CN106188482A - Nano zine oxide grafting water-based ultraviolet (UV) curable polyurethane resin and preparation method - Google Patents

Nano zine oxide grafting water-based ultraviolet (UV) curable polyurethane resin and preparation method Download PDF

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CN106188482A
CN106188482A CN201610557141.2A CN201610557141A CN106188482A CN 106188482 A CN106188482 A CN 106188482A CN 201610557141 A CN201610557141 A CN 201610557141A CN 106188482 A CN106188482 A CN 106188482A
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polyurethane resin
based ultraviolet
nano
zine oxide
nano zine
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CN106188482B (en
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叶代勇
冯俊
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • 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
    • 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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  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention belongs to technical field of coatings, disclose a kind of nano zine oxide grafting water-based ultraviolet (UV) curable polyurethane resin and preparation method.Described preparation method is: aromatic series or aliphatic diisocyanate and polyether Glycols react at catalyst and 70～90 DEG C, obtain polyurethane prepolymer I；Controlling temperature is 60～80 DEG C, and the acetone soln of dropping dihydromethyl propionic acid reacts, and obtains polyurethane prepolymer II；Then at 55～60 DEG C, add the mixed dispersion liquid containing nano-ZnO, catalyst, the Hydroxypropyl acrylate of polymerization inhibitor and pentaerythritol triacrylate and carry out graft copolymerization, nertralizer and water is added after product cooling, it is uniformly mixed rear desolvation acetone, obtains nano zine oxide grafting water-based ultraviolet (UV) curable polyurethane resin.It is good that product of the present invention has mechanical strength, and laser curing velocity is fast, the advantage such as resistance to water and excellent storage stability.

Description

Nano zine oxide grafting water-based ultraviolet (UV) curable polyurethane resin and preparation method
Technical field
The invention belongs to technical field of coatings, be specifically related to a kind of nano zine oxide grafting water-based ultraviolet (UV) curable polyurethane tree Fat and preparation method.
Background technology
Photocureable coating is applied in many fields because of advantages such as fast, the environmental protection and energy saving of its dry solidification, but there are still Some shortcomings, as needed to add light trigger with in reactive diluent regulation viscosity, solidification process；Activity dilution in the curing process The volatilization of agent and the degraded of light trigger all can produce VOC, and environment causes pollution to a certain extent, and (Wei Jie, gold is supported Intelligence. photocureable coating [M]. Chemical Industry Press, 2013).Aquosity ultraviolet light (UV) is coating material solidified combines traditional light admittedly Change coating and the advantage of water paint, use water as the viscosity of diluent regulation system, there is environmental protection and economic dispatch advantage.
Conventional light trigger in use also exists some problems, such as easy xanthochromia, has bad smell, heat stability Difference etc.；There is light-initiated effect due to ZnO, by ZnO graft modified aqueous polyurethane propylene in the presence of water Acid esters, can obtain the photocuring water-base resin with self-initiating function.
Nano-ZnO is as a kind of N-type semiconductor, and its band structure is discontinuous, is by empty higher energy conduction band and to be full of The mental retardation valence band of electronics is constituted, and is separated by forbidden band, energy gap E of ZnO the most againgFor 3.3ev, when being more than or equal to energy During the light wave irradiation ZnO of 3.3eV, ZnO will cause the electron excitation in valence band by absorbing photon, and cross forbidden band and enter Enter conduction band, in load valence band, create corresponding hole h simultaneously+, h+There is the strongest oxidisability, oxygen can be formed on the surface of ZnO Change reduction system.When the surface of ZnO is in aqueous solution, h+Can be the OH of film surface absorption-、H2O molecular oxidation generates hydroxyl Base free radical OH, therefore can be as light trigger (Dadashi Silab S, Asiri A M, Khan S B, et al.Semiconductor nanoparticles for photoinitiation of free radical polymerization in aqueous and organic media[J].Journal of Polymer Science Part A:Polymer Chemistry,2014,52(10):1500-1507)。
In order to prepare nano composite material of good performance, carry out a lot of research both at home and abroad, be to use first to receiving mostly Rice material is modified, and then re-uses nano material and polyurethane reaction.Zhang Zuliang is suitable for silane resin acceptor kh-550 to system Standby nano-ZnO is modified, and is then prepared for nano-ZnO/Waterborne polyurethane composite paint, the coating of preparation adhesive force, The performances such as resistance to water, wearability and uvioresistant all make moderate progress (Zhang Zuliang. the research of nano zinc oxide modified aqueous polyurethane [D]. HeFei University of Technology, 2011).Hu Jinxin etc. use in-situ method to be prepared for polyurethane-titanium dioxide (PU-TiO2) water-dispersible Complex, pendulum-rocker hardness and the impact strength of paint film be greatly increased (Hu Jinxin, Liu Deshan, Sun Duoxian. aqueous gather Urethane-TiO2The preparation of complex and research [J]. plastics industry, 2004,32 (5): 16-19).Chen Yongjun etc. use precipitation and Extraction phase combines, the method that silane coupling A-174 parcel is modified, is prepared for the polypropylene oxide of the nano silicon of modification Glycol dispersion liquid, and it is prepared for Nano-meter SiO_2 with it directly as raw material2Particle modified WPU material, improves the water-fast of product Property, (Chen Yongjun, minister in ancient times is peaceful, Zhao Yan, etc. the preparation of nano silicon dioxide modifying water polyurethane dispersing liquid for hardness and heat stability With sign [J]. coatings industry, 2014,44 (1): 40-45).
Nano-ZnO with after silane coupler modified, is then prepared for nano-ZnO/PUA composite by Dowan Kim etc., Improve the hardness of film, elastic modelling quantity, weatherability and ultraviolet-resistent property (KimD, Jeon K, Lee Y, et al.Preparation and characterization of UV-cured polyurethane acrylate/ZnO nanocomposite films based on surface modified ZnO[J].Progress in organic coatings,2012,74(3):435-442).GnanaprakasamChristopher etc. use oleic acid modified nano-ZnO also It is prepared for nano-ZnO/WPU nano composite material, improves nano zine oxide distribution in WPU, improve the hydrophobic of film Property and anticorrosive property (Christopher G, Kulandainathan M A, Harichandran G.Highly dispersive waterborne polyurethane/ZnO nanocomposites for corrosion protection[J].Journal of Coatings Technology and Research,2015,12(4):657- 667).Kinga Pielichowska etc. use modified nano graphite flakes to be prepared for compound polyurethane material, have obtained one There is the material of stronger heat storage capacity, the heat stability of high material and heat conductivity (Pielichowska K, BiedaJ, Szatkowski P.Polyurethane/graphite nano-platelet composites for thermal energy storage[J].Renewable Energy,2016,91:456-465).Above method is all nano material to be changed Re-using after property, modifying process is complicated, and modifying agent cost is high.
Summary of the invention
In place of solving the shortcoming and defect of above prior art, the primary and foremost purpose of the present invention is to provide a kind of nanometer The preparation method of zinc oxide grafting water-based ultraviolet (UV) curable polyurethane resin.The method directly uses nano-ZnO, according on TDI Nano-ZnO is grafted on resin by NCO group with the principle of the hydroxyl reaction on nano-ZnO surface, has easy and simple to handle, low cost Etc. advantage.
Another object of the present invention is to provide a kind of nano zine oxide grafting aqueous prepared by said method UV light-cured polyurethane resin.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of nano zine oxide grafting water-based ultraviolet (UV) curable polyurethane resin, including following preparation process:
(1) adding aromatic series or aliphatic diisocyanate and polyether Glycols mix homogeneously in the reactor, addition is urged Agent is reacted 1～3 hour at 70～90 DEG C, obtains polyurethane prepolymer I；
(2) controlling temperature is 60～80 DEG C, and the acetone soln of dropping dihydromethyl propionic acid carries out reacting 2～4 hours, obtains side Chain is with the polyurethane prepolymer II of hydrophilic chain extension group-COOH；
(3) controlling temperature is 55～60 DEG C, adds containing nano-ZnO, catalyst, the Hydroxypropyl acrylate of polymerization inhibitor And the mixed dispersion liquid of pentaerythritol triacrylate (PETA) carries out graft copolymerization 2～5 hours, obtaining nanometer (HPA) The polyurethane acrylate prepolymer of ZnO grafting；
(4) step (3) gained prepolymer is cooled to less than 40 DEG C, is subsequently adding nertralizer and neutralizes, and adds by setting solid content Enter deionized water, be uniformly mixed rear desolvation acetone, obtain nano zine oxide grafting water-based ultraviolet (UV) curable polyurethane tree Fat.
Preferably, described nano-ZnO first vacuum dried pretreatment before use；As an example, as at vacuum drying oven At a temperature of 60 DEG C, relative vacuum pressures about-0.095MPa is dried about 3 hours.
Preferably, the mean diameter of described nano-ZnO is 105nm.
Preferably, the addition of described nano-ZnO account for final gained polyurethane resin solid gross mass 0.1%～ 1.0%.
Preferably, diisocyanate described in step (1) is 6:1 with the mol ratio of polyether Glycols；Described polyethers binary The preferred mean molecule quantity of alcohol is the polyether Glycols of 100～2000.
Preferably, described catalyst refers to dibutyl tin laurate, and described in step (1), the addition of catalyst is Diisocyanate and the 0.05% of polyether Glycols gross mass～0.3%.
Preferably, the addition of dihydromethyl propionic acid described in step (2) and the mol ratio of diisocyanate be 1:(1～ 3)；In the acetone soln of described dihydromethyl propionic acid, dihydromethyl propionic acid is 1:(2～5 with the mass ratio of acetone).
Preferably, the mol ratio that Hydroxypropyl acrylate described in step (3) and pentaerythritol triacrylate add is (2 ～3): (3～7).
Preferably, the polymerization inhibitor described in step (3) refers to MEHQ.
Preferably, the nertralizer described in step (4) refers to triethylamine.
A kind of nano zine oxide grafting water-based ultraviolet (UV) curable polyurethane resin, is prepared by said method.
Preferably, C on polyurethane resin strand during described nano zine oxide is grafted water-based ultraviolet (UV) curable polyurethane resin The content of=C double bond is 2.4～4.0mmol/g.
Preparation method and the obtained product of the present invention have the advantage that and beneficial effect:
(1) proportioning by controlling dominant response material controls molecular weight.Diisocyanate and molecular weight be 100～ The mole of 2000 polyether Glycols is than for 6:1；The i.e. n of the mol ratio (-NCO) of NCO total amount and hydroxyl total amount: n (- OH) it is (1.05～1.25): 1；The double bond content of the polyurethane acrylate prepolymer of every gram of band C=C double bond be 2.4～ 4.0mmol/g.The content of double bond in resin, and then the photocuring of regulation resin can be regulated by the value of regulation HPA/PETA Speed.
(2) present invention is by the strict response time controlling each stage and temperature.The first step is reacted 1～3 hour, reaction Temperature 70～90 DEG C；Second step reacts 2～4 hours, reaction temperature 60～80 DEG C；Three-step reaction 2～5 hours, reaction temperature 55～60 DEG C；Synthesis technique is stablized controlled, and product cut size is moderate, and storage stability is good.
(3) gained polyurethane resin solid content of the present invention is high, in use without adding light trigger, it is to avoid existing There is the defect of the penetrating odor that UV curable urethane acrylate product in use causes, to more environment-friendly.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 2 gained nano-ZnO grafting water-based ultraviolet (UV) curable polyurethane resin and base polyurethane prepolymer for use as The grain size distribution of II；
Fig. 2 and Fig. 3 (partial enlarged drawing) is that the embodiment of the present invention 2 gained nano-ZnO is grafted water-based ultraviolet (UV) curable polyurethane Resin and the infrared spectrogram of base polyurethane prepolymer for use as II.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention do not limit In this.
Embodiment 1
(1) pretreatment of nano zine oxide: by nano zine oxide at 60 DEG C of vacuum drying oven, relative vacuum pressures- About 0.095MPa is dried about 3 hours；
(2) synthesis of polyurethane prepolymer I: equipped with agitator, thermometer dry four-hole boiling flask in add 26.65g Toluene-2,4-diisocyanate, 4-diisocyanate (TDI-80) and 25.51g polyether Glycols (Mw=1000), dropping 0.052g catalyst dibutyltin Dilaurylate, reaction is carried out in thermostat water bath, is warming up to 80 DEG C, keeps this thermotonus about 1.5h, di-n-butylamine Method titration nco value reach or slightly less than theoretical value time, the base polyurethane prepolymer for use as I of half end-blocking；
(3) synthesis of polyurethane prepolymer II: be cooled to 65 DEG C, weighs 8.654g dihydromethyl propionic acid (DMPA), uses 18g Acetone solution is placed in Dropping funnel, is added dropwise in four-hole boiling flask, and rate of addition is 3～4s/ to drip, and keeps this thermotonus 3h, period add proper amount of acetone regulation viscosity, di-n-butylamine method titration nco value reach or slightly less than theoretical value time, obtain side chain band There is the base polyurethane prepolymer for use as II of hydrophilic chain extension COOH group；
(4) glycerol polymerization of nano-ZnO: be cooled to 55 DEG C, is scattered in 0.1g nano-ZnO (mean diameter is 105nm) PETA, 0.03g catalyst dibutyltin dilaurylate of HPA, 25.30g of 7.36g and 0.01g polymerization inhibitor are to hydroxyl Neo-thyl Mixture in, be slowly added dropwise in polyurethane prepolymer II and carry out graft copolymerization, keep this thermotonus 3～4h, phase Between add proper amount of acetone regulation viscosity, di-n-butylamine method titration nco value reach or slightly less than theoretical value time, obtain chemical graft ZnO Polyurethane prepolymer Ш；
(5) neutralize and disperse: being cooled to less than 40 DEG C, add in above-mentioned prepolymer in 6.53g triethylamine with become salt 10min, adds 11.1g deionized water, mechanical agitation 30min by setting solid content, then in Rotary Evaporators, arranges water-bath Pot temperature is about 60 DEG C, relative vacuum pressures about-0.095MPa, and the removing time is about 4 hours, obtains nano-ZnO grafting Water-based ultraviolet (UV) curable polyurethane resin.
The present embodiment gained naval stores accelerated storage at 50 DEG C can reach more than two months, and storge quality is preferable.
Application 25 μm or 50 μm the present embodiment gained nano zine oxides grafting poly-ammonia of water-based ultraviolet (UV) curable on solid wood board Ester resin, is 80～200mJ/cm in UV light intensity2Irradiation under, the performance of paint film is as shown in table 1, it is seen that resin and the property of paint film Can be excellent.
The performance of the zinc oxide grafting water-based ultraviolet (UV) curable polyurethane resin of table 1 self-initiating
Embodiment 2
(1) pretreatment of nano zine oxide: by nano zine oxide at 60 DEG C of vacuum drying oven, relative vacuum pressures- About 0.095MPa is dried about 3 hours；
(2) synthesis of polyurethane prepolymer I: equipped with agitator, thermometer dry four-hole boiling flask in add 26.65g Toluene-2,4-diisocyanate, 4-diisocyanate (TDI-80) and 25.51g polyether Glycols (Mw=1000), dropping 0.052g catalyst dibutyltin Dilaurylate, reaction is carried out in thermostat water bath, is warming up to 85 DEG C, keeps this thermotonus about 1.5h, di-n-butylamine Method titration nco value reach or slightly less than theoretical value time, the base polyurethane prepolymer for use as I of half end-blocking；
(3) synthesis of polyurethane prepolymer II: be cooled to 65 DEG C, weighs 8.654g dihydromethyl propionic acid (DMPA), uses 18g Acetone solution is placed in Dropping funnel, is added dropwise in four-hole boiling flask, and rate of addition is 3～4s/ to drip, and keeps this thermotonus 3h, period add proper amount of acetone regulation viscosity, di-n-butylamine method titration nco value reach or slightly less than theoretical value time, obtain side chain band There is the base polyurethane prepolymer for use as II (WPUA) of hydrophilic chain extension COOH group；
(4) glycerol polymerization of nano-ZnO: be cooled to 55 DEG C, is scattered in 0.5g nano-ZnO (mean diameter is 105nm) PETA, 0.03g catalyst dibutyltin dilaurylate of HPA, 25.30g of 7.36g and 0.01g polymerization inhibitor are to hydroxyl Neo-thyl Mixture in, be slowly added dropwise in polyurethane prepolymer II and carry out graft copolymerization, keep this thermotonus 3～4h, phase Between add proper amount of acetone regulation viscosity, di-n-butylamine method titration nco value reach or slightly less than theoretical value time, obtain chemical graft ZnO Polyurethane prepolymer Ш；
(5) neutralize and disperse: being cooled to less than 40 DEG C, add in above-mentioned prepolymer in 6.53g triethylamine with become salt 10min, adds 11.1g deionized water, mechanical agitation 30min by setting solid content, then in Rotary Evaporators, arranges water-bath Pot temperature is about 60 DEG C, relative vacuum pressures about-0.095MPa, and the removing time is about 4 hours, obtains nano-ZnO grafting Water-based ultraviolet (UV) curable polyurethane resin (ZnO-WPUA).
The present embodiment gained naval stores accelerated storage at 50 DEG C can reach more than two months, and storge quality is preferable.
The present embodiment gained nano-ZnO grafting water-based ultraviolet (UV) curable polyurethane resin divides with the particle diameter of base polyurethane prepolymer for use as II Butut is as shown in Figure 1.As seen from Figure 1: the mean diameter of the base polyurethane prepolymer for use as II of non-grafted nano-ZnO is 105nm；And Nano-ZnO grafting water-based ultraviolet (UV) curable polyurethane resin mean diameter is 150nm, and after grafting, product cut size becomes big slightly.
The present embodiment gained nano-ZnO grafting water-based ultraviolet (UV) curable polyurethane resin and the infrared light of base polyurethane prepolymer for use as II Shown in spectrogram such as Fig. 2 and Fig. 3 (partial enlarged drawing), Fig. 2 and Fig. 3 can be seen that nano-ZnO is the most successfully chemically grafted to gather On urethane prepolymer strand.
Application 25 μm or 50 μm the present embodiment gained nano zine oxides grafting poly-ammonia of water-based ultraviolet (UV) curable on solid wood board Ester resin, is 80～200mJ/cm in UV light intensity2Irradiation under, the performance of paint film is as shown in table 2, it is seen that resin and the property of paint film Can be excellent.
The performance of the zinc oxide grafting water-based ultraviolet (UV) curable polyurethane resin of table 2 self-initiating
Embodiment 3
(1) pretreatment of nano zine oxide: by nano zine oxide at 60 DEG C of vacuum drying oven, relative vacuum pressures- About 0.095MPa is dried about 3 hours；
(2) synthesis of polyurethane prepolymer I: equipped with agitator, thermometer dry four-hole boiling flask in add 26.65g Toluene-2,4-diisocyanate, 4-diisocyanate (TDI-80) and 25.51g polyether Glycols (Mw=1000), drip 0.052g catalyst dibutyltin Dilaurylate, reaction is carried out in thermostat water bath, is warming up to 80 DEG C, keeps this thermotonus about 1.5h, di-n-butylamine Method titration nco value reach or slightly less than theoretical value time, the base polyurethane prepolymer for use as I of half end-blocking；
(3) synthesis of polyurethane prepolymer II: be cooled to 65 DEG C, weighs 8.654g dihydromethyl propionic acid (DMPA), uses 18g Acetone solution is placed in Dropping funnel, is added dropwise in four-hole boiling flask, and rate of addition is 3～4s/ to drip, and keeps this thermotonus 3h, period add proper amount of acetone regulation viscosity, di-n-butylamine method titration nco value reach or slightly less than theoretical value time, obtain side chain band There is the base polyurethane prepolymer for use as II of hydrophilic chain extension COOH group；
(4) glycerol polymerization of nano-ZnO: be cooled to 55 DEG C, is scattered in 1.0g nano-ZnO (mean diameter is 105nm) PETA, 0.03g catalyst dibutyltin dilaurylate of HPA, 25.30g of 7.36g and 0.01g polymerization inhibitor are to hydroxyl Neo-thyl Mixture in, be slowly added dropwise in polyurethane prepolymer II and carry out graft copolymerization, keep this thermotonus 3～4h, phase Between add proper amount of acetone regulation viscosity, di-n-butylamine method titration nco value reach or slightly less than theoretical value time, obtain chemical graft ZnO Polyurethane prepolymer Ш；
(5) neutralize and disperse: being cooled to less than 40 DEG C, add in above-mentioned prepolymer in 6.53g triethylamine with become salt 10min, adds 11.1g deionized water, mechanical agitation 30min by setting solid content, then in Rotary Evaporators, arranges water-bath Pot temperature is about 60 DEG C, relative vacuum pressures about-0.095MPa, and the removing time is about 4 hours, obtains nano-ZnO grafting Water-based ultraviolet (UV) curable polyurethane resin.
The present embodiment gained naval stores accelerated storage at 50 DEG C can reach more than two months, and storge quality is preferable.
Application 25 μm or 50 μm the present embodiment gained nano zine oxides grafting poly-ammonia of water-based ultraviolet (UV) curable on solid wood board Ester resin, is 80～200mJ/cm in UV light intensity2Irradiation under, the performance of paint film is as shown in table 3, it is seen that resin and the property of paint film Can be excellent.
The performance of the zinc oxide grafting water-based ultraviolet (UV) curable polyurethane resin of table 3 self-initiating
Embodiment 4
(1) pretreatment of nano zine oxide: by nano zine oxide at 60 DEG C of vacuum drying oven, relative vacuum pressures- About 0.095MPa is dried about 3 hours；
(2) synthesis of polyurethane prepolymer I: equipped with agitator, thermometer dry four-hole boiling flask in add 26.65g Toluene-2,4-diisocyanate, 4-diisocyanate (TDI-80) and 25.51g polyether Glycols (Mw=1000), drip 0.052g catalyst dibutyltin Dilaurylate, reaction is carried out in thermostat water bath, is warming up to 80 DEG C, keeps this thermotonus about 1.5h, di-n-butylamine Method titration nco value reach or slightly less than theoretical value time, the base polyurethane prepolymer for use as I of half end-blocking；
(3) synthesis of polyurethane prepolymer II: be cooled to 65 DEG C, weighs 8.654g dihydromethyl propionic acid (DMPA), uses 18g Acetone solution is placed in Dropping funnel, is added dropwise in four-hole boiling flask, and rate of addition is 3～4s/ to drip, and keeps this thermotonus 3h, period add proper amount of acetone regulation viscosity, di-n-butylamine method titration nco value reach or slightly less than theoretical value time, obtain side chain band There is the base polyurethane prepolymer for use as II of hydrophilic chain extension COOH group；
(4) glycerol polymerization of nano-ZnO: be cooled to 55 DEG C, is scattered in 0.3g nano-ZnO (mean diameter is 105nm) PETA, 0.03g catalyst dibutyltin dilaurylate of HPA, 27.12g of 5.14g and 0.01g polymerization inhibitor are to hydroxyl Neo-thyl Mixture in, be slowly added dropwise in polyurethane prepolymer II and carry out graft copolymerization, keep this thermotonus 3～4h, phase Between add proper amount of acetone regulation viscosity, di-n-butylamine method titration nco value reach or slightly less than theoretical value time, obtain chemical graft ZnO Polyurethane prepolymer Ш；
(5) neutralize and disperse: being cooled to less than 40 DEG C, add in above-mentioned prepolymer in 6.53g triethylamine with become salt 10min, adds 11.1g deionized water, mechanical agitation 30min by setting solid content, then in Rotary Evaporators, arranges water-bath Pot temperature is about 60 DEG C, relative vacuum pressures about-0.095MPa, and the removing time is about 4 hours, obtains nano-ZnO grafting Water-based ultraviolet (UV) curable polyurethane resin.
The present embodiment gained naval stores accelerated storage at 50 DEG C can reach more than two months, and storge quality is preferable.
Application 25 μm or 50 μm the present embodiment gained nano zine oxides grafting poly-ammonia of water-based ultraviolet (UV) curable on solid wood board Ester resin, is 80～200mJ/cm in UV light intensity2Irradiation under, the performance of paint film is as shown in table 4, it is seen that resin and the property of paint film Can be excellent.
The performance of the zinc oxide grafting water-based ultraviolet (UV) curable polyurethane resin of table 4 self-initiating
Embodiment 5
(1) pretreatment of nano zine oxide: by nano zine oxide at 60 DEG C of vacuum drying oven, relative vacuum pressures- About 0.095MPa is dried about 3 hours；
(2) synthesis of polyurethane prepolymer I: equipped with agitator, thermometer dry four-hole boiling flask in add 26.65g Toluene-2,4-diisocyanate, 4-diisocyanate (TDI-80) and 25.51g polyether Glycols (Mw=1000), dropping 0.052g catalyst dibutyltin Dilaurylate, reaction is carried out in thermostat water bath, is warming up to 80 DEG C, keeps this thermotonus about 1.5h, di-n-butylamine Method titration nco value reach or slightly less than theoretical value time, the base polyurethane prepolymer for use as I of half end-blocking；
(3) synthesis of polyurethane prepolymer II: be cooled to 65 DEG C, weighs 8.654g dihydromethyl propionic acid (DMPA), uses 18g Acetone solution is placed in Dropping funnel, is added dropwise in four-hole boiling flask, and rate of addition is 3～4s/ to drip, and keeps this thermotonus 3h, period add proper amount of acetone regulation viscosity, di-n-butylamine method titration nco value reach or slightly less than theoretical value time, obtain side chain band There is the base polyurethane prepolymer for use as II of hydrophilic chain extension COOH group；
(4) glycerol polymerization of nano-ZnO: be cooled to 55 DEG C, is scattered in 0.75g nano-ZnO (mean diameter is 105nm) PETA, 0.03g catalyst dibutyltin dilaurylate of HPA, 27.12g of 5.14g and 0.01g polymerization inhibitor are to hydroxyl Neo-thyl Mixture in, be slowly added dropwise in polyurethane prepolymer II and carry out graft copolymerization, keep this thermotonus 3～4h, phase Between add proper amount of acetone regulation viscosity, di-n-butylamine method titration nco value reach or slightly less than theoretical value time, obtain chemical graft ZnO Polyurethane prepolymer Ш；
(5) neutralize and disperse: being cooled to less than 40 DEG C, add in above-mentioned prepolymer in 6.53g triethylamine with become salt 10min, adds 11.1g deionized water, mechanical agitation 30min by setting solid content, then in Rotary Evaporators, arranges water-bath Pot temperature is about 55 DEG C, relative vacuum pressures about-0.095MPa, and the removing time is about 4 hours, obtains nano-ZnO grafting Water-based ultraviolet (UV) curable polyurethane resin.
The present embodiment gained naval stores accelerated storage at 50 DEG C can reach more than two months, and storge quality is preferable.
Application 25 μm or 50 μm the present embodiment gained nano zine oxides grafting poly-ammonia of water-based ultraviolet (UV) curable on solid wood board Ester resin, is 80～200mJ/cm in UV light intensity2Irradiation under, the performance of paint film is as shown in table 5, it is seen that resin and the property of paint film Can be excellent.
The performance of the zinc oxide grafting water-based ultraviolet (UV) curable polyurethane resin of table 5 self-initiating
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify, All should be the substitute mode of equivalence, within being included in protection scope of the present invention.

Claims (10)

1. the preparation method of a nano zine oxide grafting water-based ultraviolet (UV) curable polyurethane resin, it is characterised in that include making as follows Standby step:
(1) add aromatic series or aliphatic diisocyanate and polyether Glycols mix homogeneously in the reactor, add catalyst React 1～3 hour at 70～90 DEG C, obtain polyurethane prepolymer I；
(2) controlling temperature is 60～80 DEG C, and the acetone soln of dropping dihydromethyl propionic acid carries out reacting 2～4 hours, obtains side chain band There is the polyurethane prepolymer II of hydrophilic chain extension group-COOH；
(3) controlling temperature is 55～60 DEG C, adds containing nano-ZnO, catalyst, the Hydroxypropyl acrylate of polymerization inhibitor and season penta 4 The mixed dispersion liquid of alcohol triacrylate carries out graft copolymerization 2～5 hours, obtains the polyurethane propylene of nano-ZnO grafting Acid esters prepolymer；
(4) step (3) gained prepolymer is cooled to less than 40 DEG C, is subsequently adding nertralizer and neutralizes, and goes by setting solid content addition Ionized water, is uniformly mixed rear desolvation acetone, obtains nano zine oxide grafting water-based ultraviolet (UV) curable polyurethane resin.
The preparation method of a kind of nano zine oxide the most according to claim 1 grafting water-based ultraviolet (UV) curable polyurethane resin, It is characterized in that: the first vacuum dried pretreatment before use of described nano-ZnO.
The preparation method of a kind of nano zine oxide the most according to claim 1 grafting water-based ultraviolet (UV) curable polyurethane resin, It is characterized in that: the mean diameter of described nano-ZnO is 105nm.
The preparation method of a kind of nano zine oxide the most according to claim 1 grafting water-based ultraviolet (UV) curable polyurethane resin, It is characterized in that: the addition of described nano-ZnO accounts for the 0.1%～1.0% of final gained polyurethane resin solid gross mass.
The preparation method of a kind of nano zine oxide the most according to claim 1 grafting water-based ultraviolet (UV) curable polyurethane resin, It is characterized in that: diisocyanate described in step (1) is 6:1 with the mol ratio of polyether Glycols；Described polyether Glycols is Refer to the polyether Glycols that mean molecule quantity is 100～2000.
The preparation method of a kind of nano zine oxide the most according to claim 1 grafting water-based ultraviolet (UV) curable polyurethane resin, It is characterized in that: described catalyst refers to dibutyl tin laurate, the addition of catalyst described in step (1) is two different Cyanate and the 0.05% of polyether Glycols gross mass～0.3%.
The preparation method of a kind of nano zine oxide the most according to claim 1 grafting water-based ultraviolet (UV) curable polyurethane resin, It is characterized in that: the addition of dihydromethyl propionic acid described in step (2) and the mol ratio of diisocyanate are 1:(1～3)；Institute Stating the mass ratio of dihydromethyl propionic acid and acetone in the acetone soln of dihydromethyl propionic acid is 1:(2～5).
The preparation method of a kind of nano zine oxide the most according to claim 1 grafting water-based ultraviolet (UV) curable polyurethane resin, It is characterized in that: the mol ratio that Hydroxypropyl acrylate described in step (3) and pentaerythritol triacrylate add is (2～3): (3～7).
The preparation method of a kind of nano zine oxide the most according to claim 1 grafting water-based ultraviolet (UV) curable polyurethane resin, It is characterized in that: the polymerization inhibitor described in step (3) refers to MEHQ；Nertralizer described in step (4) refers to three Ethamine.
10. nano zine oxide grafting water-based ultraviolet (UV) curable polyurethane resin, it is characterised in that: by claim 1～9 One described method prepares；In described nano zine oxide grafting water-based ultraviolet (UV) curable polyurethane resin, polyurethane resin divides In subchain, the content of C=C double bond is 2.4～4.0mmol/g.
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