CN106928763A - A kind of preparation method of antibacterial aqueous polyurethane coating - Google Patents

A kind of preparation method of antibacterial aqueous polyurethane coating Download PDF

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Publication number
CN106928763A
CN106928763A CN201710272694.8A CN201710272694A CN106928763A CN 106928763 A CN106928763 A CN 106928763A CN 201710272694 A CN201710272694 A CN 201710272694A CN 106928763 A CN106928763 A CN 106928763A
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tio
preparation
graphene
aqueous polyurethane
added
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程俊
汤紫俊
周雪
鲁杰
戴宇
郭丽缨
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SICHUAN CARPOLY PAINT CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • C09D5/02—Emulsion paints including aerosols
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract

The invention discloses a kind of preparation method of antibacterial aqueous polyurethane coating, preparation, the preparation of coating, Graphene/TiO of the present invention including aqueous polyurethane2Preparation of composite etc., coating prepared by the present invention has antibiotic property, improves the environmental-protecting performance of coating.

Description

A kind of preparation method of antibacterial aqueous polyurethane coating
Technical field
The present invention relates to a kind of preparation method of antibacterial aqueous polyurethane coating.
Background technology
Due to having unique and excellent performance in terms of physics and chemistry, polyurethane has as coating and adhesive And be widely applied.The development of aqueous polyurethane be largely because its excellent mechanical performance, fire resistance, hypotoxicity and Low environment endangers, but the carboxyl due to hydrophilic radical for example in its strand, and it has certain colony growth environment.
Chinese patent CN105949989A discloses a kind of aqueous UV antibiotic paints and preparation method thereof, including following weight The component of number：Urethane acrylate dispersoid, 60~80 parts；Nano silver colloidal sol, 5~15 parts；Reactive diluent, 5~20 Part；Light trigger, 3~6 parts；Levelling agent, 0.1~1 part；Dispersant, 0.1~1 part；Defoamer, 0.1~1 part, the patent is also carried A kind of preparation method of aqueous UV antibiotic paints is supplied.In above-mentioned aqueous UV antibiotic paints and preparation method thereof, the aqueous UV Antibiotic paint is all up to more than 95%, good anti-bacterial effect to the sterilization rate of Escherichia coli and staphylococcus aureus.
But there is the Nano Silver of costliness in the raw material of this method, production cost is higher, without large-scale mass production Prospect.
Chinese patent CN105925151A discloses a kind of preparation method of composite antibacterial coating, including following components：It is poly- Compound emulsion, Cu-Mn-F doping MgO nano antibacterial agents, Ag-ZnTiO3Nano antibacterial agent, organic antibacterial agent, toughener, emulsification Agent, coupling agent, stabilizer and solvent.
But this complex process equipment, and coating does not possess lipid-loweringing organics function, has very to the final using effect of coating Big influence.
Chinese patent CN103194935A discloses a kind of production technology of antibiotic paint, and it comprises the following steps：Prepare Include the mixed liquor of titanium dioxide granule and dispersant；Mechanical agitation is carried out to the mixed liquor with the mixed liquor Titanium dioxide granule carries out preliminary size degradation to form primary titanium dioxide particle dispersion；To the primary titanium dioxide particle point Dispersion liquid carries out ultrasonic vibration to form the nano-titania particle dispersion liquid of average grain diameter≤200nm；And by the nanometer TiO 2 particles dispersion liquid is mixed with coating easily forms the dispersed antibiotic paint for having a nano-titania particle, In the antibiotic paint, content >=5% of the nano-titania particle.
This method preparation technology is relatively easy, and titanium dioxide is evenly distributed in coating, what antibacterial ability was still improved Leeway.
The content of the invention
In order to improve above mentioned problem, the present invention provides a kind of preparation method of antibacterial aqueous polyurethane coating.
Realize that technical scheme is as follows：
A kind of preparation method of antibacterial aqueous polyurethane coating, comprises the following steps：
The preparation of aqueous polyurethane：
IPDI, polyethylene glycol are stirred at 80~90 DEG C, dibutyl tin laurate is added As catalyst, 1.5~2.5h is incubated；After being cooled to 65~75 DEG C, the dimethylolpropionic acid that will be dissolved in acetone is added, backflow 1.5~2.5h；55~64 DEG C are cooled to, hydroxyethyl methacrylate is added, 5~7h is incubated；Room temperature is cooled to, triethylamine is added 10min is neutralized, deionized water is slowly added dropwise and 20~40min is stirred with 1300~1700r/min；
The preparation of coating：
By Graphene/TiO2Composite and light trigger are dissolved in acetone, are steamed solvent using Rotary Evaporators, obtain Graphene/TiO2F composites and photoinitiator mixtures, ultrasonic disperse in the aqueous polyurethane for preparing, normal temperature cure Film forming, obtains final product antibacterial aqueous polyurethane coating.
Further, the Graphene/TiO2The mass ratio of composite and light trigger is 2~4:1.
Yet further, the Graphene/TiO2The preparation method of composite is as follows：
The preparation of graphene oxide：
Graphite powder is put into container, and container is put into ice-water bath, to adding the concentrated sulfuric acid in container, stirring 5~ 10min；Potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed under normal temperature and stirs 21~26h；Then Container is put into ice-water bath, deionized water is added, 4~7min of ice-water bath is kept, hydrogen peroxide to bubble-free is dropwise added dropwise and is produced； Finally filter, use salt acid elution, then be washed with deionized water to neutrality, ultrasound obtains graphene oxide after peeling off；
Nano-TiO2Preparation：
Absolute ethyl alcohol is slowly dropped in butyl titanate, stirring obtains uniform mixed solution in water bath with thermostatic control；So After add hydrochloric acid, then be slowly added dropwise deionized water, continue stirring and obtain butyl titanate solution, then butyl titanate solution is carried out Dry, high-temperature calcination obtains light yellow crystal；It is ground after finally light yellow crystal is mixed with absolute ethyl alcohol, obtains final product nanometer TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, carried out in ptfe autoclave anti- Should, solvent is removed after cooling, drying and grinding obtains final product Graphene/TiO into powder2Composite.
Further, the Graphene/TiO2The preparation method of composite is as follows：
The preparation of graphene oxide：
Graphite powder is put into flask, and flask is put into ice-water bath, to adding the concentrated sulfuric acid in flask, stirring 5~ 10min；Potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed under normal temperature and stirs 21~26h；Then Container is put into ice-water bath, deionized water is added, 4~7min of ice-water bath is kept, hydrogen peroxide to bubble-free is dropwise added dropwise and is produced； Finally filter, with 30% salt acid elution, then be washed with deionized water to neutrality, ultrasound peel off after graphene oxide；
Nano-TiO2Preparation：
Absolute ethyl alcohol is slowly dropped in butyl titanate, in water bath with thermostatic control with the speed of 400r/min stirring 25~ 35min obtains uniform mixed solution；Hydrochloric acid is subsequently adding, then is slowly added dropwise deionized water, continued 2~3h of stirring and obtain metatitanic acid , then be put into butyl titanate solution in vacuum drying chamber and be dried 10~15h by butyl acetate solution, in placing into Muffle furnace, and 3~5h is calcined at 450~600 DEG C and obtains light yellow crystal；Ground after finally light yellow crystal is mixed with absolute ethyl alcohol Mill, obtains final product nano-TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, in ptfe autoclave, and 2~12h is reacted under conditions of 160~180 DEG C, solvent is removed after cooling, drying and grinding obtains final product Graphene/TiO into powder2It is compound Material.
In addition, the graphene oxide and nano-TiO2Weight ratio be 1:1~10.
The present invention has advantages below and beneficial effect：
Present invention process flow is simple, and raw material sources extensively, can effectively control to produce preparation cost；Nano TiO 2 is in environment Protection aspect have a wide range of applications, being primarily due to nano TiO 2 has strong photochemical catalytic oxidation effect, can quickly, height Effect ground decomposing organic matter, generates carbon dioxide and water.Light-catalyzed reaction is main, and by efficient photocatalyst, its Strong oxdiative ability can break The structure of bad bacterium simultaneously decomposites bacterial body, solidifies virus protein, the activity of virus is controlled, to reach efficient sterilizing purpose. The doping of some nonmetallic doping such as carbon, nitrogen, sulphur, after above-mentioned entrance Detitanium-ore-type lattice, occupies the position of oxygen, reduces Band gap width, or impurity energy level is formed, or as gap ion, enable to the light absorbs after doping to extend to visible region Domain, photo-generate electron-hole it is compound be another influence photocatalytic activity key factor, excite the electronics of generation empty by light Cave also can improve photocatalysis efficiency to being easily combined by reducing the compound of photo-generated carrier.New carbon Graphene is answered Close TiO2 and form composite, under both synergies, can reinforcing material to the photocatalysis performance of organic pollution. The hetero-junctions that Graphene interface is formed cause between light induced electron and hole it is compound be improved, composite specific surface area Increase makes material be improved the adsorption capacity of organic pollution；Coating of the invention has good antibiotic property, coating system It is standby simple for process.
Specific embodiment
With reference to embodiment, the present invention is described further, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of preparation method of antibacterial aqueous polyurethane coating, comprises the following steps：
The preparation of graphene oxide：
1g graphite powders are put into 500mL round-bottomed flasks, and flask is put into ice-water bath, to addition in flask bottle The 50mL concentrated sulfuric acids, stir 5~10min；4g potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed in often The lower stirring 24h of temperature；Then container is put into ice-water bath, adds deionized water, keep ice-water bath 5min, hydrogen peroxide is dropwise added dropwise Produced to bubble-free；Finally filter, with 30% salt acid elution, then be washed with deionized water to neutrality, ultrasound must aoxidize stone after peeling off Black alkene；
Nano-TiO2Preparation：
12.5mL butyl titanates are added in 250mL there-necked flasks, 100mL absolute ethyl alcohols are then slowly dropped to metatitanic acid In butyl ester, the speed stirring 30min with 400r/min in 25 DEG C of waters bath with thermostatic control obtains uniform mixed solution；It is subsequently adding 1.5mL hydrochloric acid, then 20mL deionized waters are slowly added dropwise, continue stirring 2.5h and obtain butyl titanate solution, then by butyl titanate Solution is dried 12h in being put into 55 DEG C of vacuum drying chambers, in placing into Muffle furnace, and 4h is calcined at 500 DEG C obtains yellowish Color crystal；It is ground after finally light yellow crystal is mixed with absolute ethyl alcohol, obtains final product nano-TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, wherein Graphene and TiO2Mass ratio be 1: 2, in ptfe autoclave, and 6h is reacted under conditions of 180 DEG C, remove solvent after cooling, drying and grinding into powder, i.e., Obtain Graphene/TiO2Composite.
The preparation of aqueous polyurethane：
13.32g IPDIs, 15g cetomacrogol 1000s are stirred at 85 DEG C, tin dilaurate is added Dibutyl tin is incubated 2h as catalyst；After being cooled to 70 DEG C, the dimethylolpropionic acid that 2.7g is dissolved in acetone is added, backflow 2h；60 DEG C are cooled to, 9.75g hydroxyethyl methacrylates are added, 6h is incubated；Room temperature is cooled to, adds triethylamine to neutralize 10min, is added dropwise 95mL deionized waters and stirs 30min with 1500r/min；
The preparation of coating：
By Graphene/TiO2Composite and light trigger TPO are dissolved in acetone, the Graphene/TiO2Composite and light The weight ratio of initiator is 3:1, solvent is steamed using Rotary Evaporators, obtain Graphene/TiO2Composite and light-initiated Agent composition, in the aqueous polyurethane for preparing, normal temperature cure film forming obtains final product antibacterial aqueous polyurethane coating to ultrasonic disperse.
Anti-microbial property test：
Its bacteriostasis can be shown through AGP test with non-stripping property antibacterial finishing agent using stripping property, it is thin by observation The number of bacterium is judging the stripping property of its antibacterial finishing agent and whether there is biocidal property, the bacteriostasis rate=(bacterial population-sample sets of contrast groups Bacterial population)/contrast groups bacterial population.
With Escherichia coli and staphylococcus aureus as strain, the anti-microbial property of antibacterial aqueous polyurethane coating is determined.With 0.2ml bacteria suspensions are spread evenly across the culture medium after solidification for sterile working, and coating is uniform.Then it is placed in training of carrying disease germs test sample is treated The center of base flat board is supported, the size of inhibition zone is observed after culture dish finally is cultivated into 18h in 37 DEG C.Compared with blank sample, plus Obvious inhibition zone is formd around the sample for entering Graphene-TiO2 composites, shows that Graphene-TiO2 composites make water Property polyurethane coating has obvious anti-microbial property.The antibiotic rate of antibacterial aqueous polyurethane coating reaches more than 0.9.
Embodiment 2
A kind of preparation method of antibacterial aqueous polyurethane coating, comprises the following steps：
The preparation of graphene oxide：
1g graphite powders are put into 500mL round-bottomed flasks, and flask is put into ice-water bath, to adding 50mL in flask The concentrated sulfuric acid, stirs 5~10min；Potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed under normal temperature and is stirred Mix 24h；Then container is put into ice-water bath, adds deionized water, keep ice-water bath 5min, hydrogen peroxide is dropwise added dropwise to without gas Bubble is produced；Finally filter, with 30% salt acid elution, then be washed with deionized water to neutrality, ultrasound peel off after graphene oxide；
Nano-TiO2Preparation：
12.5mL butyl titanates are added in 250mL there-necked flasks, 100mL absolute ethyl alcohols are then slowly dropped to metatitanic acid In butyl ester, the speed stirring 30min with 400r/min in 25 DEG C of waters bath with thermostatic control obtains uniform mixed solution；It is subsequently adding 1.5mL hydrochloric acid, then 20mL deionized waters are slowly added dropwise, continue stirring 2.5h and obtain butyl titanate solution, then by butyl titanate Solution is dried 12h in being put into 55 DEG C of vacuum drying chambers, in placing into Muffle furnace, and 4h is calcined at 500 DEG C obtains yellowish Color crystal；It is ground after finally light yellow crystal is mixed with absolute ethyl alcohol, obtains final product nano-TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, wherein Graphene and TiO2Mass ratio be 1: 4, in ptfe autoclave, and 6h is reacted under conditions of 170 DEG C, remove solvent after cooling, drying and grinding into powder, i.e., Obtain Graphene/TiO2Composite.
The preparation of aqueous polyurethane：
13.32g IPDIs, 15g cetomacrogol 1000s are stirred at 80~90 DEG C, February is added Dilaurylate is incubated 1.5~2.5h as catalyst；After being cooled to 65~75 DEG C, 2.7g is dissolved in the dihydroxy first of acetone Base butyric acid is added, and flow back 1.5~2.5h；55~64 DEG C are cooled to, 9.75g hydroxyethyl methacrylates are added, 5~7h is incubated； Be cooled to room temperature, add in appropriate triethylamine and 10min, be added dropwise 95mL deionized waters with 1300~1700r/min stirrings 20~ 40min；
The preparation of coating：
By Graphene/TiO2Composite and light trigger are dissolved in acetone, the Graphene/TiO2Composite and light draw The weight ratio for sending out agent is 2:1, solvent is steamed using Rotary Evaporators, obtain Graphene/TiO2F composites and light trigger Mixture, in the aqueous polyurethane for preparing, normal temperature cure film forming obtains final product antibacterial aqueous polyurethane coating to ultrasonic disperse.
Embodiment 3
A kind of preparation method of antibacterial aqueous polyurethane coating, comprises the following steps：
The preparation of graphene oxide：
1g graphite powders are put into 500mL round-bottomed flasks, and flask is put into ice-water bath, to adding 50mL in flask The concentrated sulfuric acid, stirs 5~10min；Potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed under normal temperature and is stirred Mix 24h；Then container is put into ice-water bath, adds deionized water, keep ice-water bath 5min, hydrogen peroxide is dropwise added dropwise to without gas Bubble is produced；Finally filter, with 30% salt acid elution, then be washed with deionized water to neutrality, ultrasound peel off after graphene oxide；
Nano-TiO2Preparation：
12.5mL butyl titanates are added in 250mL there-necked flasks, 100mL absolute ethyl alcohols are then slowly dropped to metatitanic acid In butyl ester, the speed stirring 30min with 400r/min in 25 DEG C of waters bath with thermostatic control obtains uniform mixed solution；It is subsequently adding 1.5mL hydrochloric acid, then 20mL deionized waters are slowly added dropwise, continue stirring 2.5h and obtain butyl titanate solution, then by butyl titanate Solution is dried 12h in being put into 55 DEG C of vacuum drying chambers, in placing into Muffle furnace, and 4h is calcined at 500 DEG C obtains yellowish Color crystal；It is ground after finally light yellow crystal is mixed with absolute ethyl alcohol, obtains final product nano-TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, wherein Graphene and TiO2Mass ratio be 1: 6, in ptfe autoclave, and 6h is reacted under conditions of 160 DEG C, remove solvent after cooling, drying and grinding into powder, i.e., Obtain Graphene/TiO2Composite.
The preparation of aqueous polyurethane：
13.32g IPDIs, 15g cetomacrogol 1000s are stirred at 80~90 DEG C, February is added Dilaurylate is incubated 1.5~2.5h as catalyst；After being cooled to 65~75 DEG C, 2.7g is dissolved in the dihydroxy first of acetone Base butyric acid is added, and flow back 1.5~2.5h；55~64 DEG C are cooled to, 9.75g hydroxyethyl methacrylates are added, 5~7h is incubated； Be cooled to room temperature, add in appropriate triethylamine and 10min, be added dropwise 95mL deionized waters with 1300~1700r/min stirrings 20~ 40min；
The preparation of coating：
By Graphene/TiO2Composite and light trigger are dissolved in acetone, the Graphene/TiO2Composite and light draw The weight ratio for sending out agent is 4:1, solvent is steamed using Rotary Evaporators, obtain Graphene/TiO2Composite and light trigger Mixture, in the aqueous polyurethane for preparing, normal temperature cure film forming obtains final product antibacterial aqueous polyurethane coating to ultrasonic disperse.
Embodiment 4
A kind of preparation method of antibacterial aqueous polyurethane coating, comprises the following steps：
The preparation of graphene oxide：
1g graphite powders are put into 500mL round-bottomed flasks, and flask is put into ice-water bath, to adding 50mL in flask The concentrated sulfuric acid, stirs 5~10min；Potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed under normal temperature and is stirred Mix 24h；Then container is put into ice-water bath, adds deionized water, keep ice-water bath 5min, hydrogen peroxide is dropwise added dropwise to without gas Bubble is produced；Finally filter, with 30% salt acid elution, then be washed with deionized water to neutrality, ultrasound peel off after graphene oxide；
Nano-TiO2Preparation：
12.5mL butyl titanates are added in 250mL there-necked flasks, 100mL absolute ethyl alcohols are then slowly dropped to metatitanic acid In butyl ester, the speed stirring 30min with 400r/min in 25 DEG C of waters bath with thermostatic control obtains uniform mixed solution；It is subsequently adding 1.5mL hydrochloric acid, then 20mL deionized waters are slowly added dropwise, continue stirring 2.5h and obtain butyl titanate solution, then by butyl titanate Solution is dried 12h in being put into 55 DEG C of vacuum drying chambers, in placing into Muffle furnace, and 4h is calcined at 500 DEG C obtains yellowish Color crystal；It is ground after finally light yellow crystal is mixed with absolute ethyl alcohol, obtains final product nano-TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, wherein Graphene and TiO2Mass ratio be 1: 10, in ptfe autoclave, and 2h is reacted under conditions of 180 DEG C, solvent is removed after cooling, drying and grinding into powder, Obtain final product Graphene/TiO2Composite.
The preparation of aqueous polyurethane：
13.32g IPDIs, 15g cetomacrogol 1000s are stirred at 80~90 DEG C, February is added Dilaurylate is incubated 1.5~2.5h as catalyst；After being cooled to 65~75 DEG C, 2.7g is dissolved in the dihydroxy first of acetone Base butyric acid is added, and flow back 1.5~2.5h；55~64 DEG C are cooled to, 9.75g hydroxyethyl methacrylates are added, 5~7h is incubated； Be cooled to room temperature, add in appropriate triethylamine and 10min, be added dropwise 95mL deionized waters with 1300~1700r/min stirrings 20~ 40min；
The preparation of coating：
By Graphene/TiO2Composite and light trigger are dissolved in acetone, the Graphene/TiO2Composite and light draw The weight ratio for sending out agent is 3.5:1, solvent is steamed using Rotary Evaporators, obtain Graphene/TiO2F composites and light-initiated Agent composition, in the aqueous polyurethane for preparing, normal temperature cure film forming obtains final product antibacterial aqueous polyurethane coating to ultrasonic disperse.
Embodiment 5
A kind of preparation method of antibacterial aqueous polyurethane coating, comprises the following steps：
The preparation of graphene oxide：
1g graphite powders are put into 500mL round-bottomed flasks, and flask is put into ice-water bath, to adding 50mL in flask The concentrated sulfuric acid, stirs 5~10min；Potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed under normal temperature and is stirred Mix 24h；Then container is put into ice-water bath, adds deionized water, keep ice-water bath 5min, hydrogen peroxide is dropwise added dropwise to without gas Bubble is produced；Finally filter, with 30% salt acid elution, then be washed with deionized water to neutrality, ultrasound peel off after graphene oxide；
Nano-TiO2Preparation：
12.5mL butyl titanates are added in 250mL there-necked flasks, 100mL absolute ethyl alcohols are then slowly dropped to metatitanic acid In butyl ester, the speed stirring 30min with 400r/min in 25 DEG C of waters bath with thermostatic control obtains uniform mixed solution；It is subsequently adding 1.5mL hydrochloric acid, then 20mL deionized waters are slowly added dropwise, continue stirring 2.5h and obtain butyl titanate solution, then by butyl titanate Solution is dried 12h in being put into 55 DEG C of vacuum drying chambers, in placing into Muffle furnace, and 4h is calcined at 500 DEG C obtains yellowish Color crystal；It is ground after finally light yellow crystal is mixed with absolute ethyl alcohol, obtains final product nano-TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in sewage ethanol, nano-TiO is added2, wherein Graphene and TiO2Mass ratio be 1: 5, in ptfe autoclave, and 6h is reacted under conditions of 170 DEG C, solvent is removed after cooling, freeze-drying grinds to form Powder, obtains final product Graphene/TiO2Composite.
The preparation of aqueous polyurethane：
13.32g IPDIs, 15g cetomacrogol 1000s are stirred at 80~90 DEG C, February is added Dilaurylate is incubated 1.5~2.5h as catalyst；After being cooled to 65~75 DEG C, 2.7g is dissolved in the dihydroxy first of acetone Base butyric acid is added, and flow back 1.5~2.5h；55~64 DEG C are cooled to, 9.75g hydroxyethyl methacrylates are added, 5~7h is incubated； Be cooled to room temperature, add in appropriate triethylamine and 10min, be added dropwise 95mL deionized waters with 1300~1700r/min stirrings 20~ 40min；
The preparation of coating：
By Graphene/TiO2Composite and light trigger are dissolved in acetone, the Graphene/TiO2Composite and light draw The weight ratio for sending out agent is 2.5:1, solvent is steamed using Rotary Evaporators, obtain Graphene/TiO2F composites and light-initiated Agent composition, in the aqueous polyurethane for preparing, normal temperature cure film forming obtains final product antibacterial aqueous polyurethane coating to ultrasonic disperse.
Embodiment 6
A kind of preparation method of antibacterial aqueous polyurethane coating, comprises the following steps：
The preparation of graphene oxide：
1g graphite powders are put into 500mL round-bottomed flasks, and flask is put into ice-water bath, to adding 50mL in flask The concentrated sulfuric acid, stirs 5~10min；Potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed under normal temperature and is stirred Mix 24h；Then container is put into ice-water bath, adds deionized water, keep ice-water bath 5min, hydrogen peroxide is dropwise added dropwise to without gas Bubble is produced；Finally filter, with 30% salt acid elution, then be washed with deionized water to neutrality, ultrasound peel off after graphene oxide；
Nano-TiO2Preparation：
12.5mL butyl titanates are added in 250mL there-necked flasks, 100mL absolute ethyl alcohols are then slowly dropped to metatitanic acid In butyl ester, the speed stirring 30min with 400r/min in 25 DEG C of waters bath with thermostatic control obtains uniform mixed solution；It is subsequently adding 1.5mL hydrochloric acid, then 20mL deionized waters are slowly added dropwise, continue stirring 2.5h and obtain butyl titanate solution, then by butyl titanate Solution is dried 12h in being put into 55 DEG C of vacuum drying chambers, in placing into Muffle furnace, and 4h is calcined at 500 DEG C obtains yellowish Color crystal；It is ground after finally light yellow crystal is mixed with absolute ethyl alcohol, obtains final product nano-TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, wherein Graphene and TiO2Mass ratio be 1: 7, in ptfe autoclave, and 6h is reacted under conditions of 160 DEG C, remove solvent after cooling, drying and grinding into powder, i.e., Obtain Graphene/TiO2Composite.
The preparation of aqueous polyurethane：
13.32g IPDIs, 15g cetomacrogol 1000s are stirred at 80~90 DEG C, February is added Dilaurylate is incubated 1.5~2.5h as catalyst；After being cooled to 65~75 DEG C, 2.7g is dissolved in the dihydroxy first of acetone Base butyric acid is added, and flow back 1.5~2.5h；55~64 DEG C are cooled to, 9.75g hydroxyethyl methacrylates are added, 5~7h is incubated； Be cooled to room temperature, add in appropriate triethylamine and 10min, be added dropwise 95mL deionized waters with 1300~1700r/min stirrings 20~ 40min；
The preparation of coating：
By Graphene/TiO2Composite and light trigger are dissolved in acetone, the Graphene/TiO2Composite and light draw The weight ratio for sending out agent is 3:1, solvent is steamed using Rotary Evaporators, obtain Graphene/TiO2Composite and light trigger Mixture, in the aqueous polyurethane for preparing, normal temperature cure film forming obtains final product antibacterial aqueous polyurethane coating to ultrasonic disperse.
It should be noted that above example is only used to illustrative and not limiting technical scheme, although with reference to upper Embodiment is stated to be described in detail the present invention, it will be understood by those within the art that：Still can be to the present invention Modify or equivalent, any modification or partial replacement without departing from the spirit and scope of the present invention, it all should contain Cover in scope of the presently claimed invention.

Claims (5)

1. a kind of preparation method of antibacterial aqueous polyurethane coating, it is characterised in that comprise the following steps：
The preparation of aqueous polyurethane：
IPDI, polyethylene glycol are stirred at 80~90 DEG C, dibutyl tin laurate conduct is added Catalyst, is incubated 1.5~2.5h；After being cooled to 65~75 DEG C, the dimethylolpropionic acid that will be dissolved in acetone is added, and backflow 1.5~ 2.5h；55~64 DEG C are cooled to, hydroxyethyl methacrylate is added, 5~7h is incubated；Room temperature is cooled to, adds triethylamine to neutralize 10min, is added dropwise deionized water and stirs 20~40min with 1300~1700r/min；
The preparation of coating：
By Graphene/TiO2Composite and light trigger are dissolved in acetone, are steamed solvent using Rotary Evaporators, obtain graphite Alkene/TiO2F composites and photoinitiator mixtures, ultrasonic disperse in the aqueous polyurethane for preparing, normal temperature cure film forming, Obtain final product antibacterial aqueous polyurethane coating.
2. a kind of preparation method of antibacterial aqueous polyurethane coating according to claim 1, it is characterised in that the graphite Alkene/TiO2The mass ratio of composite and light trigger is 2~4:1.
3. a kind of preparation method of antibacterial aqueous polyurethane coating according to claim 1, it is characterised in that the graphite Alkene/TiO2The preparation method of composite is as follows：
The preparation of graphene oxide：
Graphite powder is put into container, and container is put into ice-water bath, to adding the concentrated sulfuric acid in container, stirring 5~ 10min；Potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed under normal temperature and stirs 21~26h；Then Container is put into ice-water bath, deionized water is added, 4~7min of ice-water bath is kept, hydrogen peroxide to bubble-free is dropwise added dropwise and is produced； Finally filter, use salt acid elution, then be washed with deionized water to neutrality, ultrasound obtains graphene oxide after peeling off；
Nano-TiO2Preparation：
Absolute ethyl alcohol is slowly dropped in butyl titanate, stirring obtains uniform mixed solution in water bath with thermostatic control；Then plus Enter hydrochloric acid, then be slowly added dropwise deionized water, continue stirring and obtain butyl titanate solution, then done butyl titanate solution Dry, high-temperature calcination obtains light yellow crystal；It is ground after finally light yellow crystal is mixed with absolute ethyl alcohol, obtains final product nanometer TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, reacted in ptfe autoclave, it is cold But solvent is removed afterwards, and drying and grinding obtains final product Graphene/TiO into powder2Composite.
4. a kind of preparation method of antibacterial aqueous polyurethane coating according to claim 1, it is characterised in that the graphite Alkene/TiO2The preparation method of composite is as follows：
The preparation of graphene oxide：
Graphite powder is put into flask, and flask is put into ice-water bath, to adding the concentrated sulfuric acid in flask, stirring 5~ 10min；Potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed under normal temperature and stirs 21~26h；Then Container is put into ice-water bath, deionized water is added, 4~7min of ice-water bath is kept, hydrogen peroxide to bubble-free is dropwise added dropwise and is produced； Finally filter, with 30% salt acid elution, then be washed with deionized water to neutrality, ultrasound peel off after graphene oxide；
Nano-TiO2Preparation：
Absolute ethyl alcohol is slowly dropped in butyl titanate, 25~35min is stirred with the speed of 400r/min in water bath with thermostatic control Obtain uniform mixed solution；Hydrochloric acid is subsequently adding, then is slowly added dropwise deionized water, continued 2~3h of stirring and obtain butyl titanate , then be put into butyl titanate solution in vacuum drying chamber and be dried 10~15h by solution, in placing into Muffle furnace, and 450 3~5h is calcined at~600 DEG C and obtains light yellow crystal；It is ground after finally light yellow crystal is mixed with absolute ethyl alcohol, i.e., Obtain nano-TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, in ptfe autoclave, and 160~ 2~12h is reacted under conditions of 180 DEG C, solvent is removed after cooling, drying and grinding obtains final product Graphene/TiO into powder2Composite.
5. the preparation method of a kind of antibacterial aqueous polyurethane coating according to claim 3 or 4, it is characterised in that described Graphene oxide and nano-TiO2Weight ratio be 1:1~10.
CN201710272694.8A 2017-04-24 2017-04-24 A kind of preparation method of antibacterial aqueous polyurethane coating Pending CN106928763A (en)

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CN111100541A (en) * 2019-12-23 2020-05-05 王晓军 Waterborne polyurethane coating and preparation method thereof
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Application publication date: 20170707