioned first part of stock solution, ultra-sonic dispersion is even;
(3) 0.05～0.5g alkaline matter is added in 0.5～5.0mL ethanol, after the dissolving, join in above-mentioned second part of stock solution fully;
(4) under agitation condition, second part of solution dropwise is added dropwise in first part of solution, continue reaction 10～60 minutes after the mixing again, organic solvent and water are removed in underpressure distillation under 55-65 ℃ of condition again, resulting solid is repeatedly washed purifying with ethanol, obtain oil loving inorganic nanoparticles after the last vacuum-drying;
(5) be dissolved in a certain amount of oil loving inorganic nanoparticles and organic polymer in the organic solvent together, inorganic nanoparticles accounts for the 1-20% of inorganics and organism gross weight, after ultra-sonic dispersion is even, obtain organic-inorganic nano composite transparent solution, left standstill 12～72 hours; At last this clear solution is applied to carrier surface, obtains transparent film after the film forming, its thickness is in 10 nanometers～100 micron.
3. preparation method according to claim 2 is characterized in that described polyacrylamide amphoteric ion copolymer, is to be formed by cationic monomer, acrylamide monomer and hydrolytic reagent terpolymer.
4. preparation method according to claim 2, it is characterized in that said metal-salt, be copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the acetate of silicon, copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the formate of silicon, copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the carbonate of silicon, copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the nitrate of silicon, copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the vitriol of silicon, copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the fluorochemical of silicon, copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the iodide of silicon, copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the muriate of silicon, copper, zinc, magnesium, aluminium, iron, titanium, tungsten, the bromide of silicon, perhaps at least two kinds mixture in these metal-salts.
5. preparation method according to claim 2 is characterized in that said alkaline matter is the oxyhydroxide of sodium, potassium, ammonia, the sulphide salt of sodium, potassium, amine, the supercarbonate of the carbonate of sodium, potassium, ammonium or sodium, potassium, ammonium.
6. preparation method according to claim 2 is characterized in that said organic solvent is benzene,toluene,xylene, tetrahydrofuran (THF), dioxane, trichloromethane, methylene dichloride, vinyl acetic monomer, N-BUTYL ACETATE, dimethyl formamide, N,N-DIMETHYLACETAMIDE or N-N-methyl-2-2-pyrrolidone N-.
7. preparation method according to claim 2 is characterized in that said organic polymer is selected from a kind of of polymethylmethacrylate, polycarbonate and polyvinyl butyral.
8. preparation method according to claim 2 is characterized in that said film forming is to remove solvent, obtains the transparent organic/inorganic nano laminated film of exsiccant, and its bake out temperature is 45-120 ℃, and drying time is 0.5-8 hour.
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| CN102610739A (en) * | 2012-03-08 | 2012-07-25 | 华东理工大学 | Organic or inorganic transparent composite thin film capable of generating electric energy and having ultraviolet absorption characteristic |
| CN106519277B (en) * | 2016-10-17 | 2019-06-04 | 南京航空航天大学 | A kind of preparation method of visible light high transmittance film |
| CN108864673B (en) * | 2017-05-11 | 2020-01-17 | 江南大学 | High-transparency ultraviolet-blocking polymer composition and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1412258A (en) * | 2001-10-12 | 2003-04-23 | 中国科学院金属研究所 | Nano UV resistant acrylate paint |
| CN1715349A (en) * | 2004-07-01 | 2006-01-04 | 北京化工大学 | Process for preparing water polyurethane/hydrotalcite composite paint with anti-ultraviolet property |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1412258A (en) * | 2001-10-12 | 2003-04-23 | 中国科学院金属研究所 | Nano UV resistant acrylate paint |
| CN1180039C (en) * | 2001-10-12 | 2004-12-15 | 中国科学院金属研究所 | Nano UV resistant acrylate paint |
| CN1715349A (en) * | 2004-07-01 | 2006-01-04 | 北京化工大学 | Process for preparing water polyurethane/hydrotalcite composite paint with anti-ultraviolet property |
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