CN104403476A - Self-cleaning antibacterial fluorocarbon coating - Google Patents
Self-cleaning antibacterial fluorocarbon coating Download PDFInfo
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- CN104403476A CN104403476A CN201410713038.3A CN201410713038A CN104403476A CN 104403476 A CN104403476 A CN 104403476A CN 201410713038 A CN201410713038 A CN 201410713038A CN 104403476 A CN104403476 A CN 104403476A
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Abstract
The invention discloses a self-cleaning antibacterial fluorocarbon coating which comprises the following components in parts by weight: 40-60 parts of fluorine-containing polyacrylate resin, 5-13 parts of a silane coupling agent, 1-6 parts of amino resin, 3-15 parts of titanium dioxide, 2-6 parts of calcium carbonate, 10-28 parts of modified nano titanium dioxide, 2-6 parts of silicon nitride, 2-8 parts of zinc molybdate, 5-10 parts of 2,2,4-trimethyl-1,3-pentanediol isobutyrate, 0.3-1.2 parts of 5-chloro-2-methl-4-isothiazolin-3-ketone, 0.2-1.2 parts of defoaming agent, 0.5-1.8 parts of wetting agent, 0.3-0.8 parts of flatting agent, 0.6-1.5 parts of a curing agent and 30-60 parts of a solvent. The self-cleaning antibacterial fluorocarbon coating disclosed by the invention is high in self-cleaning ability and good in antibacterial property and can be applied in building outer walls.
Description
Technical field
The present invention relates to technical field of coatings, particularly relate to a kind of self-cleaning antibacterial fluorocarbon coating.
Background technology
Fluorocarbon coating mainly refers to pure fluoro-resin or the coating with specific function that is main film forming substance through modified fluoro-resin, show remarkable two thin property, weathering resistance, weather resistance, resistance to acids and bases, preservative property, insulativity and non-adhesive etc., this point is that other common coating cannot be reached, and therefore investigator is referred to as a kind of outstanding new special coating.Although common fluorocarbon resin has excellent guarantor's light tint retention, fluorocarbon coating itself does not have self-cleaning function, and its resistance to soiling and germ resistance can not meet high antibacterial requirement self-cleaning by force.
Summary of the invention
The present invention proposes a kind of self-cleaning antibacterial fluorocarbon coating, its automatically cleaning ability is strong, and germ resistance is good.
The present invention proposes a kind of self-cleaning antibacterial fluorocarbon coating, its raw material comprises following component by weight: fluorine-containing polyacrylic resin 40-60 part, silane coupling agent 5-13 part, aminoresin 1-6 part, titanium dioxide 3-15 part, calcium carbonate 2-6 part, modified nano-titanium dioxide 10-28 part, silicon nitride 2-6 part, zinc molybdate 2-8 part, 2, 2, 4-trimethylammonium-1, 3 pentanediol mono isobutyrate 5-10 parts, CMIT 0.3-1.2 part, defoamer 0.2-1.2 part, wetting agent 0.5-1.8 part, flow agent 0.3-0.8 part, solidifying agent 0.6-1.5 part, solvent 30-60 part.
Preferably, its raw material comprises following component by weight: fluorine-containing polyacrylic resin 48-51 part, silane coupling agent 9-10.5 part, aminoresin 3-4.2 part, titanium dioxide 7-8.6 part, calcium carbonate 3.6-4.3 part, modified nano-titanium dioxide 15-20 part, silicon nitride 4-5.6 part, zinc molybdate 5-6.3 part, 2,2,4-trimethylammonium-1,3 pentanediol mono isobutyrate 7-8.2 part, CMIT 0.8-0.95 part, defoamer 0.5-0.7 part, wetting agent 1.2-1.5 part, flow agent 0.5-0.65 part, solidifying agent 0.9-1.1 part, solvent 43-49 part.
Preferably, described fluorine-containing polyacrylic resin is prepared according to following technique: add stirring reaction in dimethylbenzene after cyclohexyl methacrylate, ethyl α bromopropionate, cuprous iodide and pentamethyl-diethylenetriamine being mixed, add Isooctyl methacrylate stirring reaction again, add stirring reaction after Hydroxyethyl acrylate again, add dodecafluoroheptyl methacrylate, cuprous iodide and pentamethyl-diethylenetriamine stirring reaction again, purification is carried out to reaction product and obtains described fluorine-containing polyacrylic resin.
Preferably, described fluorine-containing polyacrylic resin is prepared according to following technique: by weight by 12-18 part cyclohexyl methacrylate, 15-20 part ethyl α bromopropionate, join in 30-50 part dimethylbenzene after 10-15 part cuprous iodide and the mixing of 18-30 part pentamethyl-diethylenetriamine, stir, vacuumize rear logical nitrogen, stirring is warming up to 72-80 DEG C, reaction 1.5-2.8h, add 16-24 part Isooctyl methacrylate, stirring reaction 2-2.5h, 3.4-5h is stirred after adding 5-15 part Hydroxyethyl acrylate, add 25-45 part dodecafluoroheptyl methacrylate, 1-3 part cuprous iodide and 3-5 part pentamethyl-diethylenetriamine, stirring reaction 8-12h, join in 60-100 part ethanol after being cooled to room temperature, add salt acid for adjusting pH to 4-6, a layer product is taken off after leaving standstill, washing is to neutral, vacuum-drying obtains described fluorine-containing polyacrylic resin.
Preferably, described fluorine-containing polyacrylic resin is prepared according to following technique: by weight by 15-16.8 part cyclohexyl methacrylate, 17-18.3 part ethyl α bromopropionate, join in 38-42 part dimethylbenzene after 12-13.5 part cuprous iodide and the mixing of 22-23.6 part pentamethyl-diethylenetriamine, stir, vacuumize rear logical nitrogen, stirring is warming up to 76-78 DEG C, reaction 2.1-2.5h, add 19-21 part Isooctyl methacrylate, stirring reaction 2.2-2.35h, 4.3-4.8h is stirred after adding 9-10 part Hydroxyethyl acrylate, add 38-42 part dodecafluoroheptyl methacrylate, 1.9-2.4 part cuprous iodide and 3.7-4.2 part pentamethyl-diethylenetriamine, stirring reaction 9.8-10.3h, join in 85-93 part ethanol after being cooled to room temperature, add salt acid for adjusting pH to 5-6, a layer product is taken off after leaving standstill, washing is to neutral, vacuum-drying obtains described fluorine-containing polyacrylic resin.
Preferably, described fluorine-containing polyacrylic resin is prepared according to following technique: by weight by 15.8 parts of cyclohexyl methacrylates, 17.6 part ethyl α bromopropionate, join in 40 parts of dimethylbenzene after 13 parts of cuprous iodides and 22.7 parts of pentamethyl-diethylenetriamine mixing, stir, vacuumize rear logical nitrogen, stirring is warming up to 77 DEG C, reaction 2.3h, add 20 parts of Isooctyl methacrylates, stirring reaction 2.3h, 4.6h is stirred after adding 9.5 parts of Hydroxyethyl acrylates, add 40 parts of dodecafluoroheptyl methacrylates, 2 parts of cuprous iodides and 4 parts of pentamethyl-diethylenetriamines, stirring reaction 10h, join in 87 parts of ethanol after being cooled to room temperature, add salt acid for adjusting pH to 5, a layer product is taken off after leaving standstill, washing is to neutral, vacuum-drying obtains described fluorine-containing polyacrylic resin.
Preferably, described modified nano-titanium dioxide is prepared according to following technique: obtain solution A by after butyl (tetra) titanate and dehydrated alcohol mixing; Dehydrated alcohol, Glacial acetic acid, polyoxyethylene glycol and deionized water are mixed and obtains solution B after adding europium nitrate and Silver Nitrate stirring and dissolving; Under whipped state, solution A be added drop-wise in solution B, stirring reaction also joins after product standing and drying in toluene, then add double bond containing silane coupling agent and stirring reaction, product is washed drying and obtains described modified nano-titanium dioxide.
Preferably, described modified nano-titanium dioxide is prepared according to following technique: obtain solution A by after 5-20 part butyl (tetra) titanate and the mixing of 15-30 part dehydrated alcohol by weight; 6-15 part dehydrated alcohol, 3-10 part Glacial acetic acid, 0.3-1.5 part polyoxyethylene glycol and 2-5 part deionized water are mixed, adds 2-5 part europium nitrate and 3-5 part Silver Nitrate, after stirring and dissolving, obtain solution B; Under whipped state; solution A is added drop-wise in solution B; stir 3-5h; through leaving standstill, joining in 10-20 part toluene after drying; add the double bond containing silane coupling agent of 0.1-0.5 part, stir 20-50min and pass into nitrogen, under the protection of nitrogen, be warming up to 72-80 DEG C; stirring reaction 3-5h, obtains described modified nano-titanium dioxide through washing, drying.
Preferably, described modified nano-titanium dioxide is prepared according to following technique: obtain solution A by after 12-17 part butyl (tetra) titanate and the mixing of 20-26 part dehydrated alcohol by weight; 9-11 part dehydrated alcohol, 6-7.3 part Glacial acetic acid, 0.9-1.2 part polyoxyethylene glycol and 4-4.6 part deionized water are mixed, adds 3-3.8 part europium nitrate and 4-4.4 part Silver Nitrate, after stirring and dissolving, obtain solution B; Under whipped state; solution A is added drop-wise in solution B; stir 3.9-4.3h; through leaving standstill, joining in 15-18 part toluene after drying; add the double bond containing silane coupling agent of 0.3-0.38 part, stir 38-43min and pass into nitrogen, under the protection of nitrogen, be warming up to 76-78 DEG C; stirring reaction 4-4.5h, obtains described modified nano-titanium dioxide through washing, drying.
Preferably, described modified nano-titanium dioxide is prepared according to following technique: obtain solution A by after 15 parts of butyl (tetra) titanates and 23 parts of dehydrated alcohol mixing by weight; By 9.6 parts of dehydrated alcohols, 6.8 parts of Glacial acetic acid, 1.1 parts of polyoxyethylene glycol and 4.3 parts of deionized water mixing, add 3.3 parts of europium nitrates and 4.2 parts of Silver Nitrates, after stirring and dissolving, obtain solution B; Under whipped state; solution A is added drop-wise in solution B; stir 4.1h; through leaving standstill, joining in 16 parts of toluene after drying; add 0.36 part of double bond containing silane coupling agent, stir 39min and pass into nitrogen, under the protection of nitrogen, be warming up to 77 DEG C; stirring reaction 4.4h, obtains described modified nano-titanium dioxide through washing, drying.
Preferably, described double bond containing silane coupling agent is vinyltriethoxysilane.
Preferably, described solvent is one or more the combination in propylene glycol, glycerol, hexanaphthene, acetone, propyl carbinol.
In the present invention, have selected fluoroacrylic resin is filmogen, 2, 2, 4-trimethylammonium-1, 3 pentanediol mono isobutyrates auxiliary under, can form on the surface of protection base material the hydrophobic film that one deck has extremely low surface after film forming, and coordinate the modified nano-titanium dioxide added can produce a large amount of micro-nano mastoid process structures in hydrophobic film, more hydrophobic class lotus leaf structure is constituted in hydrophobic film, water droplet is not easily sprawled in coating, the globule one by one can be formed, the rolling of the globule can take away a part of dust, there is while making coating have water-repellancy very strong automatically cleaning ability, the fluorine monomer transformation efficiency of the fluorine-contaninig polyacrylate synthesized in optimal way is high, and the segment content on low surface is high, and as fluorine atom arrangement after filmogen film forming closely, the contact angle of film is large, and hydrophobicity is better, and automatically cleaning ability is stronger, the modified nano-titanium dioxide added not only can improve photocatalysis efficiency can also make photochemical catalysis carry out under the condition of visible ray, film is made to have germ resistance, improve the self-cleaning performance of film, select the nano titanium oxide of rare earth ion europium and noble silver codoped, and with double bond containing coupling agent, the modified nano-titanium dioxide that finishing obtains has been carried out to it, rare earth ion europium is at nano titanium oxide crystalline surface generation oxidation-reduction reaction on the one hand, phase transformation is affected by diffusion generation Lacking oxygen or brilliant gap titanium, photocatalytic activity is caused also respective change to occur, cause lattice distortion and expansion, oxygen for the Sauerstoffatom and absorption of fleeing from lattice provides extra hole and electron capture approach, improve the photo electric of nano titanium oxide, there is visible light activity, on the other hand, the silver added can at the surface deposition of nano titanium oxide semi-conductor, facilitate being separated of light induced electron and hole, extend the life-span in hole, improve Photocatalytic oxidation activity, both synergies improve the photocatalysis efficiency of nano titanium oxide and photochemical catalysis are carried out under the condition of visible ray, join in coating, double bond in properties-correcting agent can with the monomer generation bonding reaction in filmogen, be incorporated into filmogen inside firmly, improve the solid content of coating, and the irradiation of UV-light can be resisted, prevent paint film generation serious aging, with zinc molybdate, after CMIT coordinates, antibacterial good endurance, and in coating, form hydrophobic point, improve the hydrophobicity of coating, in addition, aminoresin can improve the density of film as additional crosslinker, coordinates with silicon nitride, titanium dioxide, calcium carbonate, can improve and be coated with film strength and wear resistance, can improve the frost resistance of coating while solvent plays diluting effect.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail; should understand; embodiment is only for illustration of the present invention, instead of for limiting the present invention, any amendment, equivalent replacement etc. made on basis of the present invention is all in protection scope of the present invention.
In a particular embodiment, self-cleaning antibacterial fluorocarbon coating of the present invention, in its raw material, the weight part of fluorine-containing polyacrylic resin can be 40.3, 41, 41.6, 42, 42.5, 43, 43.7, 44, 44.5, 46, 46.3, 47, 47.6, 48.4, 49, 49.7, 50, 50.3, 51.6, 52, 52.3, 53, 53.8, 54, 54.7, 55, 55.6, 56.9, 57, 57.4, 58, 58.2, 59, 59.3 parts, the weight part of silane coupling agent can be 5.3, 5.9, 6, 6.4, 7, 7.5, 8, 8.4, 9.2, 10, 10.6, 11.6, 12, 12.7 parts, the weight part of aminoresin can be 1.3, 2, 2.5, 3.7, 4, 4.5, 5, 5.6 parts, the weight part of titanium dioxide can be 3.2, 4, 4.5, 6, 6.3, 7.8, 8, 8.5, 9, 9.4, 10, 10.3, 11, 11.6, 12, 12.5, 13.7, 14, 14.5 parts, the weight part of calcium carbonate can be 2.3, 2.8, 3, 3.2, 3.7, 4, 4.8, 5, 5.6, 5.8 parts, the weight part of modified nano-titanium dioxide can be 10.3, 11, 11.5, 12, 12.6, 13, 13.7, 14, 14.6, 15.8, 16, 16.3, 17, 17.8, 18, 18.4, 19, 19.3, 20.6, 21, 21.8, 22, 22.3, 23, 23.7, 24, 24.6, 25.6, 26, 26.8, 27, 27.4 parts, the weight part of silicon nitride can be 2.3, 2.8, 3, 3.4, 4.2, 4.7, 5, 5.3, 5.8 parts, the weight part of zinc molybdate can be 2.3, 2.7, 3, 3.4, 4, 4.6, 5.3, 5.7, 6, 6.4, 6.8, 7, 7.2, 7.8 parts, the weight part of 2,2,4-trimethylammonium-1,3 pentanediol mono isobutyrate can be 5.3, 5.9, 6, 7.5, 8, 8.3, 9, 9.4, 9.7 parts, the weight part of CMIT can be 0.37, 0.4, 0.46, 0.5, 0.53, 0.6, 0.68, 0.7, 0.74, 0.9, 1.0, 1.06, 1.1, 1.15 parts, the weight part of defoamer can be 0.26, 0.3, 0.35, 0.4, 0.48, 0.59, 0.6, 0.75, 0.8, 0.86, 0.9, 0.94, 1.0, 1.03, 1.1, 1.17 parts, the weight part of wetting agent can be 0.56, 0.6, 0.63, 0.7, 0.78, 0.8, 0.86, 0.9, 0.94, 1.0, 1.06, 1.1, 1.15, 1.27, 1.38, 1.4, 1.46, 1.56, 1.6, 1.67, 1.7, 1.78 parts, the weight part of flow agent can be 0.36, 0.4, 0.45, 0.53, 0.6, 0.67, 0.7, 0.75 part, the weight part of solidifying agent can be 0.64, 0.7, 0.73, 0.8, 0.86, 0.93, 1.0, 1.05, 1.17, 1.2, 1.23, 1.3, 1.37, 1.4, 1.46 parts, the weight part of solvent can be 30.8, 31, 32, 32.6, 34, 35, 36.7, 38, 39, 40.6, 42, 45, 46.7, 48, 48.9, 50, 50.3, 51, 52, 53, 54.6, 55, 55.6, 56, 56.7, 57, 58, 58.6, 59, 59.4 parts.
Embodiment 1
Self-cleaning antibacterial fluorocarbon coating of the present invention, its raw material comprises following component by weight: fluorine-containing polyacrylic resin 40 parts, silane coupling agent 13 parts, 6 parts, aminoresin, titanium dioxide 15 parts, 2 parts, calcium carbonate, modified nano-titanium dioxide 10 parts, silicon nitride 6 parts, zinc molybdate 8 parts, 2,2,4-trimethylammonium-1,3 pentanediol mono isobutyrate 10 parts, CMIT 0.3 part, defoamer 1.2 parts, wetting agent 1.8 parts, flow agent 0.3 part, 1.5 parts, solidifying agent, solvent 30 parts.
Embodiment 2
Self-cleaning antibacterial fluorocarbon coating of the present invention, its raw material comprises following component by weight: fluorine-containing polyacrylic resin 60 parts, silane coupling agent 5 parts, 1 part, aminoresin, titanium dioxide 3 parts, 6 parts, calcium carbonate, modified nano-titanium dioxide 28 parts, silicon nitride 2 parts, zinc molybdate 2 parts, 2,2,4-trimethylammonium-1,3 pentanediol mono isobutyrate 5 parts, CMIT 1.2 parts, defoamer 0.2 part, wetting agent 0.5 part, flow agent 0.8 part, 0.6 part, solidifying agent, solvent 60 parts;
Wherein, described solvent is that hexanaphthene, acetone, propyl carbinol are by the combination of 1:4:2 weight ratio;
Described fluorine-containing polyacrylic resin is prepared according to following technique: by weight by 12 parts of cyclohexyl methacrylates, 20 parts of ethyl α bromopropionates, join in 30 parts of dimethylbenzene after 10 parts of cuprous iodides and 30 parts of pentamethyl-diethylenetriamine mixing, stir, vacuumize rear logical nitrogen, stirring is warming up to 80 DEG C, reaction 1.5h, add 24 parts of Isooctyl methacrylates, stirring reaction 2h, 3.4h is stirred after adding 15 parts of Hydroxyethyl acrylates, add 45 parts of dodecafluoroheptyl methacrylates, 1 part of cuprous iodide and 5 parts of pentamethyl-diethylenetriamines, stirring reaction 8h, join in 100 parts of ethanol after being cooled to room temperature, add salt acid for adjusting pH to 4, a layer product is taken off after leaving standstill, be washed with distilled water to neutrality, at 55 DEG C, vacuum-drying obtains described fluorine-containing polyacrylic resin,
Described modified nano-titanium dioxide is prepared according to following technique: obtain solution A by after 5 parts of butyl (tetra) titanates and 30 parts of dehydrated alcohol mixing by weight; By 6 parts of dehydrated alcohols, 10 parts of Glacial acetic acid, 0.3 part of polyoxyethylene glycol and 5 parts of deionized water mixing, add 2 parts of europium nitrates and 5 parts of Silver Nitrates, after stirring and dissolving, obtain solution B; Under whipped state; solution A is added drop-wise in solution B; stir 3h; through leaving standstill, joining in 10 parts of toluene after drying; add 0.5 part of double bond containing silane coupling agent, stir 20min and pass into nitrogen, under the protection of nitrogen, be warming up to 80 DEG C; stirring reaction 3h, obtains described modified nano-titanium dioxide through washing, drying.
Embodiment 3
Self-cleaning antibacterial fluorocarbon coating of the present invention, its raw material comprises following component by weight: fluorine-containing polyacrylic resin 47.6 parts, silane coupling agent 12 parts, 4.5 parts, aminoresin, titanium dioxide 7.8 parts, 3.2 parts, calcium carbonate, modified nano-titanium dioxide 12.6 parts, silicon nitride 4.2 parts, zinc molybdate 3.4 parts, 2,2,4-trimethylammonium-1,3 pentanediol mono isobutyrate 6.4 parts, CMIT 0.74 part, defoamer 0.8 part, wetting agent 1.1 parts, flow agent 0.45 part, 0.73 part, solidifying agent, solvent 55.6 parts;
Wherein, described solvent is propylene glycol;
Described fluorine-containing polyacrylic resin is prepared according to following technique: by weight by 18 parts of cyclohexyl methacrylates, 15 parts of ethyl α bromopropionates, join in 50 parts of dimethylbenzene after 15 parts of cuprous iodides and 18 parts of pentamethyl-diethylenetriamine mixing, stir, vacuumize rear logical nitrogen, stirring is warming up to 72 DEG C, reaction 2.8h, add 16 parts of Isooctyl methacrylates, stirring reaction 2.5h, 5h is stirred after adding 5 parts of Hydroxyethyl acrylates, add 25 parts of dodecafluoroheptyl methacrylates, 3 parts of cuprous iodides and 3 parts of pentamethyl-diethylenetriamines, stirring reaction 12h, join in 60 parts of ethanol after being cooled to room temperature, add salt acid for adjusting pH to 6, a layer product is taken off after leaving standstill, be washed with distilled water to neutrality, at 50 DEG C, vacuum-drying obtains described fluorine-containing polyacrylic resin,
Described modified nano-titanium dioxide is prepared according to following technique: obtain solution A by after 20 parts of butyl (tetra) titanates and 15 parts of dehydrated alcohol mixing by weight; By 15 parts of dehydrated alcohols, 3 parts of Glacial acetic acid, 1.5 parts of polyoxyethylene glycol and 2 parts of deionized water mixing, add 5 parts of europium nitrates and 3 parts of Silver Nitrates, after stirring and dissolving, obtain solution B; Under whipped state; solution A is added drop-wise in solution B; stir 5h; through leaving standstill, joining in 20 parts of toluene after drying; add 0.1 part of double bond containing silane coupling agent, stir 50min and pass into nitrogen, under the protection of nitrogen, be warming up to 72 DEG C; stirring reaction 5h, obtains described modified nano-titanium dioxide through washing, drying.
Embodiment 4
Self-cleaning antibacterial fluorocarbon coating of the present invention, its raw material comprises following component by weight: fluorine-containing polyacrylic resin 56 parts, silane coupling agent 11 parts, 3.4 parts, aminoresin, titanium dioxide 13 parts, 4.6 parts, calcium carbonate, modified nano-titanium dioxide 25 parts, silicon nitride 3.9 parts, zinc molybdate 7.3 parts, 2,2,4-trimethylammonium-1,3 pentanediol mono isobutyrate 6.4 parts, CMIT 0.49 part, defoamer 0.67 part, wetting agent 1.3 parts, flow agent 0.54 part, 0.94 part, solidifying agent, solvent 49 parts;
Wherein, described solvent is that propylene glycol, glycerol, hexanaphthene, acetone, propyl carbinol are by the combination of any weight ratio;
Described fluorine-containing polyacrylic resin is prepared according to following technique: by weight by 15.8 parts of cyclohexyl methacrylates, 17.6 part ethyl α bromopropionate, join in 40 parts of dimethylbenzene after 13 parts of cuprous iodides and 22.7 parts of pentamethyl-diethylenetriamine mixing, stir, vacuumize rear logical nitrogen, stirring is warming up to 77 DEG C, reaction 2.3h, add 20 parts of Isooctyl methacrylates, stirring reaction 2.3h, 4.6h is stirred after adding 9.5 parts of Hydroxyethyl acrylates, add 40 parts of dodecafluoroheptyl methacrylates, 2 parts of cuprous iodides and 4 parts of pentamethyl-diethylenetriamines, stirring reaction 10h, join in 87 parts of ethanol after being cooled to room temperature, add salt acid for adjusting pH to 5, a layer product is taken off after leaving standstill, be washed with distilled water to neutrality, at 70 DEG C, vacuum-drying obtains described fluorine-containing polyacrylic resin,
Described modified nano-titanium dioxide is prepared according to following technique: obtain solution A by after 15 parts of butyl (tetra) titanates and 23 parts of dehydrated alcohol mixing by weight; By 9.6 parts of dehydrated alcohols, 6.8 parts of Glacial acetic acid, 1.1 parts of polyoxyethylene glycol and 4.3 parts of deionized water mixing, add 3.3 parts of europium nitrates and 4.2 parts of Silver Nitrates, after stirring and dissolving, obtain solution B; Under whipped state; solution A is added drop-wise in solution B; stir 4.1h; through leaving standstill, joining in 16 parts of toluene after drying; add 0.36 part of vinyltriethoxysilane, stir 39min and pass into nitrogen, under the protection of nitrogen, be warming up to 77 DEG C; stirring reaction 4.4h, obtains described modified nano-titanium dioxide through washing, drying.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (10)
1. a self-cleaning antibacterial fluorocarbon coating, it is characterized in that, its raw material comprises following component by weight: fluorine-containing polyacrylic resin 40-60 part, silane coupling agent 5-13 part, aminoresin 1-6 part, titanium dioxide 3-15 part, calcium carbonate 2-6 part, modified nano-titanium dioxide 10-28 part, silicon nitride 2-6 part, zinc molybdate 2-8 part, 2, 2, 4-trimethylammonium-1, 3 pentanediol mono isobutyrate 5-10 parts, CMIT 0.3-1.2 part, defoamer 0.2-1.2 part, wetting agent 0.5-1.8 part, flow agent 0.3-0.8 part, solidifying agent 0.6-1.5 part, solvent 30-60 part.
2. self-cleaning antibacterial fluorocarbon coating according to claim 1, it is characterized in that, its raw material comprises following component by weight: fluorine-containing polyacrylic resin 48-51 part, silane coupling agent 9-10.5 part, aminoresin 3-4.2 part, titanium dioxide 7-8.6 part, calcium carbonate 3.6-4.3 part, modified nano-titanium dioxide 15-20 part, silicon nitride 4-5.6 part, zinc molybdate 5-6.3 part, 2, 2, 4-trimethylammonium-1, 3 pentanediol mono isobutyrate 7-8.2 parts, CMIT 0.8-0.95 part, defoamer 0.5-0.7 part, wetting agent 1.2-1.5 part, flow agent 0.5-0.65 part, solidifying agent 0.9-1.1 part, solvent 43-49 part.
3. self-cleaning antibacterial fluorocarbon coating according to claim 1 or 2, it is characterized in that, described fluorine-containing polyacrylic resin is prepared according to following technique: by cyclohexyl methacrylate, ethyl α bromopropionate, stirring reaction in dimethylbenzene is added after cuprous iodide and pentamethyl-diethylenetriamine mixing, add Isooctyl methacrylate stirring reaction again, add stirring reaction after Hydroxyethyl acrylate again, add dodecafluoroheptyl methacrylate again, cuprous iodide and pentamethyl-diethylenetriamine stirring reaction, purification is carried out to reaction product and obtains described fluorine-containing polyacrylic resin.
4. self-cleaning antibacterial fluorocarbon coating according to any one of claim 1-3, it is characterized in that, described fluorine-containing polyacrylic resin is prepared according to following technique: by weight by 12-18 part cyclohexyl methacrylate, 15-20 part ethyl α bromopropionate, join in 30-50 part dimethylbenzene after 10-15 part cuprous iodide and the mixing of 18-30 part pentamethyl-diethylenetriamine, stir, vacuumize rear logical nitrogen, stirring is warming up to 72-80 DEG C, reaction 1.5-2.8h, add 16-24 part Isooctyl methacrylate, stirring reaction 2-2.5h, 3.4-5h is stirred after adding 5-15 part Hydroxyethyl acrylate, add 25-45 part dodecafluoroheptyl methacrylate, 1-3 part cuprous iodide and 3-5 part pentamethyl-diethylenetriamine, stirring reaction 8-12h, join in 60-100 part ethanol after being cooled to room temperature, add salt acid for adjusting pH to 4-6, a layer product is taken off after leaving standstill, washing is to neutral, vacuum-drying obtains described fluorine-containing polyacrylic resin,
Preferably, described fluorine-containing polyacrylic resin is prepared according to following technique: by weight by 15-16.8 part cyclohexyl methacrylate, 17-18.3 part ethyl α bromopropionate, join in 38-42 part dimethylbenzene after 12-13.5 part cuprous iodide and the mixing of 22-23.6 part pentamethyl-diethylenetriamine, stir, vacuumize rear logical nitrogen, stirring is warming up to 76-78 DEG C, reaction 2.1-2.5h, add 19-21 part Isooctyl methacrylate, stirring reaction 2.2-2.35h, 4.3-4.8h is stirred after adding 9-10 part Hydroxyethyl acrylate, add 38-42 part dodecafluoroheptyl methacrylate, 1.9-2.4 part cuprous iodide and 3.7-4.2 part pentamethyl-diethylenetriamine, stirring reaction 9.8-10.3h, join in 85-93 part ethanol after being cooled to room temperature, add salt acid for adjusting pH to 5-6, a layer product is taken off after leaving standstill, washing is to neutral, vacuum-drying obtains described fluorine-containing polyacrylic resin.
5. self-cleaning antibacterial fluorocarbon coating according to any one of claim 1-4, it is characterized in that, described fluorine-containing polyacrylic resin is prepared according to following technique: by weight by 15.8 parts of cyclohexyl methacrylates, 17.6 part ethyl α bromopropionate, join in 40 parts of dimethylbenzene after 13 parts of cuprous iodides and 22.7 parts of pentamethyl-diethylenetriamine mixing, stir, vacuumize rear logical nitrogen, stirring is warming up to 77 DEG C, reaction 2.3h, add 20 parts of Isooctyl methacrylates, stirring reaction 2.3h, 4.6h is stirred after adding 9.5 parts of Hydroxyethyl acrylates, add 40 parts of dodecafluoroheptyl methacrylates, 2 parts of cuprous iodides and 4 parts of pentamethyl-diethylenetriamines, stirring reaction 10h, join in 87 parts of ethanol after being cooled to room temperature, add salt acid for adjusting pH to 5, a layer product is taken off after leaving standstill, washing is to neutral, vacuum-drying obtains described fluorine-containing polyacrylic resin.
6. self-cleaning antibacterial fluorocarbon coating according to any one of claim 1-5, is characterized in that, described modified nano-titanium dioxide is prepared according to following technique: obtain solution A by after butyl (tetra) titanate and dehydrated alcohol mixing; Dehydrated alcohol, Glacial acetic acid, polyoxyethylene glycol and deionized water are mixed and obtains solution B after adding europium nitrate and Silver Nitrate stirring and dissolving; Under whipped state, solution A be added drop-wise in solution B, stirring reaction also joins after product standing and drying in toluene, then add double bond containing silane coupling agent and stirring reaction, product is washed drying and obtains described modified nano-titanium dioxide.
7. self-cleaning antibacterial fluorocarbon coating according to any one of claim 1-6, is characterized in that, described modified nano-titanium dioxide is prepared according to following technique: obtain solution A by after 5-20 part butyl (tetra) titanate and the mixing of 15-30 part dehydrated alcohol by weight; 6-15 part dehydrated alcohol, 3-10 part Glacial acetic acid, 0.3-1.5 part polyoxyethylene glycol and 2-5 part deionized water are mixed, adds 2-5 part europium nitrate and 3-5 part Silver Nitrate, after stirring and dissolving, obtain solution B; Under whipped state, solution A is added drop-wise in solution B, stir 3-5h, through leaving standstill, joining in 10-20 part toluene after drying, add the double bond containing silane coupling agent of 0.1-0.5 part, stir 20-50min and pass into nitrogen, under the protection of nitrogen, be warming up to 72-80 DEG C, stirring reaction 3-5h, obtains described modified nano-titanium dioxide through washing, drying;
Preferably, described modified nano-titanium dioxide is prepared according to following technique: obtain solution A by after 12-17 part butyl (tetra) titanate and the mixing of 20-26 part dehydrated alcohol by weight; 9-11 part dehydrated alcohol, 6-7.3 part Glacial acetic acid, 0.9-1.2 part polyoxyethylene glycol and 4-4.6 part deionized water are mixed, adds 3-3.8 part europium nitrate and 4-4.4 part Silver Nitrate, after stirring and dissolving, obtain solution B; Under whipped state; solution A is added drop-wise in solution B; stir 3.9-4.3h; through leaving standstill, joining in 15-18 part toluene after drying; add the double bond containing silane coupling agent of 0.3-0.38 part, stir 38-43min and pass into nitrogen, under the protection of nitrogen, be warming up to 76-78 DEG C; stirring reaction 4-4.5h, obtains described modified nano-titanium dioxide through washing, drying.
8. self-cleaning antibacterial fluorocarbon coating according to any one of claim 1-7, is characterized in that, described modified nano-titanium dioxide is prepared according to following technique: obtain solution A by after 15 parts of butyl (tetra) titanates and 23 parts of dehydrated alcohol mixing by weight; By 9.6 parts of dehydrated alcohols, 6.8 parts of Glacial acetic acid, 1.1 parts of polyoxyethylene glycol and 4.3 parts of deionized water mixing, add 3.3 parts of europium nitrates and 4.2 parts of Silver Nitrates, after stirring and dissolving, obtain solution B; Under whipped state; solution A is added drop-wise in solution B; stir 4.1h; through leaving standstill, joining in 16 parts of toluene after drying; add 0.36 part of double bond containing silane coupling agent, stir 39min and pass into nitrogen, under the protection of nitrogen, be warming up to 77 DEG C; stirring reaction 4.4h, obtains described modified nano-titanium dioxide through washing, drying.
9. self-cleaning antibacterial fluorocarbon coating according to any one of claim 6-8, is characterized in that, described double bond containing silane coupling agent is vinyltriethoxysilane.
10. self-cleaning antibacterial fluorocarbon coating according to any one of claim 1-9, is characterized in that, described solvent is one or more the combination in propylene glycol, glycerol, hexanaphthene, acetone, propyl carbinol.
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