CN101649152B - Environmentally-friendly organic inorganic hybridized paint and preparation method and application thereof - Google Patents
Environmentally-friendly organic inorganic hybridized paint and preparation method and application thereof Download PDFInfo
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- CN101649152B CN101649152B CN2009100422680A CN200910042268A CN101649152B CN 101649152 B CN101649152 B CN 101649152B CN 2009100422680 A CN2009100422680 A CN 2009100422680A CN 200910042268 A CN200910042268 A CN 200910042268A CN 101649152 B CN101649152 B CN 101649152B
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Abstract
The invention discloses an environmentally-friendly organic inorganic hybridized paint and preparation method and application thereof. The preparation method includes that acrylosilane microemulsion is taken as binder, 2-35 parts of acrylosilane microemulsion containing hydroxyl is dissolved into 10-80 parts of alcohols solvent, 1-15 parts of tetraethoxysilane, 2-30 parts of organosiloxane and 0.5-10 parts of basic catalyst are added, hydrolysis and polycondensation are carried out in organic polymer emulsion to form hydrophobic inorganic network, so as to obtain organic inorganic hybridized acrylosilane paint. The paint is coated on the surface of water poly(methyl) acrylic ester primer and is dried, thus obtaining the organic inorganic hybridized super-hydrophobic coating with favourable mechanic performances. The adhesive force of the super-hydrophobic coating can achieve 1-2 level, water static contact angle is more than 150 degrees, and rolling angle is less than 10 degrees. The invention is simple in technology, available in raw materials and low in cost and overcomes the defects of the existing preparation technology and the disadvantage of poor mechanical performances of the super-hydrophobic coating.
Description
Technical field
The present invention relates to organic inorganic hybridized paint, be specifically related to a kind of environmentally-friendly organic inorganic hybridized paint and preparation method thereof, this coating can be used to prepare the organic inorganic hybridization super-hydrophobic coat.
Background technology
Organic-inorganic hybrid material is a kind of finely dispersed heterogeneous material, the performance advantage that has both organic polymer or inorganic polymer, its organic phase and inorganic phase size are all in nanometer range, that have or even the molecular water sane level, the meticulous mixing of this height makes hybrid material show single organic polymer material or the not available high-performance of inorganic materials at optical transparence, adjustable specific refractory power, mechanical property, high temperature resistant, wear-resistant, snappiness, aspect such as functional.
The preparation method of organic-inorganic hybrid material comprises: sol-gel method, graft process, nanoparticle completion method, self-assembly method and electrolytic polymerization method etc.Adopt sol-gel method to prepare the most widely used of organic-inorganic hybrid material, study very actively, this is owing to its unique advantage: room temperature or the final organic-inorganic hybrid material with fine structure of obtaining a little more than the preparation temperature of the gentleness of room temperature allows to introduce organic molecule, oligopolymer or superpolymer; Disperse with molecular form in each component of sol phase, so the hybrid material that obtains nano composite material normally possesses the not available character of other traditional materials.
The collosol and gel route of synthesis of organic-inorganic hybrid material mainly contains four kinds: (1) inorganic sol and organic polymer blend, this method simply is embedded in organic molecule or polymkeric substance in the inorganic machine matter, the link of no chemical bond between two kinds of components, there is significantly interface between the two-phase, easily be separated, and in moulding process, take place easily to reunite and do not reach homodisperse on the nanoscale; (2) the inorganic monomer polymerization down that exists mutually also is the main preparation methods of existing organic inorganic hybridized paint, because density variation between monomer and polymkeric substance, this method can cause mechanical stress and optical defect in material; (3) organic phase forms synchronous interpenetrating(polymer)networks mutually with inorganic, and the material that this method obtains has better homogeneity, be not separated, and insoluble polymkeric substance also can participate in the organic-inorganic network.Difficulty is very big but the reaction conditions that makes organic polymer and inorganic precursor hydrolysis, polycondensation is complementary.(4) there is the inorganic phase of formation down in organic polymer.Adopt the organic-inorganic hybrid material of this method preparation, on the basis that has kept the organic high molecular polymer good filming, with the favorable mechanical performance.Zhi Bei hybrid material mainly only is applied to optical material and stupalith at present in this way.
Though the preparation and the theoretical investigation aspect on present super-hydrophobic type surface have all obtained very big progress, have utilized prepared in various methods to go out the super hydrophobic surface of excellent performance, also exist the promotion and application that many problems have limited super-hydrophobic technology.As utilize microwave plasma enhancing chemical Vapor deposition process to obtain Al
2O
3Or TiO
2Or SiO
2Film is handled with fluorine-containing silane reagent then and is obtained the anti-green material of automatically cleaning, and adopts laser ablation sol-gel TiO
2Film preparation is super-hydrophobic, and method such as film all needs to use complicated apparatus, limits its application in the big area engineering; Employing Prepared by Sol Gel Method silicon sol is coated in silicon face, carries out finishing with the perfluoro capryl Trichloromonosilane behind the hyperthermia drying, makes to have the double-deck super hydrophobic surface of micron/nano.This preparation method is simple, good reproducibility, and non-environmental-pollution, but this method needs high bake, and film adhesive and physical strength are difficult to reach requirement, and adopt expensive perfluor siloxanes, make production cost higher.With hydrophobic polymer as presoma, porous aluminium sheet with different apertures and density distribution is a template, method by squeeze polymer melt or solution, prepare the method for polymeric nanofiber bundle with super hydrophobic surface, because of cellular porous aluminium sheet is difficult for preparation, and can't working special-shaped surface or wide area surface.Adopt wet chemical method, prepare super-hydrophobic filming by selecting suitable solvent and temperature control block polymer porous surface structure, also existing needs system with an organic solvent, and coating is in the limitation of the poor adhesive force of substrate surface etc.
Summary of the invention
The object of the present invention is to provide a kind of environmentally friendly organic inorganic hybridized paint that when possessing ultra-hydrophobicity, has good mechanical property and preparation method thereof.
Another object of the present invention is to provide that a kind of technology is simple, the preparation method of lower-cost super-hydrophobic coat.This coating is a filmogen with the polymer emulsion, and generated in-situ inorganic particulate provides the nano and micro relief of filming in organic phase, and introduces hydrophobic group, can be used for preparing the super-hydrophobic coat of organic inorganic hybridization.
Purpose of the present invention is achieved through the following technical solutions:
A kind of method of environmentally friendly organic inorganic hybridized paint comprises the steps and processing condition:
(1) in parts by weight, get 2～35 parts of hydroxyl organosilicon crylic acid latexs, be dissolved in 10～80 parts of alcoholic solvents; Described alcoholic solvent is ethanol, methyl alcohol, Virahol or propyl carbinol;
(2) in parts by weight, in step (1) gained emulsion, add 1～15 part of tetraethoxy, 2～30 parts of organo-siloxanes and 0.5～10 part of basic catalyst, stirring at room 0.5～2.5h generates the silicon-dioxide primary particle; Described organo-siloxane is Si (OR)
4And/or R ' Si (OR)
3, wherein, OR is hydrolyzable alkoxyl group, R ' is an aminopropyl, vinyl, (methyl) acryloxy, methyl or epoxy group(ing); Described hydrolyzable alkoxyl group is a methoxyl group, oxyethyl group or isopropoxy;
(3) in the reaction system in second step, add 1～10 part basic catalyst again, continue to stir 3～6h, promptly obtain the organic inorganic hybridization super hydrophobic coating;
The basic catalyst of described step (2) and step (3) is one or more of sodium hydroxide, ammoniacal liquor, potassium hydroxide, yellow soda ash, 2-amino-2-methyl propyl alcohol.
Described hydroxyl organosilicon crylic acid latex is general organosilicon crylic acid latex, is formed through letex polymerization by (methyl) acrylate, hydroxyl (methyl) acrylate monomer and vinylic organosiloxane monomer.
For further realizing the object of the invention, hydroxyl organosilicon crylic acid latex of the present invention is preparation by the following method preferably:
A is by hydroxyl organosilicon crylic acid latex prescription quality, the methyl methacrylate that accounts for formulation deionised water total mass 5～20% deionized waters, accounts for nonionic emulsifier total mass 5～20% nonionic emulsifier, accounts for the anionic emulsifier of total anionic emulsifier total mass 5～20% and account for methyl methacrylate total mass 20～50% mixed carry out pre-emulsification, make pre-emulsified seed monomer;
To the account for deionized water of ionized water total mass 10～50% of b, account for the nonionic emulsifier of nonionic emulsifier total mass 15～60%, account for butyl acrylate, hydroxyethyl methylacrylate, methacrylic acid in anionic emulsifier, the remaining methyl methacrylate of prescription and the prescription of anionic emulsifier total mass 15～60% and vinylic organosiloxane monomer and mix and carry out pre-emulsification, make pre-emulsified shell monomers;
Potassium Persulphate during c will fill a prescription is dissolved in the deionized water of the ionized water total mass 5～30% that accounts for;
D adds the sodium bicarbonate in remaining deionized water, nonionic emulsifying agent and anionic emulsifier and the prescription in the four-hole boiling flask that agitator, reflux condensing tube, thermometer are housed, be warming up to 70～85 ℃ after stirring, drip described pre-emulsified seed monomer and the persulfate aqueous solution that accounts for step c total mass 5～20%, after being incubated 30 minutes～1 hour, be warming up to 85～95 ℃, drip described pre-emulsified shell monomers then, and drip remaining persulfate aqueous solution synchronously; Dropwise the back and continue 70～85 ℃ of isothermal reaction 4～5h, cool at last, the pH value of emulsion is transferred to 7～8, obtain stable nucleocapsid structure organosilicon crylic acid latex with ammoniacal liquor to below 40 ℃;
Described hydroxyl organosilicon crylic acid latex composition of raw materials component is:
Deionized water 50～80
Nonionic emulsifier OP-10 0.01～1.5
Anionic emulsifier DNS-86 0.01～1.5
Sodium bicarbonate 0.01～1.0
Methyl methacrylate 8～30
Butyl acrylate 3～15
Hydroxyethyl methylacrylate 0.01～3.5
Vinylic organosiloxane monomer 0.05～2.0
Methacrylic acid 0.01～1.5
Potassium Persulphate 0.02～2.0
Described organo-siloxane monomer is vinyltrimethoxy silane, vinyl silane triisopropoxide, methacryloxy Trimethoxy silane, the methacryloxy triethoxyl silane, two or more in methacryloxy three isopropoxy silane and the Union carbide A-162.
Described described organo-siloxane is preferably tetraethoxysilane, aminopropyl triethoxysilane, vinyltrimethoxy silane, Union carbide A-162, one or more in methacryloxy Trimethoxy silane and the epoxy group(ing) Trimethoxy silane.
A kind of environmentally friendly organic inorganic hybridized paint, it is by method for preparing.
The friendly type organic inorganic hybridized paint of applied environment prepares the method for super-hydrophobic coat: poly-(methyl) acrylate paint 20-40 μ m of primary coat water-based on base material, behind the room temperature of the filming surface drying, immerse in the described organic inorganic hybridized paint of claim 4, lift 1～3 time, behind the room temperature of the filming surface drying, 100～130 ℃ of drying 1～3h make the super-hydrophobic coat of organic inorganic hybridization again.
The present invention compared with prior art has following advantage and beneficial effect:
1. the present invention's method of adopting in organic polymer original position to generate inorganic phase prepares organic inorganic hybridized paint, both can improve wear resistance and the hardness that organism is filmed effectively, can also improve the surfaceness of filming, and then improve the film coated surface water contact angle, prepare super-hydrophobic type and film.
2. the present invention adopts Prepared by Sol Gel Method organic inorganic hybridization super hydrophobic coating at ambient temperature, be coated on priming paint surface and adopt the method for low-temperature bake to prepare the super-hydrophobic of organic-inorganic and film, making method is simple, has overcome many deficiencies of existing super hydrophobic surface technology of preparing.As etching method equipment complex and expensive, can't working special-shaped surface.The needed foraminous die plate of template is difficult for preparation etc.The present invention does not need complex apparatus and harsh working condition, and process simply is easy to control.
3. its water contact angle of filming of the organic inorganic hybridized paint preparation of application the present invention preparation is greater than 150 °, roll angle has good mechanical property less than 10 ° when possessing ultra-hydrophobicity, strong with the base material adhesive fastness, sticking power can reach 1～2 grade, hardness 2H.
4. the organic-inorganic super hydrophobic coating energy consumption of the inventive method preparation is low, fluorine material not, and production cost is lower.
Embodiment
For the present invention can better be described, below in conjunction with embodiment the present invention is carried out explaining in detail further and introducing, but the present invention's scope required for protection is not limited to the scope that embodiment represents.
The preparation of embodiment 1 hydroxyl organosilicon crylic acid latex:
To account for 5g water, 0.1gOP-10, the DNS-86 of 0.15g, the 10g methyl methacrylate carries out pre-emulsification, prepares pre-emulsified seed monomer.
With 20g water, 0.3gOP-10, the DNS-86 of 0.10g, the 15g methyl methacrylate, the 15g butyl acrylate, the 0.5g hydroxyethyl methylacrylate, 1g methacrylic acid and 3.5g vinylic organosiloxane monomer carry out pre-emulsification, prepare pre-emulsified shell monomers.And the 0.15g Potassium Persulphate is dissolved in the 15g deionized water.
In the four-hole boiling flask that agitator, reflux condensing tube, thermometer are housed, add 50g water, 0.4gOP-10,0.10gDNS-86, behind the 0.4g NaHCO3, evenly stir, be warming up to 80 ℃, drip good seed monomer of pre-emulsification and 1.5g initiator solution, be warming up to 85 ℃ after 30 minutes, begin to drip shell pre-emulsion monomer, and drip remaining initiator solution synchronously respectively.After dropwising with 4h, continue isothermal reaction 4h, cool, obtain stable hydroxyl organosilicon crylic acid latex to transferring to about 7 with the pH value of ammoniacal liquor below 40 ℃ with emulsion.
The preparation of embodiment 2 hydroxyl organosilicon crylic acid latexs:
To account for 15g water, 0.3gOP-10, the DNS-86 of 0.05g, the 10g methyl methacrylate carries out pre-emulsification, prepares pre-emulsified seed monomer.
With 40g water, 0.2gOP-10, the DNS-86 of 0.15g, the 10g methyl methacrylate, the 17g butyl acrylate, the 4.0g hydroxyethyl methylacrylate, 1g methacrylic acid and 3.0g vinylic organosiloxane monomer carry out pre-emulsification, prepare pre-emulsified shell monomers.And the 0.15g Potassium Persulphate is dissolved in the 15g deionized water.
In the four-hole boiling flask that agitator, reflux condensing tube, thermometer are housed, add 85g water, 0.3gOP-10,0.15gDNS-86, behind the 0.4g NaHCO3, evenly stir, be warming up to 80 ℃, drip good seed monomer of pre-emulsification and 1.5g initiator solution, be warming up to 90 ℃ after 30 minutes, begin to drip shell pre-emulsion monomer, and drip remaining initiator solution synchronously respectively.After dropwising with 3h, continue isothermal reaction 4h, cool, obtain stable hydroxyl organosilicon crylic acid latex to transferring to about 7 with the pH value of ammoniacal liquor below 40 ℃ with emulsion.
The preparation of embodiment 3 hydroxyl organosilicon crylic acid latexs:
To account for 5g water, 0.2gOP-10, the DNS-86 of 0.05g, the 7g methyl methacrylate carries out pre-emulsification, prepares pre-emulsified seed monomer.
With 20g water, 0.4gOP-10, the DNS-86 of 0.15g, the 12g methyl methacrylate, the 18g butyl acrylate, the 4.5g hydroxyethyl methylacrylate, 1.5g methacrylic acid and 2.5g vinylic organosiloxane monomer carry out pre-emulsification, prepare pre-emulsified shell monomers.And the 0.15g Potassium Persulphate is dissolved in the 10g deionized water.
In the four-hole boiling flask that agitator, reflux condensing tube, thermometer are housed, add 100g water, 0.3gOP-10,0.15gDNS-86, behind the 0.3g NaHCO3, evenly stir, be warming up to 80 ℃, drip good seed monomer of pre-emulsification and 1.0g initiator solution, be warming up to 90 ℃ after 30 minutes, begin to drip shell pre-emulsion monomer, and drip remaining initiator solution synchronously respectively.After dropwising with 3.5h, continue isothermal reaction 4h, cool, obtain stable hydroxyl organosilicon crylic acid latex to transferring to about 7 with the pH value of ammoniacal liquor below 40 ℃ with emulsion.
Embodiment 4
Get the hydroxyl organosilicon crylic acid latex of 10g embodiment 1 preparation, be dissolved in the 40.18g methyl alcohol, add 11.5g epoxy group(ing) Trimethoxy silane, 3.2g tetraethoxy and 2.26g ammoniacal liquor again, stirring at room 2h, and then adding 4.13g ammoniacal liquor, continue to stir 4h, obtain environmentally friendly organic inorganic hybridized paint.
Embodiment 5
Get the hydroxyl organosilicon crylic acid latex of 10g embodiment 2 preparations, be dissolved in the 60.18g ethanol, add 15.5g Union carbide A-162,4.2g tetraethoxy and 3.0g2-amino-2-methyl-1-propyl alcohol, stirring at room 1h, add 5.26g ammoniacal liquor again, continue to stir 6h, obtain environmentally friendly organic inorganic hybridized paint.
Embodiment 6
Get the hydroxyl organosilicon crylic acid latex of 15g embodiment 3 preparations, be dissolved in the 65.68g Virahol, add 10.5g methacryloxy Trimethoxy silane, 3.8g tetraethoxy and 0.2g sodium hydroxide, stirring at room 1h, add 6.26g ammoniacal liquor again, continue to stir 6h, obtain environmentally friendly organic inorganic hybridized paint.
Embodiment 7
The primary coat build is the poly-full clear lacquer (varnish of (methyl) acrylate glass of 30 μ m water-baseds on sheet glass, Zhongshan city Ai Pusi coating company limited produces), behind the room temperature of the filming surface drying, lift 1 time in the organic inorganic hybridized paint of immersion embodiment 4 preparations, behind the room temperature of the filming surface drying, 100 ℃ of dry 1h make the super-hydrophobic coat of organic inorganic hybridization.The super-hydrophobic type adhesive force of coatings of the organic inorganic hybridization of preparation can reach 1～2 grade, and hardness 2H, water static contact angle are 152 °, and roll angle is less than 10 °.
Embodiment 8
The primary coat build is the poly-full clear lacquer (varnish of (methyl) acrylate glass of 20 water-baseds on sheet glass, Zhongshan city Ai Pusi coating company limited produces), behind the room temperature of the filming surface drying, lift 3 times in the organic inorganic hybridized paint of immersion embodiment 5 preparations, behind the room temperature of the filming surface drying, 130 ℃ of dry 2h make the super-hydrophobic coat of organic inorganic hybridization.The super-hydrophobic type adhesive force of coatings of the organic inorganic hybridization of preparation can reach 1～2 grade, and hardness 2H, water static contact angle are 169 °, and roll angle is less than 10 °.
Embodiment 9
The primary coat build is the poly-full clear lacquer (varnish of (methyl) acrylate glass of 40 μ m water-baseds on sheet glass, Zhongshan city Ai Pusi coating company limited produces), behind the room temperature of the filming surface drying, lift 1 time in the organic inorganic hybridized paint of immersion embodiment 6 preparations, behind the room temperature of the filming surface drying, 110 ℃ of dry 2h make the super-hydrophobic coat of organic inorganic hybridization.The super-hydrophobic type adhesive force of coatings of the organic inorganic hybridization of preparation can reach 1～2 grade, and hardness 2H, water static contact angle are 161 °, and roll angle is less than 10 °.
Claims (4)
1. the preparation method of an environmentally-friendly organic inorganic hybridized paint is characterized in that comprising the steps and processing condition:
(1) in parts by weight, get 2～35 parts of hydroxyl organosilicon crylic acid latexs, be dissolved in 10～80 parts of alcoholic solvents; Described alcoholic solvent is ethanol, methyl alcohol, Virahol or propyl carbinol;
(2) in parts by weight, in step (1) gained emulsion, add 1～15 part of tetraethoxy, 2～30 parts of organo-siloxanes and 0.5～10 part of basic catalyst, stirring at room 0.5～2.5h generates the silicon-dioxide primary particle; Described organo-siloxane is Si (OR)
4And/or R ' Si (OR)
3, wherein, OR is hydrolyzable alkoxyl group, R ' is an aminopropyl, vinyl, (methyl) acryloxy, methyl or epoxy group(ing); Described hydrolyzable alkoxyl group is a methoxyl group, oxyethyl group or isopropoxy;
(3) in the reaction system in second step, add 1～10 part basic catalyst again, continue to stir 3～6h, promptly obtain the organic inorganic hybridization super hydrophobic coating;
The basic catalyst of described step (2) and step (3) is one or more in sodium hydroxide, ammoniacal liquor, potassium hydroxide, yellow soda ash, the 2-amino-2-methyl-1-propanol.
Described hydroxyl organosilicon crylic acid latex prepares by the following method:
A is by hydroxyl organosilicon crylic acid latex prescription quality, the methyl methacrylate that accounts for formulation deionised water total mass 5～20% deionized waters, accounts for nonionic emulsifier total mass 5～20% nonionic emulsifier, accounts for the anionic emulsifier of total anionic emulsifier total mass 5～20% and account for methyl methacrylate total mass 20～50% mixed carry out pre-emulsification, make pre-emulsified seed monomer;
To the account for deionized water of ionized water total mass 10～50% of b, account for the nonionic emulsifier of nonionic emulsifier total mass 15～60%, account for butyl acrylate, hydroxyethyl methylacrylate, methacrylic acid in anionic emulsifier, the remaining methyl methacrylate of prescription and the prescription of anionic emulsifier total mass 15～60% and vinylic organosiloxane monomer and mix and carry out pre-emulsification, make pre-emulsified shell monomers;
Potassium Persulphate during c will fill a prescription is dissolved in the deionized water of the ionized water total mass 5～30% that accounts for;
D adds the sodium bicarbonate in remaining deionized water, nonionic emulsifying agent and anionic emulsifier and the prescription in the four-hole boiling flask that agitator, reflux condensing tube, thermometer are housed, be warming up to 70～85 ℃ after stirring, drip described pre-emulsified seed monomer and the persulfate aqueous solution that accounts for step c total mass 5～20%, after being incubated 30 minutes～1 hour, be warming up to 85～95 ℃, drip described pre-emulsified shell monomers then, and drip remaining persulfate aqueous solution synchronously; Dropwise the back and continue 70～85 ℃ of isothermal reaction 4～5h, cool at last, the pH value of emulsion is transferred to 7～8, obtain stable nucleocapsid structure organosilicon crylic acid latex with ammoniacal liquor to below 40 ℃;
Described hydroxyl organosilicon crylic acid latex composition of raw materials component is:
Deionized water 50～80
Nonionic emulsifier OP-10 0.01～1.5
Anionic emulsifier DNS-86 0.01～1.5
Sodium bicarbonate 0.01～1.0
Methyl methacrylate 8～30
Butyl acrylate 3～15
Hydroxyethyl methylacrylate 0.01～3.5
Vinylic organosiloxane monomer 0.05～2.0
Methacrylic acid 0.01～1.5
Potassium Persulphate 0.02～2.0
Described organo-siloxane monomer is vinyltrimethoxy silane, vinyl silane triisopropoxide, methacryloxy Trimethoxy silane, the methacryloxy triethoxyl silane, two or more in methacryloxy three isopropoxy silane and the Union carbide A-162.
2. the preparation method of environmentally-friendly organic inorganic hybridized paint according to claim 1, it is characterized in that described described organo-siloxane is tetraethoxysilane, aminopropyl triethoxysilane, vinyltrimethoxy silane, Union carbide A-162, one or more in methacryloxy Trimethoxy silane and the epoxy group(ing) Trimethoxy silane.
3. environmentally friendly organic inorganic hybridized paint, it is by each described method preparation of claim 1-2.
4. the environmentally friendly organic inorganic hybridized paint of application rights requirement 3 prepares the method for super-hydrophobic coat, it is characterized in that: poly-(methyl) acrylate paint 20-40 μ m of primary coat water-based on base material, behind the room temperature of the filming surface drying, immerse in the described organic inorganic hybridized paint of claim 4, lift 1～3 time, behind the room temperature of the filming surface drying, 100～130 ℃ of drying 1～3h make the super-hydrophobic coat of organic inorganic hybridization again.
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