CN106752820A - A kind of super-amphiphobic organic inorganic hybridized paint of Fe2O3 doping titanium dioxide - Google Patents

Abstract

The invention discloses a kind of super-amphiphobic organic inorganic hybridized paint of Fe2O3 doping titanium dioxide, it is made up of following raw material：Perfluoroalkyl ethanol, methyl iso-butyl ketone (MIBK), HDI trimer, methyl methacrylate, styrene, hydroxyethyl methacrylate, the trifluoro monooctyl ester of methacrylic acid ten, benzoyl peroxide, methyl alcohol Ludox, propylene glycol methyl ether acetate, 5% ammoniacal liquor is appropriate, appropriate MTMS, appropriate MethylethoxylsiliconFluid Fluid, 10% dibutyl tin laurate is appropriate, dispersant, levelling agent, defoamer, appropriate butyl acetate, titanium tetrachloride, appropriate Iron(III) chloride hexahydrate, appropriate deionized water；The super-amphiphobic Paint preparation technology for preparing of the invention is simple, low cost, and raw material sources are wide, and coating hardness is good, not easy to wear, and adhesive force is high, and the performance such as super-hydrophobic oleophobic, antibacterial, wear-resisting, corrosion-resistant, and excellent performance is worthy to be popularized.

Description

A kind of super-amphiphobic organic inorganic hybridized paint of Fe2O3 doping titanium dioxide

Technical field

The present invention relates to technical field of coatings, more particularly to a kind of super-amphiphobic organic inorganic hybridization of Fe2O3 doping titanium dioxide Coating.

Background technology

Wetability is a key property of the surface of solids, it is conventionally believed that the microstructure and chemical group of the surface of solids The wetability that it is shown in pairs plays a key effect.The wetability of the surface of solids rises in daily life and industrial and agricultural production Critically important effect, such as washing, printing and dyeing, the dispersion of coating, the use of lubricating oil and the infiltration of skin care item.Current people Do not got wet this, and the phenomenon that water droplet can be tumbled with oneself is referred to as super-hydrophobic phenomenon, and the surface with this property is claimed Be super hydrophobic surface, researcher is more for the research of super hydrophobic coating, but the type coating be often easily stained with oil stain and compared with Hardly possible removal, therefore greatly limit the application and popularization of the type coating.Double open coats are due to alienation while it is for water and oil Effect, simple super-hydrophobic coat of holding one's breath is easier to be applied in the middle of daily life and industrial production.But it is existing at present Super-hydrophobic oleophobic coating preparation method has the following disadvantages：Need special installation（Plasma, laser ablation）, be unfavorable for large area Construction, has particular/special requirement to ground, is only applicable to particular surface, and universal complex forming technology, with high costs, therefore seriously Limit the extensive use of such material.

Xu Runbin exists《The preparation of super-hydrophobic/oleophobic coating and research》In one text nanometer is prepared for by conventional grinding methods Alundum (Al2O3) particle, nano-silicon dioxide particle is prepared for using sol-gel process, is distinguished using fluorine-containing silane coupler Surface grafting treatment is carried out to both, the nano-particle and micro particles of surface fluorine modification has been obtained as color stuffing, next is adopted A kind of fluorine-containing Hydroxylated acrylic resin is prepared as the main resin of adhesive, selection perfluoroalkyl with polytype acrylic monomers Ethanol and hexamethylene diisocyanate trimer prepare a kind of fluorine-containing isocyanate curing agent, and as a result paint is matched somebody with somebody in surface by mixing The acroleic acid polyurethane varnish paint film property of preparation is good, adhesion 1 grade, pliability 1mm, impact 50cm, hardness 2H, for water Static contact angle reach as high as 104 °, finally obtained nanometer, micro particles are scattered in fluorine-containing Hydroxylated acrylic resin, Adjustment pigment and nano/micrometre particle ratio, and be equipped with dispersant, anti-settling auxiliary agent and curing agent be obtained it is various super thin Water-oleophobic coating, testing result display coating there is preferable adhesive force, pliability and paint film intensity, now film for water, The static contact angle of rapeseed oil and aircraft fluid is respectively 154 °, 100 ° and 94 °, illustrates that the coating shows to water and oil Good alienation effect, although the preparation method proposed in this article has certain effect in terms of hydrophobic and oleophobic, but It is not reaching to the contact angle of oil more than 150 °, and the intensity of coating, wearability, durability, stability and mechanical performance one As, actual use demand is can not meet, limit the commercial Application of super-amphiphobic coating.

The content of the invention

The object of the invention is exactly to make up the defect of prior art, there is provided a kind of super-amphiphobic of Fe2O3 doping titanium dioxide has Machine inorganic hybridization coating.

The present invention is achieved by the following technical solutions：

A kind of super-amphiphobic organic inorganic hybridized paint of Fe2O3 doping titanium dioxide, is made up of the raw material of following weight portion：Entirely Fluoroalkyl ethanol 32-35, methyl iso-butyl ketone (MIBK) 40-50, HDI trimer 90-100, methyl methacrylate 30-35, styrene 20-23, hydroxyethyl methacrylate 8.5-9, the trifluoro monooctyl ester 17-19 of methacrylic acid ten, benzoyl peroxide 0.6-0.8, first Alcohol Ludox 25-28, propylene glycol methyl ether acetate 25-26, appropriate 5% ammoniacal liquor, appropriate MTMS, methyl second Epoxide silicone oil is appropriate, 10% dibutyl tin laurate is appropriate, dispersant 0.6-1, levelling agent 0.6-0.8, defoamer 0.4-0.6, Appropriate butyl acetate, titanium tetrachloride 13-15, appropriate Iron(III) chloride hexahydrate, appropriate deionized water.

A kind of super-amphiphobic organic inorganic hybridized paint of Fe2O3 doping titanium dioxide, is prepared by step in detail below and made Into：

（1）Perfluoroalkyl ethanol is mixed with the methyl iso-butyl ketone (MIBK) of butyl acetate, 2/3 times of amount, is added in reaction bulb, start to rise Temperature is simultaneously slowly stirred to perfluoroalkyl ethanol and is completely dissolved, and instills the dibutyl tin laurate of 8-10 drops 10%, and liter high-temperature is extremely After 70 DEG C, the mixed liquor of HDI trimer and butyl acetate is added dropwise, it is ensured that the completion of dropping in 1h, is stepped up temperature to 90 DEG C, Cooling down is standby as component A to room temperature after insulation 2-3h；

（2）Appropriate butyl acetate is added to vessel in heating to the insulation 20min that flows back, then by methyl methacrylate, benzene second The mixing of alkene, hydroxyethyl methacrylate, remaining methyl iso-butyl ketone (MIBK), 80% benzoyl peroxide and butyl acetate, wherein vinegar Acid butyl ester is 3 with the volume ratio of methyl iso-butyl ketone (MIBK):1, the butyl acetate of above-mentioned backflow insulation is slowly dropped to after stirring and dissolving In solution, it is ensured that completion of dropping in 1.5h, the trifluoro monooctyl ester of methacrylic acid ten is then rapidly added, rises high-temperature to 95 DEG C of backflows Insulation 2h, then 10% benzoyl peroxide and appropriate butyl acetate are mixed disposably be added in container, insulation reaction 1- Remaining benzoyl peroxide and appropriate butyl acetate are mixed again after 1.5h and is disposably added, insulation reaction 1-1.5h, with After be cooled to 50 DEG C, seal standby；

（3）By titanium tetrachloride solution according to volume ratio 3:200 are added in frozen water, are stirring evenly and then adding into Iron(III) chloride hexahydrate, Wherein n（Fe3+）：n（Ti4+）It is 0.1%, ammonia spirit stirring simultaneously to the pH value of solution for adding 5% is 8, filtration washing Until without impurity such as chlorions in precipitation, products therefrom is then added to ultrasonic disperse in deionized water, adds 30% peroxide Change hydrogen magnetic agitation 0.5-1h, then rise high-temperature to 100 DEG C, 3-4h is heated to reflux at this temperature, product is dried；

（4）Methyl alcohol Ludox is placed in the container that bath temperature is 60 DEG C, total system quality is slowly added under agitation Fraction is 12% MTMS, and isothermal reaction 1h adds total system mass fraction for 3% MethylethoxylsiliconFluid Fluid Continue to react 1h, be subsequently adding after propylene glycol methyl ether acetate is well mixed and be transferred on rotary evaporator, vacuum distillation is removed Methyl alcohol, obtains hydrophobically modified Ludox；

（5）By step（3）The product of preparation is added to step（4）In, being placed in fully shaking in ultrasonator uniformly, then will be mixed Compound is added to step（2）It is slowly stirred in the product of preparation to being uniformly dispersed, adds dispersant, levelling agent and defoamer at a high speed Stirring 30-50min, rotating speed is controlled to 1000-1200r/min, and then ultrasonic disperse 30-40min, then continues to high-speed stirred 20-30min, rotating speed is controlled to 700r/min, obtains component B, then by component A and component B according to mass ratio 1：3.2 mixing, Room temperature is placed 10-15min and is cured, and is adjusted to suitable viscosity with ethyl acetate and is sprayed or brush after workpiece surface, surface drying In baking-curing at 80 DEG C.

It is an advantage of the invention that：Polyurethane resin has good adhesive force, mechanical endurance and toughness, and film is acidproof Alkali, chemical-resistant resistance, saline solution etc., film can in -50 DEG C of -120 DEG C of long-term uses, acrylic resin have weatherability it is good, protect Light colour retention is excellent, heat-resist, there is certain decay resistance, and the acrylic resin of hydroxyl can with polyisocyanates reaction The acroleic acid polyurethane film of function admirable is obtained, it is widely used, in order to reach requirement of double open coats for low-surface-energy, Acrylic acid fluorochemical monomer is introduced during synthesis of hydroxy acrylic resin, fluorine is introduced by perfluoroalkyl ethanol in isocyanate component Element, resin system of the synthesis with low-surface-energy, and further increase the chemical-resistant of coating, anticorrosive property, resistance to Cold performance, the silanol for also being produced using MTMS hydrolysis and the silica particle surface in Ludox such as heat-resisting There is intermolecular dehydration in a part of hydroxyl, add MethylethoxylsiliconFluid Fluid, the silanol and titanium dioxide silicon grain produced after hydrolysis The remaining hydroxyl in sublist face continues intermolecular dehydration, obtains modified hydrophobic Ludox, and modified iron ion Doped nano titanium dioxide, builds the roughness in super-amphiphobic coating, makes it on the whole in microstructure and surface composition Meet the requirement of double open coats, improve the easily dispersion effect enhanced with photo-catalysis capability in coating, and good penetrability, energy The pore of substrate surface is enough blocked, open hole count is reduced, absorption of the basic unit to coating solvents is reduced so that coating is dried to be become Uniformly, the adhesive force of coating is strengthened, super-amphiphobic Paint preparation technology prepared by the present invention is simple, low cost, raw material sources are wide, apply Layer hardness is good, and not easy to wear, adhesive force is high, and the performance such as super-hydrophobic oleophobic, antibacterial, wear-resisting, corrosion-resistant, excellent performance, value Must promote.

Specific embodiment

A kind of super-amphiphobic organic inorganic hybridized paint of Fe2O3 doping titanium dioxide, by following weight portion（Kilogram）Raw material system Prepare into：Perfluoroalkyl ethanol 32, methyl iso-butyl ketone (MIBK) 40, HDI trimer 90, methyl methacrylate 30, styrene 20, first Base hydroxy-ethyl acrylate 8.5, the trifluoro monooctyl ester 17 of methacrylic acid ten, benzoyl peroxide 0.6, methyl alcohol Ludox 25, propane diols The ammoniacal liquor of methyl ether acetate 25,5% is appropriate, appropriate MTMS, appropriate MethylethoxylsiliconFluid Fluid, 10% tin dilaurate Appropriate dibutyl tin, dispersant 0.6, levelling agent 0.6, defoamer 0.4, appropriate butyl acetate, the hydration trichlorine of titanium tetrachloride 13, six Change iron is appropriate, appropriate deionized water.

A kind of super-amphiphobic organic inorganic hybridized paint of Fe2O3 doping titanium dioxide, is prepared by step in detail below and made Into：

（1）Perfluoroalkyl ethanol is mixed with the methyl iso-butyl ketone (MIBK) of butyl acetate, 2/3 times of amount, is added in reaction bulb, start to rise Temperature is simultaneously slowly stirred to perfluoroalkyl ethanol and is completely dissolved, and instills the dibutyl tin laurates of 8 drops 10%, rises high-temperature to 70 After DEG C, the mixed liquor of HDI trimer and butyl acetate is added dropwise, it is ensured that the completion of dropping in 1h, is stepped up temperature to 90 DEG C, protect Cooling down is standby as component A to room temperature after warm 2h；

（2）Appropriate butyl acetate is added to vessel in heating to the insulation 20min that flows back, then by methyl methacrylate, benzene second The mixing of alkene, hydroxyethyl methacrylate, remaining methyl iso-butyl ketone (MIBK), 80% benzoyl peroxide and butyl acetate, wherein vinegar Acid butyl ester is 3 with the volume ratio of methyl iso-butyl ketone (MIBK):1, the butyl acetate of above-mentioned backflow insulation is slowly dropped to after stirring and dissolving In solution, it is ensured that completion of dropping in 1.5h, the trifluoro monooctyl ester of methacrylic acid ten is then rapidly added, rises high-temperature to 95 DEG C of backflows Insulation 2h, then 10% benzoyl peroxide and appropriate butyl acetate are mixed disposably be added in container, insulation reaction 1h Remaining benzoyl peroxide and appropriate butyl acetate are mixed into disposable addition again afterwards, insulation reaction 1h is then cooled to 50 DEG C, seal standby；

（3）By titanium tetrachloride solution according to volume ratio 3:200 are added in frozen water, are stirring evenly and then adding into Iron(III) chloride hexahydrate, Wherein n（Fe3+）：n（Ti4+）It is 0.1%, ammonia spirit stirring simultaneously to the pH value of solution for adding 5% is 8, filtration washing Until without impurity such as chlorions in precipitation, products therefrom is then added to ultrasonic disperse in deionized water, adds 30% peroxide Change hydrogen magnetic agitation 0.5h, then rise high-temperature to 100 DEG C, 3h is heated to reflux at this temperature, product is dried；

（4）Methyl alcohol Ludox is placed in the container that bath temperature is 60 DEG C, total system quality is slowly added under agitation Fraction is 12% MTMS, and isothermal reaction 1h adds total system mass fraction for 3% MethylethoxylsiliconFluid Fluid Continue to react 1h, be subsequently adding after propylene glycol methyl ether acetate is well mixed and be transferred on rotary evaporator, vacuum distillation is removed Methyl alcohol, obtains hydrophobically modified Ludox；

（5）By step（3）The product of preparation is added to step（4）In, being placed in fully shaking in ultrasonator uniformly, then will be mixed Compound is added to step（2）It is slowly stirred in the product of preparation to being uniformly dispersed, adds dispersant, levelling agent and defoamer at a high speed Stirring 30min, rotating speed is controlled to 1000r/min, and then ultrasonic disperse 30min, then continues to high-speed stirred 20min, rotating speed control 700r/min is made as, component B is obtained, then by component A and component B according to mass ratio 1：3.2 mixing, room temperature is placed 10min and is entered Row curing, is adjusted to suitable viscosity with ethyl acetate and sprays or brush in workpiece surface, and surface drying is after baking-curing at 80 DEG C Can.

Preparation method according to embodiment carries out performance test to its coating, as a result as follows：

Adhesive force:1 grade；Pliability：1mm；Hardness：5H；Impact strength：50mm；It it is 155-160 ° with the contact angle of deionized water； It it is 152-156 ° with peanut oil contact angle；4 ° of roll angle ＜.

Claims (2)

1. a kind of super-amphiphobic organic inorganic hybridized paint of Fe2O3 doping titanium dioxide, it is characterised in that by the original of following weight portion Material preparation is made：Perfluoroalkyl ethanol 32-35, methyl iso-butyl ketone (MIBK) 40-50, HDI trimer 90-100, methyl methacrylate 30-35, styrene 20-23, hydroxyethyl methacrylate 8.5-9, the trifluoro monooctyl ester 17-19 of methacrylic acid ten, benzoyl peroxide first Acyl 0.6-0.8, methyl alcohol Ludox 25-28, propylene glycol methyl ether acetate 25-26,5% ammoniacal liquor are appropriate, MTMS In right amount, appropriate MethylethoxylsiliconFluid Fluid, 10% dibutyl tin laurate be appropriate, dispersant 0.6-1, levelling agent 0.6-0.8, disappear Infusion 0.4-0.6, appropriate butyl acetate, titanium tetrachloride 13-15, appropriate Iron(III) chloride hexahydrate, appropriate deionized water.

2. a kind of super-amphiphobic organic inorganic hybridized paint of Fe2O3 doping titanium dioxide according to claim 1, it is characterised in that It is made up of step in detail below：

（1）Perfluoroalkyl ethanol is mixed with the methyl iso-butyl ketone (MIBK) of butyl acetate, 2/3 times of amount, is added in reaction bulb, start to rise Temperature is simultaneously slowly stirred to perfluoroalkyl ethanol and is completely dissolved, and instills the dibutyl tin laurate of 8-10 drops 10%, and liter high-temperature is extremely After 70 DEG C, the mixed liquor of HDI trimer and butyl acetate is added dropwise, it is ensured that the completion of dropping in 1h, is stepped up temperature to 90 DEG C, Cooling down is standby as component A to room temperature after insulation 2-3h；

（2）Appropriate butyl acetate is added to vessel in heating to the insulation 20min that flows back, then by methyl methacrylate, benzene second The mixing of alkene, hydroxyethyl methacrylate, remaining methyl iso-butyl ketone (MIBK), 80% benzoyl peroxide and butyl acetate, wherein vinegar Acid butyl ester is 3 with the volume ratio of methyl iso-butyl ketone (MIBK):1, the butyl acetate of above-mentioned backflow insulation is slowly dropped to after stirring and dissolving In solution, it is ensured that completion of dropping in 1.5h, the trifluoro monooctyl ester of methacrylic acid ten is then rapidly added, rises high-temperature to 95 DEG C of backflows Insulation 2h, then 10% benzoyl peroxide and appropriate butyl acetate are mixed disposably be added in container, insulation reaction 1- Remaining benzoyl peroxide and appropriate butyl acetate are mixed again after 1.5h and is disposably added, insulation reaction 1-1.5h, with After be cooled to 50 DEG C, seal standby；

（3）By titanium tetrachloride solution according to volume ratio 3:200 are added in frozen water, are stirring evenly and then adding into Iron(III) chloride hexahydrate, Wherein n（Fe3+）：n（Ti4+）It is 0.1%, ammonia spirit stirring simultaneously to the pH value of solution for adding 5% is 8, filtration washing Until without impurity such as chlorions in precipitation, products therefrom is then added to ultrasonic disperse in deionized water, adds 30% peroxide Change hydrogen magnetic agitation 0.5-1h, then rise high-temperature to 100 DEG C, 3-4h is heated to reflux at this temperature, product is dried；

（4）Methyl alcohol Ludox is placed in the container that bath temperature is 60 DEG C, total system quality is slowly added under agitation Fraction is 12% MTMS, and isothermal reaction 1h adds total system mass fraction for 3% MethylethoxylsiliconFluid Fluid Continue to react 1h, be subsequently adding after propylene glycol methyl ether acetate is well mixed and be transferred on rotary evaporator, vacuum distillation is removed Methyl alcohol, obtains hydrophobically modified Ludox；

（5）By step（3）The product of preparation is added to step（4）In, being placed in fully shaking in ultrasonator uniformly, then will be mixed Compound is added to step（2）It is slowly stirred in the product of preparation to being uniformly dispersed, adds dispersant, levelling agent and defoamer at a high speed Stirring 30-50min, rotating speed is controlled to 1000-1200r/min, and then ultrasonic disperse 30-40min, then continues to high-speed stirred 20-30min, rotating speed is controlled to 700r/min, obtains component B, then by component A and component B according to mass ratio 1：3.2 mixing, Room temperature is placed 10-15min and is cured, and is adjusted to suitable viscosity with ethyl acetate and is sprayed or brush after workpiece surface, surface drying In baking-curing at 80 DEG C.