CN116218278A - Modified luminous nano zinc oxide for photo-curing thick coating paint and preparation and application thereof - Google Patents

Modified luminous nano zinc oxide for photo-curing thick coating paint and preparation and application thereof Download PDF

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CN116218278A
CN116218278A CN202310145997.9A CN202310145997A CN116218278A CN 116218278 A CN116218278 A CN 116218278A CN 202310145997 A CN202310145997 A CN 202310145997A CN 116218278 A CN116218278 A CN 116218278A
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zinc oxide
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nano zinc
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叶代勇
默圆
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South China University of Technology SCUT
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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • 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
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/54—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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Abstract

The invention belongs to the technical field of paint, and discloses modified luminous nano zinc oxide for a photo-curing thick-coating paint, and preparation and application thereof. The preparation method of the modified luminescent nano zinc oxide comprises the following steps: in an organic solvent, reacting nano zinc oxide with diisocyanate under the action of a catalyst; then adding hydroxy acrylic ester and a catalyst, reacting, and carrying out subsequent treatment to obtain the modified luminescent nano zinc oxide. The modified luminescent nano zinc oxide is used for preparing the photo-curing thick coating. The modified luminescent nano zinc oxide solves the problems of weak ultraviolet light penetrability and poor light curing depth caused by absorption and reflection of substances in a curing system. The dispersibility of the modified zinc oxide in the photo-curing resin coating is increased, and meanwhile, the luminous intensity is increased, so that the light intensity of the deep layer of the coating is enhanced, and the photo-curing depth is increased. The invention breaks through the limit of the traditional photo-curing coating with the thickness of only a few micrometers, and enhances the performance of the coating film while improving the photo-curing depth.

Description

Modified luminous nano zinc oxide for photo-curing thick coating paint and preparation and application thereof
Technical Field
The invention belongs to the technical field of paint, and particularly relates to modified luminescent nano zinc oxide, a preparation method thereof and an application thereof in photo-curing thick coating paint.
Background
The ultraviolet curing coating has the advantages of high efficiency, energy conservation, low or no VOC and the like. Fillers and pigments are one of the indispensable components in the paint, and can improve physical and chemical properties such as hiding property, chemical resistance, glossiness, mechanical strength, and the like of the paint, and also can provide effects of decoration, cost reduction, and the like. However, the filler and pigment are added to absorb and reflect light, so that the light is difficult to reach the inside of the coating, and the thick coating is difficult to cure.
In order to obtain a higher curing depth, many methods have been proposed. It is a common approach to introduce a longer wavelength light source with greater penetration. Chinese patent CN111925767a discloses a visible light adhesive, which can be cured to a thickness of 2mm by irradiation for 5s at a wavelength of 470 nm. Document (A.H.Bonardi, F.Dumur, T.M.Grant, et al high performance near-infra (NIR) photoinitiating systems operating under low light intensity and in the presence of oxygenn [ J)]Macromolecules,2018, 51 (4): 1314-1324) discloses IR-140/4-dppba/Ar 2 I + PF 6 - For a three-component initiation system, for a formula with 75% filler, a sample with a height of 1cm can be obtained by irradiating for 30s under a 785nm laser diode, and ultraviolet and blue polymerization can only reach 2-4 mm. Chinese patent CN111590877a discloses a method for preparing near infrared photopolymerization ink, wherein the line diameter is increased from 0.41mm to 4mm, and the conversion rate is about 50%. The conversion rate of the formula with color paste of different colors is about 40 percent. This demonstrates that the high penetration of near infrared light can achieve curing of thick and colored samples. The high penetration of visible light and infrared light greatly improves the curing depth of the sample, but for paint production, ultraviolet light also occupies the mainstream position for a long time, and the improvement of the curing depth of the light under the premise of not changing a light source is still a challenge.
Under the condition of not changing the ultraviolet light source, the most common method is a composite curing technology, chinese patent CN112011301A discloses a preparation method of an ultraviolet light-heat dual-curing adhesive, and a photoinitiator is added into epoxy resin at the same timeAnd the mixture is irradiated by the thermal initiator for 5 seconds to quickly cure, and then deep curing can be realized by thermal post-curing. Chinese patent application CN112062964a discloses a method for preparing UV/moisture dual-curing acrylate polysiloxane, wherein the advantages of UV-cured acryloyloxy group and moisture-cured siloxy group are complementary, and the obtained product has excellent flexibility and can realize rapid and complete curing. The curing depth is improved to a certain extent by the methods, however, the method of thermal and moisture post-curing is long in time consumption and greatly affected by environment, and the EB curing equipment also has the problems of high price, strict operation management and the like. There are also improvements to the composition of the coating, monomer (Farmod Mirshahi, saeed Bastani, morteza Ganjaee Sari.Smdyning the effect of hyperbranched polymer modification on the kinetics of curing reactions and physical/mechanical properties of UV-curable coatings [ J ]]Progress in Organic Coatings,2016, 90: 187-199), filler (Huang Rongji, jiang Qiangguo, wu Haidong, et al Fabry of complex shaped ceramic parts with surface-oxaidized Si3N4 powder via digital light processing based stereolithography method [ J ]]Ceramics International,2019, 45 (4): 5158-5162.), combined photoinitiators (Mariem Bouzrati-Zerell, maximilan Maier, christoph P Fik, et al A low migration phosphine to overcome the oxygen inhibition in new high performance photoinitiating systems for photocurable dental type resins [ J)]Polymer International,2016, 66 (4): 504-511) and photobleaching photoinitiators (Liao Wen, xu Can, wu Xiang, et al Photoleachable cinnamoyl dyes for radical visible photoinitiators [ J ]]Dyes and Pigments,2020, 178, 108350) and the like also have an increasing effect on the depth of photocuring, but the range of application of improvements to single monomers, fillers is narrower, and the photobleaching initiator takes a longer time to reach complete photobleaching and is accompanied by residual problems. Literature (Masoume Kaviani Darani, saeed Bastani, mehdihahahari, et al Down-conversion particles as intemal UV-source assist in UV-fastening systems: physical and mechanical properties of UV-fastening micro-composites [ J)]Progress in Organic Coatings,2018, 122: 263-269.) provides an advantageBy using the idea of down-converting luminescent particles, naYF is adopted 4 ：Yb 3 + /Tm 3 + In combination with a photoinitiator benzophenone and an amine, naYF 4 ：Yb 3 + /Tm 3 + The particles play a role of secondary light source, and the light source is introduced into the system, so that the conversion rate is increased. However, only the improvement in conversion is mentioned and does not relate to a specific depth of cure, and NaYF is utilized 4 ：Yb 3 + /Tm 3 + The cost is also high as down-converting luminescent particles.
The invention provides modified luminous nano zinc oxide which is used as an endogenous luminescent material and an inorganic photoinitiator in a coating and is used for a thick coating ultraviolet light curing coating to solve the problems of weak ultraviolet light penetrating power and poor light curing depth caused by absorption and reflection of substances in a curing system.
Disclosure of Invention
The invention aims to provide modified luminescent nano zinc oxide and preparation and application thereof in photo-curing thick coating paint, aiming at the defect of poor curing depth of the existing ultraviolet curing product.
The invention prepares nano zinc oxide by a sol method, and then uses hydroxy acrylic ester for modification. The dispersion performance and luminous intensity of the prepared modified nano zinc oxide particles are increased, and the emitted light is used for improving the light curing depth of the thick coating.
The invention aims at realizing the following technical scheme:
the preparation method of the modified luminescent nano zinc oxide for the photo-cured thick coating paint comprises the following steps:
in an organic solvent, reacting nano zinc oxide with diisocyanate under the action of a catalyst; then adding hydroxy acrylic ester and a catalyst, reacting for 3-7 hours at 50-80 ℃, and carrying out subsequent treatment to obtain the modified luminescent nano zinc oxide.
The organic solvent is more than one of toluene, dimethylbenzene, benzene, ethyl acetate and butyl acetate;
the hydroxy acrylic ester is at least one of hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl acrylate and hydroxy propyl methacrylate.
The molar weight ratio of the nano zinc oxide to the diisocyanate is 1:0.3-3;
the molar weight ratio of the hydroxy acrylic ester to the diisocyanate is 1:1-3;
the diisocyanate is at least one of 2, 4-toluene diisocyanate, isophorone diisocyanate and 1, 6-hexamethylene diisocyanate.
The catalyst is at least one of dibutyl tin dilaurate, stannous isooctanoate, zinc isooctanoate and bismuth isooctanoate.
After diisocyanate is added, the reaction temperature is 40-70 ℃ and the reaction time is 3-5 h.
After the hydroxy acrylic ester is added, the reaction temperature is 50-80 ℃ and the reaction time is 3-7 h.
The catalyst is added into the hydroxy acrylic ester and the catalyst, and the dosage of the catalyst is 0.1 to 1 percent of the diisocyanate.
In the reaction of nano zinc oxide and diisocyanate under the action of a catalyst, the dosage of the catalyst is 0.1-1% of that of the diisocyanate.
The subsequent treatment refers to centrifugation, washing and drying.
The centrifugal condition is that the rotating speed is 8000-10000 r/min for 5-10 min; the washing is isopropanol and acetone washing; the drying refers to drying for 12-24 hours at 55-65 ℃.
The nano zinc oxide is prepared by the following method:
dripping the ethanol solution of sodium hydroxide into the ethanol solution of zinc acetate dihydrate, and stirring and reacting at 0-5 ℃.
The concentration of the ethanol solution of zinc acetate dihydrate is 0.001-0.1M;
the mol ratio of the zinc acetate dihydrate to the sodium hydroxide is 1:1-3;
the stirring speed is 1000-2600 r/min; the dropping speed of the ethanol solution of sodium hydroxide is 15-80 drops/min.
In the preparation of nano zinc oxide, after the reaction is finished, the nano zinc oxide is centrifuged, washed and dried. In the preparation of nano zinc oxide, the centrifugal condition is that the rotating speed is 8000-12000 r/min and the centrifugal is 10-30 min; the washing is carried out by using absolute ethyl alcohol; the drying condition is that the drying is carried out for 12-30 hours at 35-60 ℃. The drying is vacuum drying.
The mass volume ratio of the sodium hydroxide to the ethanol in the ethanol solution of the sodium hydroxide is (0.1-0.5) g to 50mL.
After the ethanol solution of sodium hydroxide is dripped, the reaction is continued for 20 to 60 minutes.
The ethanol solution of sodium hydroxide is prepared by dispersing sodium hydroxide in absolute ethanol in 20-40 min.
The ethanol solution of zinc acetate dihydrate disperses zinc acetate dihydrate in absolute ethanol in 20-40 min.
The modified luminescent nano zinc oxide is used for preparing the photo-curing thick coating.
A preparation method of a photo-curing thick coating comprises the following steps:
s1: uniformly dispersing the modified nano zinc oxide, the photoinitiator and the monomer in an organic solvent to obtain a mixed solution; or adding polyurethane acrylic ester into the mixed solution, and uniformly mixing to obtain the photo-curing thick coating;
s2: photo-curing the mixed solution to obtain a coating; or coating the photo-curing thick coating, standing, drying and photo-curing to obtain a photo-curing film;
the monomer is at least one of 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate and trimethylolpropane triacrylate.
The organic solvent is ethanol.
The dosage of the modified nano zinc oxide is 0.2-1% of the total mass of the organic solvent (ethanol) and the monomer;
the photoinitiator is at least one of phenyl bis (2, 4, 6-trimethylphenyl acyl) phosphine oxide (819), 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide (TPO) and photoinitiator 4265.
The dosage of the photoinitiator is 0.02-0.1% of the total mass of the organic solvent and the monomer.
The mass ratio of the organic solvent to the monomer is 1:4.
The photo-curing is ultraviolet curing, and the irradiation time is 30-120 s.
The time for placing is 25-35 min, the temperature for drying is 55-65 ℃ and the time for drying is 50-65 min.
The photo-curing power is 0.5-2 kW.
The dispersion granularity of the modified zinc oxide in the resin is 77-550 nm, and the modified grafting rate is 10-50%.
The modified luminescent nano zinc oxide provided by the invention is used as an endogenous luminescent inorganic photoinitiator in a coating, and is used for solving the problems of weak ultraviolet light penetrability and poor light curing depth caused by absorption and reflection of substances in a curing system. The dispersibility of the modified zinc oxide in the photo-curing resin coating is increased, and meanwhile, the luminous intensity of the modified zinc oxide is increased, so that the light intensity of the deep layer of the coating is enhanced, the photo-curing depth is increased, and the modified zinc oxide can be used for curing thicker photo-curing coating. The maximum curing depth of the photo-curing coating can reach 18.6mm, and the depth of the unmodified photo-curing coating containing zinc oxide is 4.6mm. The invention breaks through the limit of the traditional photo-curing coating with the thickness of only a few micrometers, has simple and convenient method and easy implementation, and can enhance the performance of the coating film while improving the photo-curing depth.
The invention has the following advantages and beneficial effects:
(1) The method for preparing the modified nano zinc oxide is simple, and can effectively improve the luminous performance and the dispersion performance of the zinc oxide, thereby enhancing the illumination intensity of deep layers and increasing the photo-curing depth.
(2) According to the preparation method, the preparation conditions of the modified zinc oxide with the optimal curing depth are obtained by changing the conditions of the modified zinc oxide.
(3) The modified nano zinc oxide obtained by the invention has better dispersion performance in a paint film.
Drawings
FIG. 1 shows photoluminescence spectra of the nano zinc oxide obtained in example 1 and the modified zinc oxides prepared in examples 1 to 5;
FIG. 2 is a scanning electron micrograph of the paint film prepared in comparative example 1 and the paint film prepared in example 7.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
The main raw material sources involved in the following examples are as follows:
the phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (819): basf limited, technical grade; the 1, 6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), trimethylol propane triacrylate (TMPTA), mono-functional urethane acrylates, di-functional urethane acrylates, tri-functional urethane acrylates, tetra-functional urethane acrylates: a long-emerging chemical material (pearl sea) limited, technical grade; the sodium hydroxide: guangzhou chemical reagent plant, analytical grade; the zinc acetate dihydrate: the Tianjin metallocene chemical reagent plant, analytically pure; the absolute ethyl alcohol: chengdu Colon chemical Co., ltd., analytically pure; dibutyl tin dilaurate (DBTDL): the Tianjin metallocene chemical reagent plant, analytically pure; the toluene: chengdu Colon chemical Co., ltd., analytically pure; the isopropyl alcohol: the national drug group chemical reagent company, inc., analytical purity; the acetone: guangzhou chemical reagent plant, analytical grade; the hydroxyethyl methacrylate (HEMA): guangzhou super cloud chemical industry Co., ltd.
Example 1
(1) 1.1g Zn (CH) 3 COO) 2 ·2H 2 Adding O into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of zinc acetate; adding 0.4g of NaOH into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of sodium hydroxide; then, the ethanol solution of sodium hydroxide is dripped into the ethanol solution of zinc acetate at the speed of 40 drops/min, the reaction is carried out at the temperature of 0 ℃ under the stirring speed of 2200r/min, and the reaction is continued for 30min after the dripping is finished. Centrifuging the product at 12000r/min for 15min after the reactionWashing with absolute ethyl alcohol for three times, and finally drying at 60 ℃ for 24 hours to obtain nano zinc oxide powder.
(2) 1.0g of the dried ZnO NPs powder was added to 50.0g of anhydrous toluene and ultrasonically dispersed for 30min, followed by transfer into a reaction vessel; 0.7g of TDI and DBTDL (0.1 wt% TDI) were added to 5.0g of dry toluene, and added to the reaction vessel after mixing well; stirred at 55℃for 5h, then 0.5g HEMA and DBTDL (0.1 wt% TDI) were added and reacted at 75℃for 3h. After the reaction was completed, the mixture was centrifuged at 8000rpm for 5 minutes, and washed 3 times with isopropyl alcohol and acetone, respectively, and the solid was dried at 60℃for 24 hours in a vacuum oven to obtain a modified zinc oxide powder sample.
Example 2
(1) 1.1g Zn (CH) 3 COO) 2 .2H 2 Adding O into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain ethanol solution of zinc acetate; adding 0.4g of NaOH into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of sodium hydroxide; then dripping the ethanol solution of sodium hydroxide into the ethanol solution of zinc acetate at the speed of 40 drops/min, and reacting at the temperature of 0 ℃ under the stirring speed of 2200 r/min; after the dripping is finished, continuing to react for 30min; after the reaction is finished, centrifugally separating the product at the speed of 12000r/min for 15min, and washing the product with absolute ethyl alcohol for three times; finally, drying for 24 hours at 60 ℃ to obtain the nano zinc oxide powder.
(2) 1.0g of the dried ZnO NPs powder was added to 50.0g of anhydrous toluene and ultrasonically dispersed for 30min, followed by transfer into a reaction vessel; 2.1g of TDI and DBTDL (0.1 wt% TDI) were added to 5.0g of dry toluene, mixed well and added to the reaction vessel; stirring at 55deg.C for 5 hr; 3.2g HEMA and DBTDL (0.1 wt% TDI) were then added and reacted at 75℃for 3h; after the reaction was completed, the mixture was centrifuged at 8000rpm for 5 minutes, and washed 3 times with isopropyl alcohol and acetone, respectively, and the solid was dried at 60℃for 24 hours in a vacuum oven to obtain a modified zinc oxide powder sample.
Example 3
(1) 1.1g Zn (CH) 3 COO) 2 .2H 2 Adding O into 50m1 ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of zinc acetate; adding 0.4g NaOH into 50m1 ethanol, and performing ultrasonic dispersion for 30min to obtain hydrogenEthanol solution of sodium oxide; then, the ethanol solution of sodium hydroxide was added dropwise to the ethanol solution of zinc acetate at a rate of 40 drops/min, and the mixture was reacted at a stirring rate of 2200r/min and at 0 ℃. After the completion of the dropwise addition, the reaction was continued for 30 minutes. After the reaction was completed, the product was centrifuged at 12000r/min for 15min and washed three times with absolute ethanol. Finally, drying for 24 hours at 60 ℃ to obtain the nano zinc oxide powder.
(2) 1.0g of the dried ZnO NPs powder was added to 50.0g of anhydrous toluene and dispersed ultrasonically for 30min, followed by transfer into a reaction vessel. 6.4g of TDI and DBTDL (0.1 wt% TDI) were added to 5.0g of dry toluene, mixed well and added to the reaction vessel. Stirred at 55℃for 5h. 7.2g HEMA and DBTDL (0.1 wt% TDI) were then added and reacted at 75℃for 3h. After the reaction was completed, the mixture was centrifuged at 8000rpm for 5 minutes, and washed 3 times with isopropyl alcohol and acetone, respectively, and the solid was dried at 60℃for 24 hours in a vacuum oven to obtain a modified zinc oxide powder sample.
Example 4
(1) 1.1g Zn (CH) 3 COO) 2 .2H 2 Adding O into 50m1 ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of zinc acetate; adding 0.4g of NaOH into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of sodium hydroxide; then, the ethanol solution of sodium hydroxide was added dropwise to the ethanol solution of zinc acetate at a rate of 40 drops/min, and the mixture was reacted at a stirring rate of 2200r/min and at 0 ℃. After the completion of the dropwise addition, the reaction was continued for 30 minutes. After the reaction was completed, the product was centrifuged at 12000r/min for 15min and washed three times with absolute ethanol. Finally, drying for 24 hours at 60 ℃ to obtain the nano zinc oxide powder.
(2) 1.0g of the dried ZnO NPs powder was added to 50.0g of anhydrous toluene and dispersed ultrasonically for 30min, followed by transfer into a reaction vessel. 6.4g of TDI and DBTDL (0.1 wt% TDI) were added to 5.0g of dry toluene, mixed well and added to the reaction vessel. Stirred at 55℃for 5h. 9.6g HEMA and DBTDL (0.1 wt% TDI) were then added and reacted at 75℃for 3h. After the reaction was completed, the mixture was centrifuged at 8000rpm for 5 minutes, and washed 3 times with isopropyl alcohol and acetone, respectively, and the solid was dried at 60℃for 24 hours in a vacuum oven to obtain a modified zinc oxide powder sample.
Example 5
(1) 1.1g Zn (CH) 3 COO) 2 .2H 2 Adding O into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of zinc acetate; adding 0.4g of NaOH into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of sodium hydroxide; then, the ethanol solution of sodium hydroxide was added dropwise to the ethanol solution of zinc acetate at a rate of 40 drops/min, and the mixture was reacted at a stirring rate of 2200r/min and at 0 ℃. After the completion of the dropwise addition, the reaction was continued for 30 minutes. After the reaction was completed, the product was centrifuged at 12000r/min for 15min and washed three times with absolute ethanol. Finally, drying for 24 hours at 60 ℃ to obtain the nano zinc oxide powder.
(2) 1.0g of the dried ZnO NPs powder was added to 50.0g of anhydrous toluene and dispersed ultrasonically for 30min, followed by transfer into a reaction vessel. 6.4g of TDI and DBTDL (0.1 wt% TDI) were added to 5.0g of dry toluene, mixed well and added to the reaction vessel. Stirred at 55℃for 5h. 12.0g HEMA and DBTDL (0.1 wt% TDI) were then added and reacted at 75℃for 3h. After the reaction was completed, the mixture was centrifuged at 8000rpm for 5 minutes, and washed 3 times with isopropyl alcohol and acetone, respectively, and the solid was dried at 60℃for 24 hours in a vacuum oven to obtain a modified zinc oxide powder sample.
Example 6
(1) 1.1g Zn (CH) 3 COO) 2 .2H 2 Adding O into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of zinc acetate; adding 0.4g of NaOH into 50m1 of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of sodium hydroxide; then, the ethanol solution of sodium hydroxide was added dropwise to the ethanol solution of zinc acetate at a rate of 40 drops/min, and the mixture was reacted at a stirring rate of 2200r/min and at 0 ℃. After the completion of the dropwise addition, the reaction was continued for 30 minutes. After the reaction was completed, the product was centrifuged at 12000r/min for 15min and washed three times with absolute ethanol. Finally, drying for 24 hours at 60 ℃ to obtain the nano zinc oxide powder.
(2) 1.0g of the dried ZnO NPs powder was added to 50.0g of anhydrous toluene and dispersed ultrasonically for 30min, followed by transfer into a reaction vessel. 6.4g of TDI and DBTDL (0.1 wt% TDI) were added to 5.0g of dry toluene, mixed well and added to the reaction vessel. Stirred at 55℃for 5h. 12.0g HEMA and DBTDL (0.1 wt% TDI) were then added to the reaction vessel and reacted at 75℃for 3h. After the reaction was completed, the mixture was centrifuged at 8000rpm for 5 minutes, and washed 3 times with isopropyl alcohol and acetone, respectively, and the solid was dried at 60℃for 24 hours in a vacuum oven to obtain a modified zinc oxide powder sample.
(3) 0.01g of modified nano zinc oxide powder is added into 1g of absolute ethyl alcohol and dispersed for 1h by ultrasonic. Then, 0.0030g of photoinitiator 819 and 4g of HDDA were added thereto, and the mixture was subjected to ultrasonic dispersion for 30 minutes. The resulting mixture was poured into 6mm plastic tubes and cured under a 1kW mercury lamp for 45s.
Example 7
(1) 1.1g Zn (CH) 3 COO) 2 .2H 2 Adding O into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of zinc acetate; adding 0.4g of NaOH into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of sodium hydroxide; then, the ethanol solution of sodium hydroxide was added dropwise to the ethanol solution of zinc acetate at a rate of 40 drops/min, and the mixture was reacted at a stirring rate of 2200r/min and at 0 ℃. After the completion of the dropwise addition, the reaction was continued for 30 minutes. After the reaction was completed, the product was centrifuged at 12000r/min for 15min and washed three times with absolute ethanol. Finally, drying for 24 hours at 60 ℃ to obtain the nano zinc oxide powder.
(2) 1.0g of the dried ZnO NPs powder was added to 50.0g of anhydrous toluene and dispersed ultrasonically for 30min, followed by transfer into a reaction vessel. 6.4g of TDI and DBTDL (0.1 wt% TDI) were added to 5.0g of dry toluene, mixed well and added to the reaction vessel. Stirred at 55℃for 5h. 12.0g HEMA and DBTDL (0.1 wt% TDI) were then added to the reaction vessel and reacted at 75℃for 3h. After the reaction was completed, the mixture was centrifuged at 8000rpm for 5 minutes, and washed 3 times with isopropyl alcohol and acetone, respectively, and the solid was dried at 60℃for 24 hours in a vacuum oven to obtain a modified zinc oxide powder sample.
(3) 0.02g of modified nano zinc oxide powder is added into 1g of absolute ethyl alcohol, and the mixture is dispersed for 1h by ultrasonic. Adding 0.0030g of photoinitiator 819 and 4g of HDDA, and performing ultrasonic dispersion for 30min to obtain a mixture; the resulting mixture was poured into 6mm plastic tubes and cured under a 1kW mercury lamp for 45s.
Alternatively, 0.04g of the modified nano zinc oxide powder was added to 1g of ethanol and stirred for 1h. Then, 0.0030g of photoinitiator 819 and 4g of HDDA were added thereto, and the mixture was subjected to ultrasonic dispersion for 30 minutes. Then 5g of polyurethane acrylate is added and stirred uniformly. After that, the film was coated (thickness: 20 to 30 μm) and left at room temperature for 30 minutes, dried in an oven at 60℃for 1 hour, and then cured under a mercury lamp of 1kW for 45 seconds, to give a photo-cured film.
Example 8
(1) 1.1g Zn (CH) 3 COO) 2 .2H 2 Adding O into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of zinc acetate; adding 0.4g of NaOH into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of sodium hydroxide; then, the ethanol solution of sodium hydroxide was added dropwise to the ethanol solution of zinc acetate at a rate of 40 drops/min, and the mixture was reacted at a stirring rate of 2200r/min and at 0 ℃. After the completion of the dropwise addition, the reaction was continued for 30 minutes. After the reaction was completed, the product was centrifuged at 12000r/min for 15min and washed three times with absolute ethanol. Finally, drying for 24 hours at 60 ℃ to obtain the nano zinc oxide powder.
(2) 1.0g of the dried ZnO NPs powder was added to 50.0g of anhydrous toluene and dispersed ultrasonically for 30min, followed by transfer into a reaction vessel. 6.4g of TDI and DBTDL (0.1 wt% TDI) were added to 5.0g of dry toluene, mixed well and added to the reaction vessel. Stirred at 55℃for 5h. 12.0g HEMA and DBTDL (0.1 wt% TDI) were then added to the reaction vessel and reacted at 75℃for 3h. After the reaction was completed, the mixture was centrifuged at 8000rpm for 5 minutes, and washed 3 times with isopropyl alcohol and acetone, respectively, and the solid was dried at 60℃for 24 hours in a vacuum oven to obtain a modified zinc oxide powder sample.
(3) 0.03g of modified nano zinc oxide powder is added into 1g of absolute ethyl alcohol, and the mixture is dispersed for 1h by ultrasonic. After adding 0.0030g of photoinitiator 819 and 4g of HDDA, the mixture was obtained by ultrasonic dispersion for 30min. The resulting mixture was poured into 6mm plastic tubes and cured under a 1kW mercury lamp for 45s.
Example 9
(1) 1.1g Zn (CH) 3 COO) 2 .2H 2 Adding O into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of zinc acetate; adding 0.4g NaOH into 50ml ethanol, and ultrasonic dispersing for 30min to obtain hydrogenEthanol solution of sodium oxide; then, the ethanol solution of sodium hydroxide was added dropwise to the ethanol solution of zinc acetate at a rate of 40 drops/min, and the mixture was reacted at a stirring rate of 2200r/min and at 0 ℃. After the completion of the dropwise addition, the reaction was continued for 30 minutes. After the reaction was completed, the product was centrifuged at 12000r/min for 15min and washed three times with absolute ethanol. Finally, drying for 24 hours at 60 ℃ to obtain the nano zinc oxide powder.
(2) 1.0g of the dried ZnO NPs powder was added to 50.0g of anhydrous toluene and dispersed ultrasonically for 30min, followed by transfer into a reaction vessel. 6.4g of TDI and DBTDL (0.1 wt% TDI) were added to 5.0g of dry toluene, mixed well and added to the reaction vessel. Stirred at 55℃for 5h. 12.0g HEMA and DBTDL (0.1 wt% TDI) were then added to the reaction vessel and reacted at 75℃for 3h. After the reaction was completed, the mixture was centrifuged at 8000rpm for 5 minutes, and washed 3 times with isopropyl alcohol and acetone, respectively, and the solid was dried at 60℃for 24 hours in a vacuum oven to obtain a modified zinc oxide powder sample.
(3) 0.04g of modified nano zinc oxide powder is added into 1g of absolute ethyl alcohol, and the mixture is dispersed for 1h by ultrasonic. After adding 0.0030g of photoinitiator 819 and 4g of HDDA, the mixture was obtained by ultrasonic dispersion for 30min. The resulting mixture was poured into 6mm plastic tubes and cured under a 1kW mercury lamp for 45s.
Example 10
(1) 1.1g Zn (CH) 3 COO) 2 .2H 2 Adding O into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of zinc acetate; adding 0.4g of NaOH into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of sodium hydroxide; then, the ethanol solution of sodium hydroxide was added dropwise to the ethanol solution of zinc acetate at a rate of 40 drops/min, and the mixture was reacted at a stirring rate of 2200r/min and at 0 ℃. After the completion of the dropwise addition, the reaction was continued for 30 minutes. After the reaction, the product was centrifuged at 12000r/min for 15mi n And washed three times with absolute ethanol. Finally, drying for 24 hours at 60 ℃ to obtain the nano zinc oxide powder.
(2) 1.0g of the dried ZnO NPs powder was added to 50.0g of anhydrous toluene and dispersed ultrasonically for 30min, followed by transfer into a reaction vessel. 6.4g of TDI and DBTDL (0.1 wt% TDI) were added to 5.0g of dry toluene, mixed well and added to the reaction vessel. The reaction was stirred at 55℃for 5h. 12.0g HEMA and DBTDL (0.1 wt% TDI) were then added to the reaction vessel and reacted at 75℃for 3h. After the reaction was completed, the mixture was centrifuged at 8000rpm for 5 minutes, and washed 3 times with isopropyl alcohol and acetone, respectively, and the solid was dried at 60℃for 24 hours in a vacuum oven to obtain a modified zinc oxide powder sample.
(3) 0.05g of modified nano zinc oxide powder is added into 1g of absolute ethyl alcohol, and the mixture is dispersed for 1h by ultrasonic. After adding 0.0030g of photoinitiator 819 and 4g of HDDA, the mixture was obtained by ultrasonic dispersion for 30min. The resulting mixture was poured into 6mm plastic tubes and cured under a 1kW mercury lamp for 45s.
Comparative example 1
(1) 1.1g Zn (CH) 3 COO) 2 .2H 2 Adding O into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of zinc acetate; adding 0.4g of NaOH into 50ml of ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol solution of sodium hydroxide; then, the ethanol solution of sodium hydroxide was added dropwise to the ethanol solution of zinc acetate at a rate of 40 drops/min, and the mixture was reacted at a stirring rate of 2200r/min and at 0 ℃. After the completion of the dropwise addition, the reaction was continued for 30 minutes. After the reaction was completed, the product was centrifuged at 12000r/min for 15min and washed three times with absolute ethanol. Finally, drying for 24 hours at 60 ℃ to obtain the nano zinc oxide powder.
(2) 0.02g of nano zinc oxide powder is added into 1g of absolute ethyl alcohol and dispersed for 1h by ultrasonic. After adding 0.0030g of photoinitiator 819 and 4g of HDDA, the mixture was obtained by ultrasonic dispersion for 30min. The resulting mixture was poured into 6mm plastic tubes (for testing maximum photo-curing depth) and cured under a 1kW mercury lamp for 45s.
Alternatively, 0.04g of nano zinc oxide powder was added to 1g of ethanol and stirred for 1h. Then, 0.0030g of photoinitiator 819 and 4g of HDDA were added thereto, and the mixture was subjected to ultrasonic dispersion for 30 minutes. Then 5g of polyurethane acrylate is added and stirred uniformly. After that, the film was coated and left at room temperature for 30 minutes, dried in an oven for 1 hour, and then cured under a mercury lamp of 1kW for 45 seconds, to obtain a photo-cured paint film.
The performance tests of examples 1 to 10 and comparative example 1 are shown in tables 1 to 3.
FIG. 1 shows photoluminescence spectra of the nano zinc oxide obtained in example 1 and the modified zinc oxides prepared in examples 1 to 5; example 1: znO: TDI: HEMA=3:1:2, example 2: znO: TDI: HEMA=1:1:2; example 4: znO: TDI: HEMA=1:3:6; example 3: znO: TDI: HEMA=1:3:4.5; example 5: znO: TDI: HEMA=1:3:7.5;
FIG. 2 is a scanning electron micrograph of the paint film prepared in comparative example 1 and the paint film prepared in example 7. (ZnO NPs corresponding pair example 1)
TABLE 1 particle size and grafting ratio of modified Zinc oxide of examples 1 to 5, zinc oxide of comparative example 1 in solution
Figure BDA0004089190190000121
The grafting ratio refers to the grafting ratio of the modified zinc oxide or zinc oxide in the coating polymer.
TABLE 2 depth of cure obtained for examples 6-10, comparative example 1
Figure BDA0004089190190000122
TABLE 3 results of the paint film Performance test obtained in example 7, comparative example 1
Figure BDA0004089190190000131
The results in FIG. 1 show the luminescence spectra of zinc oxide before and after modification, the luminescence intensity of zinc oxide after modification is increased, and the luminescence intensity is maximized when the molar ratio of ZnO NPs to TDI to HEMA is 1:3:7.5. FIG. 2 shows a scanning electron microscope image of the zinc oxide paint film planes before and after modification, unmodified zinc oxide has obvious agglomeration, and the dispersibility of modified zinc oxide in the paint film is improved.
The results in table 1 show that the modified luminescent nano zinc oxide has reduced dispersion particle size in the solution, indicating that the modified zinc oxide has improved dispersion properties. The grafting rate of modification is maximum when the mole ratio of ZnO NPs to TDI to HEMA is 1:3:7.5.
The results in table 2 show that the modified luminescent nano zinc oxide can increase the photo-curing depth. 0.4wt% is the optimum addition, the modified zinc oxide sample has a cure depth of 18.6mm, while the unmodified zinc oxide sample has a cure depth of 14mm at the same addition.
The results of Table 3 show that the glossiness of the paint film obtained by the modified nano zinc oxide is slightly improved, which benefits from the improvement of the dispersibility of the modified nano zinc oxide, so that the particles are dispersed more uniformly in the paint film. Other properties were not significantly changed, similar to those of unmodified zinc oxide.

Claims (10)

1. A preparation method of modified luminescent nano zinc oxide for a photo-curing thick coating is characterized by comprising the following steps: the method comprises the following steps:
in an organic solvent, reacting nano zinc oxide with diisocyanate under the action of a catalyst; then adding hydroxy acrylic ester and a catalyst, reacting for 3-7 hours at 50-80 ℃, and carrying out subsequent treatment to obtain modified luminescent nano zinc oxide;
the hydroxy acrylic ester is at least one of hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl acrylate and hydroxy propyl methacrylate.
2. The method for preparing the modified luminescent nano zinc oxide for the photo-curing thick coating paint according to claim 1, which is characterized in that: the molar ratio of the nano zinc oxide to the diisocyanate is 1:0.3-3;
the mol ratio of the hydroxy acrylic ester to the diisocyanate is 1:1-3;
the diisocyanate is at least one of 2, 4-toluene diisocyanate, isophorone diisocyanate and 1, 6-hexamethylene diisocyanate.
3. The method for preparing the modified luminescent nano zinc oxide for the photo-curing thick coating paint according to claim 1, which is characterized in that: after diisocyanate is added, the reaction temperature is 40-70 ℃ and the reaction time is 3-5 h;
the organic solvent is more than one of toluene, dimethylbenzene, benzene, ethyl acetate and butyl acetate;
the nano zinc oxide is prepared by the following method: dripping the ethanol solution of sodium hydroxide into the ethanol solution of zinc acetate dihydrate, and stirring and reacting at 0-5 ℃.
4. The method for preparing modified luminescent nano zinc oxide for photo-curing thick coating paint according to claim 3, wherein the method comprises the following steps:
in the preparation of the nano zinc oxide,
the concentration of the ethanol solution of zinc acetate dihydrate is 0.001-0.1M;
the mol ratio of the zinc acetate dihydrate to the sodium hydroxide is 1:1-3;
the stirring speed is 1000-2600 r/min; the dropping speed of the ethanol solution of sodium hydroxide is 15-80 drops/min;
after the ethanol solution of sodium hydroxide is completely dripped, continuing to react for 20-60 min;
in the preparation of nano zinc oxide, after the reaction is finished, the nano zinc oxide is centrifuged, washed and dried.
5. The method for preparing the modified luminescent nano zinc oxide for the photo-curing thick coating paint according to claim 4, which is characterized in that: in the preparation of nano zinc oxide, the centrifugal condition is that the rotating speed is 8000-12000 r/min and the centrifugal is 10-30 min; the washing is carried out by using absolute ethyl alcohol; the drying condition is that the drying is carried out for 12-24 hours at 35-60 ℃.
6. A modified luminescent nano zinc oxide for a photo-cured thick coating material obtained by the production method according to any one of claims 1 to 5.
7. The use of modified luminescent nano zinc oxide according to claim 6, characterized in that: the modified luminescent nano zinc oxide is used for preparing the photo-curing thick coating.
8. A preparation method of a photo-curing thick coating is characterized in that: the method comprises the following steps:
s1: uniformly dispersing the modified nano zinc oxide, the photoinitiator and the monomer in an organic solvent to obtain a mixed solution; or adding polyurethane acrylic ester into the mixed solution, and uniformly mixing to obtain the photo-curing thick coating; the modified nano zinc oxide is as defined in claim 6;
s2: photo-curing the mixed solution to obtain a photo-cured product; or coating the photo-curing thick coating, standing, drying and photo-curing to obtain a photo-curing film;
the monomer is at least one of 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate and trimethylolpropane triacrylate.
9. The method for preparing a photo-curable thick coating according to claim 8, wherein: the dosage of the modified nano zinc oxide is 0.2-1% of the total mass of the organic solvent and the monomer;
the photoinitiator is at least one of phenyl bis (2, 4, 6-trimethylphenyl acyl) phosphine oxide, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and photoinitiator 4265;
the dosage of the photoinitiator is 0.02% -0.1% of the total mass of the organic solvent and the monomer;
the mass ratio of the organic solvent to the monomer is 1:4.
10. the method for preparing a photo-curable thick coating according to claim 8, wherein: the photo-curing is ultraviolet curing, and the irradiation time is 30-200 s; the power of the photo-curing is 0.5-2kW;
the time for placing is 25-35 min, the temperature for drying is 55-65 ℃ and the time for drying is 50-65 min.
CN202310145997.9A 2023-02-21 2023-02-21 Modified luminous nano zinc oxide for photo-curing thick coating paint and preparation and application thereof Pending CN116218278A (en)

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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN108409893A (en) * 2018-03-07 2018-08-17 华南理工大学 A kind of surface-modified nano ZnO photoinitiators and preparation method thereof
CN110922807A (en) * 2019-12-03 2020-03-27 上海大学 Modified nano zinc oxide and application thereof in photocureable coating

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Publication number Priority date Publication date Assignee Title
CN108409893A (en) * 2018-03-07 2018-08-17 华南理工大学 A kind of surface-modified nano ZnO photoinitiators and preparation method thereof
CN110922807A (en) * 2019-12-03 2020-03-27 上海大学 Modified nano zinc oxide and application thereof in photocureable coating

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