CN103145912A - Preparation method of titanium dioxide nano powder-modified fluorine-containing acrylate emulsion - Google Patents
Preparation method of titanium dioxide nano powder-modified fluorine-containing acrylate emulsion Download PDFInfo
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- CN103145912A CN103145912A CN2013100767292A CN201310076729A CN103145912A CN 103145912 A CN103145912 A CN 103145912A CN 2013100767292 A CN2013100767292 A CN 2013100767292A CN 201310076729 A CN201310076729 A CN 201310076729A CN 103145912 A CN103145912 A CN 103145912A
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Abstract
The invention discloses a TiO2 nano powder-modified fluorine-containing acrylate aqueous emulsion, and a preparation method and application thereof in preparing a composite paint. The nano powder-modified copolymer aqueous emulsion can be prepared by the following steps: (1) carrying out surface modification on self-made nano powder with a surface modifier; (2) mixing the modified nano powder with monomer, stirring and carrying out ultrasonic dispersion; and (3) adding emulsion polymerization raw materials, including water, fluorine-containing acrylate monomer, anionic/nonionic compound emulsifier and oxidation-reduction initiator in a reaction vessel provided with stirring, N2 protection, reflux condensing and feeding devices, and carrying out pre-emulsification and synthetic reaction by semicontinuous emulsion polymerization under water bath heating conditions. The inorganic nano powder-modified fluorine-containing acrylate aqueous emulsion provided by the invention has traditional dilution, storage, pH, high temperature and freeze-thawing stability, and also has anti-fouling and self-cleaning properties. In addition, the preparation technique is simple, and has the advantages of low price and no environment pollution.
Description
Technical field
The invention belongs to the field of chemical functional paint technology, particularly a kind of preparation method and application from the layering fluorinated acrylate emulsion of inorganic nano particle modified low fluorine content.
Background technology
The pure acrylate emulsion and film have better weathering resistance, the transparency, seasoning performance, glossiness good (inhibited from yellowing); Especially has excellent sticking power, especially occupy critical role aspect decorative paint in coatings industry, but itself intrinsic shortcoming: and poor water resistance, water vapour permeability is poor, hardness of film is low, " cold short hot sticky ", snappiness are poor etc. has greatly limited again its range of application.Fluorine resin mainly refers to the high molecular polymer after the hydrogen that is connected with the direct covalency of carbon atom in organic polymer main chain or side chain is by all or part of replacement of fluorine, has a series of excellent properties, the C-F key has bond energy maximum in covalent linkage, up to 485kJ/mol, therefore have extremely low surface free energy and thermotolerance, can life-time service and good low temperature flexibility is arranged at 250 ° of C; The strongest electronegativity (4.0), a large amount of C-F groups exist and make fluoropolymer present excellent thermotolerance, chemical resistance, weather resistance, weathering resistance, low combustible, high light transmittance, low frictional properties, low-refraction, low electric capacity, low surface energy (two thin property), agent of low hygroscopicity energy and superpower oxidation resistent susceptibility.Fluorinated acrylate polymer contains the perfluoroalkyl of 3 above carbon atoms usually, and these perfluoro alkyl groups can be connected on not fluorine-containing skeleton on polymer chain by various linking groups.Adopt the emulsion synthesis method make its with the pure acrylate copolymerization after, introducing-OH ,-COOH ,-O-,-groups such as COOR, make copolymer resins have good pigment reactivity, improved base material sticking power.And by both special propertys separately, make up deficiency separately, have at last both advantages concurrently.In addition, because nanoparticle in recent years has excellent physical and chemical performance, make its research in paint field obtain fast development.After inorganic nano-particle is mixed by certain means with organic monomer, due to special effectses such as the small-size effect of nanoparticle, surface effectss, can significantly improve traditional performance of emulsion, and give the new functional performance that has of filming.Nano-TiO
2Particle has photocatalysis performance, if itself and emulsion are organically combined, the low surface energy component that recycling fluorinated acrylate polymer system causes because of surface tension makes it in film process, with nano-TiO to the character of surperficial Autonomic Migration Framework
2Particle brings to the surface, and will make films has photocatalysis performance, and then obtains better antibiotic, anti-fouling and self-cleaning function.But inorganic nano-particle is because particle diameter is little, causes specific surface area and the surface can be very large, and the serious coordination of surface atom is not enough, is easy to reunite in organic emulsion, and lower dispersiveness can make even that the Performance Ratio of filming is original to descend or poorer.Therefore with inorganic nano TiO
2Particle need to be to its surface modification with before organic monomer mixes.
Innovative point of the present invention is the organic monomer that adopts different systems, the inorganic nano TiO with photocatalytic of bonding properties excellence
2Particle utilizes two kinds of capillary differences of organic system, with TiO
2Particle brings to film coated surface in film process.To guarantee at utmost to bring into play its photocatalysis performance.
Summary of the invention
The objective of the invention is the easy problem of reuniting to get for above-mentioned pure acrylate emulsion, fluorine carbon emulsion, inorganic nano-particle.A kind of preparation method of the functional emulsion of fluorinated acrylate copolymerization of the novel modification that contains inorganic nano-particle is provided, and this method makes that in product system, three's performance obtains perfect combination.
Another object of the present invention is to provide the practical application of above-mentioned water miscible liquid, and make composite coating and method thereof.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of nano TiO 2 powder modified fluoride-containing acrylic ester emulsion is characterized in that the step for preparing is:
(1), with inorganic TiO
2Nano-powder utilizes surface-modifying agent to carry out modification;
(2), with the nano-TiO after modification
2Powder and polymerization single polymerization monomer mix, magnetic agitation 1～2h at first, then carry out ultra-sonic dispersion 1～2h;
(3), with letex polymerization raw water, monomer and TiO
2Nano-powder mixture, the moon/nonionic composite emulsifier, oxidation-reducting system initiator are placed in stirring, N
2In the reaction vessel of protection, reflux condensation mode and feeding device, adopt semi-continuous emulsion polymerization to synthesize under condition of water bath heating.
Further, in the described step of described method (1), the inorganic nanometer powder that is used for surface modification is the titanium dioxide nano-particle that adopts the homemade magnesium-yttrium-transition metal v element of sol-gel method and nonmetal nitrogen element codoped: V/N-TiO
2, its size scope is 5～50nm, consumption is 0.20%～1.20% of monomer total amount; The surface-modifying agent that is used for the inorganic nanometer-powder surface modification is silane coupling agent (KH-570) or oleic acid or its mixture, and optimum amount is 4%～6% (volume ratio) of alcohol dispersion liquid; Concrete grammar is as follows:
In the 500mL there-necked flask, add the 1g nano-TiO
2Powder, be dispersed in 200mL ethanol, first carry out ultra-sonic dispersion 30min, then add silane coupling agent (KH-570) or oleic acid or its mixture, continue ultra-sonic dispersion 40～60min, then be heated to 65～85 ° of C with water-bath, condensing reflux 2～4h gets homodisperse liquid, with the liquid that obtains with toluene wash extraction, suction filtration, this process is 4～7 times repeatedly, and under normal temperature, vacuum-drying obtains the nano modification powder after grinding.
Further, the semi-continuous emulsion polymerizing of the described step of described method (3) carries out the method for synthesizing stable emulsion, and the step of preparation is:
1), agitator, reflux exchanger, N are being housed
2In protection and the 500mL four-hole bottle of feeding device, add the deionized water total amount 4/5, the composite emulsifier for preparing in proportion, violent stirring 15～20min obtains emulsifier aqueous solution;
2), above-mentioned all kinds of monomers are sequentially added in four-hole bottle in the ratio after calculating, at ambient temperature, add the nano-powder of modification, at first high speed dispersion 30～60min, then ultra-sonic dispersion 60～120min, preparation mixed solution;
3), mix completely, it is joined emulsifier aqueous solution; Simultaneously, with remaining deionized water, the dissolving of the initiator of load weighted redox system is prepared into solution;
4), pre-emulsion is divided into two portions, the pre-emulsion with 10%～20% joins in the polymerization four-hole bottle, and as seed emulsion, warming-in-water to 70～75 ° C after temperature-stable 10～15min, under agitation condition, adds 1/3 initiator solution; After blue light appears in reaction solution, will remain emulsion and synchronize with initiator solution and drip and stir; Be controlled at and drip in 2～3h fully;
5), reinforced complete, the rising system temperature, more than C, slaking 30min is carried out in insulation 5～10 ° of temperature of reaction; Be cooled to 55～60 ° of C and carry out rear elimination, be incubated approximately 30min at 58～63 ° of C, be down to room temperature after end, filter with 200 order copper mesh; Regulate pH value to 8～9 with ammoniacal liquor; Obtain stable " from layering/automatically cleaning " functional inorganic TiO
2Nano powder modified fluorinated acrylate emulsion.
Further, described method utilizes semi-continuous emulsion polymerizing to carry out the method for synthesizing stable emulsion, and described monomer comprises:
A), based on fluoroalkyl acrylate monomer or its mixture of array structure under the having of total monomer weight 10%～30%:
CH
2=C(R)C(O)OCH
2CH
2—C
nF
2n+1
Wherein R is: H or CH
3, n is 2～10 natural number; As perfluoro butyl ethyl propylene acid esters, perfluoro hexyl ethyl propylene acid esters, perfluoro hexyl ethyl-methyl acrylate etc.;
B), based on the soft or hard monomer of total monomer weight 65%～85%, namely have C
2～C
15Alkyl acrylate and alkyl methacrylate, wherein:
Soft monomer: have C
2～C
15Alkyl acrylate 40%～55%
Hard monomer: have C
2～C
15Alkyl methacrylate 25%～30%
Wherein said C
2～C
15Alkyl acrylate comprises one or more in ethyl propenoate, propyl acrylate, n-butyl acrylate, Isooctyl acrylate monomer, 2-ethylhexyl acrylate, vinylformic acid ester in the positive last of the ten Heavenly stems, dodecyl acrylate, tetradecyl acrylate;
Wherein said C
2～C
15Alkyl methacrylate comprises one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, Isooctyl methacrylate, methacrylic acid ester in the positive last of the ten Heavenly stems, methacrylic dodecyl gallate, tetradecyl methylacrylate;
C), based on N hydroxymethyl acrylamide, Methacrylamide, the vinyl cyanide of total monomer weight 0.5%～2%;
D), based on the hydroxyethyl methylacrylate of total monomer weight 0.5%～4%.
Further, described method utilizes semi-continuous emulsion polymerizing to carry out the method for synthesizing stable emulsion, described the moon/non-composite emulsifier:
E), based on the anion surfactant of total monomer weight 0.5%～2%, can be that an alkali metal salt, succsinic acid polyoxyethylene nonylphenol ether monoesters sulfonate or higher fatty acid salt, the fluorine carbon emulsifying agent of the alkylsulphonic acid of long-chain is perfluoro octyl sulfonic acid potassium (FC-95) or ammonium perfluorocaprylate;
F), based on the nonionogenic tenside of total monomer weight 1.0%～2.5%, can be polyoxyethylene high-grade aliphatic ester or Voranol EP 2001, as Polyethylene Octylphenol Ether or polyoxyethylene nonylphenol ether.
Further, described method utilizes semi-continuous emulsion polymerizing to carry out the method for synthesizing stable emulsion, and in described oxidation-reducting system initiator: described initiator can be any one in Potassium Persulphate-sodium bisulfite, Sodium Persulfate-Potassium hydrogen sulfite, Potassium Persulphate-Potassium Thiosulphate, ammonium persulfate-sodium bisulfite, ammonium persulphate-Potassium Thiosulphate; Be 0.2%～1.0% of total monomer weight.
Purposes according to the nano TiO 2 powder modified fluoride-containing acrylic ester emulsion of described method preparation is characterized in that: be used for preparing composite coating.
Further, described method composite coating is characterized in that: the Fluorine-Containing Copolymer Emulsion that is added with 5～40 weight parts in the coating composition of 100 weight parts.
Further, composite coating, it is characterized in that: except containing the above-mentioned functions copolymer emulsion, all the other also comprise conventional various components, comprise thickening material, flow agent, pigment, filler, defoamer, wetting agent, tensio-active agent, sanitas, antioxidant etc.
Further, the preparation method of described composite coating is characterized in that, step is as follows: first defoamer, neutralizing agent, dispersion agent and wetting agent etc. are mixed; Then add face, filler, after being ground to desired particle size, add the compositions such as membrane-forming agent and thickening material, after all mixing, add nano TiO 2 powder modified fluoride-containing acrylic ester emulsion, namely get composite coating.
Principle of the present invention is: when two kinds of two kinds of larger emulsions of surface tension performance difference are mixed or synthesized, in film process, wherein hydrophobic a kind of component can be to surface transport, and the less hydrophobic polymer of particle diameter covers the larger particle surface of particle diameter fully, falls low surface energy.
Its beneficial effect of the present invention shows as:
1), utilize inventive principle that the functional nano particle is brought to the surface, farthest bring into play its photic self-cleaning property and anti-microbial effect;
Crystallization occurs when 2), fluoropolymer migrates to the surface, the tap density of polymer segment increases greatly, the continuity of filming improves " the cold short thermal viscosity " of amorphous polymer (as differ from), and then makes to film and obtain excellent surface property and range of application widely.
3), adopt the semicontinuous dropping method of monomer, can make the quantity of monomer droplet in system relatively reduce, and then reduce the generation of flocculation polymers; This method is with respect to the emulsion of the gained that once feeds intake, and latex particle size is of moderate size, and every stability of emulsion improves greatly.
4), under the prerequisite that does not affect the organic fluorine surface property, greatly reduce the emulsion cost.
Characteristics of the present invention and beneficial effect are: adopt the liquid phase modification, but the nano-powder stable existence that obtains under ultrasonication, can be eliminated reunion in water-oil interface, reaches the nano level dispersion state; The present invention combines acrylate to base material and face, the excellent cohesiveness of filler and the surface property of fluorine-containing latex excellence, and the composite emulsion of gained has excellent water-fast, oil-proofness, resistant physical property and resistance to deterioration; And have tensile strength, hardness, rub resistance, wear-and corrosion-resistant and ultraviolet-resistent property preferably; Carry out the compound nano-TiO of organic/inorganic by above-mentioned two kinds of excellent product
2Another characteristics of/fluorinated acrylate blending emulsion are to coordinate other additive preparation coating.Obtain the low-cost self-cleaning coating of over-all properties.
Description of drawings
Contact angle schematic diagram in the different embodiment of Fig. 1.
Fig. 2,3 is respectively emulsion institute's film formation surface and the fluorine element content at back end place and the detected result of titanium elements content in embodiment 1, result shows, fluorine element in emulsion is as the technological invention content is described, highly enriched to the surface, and then making it have the performance that has excellence as pure fluoride varnish, this result also shows simultaneously, after layering, contact substrate be acrylic resin, have good sticking power; Simultaneously, the distribution of titanium elements shows, nano-powder is taken to the surface from stratification effect by emulsion, and then can bring into play better photic self_cleaning effect.
Embodiment
Embodiment 1:
Agitator, reflux exchanger, N are being housed
2In the 500mL four-hole bottle of protection and feeding device, composite emulsifier (the 1gMS-1 that add the 240g of deionized water total amount, will prepare in proportion again, succsinic acid polyoxyethylene nonylphenol ether monoesters sodium sulfonate, 0.5FC-95, perfluoro octyl sulfonic acid potassium, 0.5gOP-10, polyoxyethylene nonylphenol ether, 0.5gNP-40, Polyethylene Octylphenol Ether) add wherein, violent stirring 15～20min obtains emulsifier aqueous solution; With above-mentioned all kinds of monomers in ratio (the 18g methyl methacrylate after calculating, 2.25g vinylformic acid, 2.25g vinyl cyanide, 26.25g n-butyl acrylate, 26.25g ethyl acrylate, the 2gN-n-methylolacrylamide, 3g hydroxyethyl methylacrylate and 20g dodecafluoroheptyl methacrylate) add in four-hole bottle, add at ambient temperature the nano-powder of modification, first high speed dispersion 30～60min, ultra-sonic dispersion 60～120min, prepare mixed solution again; Mix completely, it is joined emulsifier aqueous solution.Simultaneously, use the 60g deionized water that initiator (0.2g ammonium persulphate, the 0.3g sodium bisulfite) dissolving of load weighted redox system is prepared into solution; Pre-emulsion is divided into two portions, and the pre-emulsion with 10%～20% joins in the polymerization four-hole bottle, and as seed emulsion, warming-in-water to 70～75 ° C after temperature-stable 10～15min, under agitation condition, adds 1/3 initiator solution.After blue light appears in reaction solution, will remain emulsion and synchronize with initiator solution and drip and stir.Be controlled at and drip in 2～3h fully; Reinforced complete, rising system temperature (5～10 ° of temperature of reaction more than C), slaking 30min is carried out in insulation; Be cooled to 55～60 ° of C and carry out rear elimination, be incubated approximately 30min at 58～63 ° of C, be down to room temperature after end, filter with 200 order copper mesh; Regulate pH value to 8～9 with ammoniacal liquor.Obtain stable " from layering/automatically cleaning " functional inorganic TiO
2Nano powder modified fluorinated acrylate emulsion.
Then measure the properties of emulsion and film forming thereof.
Comparative Examples 1
All the other steps are identical with parameter, only do not contain fluorine resin.
Comparative Examples 2
All the other steps are identical with parameter.Do not contain nano-powder and fluorine resin.
Surface property in table 1 embodiment and Comparative Examples after emulsion film forming and resistance to soiling are relatively
Claims (10)
1. the preparation method of a nano TiO 2 powder modified fluoride-containing acrylic ester emulsion is characterized in that the step for preparing is:
(1), with inorganic TiO
2Nano-powder utilizes surface-modifying agent to carry out modification;
(2), with the nano-TiO after modification
2Powder and polymerization single polymerization monomer mix, magnetic agitation 1～2h at first, then carry out ultra-sonic dispersion 1～2h;
(3), with letex polymerization raw water, monomer and TiO
2Nano-powder mixture, the moon/nonionic composite emulsifier, oxidation-reducting system initiator are placed in stirring, N
2In the reaction vessel of protection, reflux condensation mode and feeding device, adopt semi-continuous emulsion polymerization to synthesize under condition of water bath heating.
2. method according to claim 1 is characterized in that:
In described step (1), the inorganic nanometer powder that is used for surface modification is the titanium dioxide nano-particle that adopts the homemade magnesium-yttrium-transition metal v element of sol-gel method and nonmetal nitrogen element codoped: V/N-TiO
2, its size scope is 5～50nm, consumption is 0.20%～1.20% of monomer total amount; The surface-modifying agent that is used for the inorganic nanometer-powder surface modification is silane coupling agent (KH-570) or oleic acid or its mixture, and optimum amount is 4%～6% (volume ratio) of alcohol dispersion liquid; Concrete grammar is as follows:
In the 500mL there-necked flask, add the 1g nano-TiO
2Powder, be dispersed in 200mL ethanol, first carry out ultra-sonic dispersion 30min, then add silane coupling agent (KH-570) or oleic acid or its mixture, continue ultra-sonic dispersion 40～60min, then be heated to 65～85 ° of C with water-bath, condensing reflux 2～4h gets homodisperse liquid, with the liquid that obtains with toluene wash extraction, suction filtration, this process is 4～7 times repeatedly, and under normal temperature, vacuum-drying obtains the nano modification powder after grinding.
3. method according to claim 1, it is characterized in that: the semi-continuous emulsion polymerizing of described step (3) carries out the method for synthesizing stable emulsion, and the step of preparation is:
1), agitator, reflux exchanger, N are being housed
2In protection and the 500mL four-hole bottle of feeding device, add the deionized water total amount 4/5, the composite emulsifier for preparing in proportion, violent stirring 15～20min obtains emulsifier aqueous solution;
2), above-mentioned all kinds of monomers are sequentially added in four-hole bottle in the ratio after calculating, at ambient temperature, add the nano-powder of modification, at first high speed dispersion 30～60min, then ultra-sonic dispersion 60～120min, preparation mixed solution;
3), mix completely, it is joined emulsifier aqueous solution; Simultaneously, with remaining deionized water, the dissolving of the initiator of load weighted redox system is prepared into solution;
4), pre-emulsion is divided into two portions, the pre-emulsion with 10%～20% joins in the polymerization four-hole bottle, and as seed emulsion, warming-in-water to 70～75 ° C after temperature-stable 10～15min, under agitation condition, adds 1/3 initiator solution; After blue light appears in reaction solution, will remain emulsion and synchronize with initiator solution and drip and stir; Be controlled at and drip in 2～3h fully;
5), reinforced complete, the rising system temperature, more than C, slaking 30min is carried out in insulation 5～10 ° of temperature of reaction; Be cooled to 55～60 ° of C and carry out rear elimination, be incubated approximately 30min at 58～63 ° of C, be down to room temperature after end, filter with 200 order copper mesh; Regulate pH value to 8～9 with ammoniacal liquor; Obtain stable " from layering/automatically cleaning " functional inorganic TiO
2Nano powder modified fluorinated acrylate emulsion.
4. method according to claim 3, it is characterized in that: utilize semi-continuous emulsion polymerizing to carry out the method for synthesizing stable emulsion, described monomer comprises:
A), based on fluoroalkyl acrylate monomer or its mixture of array structure under the having of total monomer weight 10%～30%:
CH
2=C(R)C(O)OCH
2CH
2—C
nF
2n+1
Wherein R is: H or CH
3, n is 2～10 natural number; As perfluoro butyl ethyl propylene acid esters, perfluoro hexyl ethyl propylene acid esters, perfluoro hexyl ethyl-methyl acrylate etc.;
B), based on the soft or hard monomer of total monomer weight 65%～85%, namely have C
2～C
15Alkyl acrylate and alkyl methacrylate, wherein:
Soft monomer: have C
2～C
15Alkyl acrylate 40%～55%
Hard monomer: have C
2～C
15Alkyl methacrylate 25%～30%
Wherein said C
2～C
15Alkyl acrylate comprises one or more in ethyl propenoate, propyl acrylate, n-butyl acrylate, Isooctyl acrylate monomer, 2-ethylhexyl acrylate, vinylformic acid ester in the positive last of the ten Heavenly stems, dodecyl acrylate, tetradecyl acrylate;
Wherein said C
2～C
15Alkyl methacrylate comprises one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, Isooctyl methacrylate, methacrylic acid ester in the positive last of the ten Heavenly stems, methacrylic dodecyl gallate, tetradecyl methylacrylate;
C), based on N hydroxymethyl acrylamide, Methacrylamide, the vinyl cyanide of total monomer weight 0.5%～2%;
D), based on the hydroxyethyl methylacrylate of total monomer weight 0.5%～4%.
5. according to claim 3 method is characterized in that: utilize semi-continuous emulsion polymerizing to carry out the method for synthesizing stable emulsion, described the moon/non-composite emulsifier:
E), based on the anion surfactant of total monomer weight 0.5%～2%, can be that an alkali metal salt, succsinic acid polyoxyethylene nonylphenol ether monoesters sulfonate or higher fatty acid salt, the fluorine carbon emulsifying agent of the alkylsulphonic acid of long-chain is perfluoro octyl sulfonic acid potassium (FC-95) or ammonium perfluorocaprylate;
F), based on the nonionogenic tenside of total monomer weight 1.0%～2.5%, can be polyoxyethylene high-grade aliphatic ester or Voranol EP 2001, as Polyethylene Octylphenol Ether or polyoxyethylene nonylphenol ether.
6. according to claim 3 method, it is characterized in that: utilize semi-continuous emulsion polymerizing to carry out the method for synthesizing stable emulsion, in described oxidation-reducting system initiator: described initiator can be any one in Potassium Persulphate-sodium bisulfite, Sodium Persulfate-Potassium hydrogen sulfite, Potassium Persulphate-Potassium Thiosulphate, ammonium persulfate-sodium bisulfite, ammonium persulphate-Potassium Thiosulphate; Be 0.2%～1.0% of total monomer weight.
7. the purposes of the nano TiO 2 powder modified fluoride-containing acrylic ester emulsion of method preparation according to claim 1, is characterized in that: be used for preparing composite coating.
8. a composite coating that contains the nano TiO 2 powder modified fluoride-containing acrylic ester emulsion of method preparation according to claim 1, is characterized in that: the Fluorine-Containing Copolymer Emulsion that is added with 5～40 weight parts in the coating composition of 100 weight parts.
9. composite coating according to claim 8, it is characterized in that: except containing the above-mentioned functions copolymer emulsion, all the other also comprise conventional various components, comprise thickening material, flow agent, pigment, filler, defoamer, wetting agent, tensio-active agent, sanitas, antioxidant etc.
10. according to the preparation method of right 9 described composite coatings, it is characterized in that, step is as follows: first defoamer, neutralizing agent, dispersion agent and wetting agent etc. are mixed; Then add face, filler, after being ground to desired particle size, add the compositions such as membrane-forming agent and thickening material, after all mixing, add nano TiO 2 powder modified fluoride-containing acrylic ester emulsion, namely get composite coating.
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| CN103387645A (en) * | 2013-07-12 | 2013-11-13 | 南京理工大学 | Fluorine-containing copolymer grafted modified nano TiO2 compound particle and preparation method thereof |
| CN104277619A (en) * | 2014-09-04 | 2015-01-14 | 上海露蕾化工（六安）有限公司 | Hydrophobic self-cleaning paint |
| CN104845482B (en) * | 2015-04-29 | 2017-03-08 | 广德嘉宝莉化工有限公司 | A kind of high adhesion force shock resistance corrosion-resistant machinery coating |
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| CN106366826A (en) * | 2016-08-31 | 2017-02-01 | 浙江润阳新材料科技股份有限公司 | Nano-TiO2 self-cleaning coating and preparation method thereof |
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| CN112341891A (en) * | 2020-11-26 | 2021-02-09 | 简珍霞 | Water-based antifouling paint and preparation method thereof |
| CN112239618A (en) * | 2020-12-08 | 2021-01-19 | 虎丘影像（苏州）有限公司 | Preparation method and application of coating liquid |
| CN112745705A (en) * | 2020-12-14 | 2021-05-04 | 安徽庆润新材料技术有限公司 | Fluoropolymer nanoparticle modified photocuring fluorocarbon coating and preparation method thereof |
| CN112745705B (en) * | 2020-12-14 | 2022-04-19 | 安徽庆润新材料技术有限公司 | Fluoropolymer nanoparticle modified photocuring fluorocarbon coating and preparation method thereof |
| CN112552806A (en) * | 2021-01-13 | 2021-03-26 | 时嘉 | Preparation method of high-durability nano composite antibacterial paint |
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