CN107502272A - A kind of ultraviolet cured adhesive of doped nano titanium dioxide sticks agent and preparation method thereof - Google Patents

A kind of ultraviolet cured adhesive of doped nano titanium dioxide sticks agent and preparation method thereof Download PDF

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Publication number
CN107502272A
CN107502272A CN201710658396.2A CN201710658396A CN107502272A CN 107502272 A CN107502272 A CN 107502272A CN 201710658396 A CN201710658396 A CN 201710658396A CN 107502272 A CN107502272 A CN 107502272A
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parts
acrylate
powder
cured adhesive
acrylate prepolymer
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CN107502272B (en
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李不悔
李峰
贺国新
张利文
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Yantai Seayu New Materials Corp Ltd
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Yantai Seayu New Materials Corp 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The present invention relates to a kind of ultraviolet cured adhesive of doped nano titanium dioxide to stick agent and preparation method thereof, is made up of the raw material of following parts by weight：Make 20~60 parts of bifunctionality polyurethane acrylate prepolymer by oneself, 5~15 parts of polyfunctionality polyurethane acrylate prepolymer, 5~15 parts of polyester acrylate performed polymer, 5~20 parts of reactive amine compounding ingredient, 10~30 parts of acrylics reactive diluent, levelling wetting agent 0.5~5%, light trigger 1~5%, 0.5~3 part of nano TiO 2 powder, 0.1~10 part of aerosil.The present invention protects temporarily suitable for metal shell, is played a protective role in CNC end processing sequences, can easily be peeled off again after CNC is treated, glue noresidue on metal shell, nothing comes off.

Description

A kind of ultraviolet cured adhesive of doped nano titanium dioxide sticks agent and preparation method thereof
Technical field
The present invention relates to a kind of ultraviolet cured adhesive of doped nano titanium dioxide to stick agent and preparation method thereof.
Background technology
With in the electronic product such as continuous extension, mobile phone, TV, computer in ultraviolet Technology Application field, ultraviolet light solidifies Glue all plays an important role.In this Consumer's Experience extremely valued age, increasing mobile phone, notebook, can wear Equipment vendors are worn to start to have an effect on enclosure material.Only from the point of view of field of mobile phones, enclosure material also just gradually from engineering plastics to Metal transfer.One puies forward all-metal, must carry CNC.At present, the full metal jacket of 3C Product is substantially by Digit Control Machine Tool （Computer numerical control machine tools, CNC）Processing.CNC is because of its efficiency high, precision is high, adds The advantages of work steady quality, turn into the necessary equipment of 3C shells manufacturer.And in CNC end processing sequences（Polishing, sandblasting, sun Pole is handled）, there are on metal shell many places to need interim protection, to prevent the destruction in processing procedure to metal shell.It is existing Plug-hole is brought using rubber stopper or pressure sensitive adhesive more in technique, manual operation is slow, and accuracy is low, and in CNC processing procedures easily Phenomena such as falling off, product yield is caused to be decreased obviously.
It there is no at present and agent sticked to the ultraviolet cured adhesive of the interim protection of metal shell.
The content of the invention
The technical problem to be solved by the invention is to provide a kind of ultraviolet cured adhesive of doped nano titanium dioxide to stick agent And preparation method thereof, the present invention solves adhesive and made applied to protection during interim protection, is played in CNC technical process in early stage With the later stage readily peels off, and glue noresidue on metal shell, and nothing comes off.
In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：
It is made up of the raw material of following parts by weight：Make 20~60 parts of bifunctionality polyurethane acrylate prepolymer, polyfunctionality by oneself 5~15 parts of polyurethane acrylate prepolymer, 5~15 parts of polyester acrylate performed polymer, 5~20 parts of reactive amine compounding ingredient, 10~30 parts of acrylics reactive diluent, 0.5~5 part of levelling wetting agent, 1~5 part of light trigger, titanic oxide nano 0.5~5 part of body, 0.1~10 part of aerosil；
The self-control bifunctionality polyurethane acrylate prepolymer follows the steps below：
By polyether Glycols temperature be 110 DEG C~120 DEG C, pressure be -0.095~-0.85MPa under conditions of be dehydrated 1.5~2 Hour；It is 50 DEG C~70 DEG C that diisocyanate, which is added, in temperature, under conditions of pressure is -0.095~-0.85, stirring 0.5~ 1h, catalyst is added, be 70 DEG C~80 DEG C in temperature, pressure reacts 2~3h under conditions of being -0.095~-0.85MPa；Successively Add the acrylate of polymerization inhibitor and hydroxyl and be 60 DEG C~80 DEG C in temperature, pressure is -0.095~-0.85MPa condition 2~3h of lower stirring, the content of NCO group is analyzed with infrared spectrometer every 30min samplings, when NCO peak is wholly absent, is stopped Only heating response, produce bifunctionality polyurethane acrylate prepolymer；The polyether Glycols, diisocyanate and hydroxyl Acrylate mol ratio be 1:1.6~2.0:1.6~2.2, catalyst and polymerization inhibitor respectively account for self-control bifunctionality polyurethane third 0.1 ‰~the 1 ‰ of olefin(e) acid ester pre-polymerization body weight；
The nano TiO 2 powder follows the steps below：
1) precursors are prepared：10mL tetra-n-butyl titanates are added in the container for filling 250mL ethylene glycol, and at 30 DEG C
Under the conditions of stir 8h, gained colourless transparent solution is precursors；
2) Ti0 is prepared2Powder：1mL glacial acetic acid is added in the container for filling 500mL acetone, is 200~300r/ in rotating speed min
Under conditions of precursors are poured into the container for filling acetone, stir 30min, be aged 30min, obtain white Ti02 Suspension, by suspension centrifugal filtration, and with water and the washed screening of ethanol, by filtrate under the conditions of 60 DEG C freeze-day with constant temperature 12h, obtain Ti02Powder；
3）Prepare Ti02Nano-powder：By TiO2Powder is positioned in Muffle furnace, and 2h is calcined under the conditions of 500 DEG C, is ground, and is used The screen cloth sieving of 400 mesh specifications, obtains Ti02Nano-powder;
The ultraviolet cured adhesive follows the steps below：
Will 20~60 parts of self-control bifunctionality polyurethane acrylate prepolymer, polyfunctionality polyurethane acrylate prepolymer 5 ~15 parts, 5~15 parts of polyester acrylate performed polymer, 5~20 parts of reactive amine compounding ingredient, acrylics reactive diluent 10 0.5~3 part of~30 parts, 0.5~5 part of levelling wetting agent and nano TiO 2 powder, sequentially add to double-planet power and mix In kettle, open revolution stirring and high speed be scattered, persistently stir 1~2h, be well mixed system, add 1~5 part of light trigger, Continue 1~2h of stirring, add 0.1~10 part of aerosil, stir 1~2h, be -0.095~-0.85 condition in pressure Lower deaeration, discharging, produce the ultraviolet cured adhesive for protecting temporarily and stick agent；
The PTMEG includes two of one kind or arbitrary proportion in polyethylene glycol, polypropylene glycol and PTMG More than kind, the molecular weight of PTMEG is 650~3000；
The diisocyanate includes toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, the isocyanic acid of phenylenedimethylidyne two One kind or arbitrary proportion in ester, hexamethylene diisocyanate and IPDI it is two or more；
The acrylate of the hydroxyl includes hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, methyl-prop One kind or arbitrary proportion of olefin(e) acid hydroxypropyl acrylate and trimethylolpropane diacrylate it is two or more；
The polymerization inhibitor is hydroquinones, MEHQ and 2, one kind or arbitrary proportion in 6 toluene di-tert-butyl phenols It is two or more；
The catalyst is dibutyl tin laurate；
The polyester acrylate performed polymer is that the C3108 of Sartomer, the CN704 of Sartomer, state refine and learn share One kind in the 3400Z of Co., Ltd, the 6349 of Changxing chemical material Co., Ltd and Changxing chemical material Co., Ltd 6363 Or arbitrary proportion is two or more；
The acrylics reactive diluent includes tetrahydrofuran methyl acrylate, tetrahydrofuran acrylate, methyl-prop One kind or any in olefin(e) acid isobornyl thiocyanoacetate, hydroxyethyl methacrylate, hydroxy propyl methacrylate and isodecyl acrylate Ratio it is two or more；
The polyfunctionality polyurethane acrylate prepolymer is the CN975 of Sartomer, Changxing chemical material Co., Ltd 6146-100,6147, the 4312 of RAHN companies of Changxing chemical material Co., Ltd and the 4316 of RAHN companies in one kind Or arbitrary proportion is two or more；
The reactive amine compounding ingredient be state refine learn limited company GC1100W, GC1100Z and GC1200C in one The mixture of kind or two or more any ratios；
The levelling wetting agent include one kind in TEGO-4000, TEGO-4100 and BYK-3510 or two kinds of arbitrary proportion with On；The light trigger is 2- hydroxy-2-methyl -1- phenylacetones, 1- hydroxy cyclohexyl phenylketones, phenyl pair（2,4,6- tri- Methyl benzoyl）Phosphorous oxide, 2,2- dimethoxy -2- phenyl acetophenones, isopropyl thioxanthone, benzophenone and 2,4, One kind or arbitrary proportion in 6- trimethyl benzoyl diphenyl base phosphorous oxides it is two or more；
The fumed silica includes R202 the and Ying Chuan companies of TS-720, EH-5, Ying Chuan company of Cabot Co., Ltd One kind or arbitrary proportion in A200 it is two or more；
The revolution speed of agitator is 20r/min, and scattered rotating speed is 600r/min at a high speed.
Si/Ti mol ratios are 2~4 in the gaseous mixture:1, general gas flow is 1000~1500sccm.
The ultraviolet cured adhesive completes the ultraviolet irradiation energy of solidification in 600~1200mJ/cm2；The ultraviolet light The ultraviolet irradiation energy that solidification glue is peeled off is in 3000~6000mJ/cm2。
The viscosity of ultraviolet cured adhesive is 2000m~28000mPas；Thixotropic index is 1.2~12.
Preferably, it is made up of the raw material of following parts by weight：Make 40 parts of bifunctionality polyurethane acrylate prepolymer by oneself, it is more 10 parts of degree of functionality polyurethane acrylate prepolymer, 8 parts of polyester acrylate performed polymer, 12 parts of reactive amine compounding ingredient, propylene Sour 20 parts of lipid reactive diluent, 2 parts of levelling wetting agent, 2 parts of light trigger, 2 parts of nano TiO 2 powder, gas phase titanium dioxide 4 parts of silicon；
The self-control bifunctionality polyurethane acrylate prepolymer follows the steps below：
By polyether Glycols temperature be 110 DEG C, pressure be -0.098MPa under conditions of be dehydrated 1.5 hours；Add two isocyanic acids Ester temperature be 60 DEG C, pressure be -0.098 under conditions of, stir 0.6h, add catalyst, temperature be 75 DEG C, pressure for - 2h is reacted under conditions of 0.098MPa；Sequentially add the acrylate of polymerization inhibitor and hydroxyl and temperature be 70 DEG C, pressure for- 2h is stirred under conditions of 0.098MPa, the content of NCO group is analyzed with infrared spectrometer every 30min samplings, when NCO peak is complete When totally disappeared mistake, stop heating response, produce bifunctionality polyurethane acrylate prepolymer；The polyether Glycols, two isocyanides The acrylate mol ratio of acid esters and hydroxyl is 1:1.8:1.8, catalyst and polymerization inhibitor respectively account for self-control bifunctionality polyurethane The 0.2 ‰ of acrylate prepolymer body weight；The PTMEG is polyethylene glycol, and its molecular weight is 800；The diisocyanate It is toluene di-isocyanate(TDI), hexamethylene diisocyanate and IPDI according to mass ratio 1:2:3 combination Thing；The acrylate of the hydroxyl is hydroxy-ethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate according to quality Than 3:2:1 composition；The catalyst is dibutyl tin laurate；The polymerization inhibitor is hydroquinones and para hydroxybenzene first Ether is according to mass ratio 2:1 composition；
The nano TiO 2 powder follows the steps below：
1) precursors are prepared：10mL tetra-n-butyl titanates are added in the container for filling 250mL ethylene glycol, and at 30 DEG C
Under the conditions of stir 8h, gained colourless transparent solution is precursors；
2) Ti0 is prepared2Powder：1mL glacial acetic acid is added in the container for filling 500mL acetone, is 200~300r/ in rotating speed min
Under conditions of precursors are poured into the container for filling acetone, stir 30min, be aged 30min, obtain white Ti02 Suspension, by suspension centrifugal filtration, and with water and the washed screening of ethanol, by filtrate under the conditions of 60 DEG C freeze-day with constant temperature 12h, obtain Ti02Powder；
3）Prepare Ti02Nano-powder：By TiO2Powder is positioned in Muffle furnace, and 2h is calcined under the conditions of 500 DEG C, is ground, and is used The screen cloth sieving of 400 mesh specifications, obtains Ti02Nano-powder;
The ultraviolet cured adhesive follows the steps below：
Will 40 parts of self-control bifunctionality polyurethane acrylate prepolymer, 10 parts of polyfunctionality polyurethane acrylate prepolymer, 8 parts of polyester acrylate performed polymer, 12 parts of reactive amine compounding ingredient, 20 parts of acrylics reactive diluent, levelling wetting agent 2 2 parts of part and nano TiO 2 powder, are sequentially added into double-planet power mixing kettle, and unlatching revolution is stirred and disperseed at a high speed, 1h is persistently stirred, is well mixed system, adds 2 parts of light trigger, continues to stir 1h, adds 5 parts of aerosil, stirring 1h, deaeration under the conditions of being -0.098 in pressure, discharging, produce the ultraviolet cured adhesive for protecting temporarily and stick agent；The revolution Speed of agitator is 20r/min, and scattered rotating speed is 600r/min at a high speed；The polyester acrylate performed polymer is Sartomer C3108；
The acrylics reactive diluent includes tetrahydrofuran methyl acrylate and isodecyl acrylate according to quality Than 1:1 composition；The polyfunctionality polyurethane acrylate prepolymer is the CN975 of Sartomer；The reactivity Amine compounding ingredient be state refine learn limited company GC1100W；The levelling wetting agent is TEGO-4000；It is described light-initiated Agent is that 2- hydroxyls -2- methyl isophthalic acids-phenylacetone and phenyl are double（2,4,6- trimethylbenzoyls）Phosphorous oxide, 2,2- bis- Methoxyl group -2- phenyl acetophenones are according to mass ratio 1:1 composition；The fumed silica is the TS- of Cabot Co., Ltd 720。
Invention has following advantageous effects：
1st, with make by oneself bifunctionality polyurethane acrylate prepolymer, self-control nano TiO 2 powder, polyester acrylate resin, Polyfunctionality polyurethane acrylic resin, reactive amine compounding ingredient and acrylic ester monomer are primary raw material, are made into ultraviolet light Solidification glue, the adhesive have suitable thixotropy viscosity, and hardness is low, high-tensile, high solidification depth, is set applied to electronics Standby interim protection of the metal shell in CNC technical process, improves production efficiency, Improving The Quality of Products, and reduce cost.
2nd, the nano titanium oxide that the present invention adds hardly participates in reaction at low energies.When energy further improves When, titanium dioxide surface, which is stimulated, can produce electron-hole pair, can be with adsorbing the part small-molecular-weight organic matter in material surface Generation redox reaction, make its degraded, reduce attachment of the adhesive to base material, make it have rippability.
3rd, nano TiO 2 powder specific surface area is very big, and the thing that is degraded is more easy to be adsorbed, and titanic oxide nano Body diameter is small, reduces electronics and hole in TiO2Internal recombination probability, improves TiO2Photocatalytic activity.
Embodiment
Embodiment 1
It is made up of the raw material of following parts by weight：Make 40 parts of bifunctionality polyurethane acrylate prepolymer, the poly- ammonia of polyfunctionality by oneself 10 parts of ester acrylate prepolymer body, 8 parts of polyester acrylate performed polymer, 12 parts of reactive amine compounding ingredient, acrylics activity 20 parts of diluent, 2 parts of levelling wetting agent, 2 parts of light trigger, 1 part of nano TiO 2 powder, 5 parts of aerosil；
The self-control bifunctionality polyurethane acrylate prepolymer follows the steps below：
By polyether Glycols temperature be 110 DEG C, pressure be -0.098MPa under conditions of be dehydrated 1.5 hours；Add two isocyanic acids Ester temperature be 60 DEG C, pressure be -0.098 under conditions of, stir 0.6h, add catalyst, temperature be 75 DEG C, pressure for - 2h is reacted under conditions of 0.098MPa；Sequentially add the acrylate of polymerization inhibitor and hydroxyl and temperature be 70 DEG C, pressure for- 2h is stirred under conditions of 0.098MPa, the content of NCO group is analyzed with infrared spectrometer every 30min samplings, when NCO peak is complete When totally disappeared mistake, stop heating response, produce bifunctionality polyurethane acrylate prepolymer；The polyether Glycols, two isocyanides The acrylate mol ratio of acid esters and hydroxyl is 1:1.8:1.8, catalyst and polymerization inhibitor respectively account for self-control bifunctionality polyurethane The 0.2 ‰ of acrylate prepolymer body weight；The PTMEG is polyethylene glycol, and its molecular weight is 800；The diisocyanate It is toluene di-isocyanate(TDI), hexamethylene diisocyanate and IPDI according to mass ratio 1:2:3 combination Thing；The acrylate of the hydroxyl is hydroxy-ethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate according to quality Than 3:2:1 composition；The catalyst is dibutyl tin laurate；The polymerization inhibitor is hydroquinones and para hydroxybenzene first Ether is according to mass ratio 2:1 composition；
The nano TiO 2 powder follows the steps below：
1) precursors are prepared：10mL tetra-n-butyl titanates are added in the container for filling 250mL ethylene glycol, and at 30 DEG C
Under the conditions of stir 8h, gained colourless transparent solution is precursors；
2) Ti0 is prepared2Powder：1mL glacial acetic acid is added in the container for filling 500mL acetone, is 200~300r/ in rotating speed min
Under conditions of precursors are poured into the container for filling acetone, stir 30min, be aged 30min, obtain white Ti02 Suspension, by suspension centrifugal filtration, and with water and the washed screening of ethanol, by filtrate under the conditions of 60 DEG C freeze-day with constant temperature 12h, obtain Ti02Powder；
3）Prepare Ti02Nano-powder：By TiO2Powder is positioned in Muffle furnace, and 2h is calcined under the conditions of 500 DEG C, is ground, and is used The screen cloth sieving of 400 mesh specifications, obtains Ti02Nano-powder;
The ultraviolet cured adhesive follows the steps below：
Will 40 parts of self-control bifunctionality polyurethane acrylate prepolymer, 10 parts of polyfunctionality polyurethane acrylate prepolymer, 8 parts of polyester acrylate performed polymer, 12 parts of reactive amine compounding ingredient, 20 parts of acrylics reactive diluent, levelling wetting agent 2 2 parts of part and nano TiO 2 powder, are sequentially added into double-planet power mixing kettle, and unlatching revolution is stirred and disperseed at a high speed, 1h is persistently stirred, is well mixed system, adds 2 parts of light trigger, continues to stir 1h, adds 5 parts of aerosil, stirring 1h, deaeration under the conditions of being -0.098 in pressure, discharging, produce the ultraviolet cured adhesive for protecting temporarily and stick agent；The revolution Speed of agitator is 20r/min, and scattered rotating speed is 600r/min at a high speed；The polyester acrylate performed polymer is Sartomer C3108；
The acrylics reactive diluent includes tetrahydrofuran methyl acrylate and isodecyl acrylate according to quality Than 1:1 composition；The polyfunctionality polyurethane acrylate prepolymer is the CN975 of Sartomer；The reactivity Amine compounding ingredient be state refine learn limited company GC1100W；The levelling wetting agent is TEGO-4000；It is described light-initiated Agent is that 2- hydroxyls -2- methyl isophthalic acids-phenylacetone and phenyl are double（2,4,6- trimethylbenzoyls）Phosphorous oxide, 2,2- bis- Methoxyl group -2- phenyl acetophenones are according to mass ratio 1:1 composition；The fumed silica is the TS- of Cabot Co., Ltd 720。
Embodiment 2
It is made up of the raw material of following parts by weight：Make 40 parts of bifunctionality polyurethane acrylate prepolymer, the poly- ammonia of polyfunctionality by oneself 10 parts of ester acrylate prepolymer body, 8 parts of polyester acrylate performed polymer, 12 parts of reactive amine compounding ingredient, acrylics activity 20 parts of diluent, 2 parts of levelling wetting agent, 2 parts of light trigger, 1.5 parts of nano TiO 2 powder, 4.5 parts of aerosil；
The self-control bifunctionality polyurethane acrylate prepolymer follows the steps below：
By polyether Glycols temperature be 110 DEG C, pressure be -0.098MPa under conditions of be dehydrated 1.5 hours；Add two isocyanic acids Ester temperature be 60 DEG C, pressure be -0.098 under conditions of, stir 0.6h, add catalyst, temperature be 75 DEG C, pressure for - 2h is reacted under conditions of 0.098MPa；Sequentially add the acrylate of polymerization inhibitor and hydroxyl and temperature be 70 DEG C, pressure for- 2h is stirred under conditions of 0.098MPa, the content of NCO group is analyzed with infrared spectrometer every 30min samplings, when NCO peak is complete When totally disappeared mistake, stop heating response, produce bifunctionality polyurethane acrylate prepolymer；The polyether Glycols, two isocyanides The acrylate mol ratio of acid esters and hydroxyl is 1:1.8:1.8, catalyst and polymerization inhibitor respectively account for self-control bifunctionality polyurethane The 0.2 ‰ of acrylate prepolymer body weight；The PTMEG is polyethylene glycol, and its molecular weight is 800；The diisocyanate It is toluene di-isocyanate(TDI), hexamethylene diisocyanate and IPDI according to mass ratio 1:2:3 combination Thing；The acrylate of the hydroxyl is hydroxy-ethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate according to quality Than 3:2:1 composition；The catalyst is dibutyl tin laurate；The polymerization inhibitor is hydroquinones and para hydroxybenzene first Ether is according to mass ratio 2:1 composition；
The nano TiO 2 powder follows the steps below：
1) precursors are prepared：10mL tetra-n-butyl titanates are added in the container for filling 250mL ethylene glycol, and at 30 DEG C
Under the conditions of stir 8h, gained colourless transparent solution is precursors；
2) Ti0 is prepared2Powder：1mL glacial acetic acid is added in the container for filling 500mL acetone, is 200~300r/ in rotating speed min
Under conditions of precursors are poured into the container for filling acetone, stir 30min, be aged 30min, obtain white Ti02 Suspension, by suspension centrifugal filtration, and with water and the washed screening of ethanol, by filtrate under the conditions of 60 DEG C freeze-day with constant temperature 12h, obtain Ti02Powder；
3）Prepare Ti02Nano-powder：By TiO2Powder is positioned in Muffle furnace, and 2h is calcined under the conditions of 500 DEG C, is ground, and is used The screen cloth sieving of 400 mesh specifications, obtains Ti02Nano-powder;
The ultraviolet cured adhesive follows the steps below：
Will 40 parts of self-control bifunctionality polyurethane acrylate prepolymer, 10 parts of polyfunctionality polyurethane acrylate prepolymer, 8 parts of polyester acrylate performed polymer, 12 parts of reactive amine compounding ingredient, 20 parts of acrylics reactive diluent, levelling wetting agent 2 2 parts of part and nano TiO 2 powder, are sequentially added into double-planet power mixing kettle, and unlatching revolution is stirred and disperseed at a high speed, 1h is persistently stirred, is well mixed system, adds 2 parts of light trigger, continues to stir 1h, adds 5 parts of aerosil, stirring 1h, deaeration under the conditions of being -0.098 in pressure, discharging, produce the ultraviolet cured adhesive for protecting temporarily and stick agent；The revolution Speed of agitator is 20r/min, and scattered rotating speed is 600r/min at a high speed；The polyester acrylate performed polymer is Sartomer C3108；
The acrylics reactive diluent includes tetrahydrofuran methyl acrylate and isodecyl acrylate according to quality Than 1:1 composition；The polyfunctionality polyurethane acrylate prepolymer is the CN975 of Sartomer；The reactivity Amine compounding ingredient be state refine learn limited company GC1100W；The levelling wetting agent is TEGO-4000；It is described light-initiated Agent is that 2- hydroxyls -2- methyl isophthalic acids-phenylacetone and phenyl are double（2,4,6- trimethylbenzoyls）Phosphorous oxide, 2,2- bis- Methoxyl group -2- phenyl acetophenones are according to mass ratio 1:1 composition；The fumed silica is the TS- of Cabot Co., Ltd 720。
Embodiment 3
It is made up of the raw material of following parts by weight：Make 40 parts of bifunctionality polyurethane acrylate prepolymer, the poly- ammonia of polyfunctionality by oneself 10 parts of ester acrylate prepolymer body, 8 parts of polyester acrylate performed polymer, 12 parts of reactive amine compounding ingredient, acrylics activity 20 parts of diluent, 2 parts of levelling wetting agent, 2 parts of light trigger, 2 parts of nano TiO 2 powder, 4 parts of aerosil；
The self-control bifunctionality polyurethane acrylate prepolymer follows the steps below：
By polyether Glycols temperature be 110 DEG C, pressure be -0.098MPa under conditions of be dehydrated 1.5 hours；Add two isocyanic acids Ester temperature be 60 DEG C, pressure be -0.098 under conditions of, stir 0.6h, add catalyst, temperature be 75 DEG C, pressure for - 2h is reacted under conditions of 0.098MPa；Sequentially add the acrylate of polymerization inhibitor and hydroxyl and temperature be 70 DEG C, pressure for- 2h is stirred under conditions of 0.098MPa, the content of NCO group is analyzed with infrared spectrometer every 30min samplings, when NCO peak is complete When totally disappeared mistake, stop heating response, produce bifunctionality polyurethane acrylate prepolymer；The polyether Glycols, two isocyanides The acrylate mol ratio of acid esters and hydroxyl is 1:1.8:1.8, catalyst and polymerization inhibitor respectively account for self-control bifunctionality polyurethane The 0.2 ‰ of acrylate prepolymer body weight；The PTMEG is polyethylene glycol, and its molecular weight is 800；The diisocyanate It is toluene di-isocyanate(TDI), hexamethylene diisocyanate and IPDI according to mass ratio 1:2:3 combination Thing；The acrylate of the hydroxyl is hydroxy-ethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate according to quality Than 3:2:1 composition；The catalyst is dibutyl tin laurate；The polymerization inhibitor is hydroquinones and para hydroxybenzene first Ether is according to mass ratio 2:1 composition；
The nano TiO 2 powder follows the steps below：
1) precursors are prepared：10mL tetra-n-butyl titanates are added in the container for filling 250mL ethylene glycol, and at 30 DEG C
Under the conditions of stir 8h, gained colourless transparent solution is precursors；
2) Ti0 is prepared2Powder：1mL glacial acetic acid is added in the container for filling 500mL acetone, is 200~300r/ in rotating speed min
Under conditions of precursors are poured into the container for filling acetone, stir 30min, be aged 30min, obtain white Ti02 Suspension, by suspension centrifugal filtration, and with water and the washed screening of ethanol, by filtrate under the conditions of 60 DEG C freeze-day with constant temperature 12h, obtain Ti02Powder；
3）Prepare Ti02Nano-powder：By TiO2Powder is positioned in Muffle furnace, and 2h is calcined under the conditions of 500 DEG C, is ground, and is used The screen cloth sieving of 400 mesh specifications, obtains Ti02Nano-powder;
The ultraviolet cured adhesive follows the steps below：
Will 40 parts of self-control bifunctionality polyurethane acrylate prepolymer, 10 parts of polyfunctionality polyurethane acrylate prepolymer, 8 parts of polyester acrylate performed polymer, 12 parts of reactive amine compounding ingredient, 20 parts of acrylics reactive diluent, levelling wetting agent 2 2 parts of part and nano TiO 2 powder, are sequentially added into double-planet power mixing kettle, and unlatching revolution is stirred and disperseed at a high speed, 1h is persistently stirred, is well mixed system, adds 2 parts of light trigger, continues to stir 1h, adds 5 parts of aerosil, stirring 1h, deaeration under the conditions of being -0.098 in pressure, discharging, produce the ultraviolet cured adhesive for protecting temporarily and stick agent；The revolution Speed of agitator is 20r/min, and scattered rotating speed is 600r/min at a high speed；The polyester acrylate performed polymer is Sartomer C3108；
The acrylics reactive diluent includes tetrahydrofuran methyl acrylate and isodecyl acrylate according to quality Than 1:1 composition；The polyfunctionality polyurethane acrylate prepolymer is the CN975 of Sartomer；The reactivity Amine compounding ingredient be state refine learn limited company GC1100W；The levelling wetting agent is TEGO-4000；It is described light-initiated Agent is that 2- hydroxyls -2- methyl isophthalic acids-phenylacetone and phenyl are double（2,4,6- trimethylbenzoyls）Phosphorous oxide, 2,2- bis- Methoxyl group -2- phenyl acetophenones are according to mass ratio 1:1 composition；The fumed silica is the TS- of Cabot Co., Ltd 720。
Embodiment 4
It is made up of the raw material of following parts by weight：Make 40 parts of bifunctionality polyurethane acrylate prepolymer, the poly- ammonia of polyfunctionality by oneself 10 parts of ester acrylate prepolymer body, 8 parts of polyester acrylate performed polymer, 12 parts of reactive amine compounding ingredient, acrylics activity 20 parts of diluent, 2 parts of levelling wetting agent, 2 parts of light trigger, 2.5 parts of nano TiO 2 powder, 3.5 parts of aerosil；
The self-control bifunctionality polyurethane acrylate prepolymer follows the steps below：
By polyether Glycols temperature be 110 DEG C, pressure be -0.098MPa under conditions of be dehydrated 1.5 hours；Add two isocyanic acids Ester temperature be 60 DEG C, pressure be -0.098 under conditions of, stir 0.6h, add catalyst, temperature be 75 DEG C, pressure for - 2h is reacted under conditions of 0.098MPa；Sequentially add the acrylate of polymerization inhibitor and hydroxyl and temperature be 70 DEG C, pressure for- 2h is stirred under conditions of 0.098MPa, the content of NCO group is analyzed with infrared spectrometer every 30min samplings, when NCO peak is complete When totally disappeared mistake, stop heating response, produce bifunctionality polyurethane acrylate prepolymer；The polyether Glycols, two isocyanides The acrylate mol ratio of acid esters and hydroxyl is 1:1.8:1.8, catalyst and polymerization inhibitor respectively account for self-control bifunctionality polyurethane The 0.2 ‰ of acrylate prepolymer body weight；The PTMEG is polyethylene glycol, and its molecular weight is 800；The diisocyanate It is toluene di-isocyanate(TDI), hexamethylene diisocyanate and IPDI according to mass ratio 1:2:3 combination Thing；The acrylate of the hydroxyl is hydroxy-ethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate according to quality Than 3:2:1 composition；The catalyst is dibutyl tin laurate；The polymerization inhibitor is hydroquinones and para hydroxybenzene first Ether is according to mass ratio 2:1 composition；
The nano TiO 2 powder follows the steps below：
1) precursors are prepared：10mL tetra-n-butyl titanates are added in the container for filling 250mL ethylene glycol, and at 30 DEG C
Under the conditions of stir 8h, gained colourless transparent solution is precursors；
2) Ti0 is prepared2Powder：1mL glacial acetic acid is added in the container for filling 500mL acetone, is 200~300r/ in rotating speed min
Under conditions of precursors are poured into the container for filling acetone, stir 30min, be aged 30min, obtain white Ti02 Suspension, by suspension centrifugal filtration, and with water and the washed screening of ethanol, by filtrate under the conditions of 60 DEG C freeze-day with constant temperature 12h, obtain Ti02Powder；
3）Prepare Ti02Nano-powder：By TiO2Powder is positioned in Muffle furnace, and 2h is calcined under the conditions of 500 DEG C, is ground, and is used The screen cloth sieving of 400 mesh specifications, obtains Ti02Nano-powder;
The ultraviolet cured adhesive follows the steps below：
Will 40 parts of self-control bifunctionality polyurethane acrylate prepolymer, 10 parts of polyfunctionality polyurethane acrylate prepolymer, 8 parts of polyester acrylate performed polymer, 12 parts of reactive amine compounding ingredient, 20 parts of acrylics reactive diluent, levelling wetting agent 2 2 parts of part and nano TiO 2 powder, are sequentially added into double-planet power mixing kettle, and unlatching revolution is stirred and disperseed at a high speed, 1h is persistently stirred, is well mixed system, adds 2 parts of light trigger, continues to stir 1h, adds 5 parts of aerosil, stirring 1h, deaeration under the conditions of being -0.098 in pressure, discharging, produce the ultraviolet cured adhesive for protecting temporarily and stick agent；The revolution Speed of agitator is 20r/min, and scattered rotating speed is 600r/min at a high speed；The polyester acrylate performed polymer is Sartomer C3108；
The acrylics reactive diluent includes tetrahydrofuran methyl acrylate and isodecyl acrylate according to quality Than 1:1 composition；The polyfunctionality polyurethane acrylate prepolymer is the CN975 of Sartomer；The reactivity Amine compounding ingredient be state refine learn limited company GC1100W；The levelling wetting agent is TEGO-4000；It is described light-initiated Agent is that 2- hydroxyls -2- methyl isophthalic acids-phenylacetone and phenyl are double（2,4,6- trimethylbenzoyls）Phosphorous oxide, 2,2- bis- Methoxyl group -2- phenyl acetophenones are according to mass ratio 1:1 composition；The fumed silica is the TS- of Cabot Co., Ltd 720。
Embodiment 5
It is made up of the raw material of following parts by weight：Make 40 parts of bifunctionality polyurethane acrylate prepolymer, the poly- ammonia of polyfunctionality by oneself 10 parts of ester acrylate prepolymer body, 8 parts of polyester acrylate performed polymer, 12 parts of reactive amine compounding ingredient, acrylics activity 20 parts of diluent, 2 parts of levelling wetting agent, 2 parts of light trigger, 3 parts of nano TiO 2 powder, 3 parts of aerosil；
The self-control bifunctionality polyurethane acrylate prepolymer follows the steps below：
By polyether Glycols temperature be 110 DEG C, pressure be -0.098MPa under conditions of be dehydrated 1.5 hours；Add two isocyanic acids Ester temperature be 60 DEG C, pressure be -0.098 under conditions of, stir 0.6h, add catalyst, temperature be 75 DEG C, pressure for - 2h is reacted under conditions of 0.098MPa；Sequentially add the acrylate of polymerization inhibitor and hydroxyl and temperature be 70 DEG C, pressure for- 2h is stirred under conditions of 0.098MPa, the content of NCO group is analyzed with infrared spectrometer every 30min samplings, when NCO peak is complete When totally disappeared mistake, stop heating response, produce bifunctionality polyurethane acrylate prepolymer；The polyether Glycols, two isocyanides The acrylate mol ratio of acid esters and hydroxyl is 1:1.8:1.8, catalyst and polymerization inhibitor respectively account for self-control bifunctionality polyurethane The 0.2 ‰ of acrylate prepolymer body weight；The PTMEG is polyethylene glycol, and its molecular weight is 800；The diisocyanate It is toluene di-isocyanate(TDI), hexamethylene diisocyanate and IPDI according to mass ratio 1:2:3 combination Thing；The acrylate of the hydroxyl is hydroxy-ethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate according to quality Than 3:2:1 composition；The catalyst is dibutyl tin laurate；The polymerization inhibitor is hydroquinones and para hydroxybenzene first Ether is according to mass ratio 2:1 composition；
The nano TiO 2 powder follows the steps below：
1) precursors are prepared：10mL tetra-n-butyl titanates are added in the container for filling 250mL ethylene glycol, and at 30 DEG C
Under the conditions of stir 8h, gained colourless transparent solution is precursors；
2) Ti0 is prepared2Powder：1mL glacial acetic acid is added in the container for filling 500mL acetone, is 200~300r/ in rotating speed min
Under conditions of precursors are poured into the container for filling acetone, stir 30min, be aged 30min, obtain white Ti02 Suspension, by suspension centrifugal filtration, and with water and the washed screening of ethanol, by filtrate under the conditions of 60 DEG C freeze-day with constant temperature 12h, obtain Ti02Powder；
3）Prepare Ti02Nano-powder：By TiO2Powder is positioned in Muffle furnace, and 2h is calcined under the conditions of 500 DEG C, is ground, and is used The screen cloth sieving of 400 mesh specifications, obtains Ti02Nano-powder;
The ultraviolet cured adhesive follows the steps below：
Will 40 parts of self-control bifunctionality polyurethane acrylate prepolymer, 10 parts of polyfunctionality polyurethane acrylate prepolymer, 8 parts of polyester acrylate performed polymer, 12 parts of reactive amine compounding ingredient, 20 parts of acrylics reactive diluent, levelling wetting agent 2 2 parts of part and nano TiO 2 powder, are sequentially added into double-planet power mixing kettle, and unlatching revolution is stirred and disperseed at a high speed, 1h is persistently stirred, is well mixed system, adds 2 parts of light trigger, continues to stir 1h, adds 5 parts of aerosil, stirring 1h, deaeration under the conditions of being -0.098 in pressure, discharging, produce the ultraviolet cured adhesive for protecting temporarily and stick agent；The revolution Speed of agitator is 20r/min, and scattered rotating speed is 600r/min at a high speed；The polyester acrylate performed polymer is Sartomer C3108；
The acrylics reactive diluent includes tetrahydrofuran methyl acrylate and isodecyl acrylate according to quality Than 1:1 composition；The polyfunctionality polyurethane acrylate prepolymer is the CN975 of Sartomer；The reactivity Amine compounding ingredient be state refine learn limited company GC1100W；The levelling wetting agent is TEGO-4000；It is described light-initiated Agent is that 2- hydroxyls -2- methyl isophthalic acids-phenylacetone and phenyl are double（2,4,6- trimethylbenzoyls）Phosphorous oxide, 2,2- bis- Methoxyl group -2- phenyl acetophenones are according to mass ratio 1:1 composition；The fumed silica is the TS- of Cabot Co., Ltd 720。
Embodiment 6
It is made up of the raw material of following parts by weight：Make 50 parts of bifunctionality polyurethane acrylate prepolymer, the poly- ammonia of polyfunctionality by oneself 7 parts of ester acrylate prepolymer body, 7 parts of polyester acrylate performed polymer, 14 parts of reactive amine compounding ingredient, acrylics activity is dilute Release 12 parts of agent, 1.5 parts of levelling wetting agent, 1.5 parts of light trigger, 2 parts of nano TiO 2 powder, 5 parts of aerosil；
The self-control bifunctionality polyurethane acrylate prepolymer follows the steps below：
By polyether Glycols temperature be 120 DEG C, pressure be -0.298MPa under conditions of be dehydrated 1.5 hours；Add two isocyanic acids Ester temperature be 65 DEG C, pressure be -0.098 under conditions of, stir 1h, add catalyst, temperature be 75 DEG C, pressure for - 2h is reacted under conditions of 0.198MPa；Sequentially add the acrylate of polymerization inhibitor and hydroxyl and temperature be 70 DEG C, pressure for- 2h is stirred under conditions of 0.098MPa, the content of NCO group is analyzed with infrared spectrometer every 30min samplings, when NCO peak is complete When totally disappeared mistake, stop heating response, produce bifunctionality polyurethane acrylate prepolymer；The polyether Glycols, two isocyanides The acrylate mol ratio of acid esters and hydroxyl is 1:1.7:2, catalyst and polymerization inhibitor respectively account for self-control bifunctionality polyurethane third The 0.4 ‰ of olefin(e) acid ester pre-polymerization body weight；The PTMEG is polyethylene glycol, and its molecular weight is 1600；The diisocyanate It is toluene di-isocyanate(TDI) and IPDI according to mass ratio 1:2 composition；The acrylic acid of the hydroxyl Ester is hydroxy-ethyl acrylate；The catalyst is dibutyl tin laurate；The polymerization inhibitor is MEHQ；Obtain double officials Energy degree polyurethane acrylate prepolymer；
The nano TiO 2 powder follows the steps below：
1) precursors are prepared：10mL tetra-n-butyl titanates are added in the container for filling 250mL ethylene glycol, and at 30 DEG C
Under the conditions of stir 8h, gained colourless transparent solution is precursors；
2) Ti0 is prepared2Powder：1mL glacial acetic acid is added in the container for filling 500mL acetone, is 200~300r/ in rotating speed min
Under conditions of precursors are poured into the container for filling acetone, stir 30min, be aged 30min, obtain white Ti02 Suspension, by suspension centrifugal filtration, and with water and the washed screening of ethanol, by filtrate under the conditions of 60 DEG C freeze-day with constant temperature 12h, obtain Ti02Powder；
3）Prepare Ti02Nano-powder：By TiO2Powder is positioned in Muffle furnace, and 2h is calcined under the conditions of 500 DEG C, is ground, and is used The screen cloth sieving of 400 mesh specifications, obtains Ti02Nano-powder;
The ultraviolet cured adhesive follows the steps below：
50 parts of bifunctionality polyurethane acrylate prepolymer, 7 parts of polyfunctionality polyurethane acrylate prepolymer will be made by oneself, gathered 7 parts of ester acrylate prepolymer body, 14 parts of reactive amine compounding ingredient, 12 parts of acrylics reactive diluent, levelling wetting agent 1.5 2 parts of part and nano TiO 2 powder, are sequentially added into double-planet power mixing kettle, and unlatching revolution is stirred and disperseed at a high speed, 1h is persistently stirred, is well mixed system, adds 1.5 parts of light trigger, continues to stir 1h, adds 5 parts of aerosil, stir 1h is mixed, deaeration under the conditions of being -0.098 in pressure, discharging, the ultraviolet cured adhesive for protecting temporarily is produced and sticks agent；The public affairs It is 20r/min to turn speed of agitator, and scattered rotating speed is 600r/min at a high speed；The polyester acrylate performed polymer is Sartomer C3108；
The acrylics reactive diluent includes tetrahydrofuran methyl acrylate and isodecyl acrylate according to quality Than 1:1 composition；The polyfunctionality polyurethane acrylate prepolymer is the CN975 of Sartomer；The reactivity Amine compounding ingredient be state refine learn limited company GC1100W；The levelling wetting agent is TEGO-4000；It is described light-initiated Agent is that 2- hydroxyls -2- methyl isophthalic acids-phenylacetone and phenyl are double（2,4,6- trimethylbenzoyls）Phosphorous oxide, 2,2- bis- Methoxyl group -2- phenyl acetophenones are according to mass ratio 1:1 composition；The fumed silica is the TS- of Cabot Co., Ltd 720。
The present invention is further illustrated with reference to instantiation：
Beneficial effects of the present invention are further illustrated with reference to experimental data：
1 materials and methods：
1.1 test site：Yantai Xin You new materials limited company laboratory.
1.2 experiment detections：Agent irradiation is sticked to the ultraviolet cured adhesive being in the milk in cap nut using ultraviolet, works as ultraviolet Energy reaches 6000mJ/cm2When, agent is sticked to ultraviolet cured adhesive and peeled off, the stripping that detection ultraviolet cured adhesive sticks agent is complete Whole degree.
1.3 material to be tested：Contrast 1（In addition to titanium dioxide nano thread is not added, other preparation methods with embodiment 3 one Cause）, contrast 2（Except addition titanium dioxide for sulfuric acid process prepare titanium dioxide in addition to, other preparation methods with embodiment 3 one Cause）, contrast 3（Except addition titanium dioxide for chloridising prepare titanium dioxide in addition to, other preparation methods with embodiment 3 one Cause）, embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5.
2 results and analysis
It can be seen from the results above that adding titanium dioxide, after ultraviolet irradiates, the stripping that can significantly improve adhesive is complete Degree, wherein the integrity degree of peeling off for adding the titanium dioxide nano thread prepared according to the present invention is significantly better than prepared by conventional commercial Titanium dioxide, the present invention are compared by the data of embodiment 1 to 5, it is found that the stripping integrity degree of embodiment 3 is best, therefore implement The best results of example 3.
The embodiment of the present invention 3 is applied to the CNC techniques in the enterprise of Shanghai production metal notebook computer shell, solves it The problem of metal shell is protected temporarily, by client's favorable comment.Can solve metal shell through the practice test embodiment of the present invention 3 to exist Interim protection problem in CNC techniques.

Claims (5)

1. a kind of ultraviolet cured adhesive of doped nano titanium dioxide sticks agent and preparation method thereof, it is characterised in that：
It is made up of the raw material of following parts by weight：Make 20~60 parts of bifunctionality polyurethane acrylate prepolymer, polyfunctionality by oneself 5~15 parts of polyurethane acrylate prepolymer, 5~15 parts of polyester acrylate performed polymer, 5~20 parts of reactive amine compounding ingredient, 10~30 parts of acrylics reactive diluent, 0.5~5 part of levelling wetting agent, 1~5 part of light trigger, titanic oxide nano 0.5~3 part of body, 0.1~10 part of aerosil；
The self-control bifunctionality polyurethane acrylate prepolymer follows the steps below：
By polyether Glycols temperature be 110 DEG C~120 DEG C, pressure be -0.095~-0.85MPa under conditions of be dehydrated 1.5~2 Hour；It is 50 DEG C~70 DEG C that diisocyanate, which is added, in temperature, under conditions of pressure is -0.095~-0.85, stirring 0.5~ 1h, catalyst is added, be 70 DEG C~80 DEG C in temperature, pressure reacts 2~3h under conditions of being -0.095~-0.85MPa；Successively Add the acrylate of polymerization inhibitor and hydroxyl and be 60 DEG C~80 DEG C in temperature, pressure is -0.095~-0.85MPa condition 2~3h of lower stirring, the content of NCO group is analyzed with infrared spectrometer every 30min samplings, when NCO peak is wholly absent, is stopped Only heating response, produce bifunctionality polyurethane acrylate prepolymer；The polyether Glycols, diisocyanate and hydroxyl Acrylate mol ratio be 1:1.6~2.0:1.6~2.2, catalyst and polymerization inhibitor respectively account for self-control bifunctionality polyurethane third 0.1 ‰~the 1 ‰ of olefin(e) acid ester pre-polymerization body weight；
The nano TiO 2 powder follows the steps below：
Prepare precursors：10mL tetra-n-butyl titanates are added in the container for filling 250mL ethylene glycol, and at 30 DEG C
Under the conditions of stir 8h, gained colourless transparent solution is precursors；
Prepare Ti02Powder：1mL glacial acetic acid is added in the container for filling 500mL acetone, is 200~300r/min in rotating speed
Under conditions of precursors are poured into the container for filling acetone, stir 30min, be aged 30min, obtain white Ti02 Suspension, by suspension centrifugal filtration, and with water and the washed screening of ethanol, by filtrate under the conditions of 60 DEG C freeze-day with constant temperature 12h, obtain Ti02Powder；
3）Prepare Ti02Nano-powder：By TiO2Powder is positioned in Muffle furnace, and 2h is calcined under the conditions of 500 DEG C, grinding, with 400 The screen cloth sieving of mesh specification, obtains Ti02Nano-powder;
The ultraviolet cured adhesive follows the steps below：
Will 20~60 parts of self-control bifunctionality polyurethane acrylate prepolymer, polyfunctionality polyurethane acrylate prepolymer 5 ~15 parts, 5~15 parts of polyester acrylate performed polymer, 5~20 parts of reactive amine compounding ingredient, acrylics reactive diluent 10 0.5~3 part of~30 parts, 0.5~5 part of levelling wetting agent and nano TiO 2 powder, sequentially add to double-planet power and mix In kettle, open revolution stirring and high speed be scattered, persistently stir 1~2h, be well mixed system, add 1~5 part of light trigger, Continue 1~2h of stirring, add 0.1~10 part of aerosil, stir 1~2h, be -0.095~-0.85 condition in pressure Lower deaeration, discharging, produce the ultraviolet cured adhesive for protecting temporarily and stick agent；
The PTMEG includes two of one kind or arbitrary proportion in polyethylene glycol, polypropylene glycol and PTMG More than kind, the molecular weight of PTMEG is 650~3000；
The diisocyanate includes toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, the isocyanic acid of phenylenedimethylidyne two One kind or arbitrary proportion in ester, hexamethylene diisocyanate and IPDI it is two or more；
The acrylate of the hydroxyl includes hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, methyl-prop One kind or arbitrary proportion of olefin(e) acid hydroxypropyl acrylate and trimethylolpropane diacrylate it is two or more；
The polymerization inhibitor is hydroquinones, MEHQ and 2, one kind or arbitrary proportion in 6 toluene di-tert-butyl phenols It is two or more；
The catalyst is dibutyl tin laurate；
The polyester acrylate performed polymer is that the C3108 of Sartomer, the CN704 of Sartomer, state refine and learn share One kind in the 3400Z of Co., Ltd, the 6349 of Changxing chemical material Co., Ltd and Changxing chemical material Co., Ltd 6363 Or arbitrary proportion is two or more；
The acrylics reactive diluent includes tetrahydrofuran methyl acrylate, tetrahydrofuran acrylate, methyl-prop One kind or any in olefin(e) acid isobornyl thiocyanoacetate, hydroxyethyl methacrylate, hydroxy propyl methacrylate and isodecyl acrylate Ratio it is two or more；
The polyfunctionality polyurethane acrylate prepolymer is the CN975 of Sartomer, Changxing chemical material Co., Ltd 6146-100,6147, the 4312 of RAHN companies of Changxing chemical material Co., Ltd and the 4316 of RAHN companies in one kind Or arbitrary proportion is two or more；
The reactive amine compounding ingredient be state refine learn limited company GC1100W, GC1100Z and GC1200C in one The mixture of kind or two or more any ratios；
The levelling wetting agent include one kind in TEGO-4000, TEGO-4100 and BYK-3510 or two kinds of arbitrary proportion with On；The light trigger is 2- hydroxy-2-methyl -1- phenylacetones, 1- hydroxy cyclohexyl phenylketones, phenyl pair（2,4,6- tri- Methyl benzoyl）Phosphorous oxide, 2,2- dimethoxy -2- phenyl acetophenones, isopropyl thioxanthone, benzophenone and 2,4, One kind or arbitrary proportion in 6- trimethyl benzoyl diphenyl base phosphorous oxides it is two or more；
The fumed silica includes R202 the and Ying Chuan companies of TS-720, EH-5, Ying Chuan company of Cabot Co., Ltd One kind or arbitrary proportion in A200 it is two or more；
The revolution speed of agitator is 20r/min, and scattered rotating speed is 600r/min at a high speed.
2. the ultraviolet cured adhesive of doped nano titanium dioxide as claimed in claim 1 sticks agent and preparation method thereof, its feature It is：Si/Ti mol ratios are 2~4 in the gaseous mixture:1, general gas flow is 1000~1500sccm.
3. the ultraviolet cured adhesive of doped nano titanium dioxide as claimed in claim 1 sticks agent and preparation method thereof, its feature It is：The ultraviolet cured adhesive completes the ultraviolet irradiation energy of solidification in 600~1200mJ/cm2；The ultraviolet light solidification The ultraviolet irradiation energy that glue is peeled off is in 3000~6000mJ/cm2。
4. the ultraviolet cured adhesive of doped nano titanium dioxide as claimed in claim 1 sticks agent and preparation method thereof, its feature It is：The viscosity of ultraviolet cured adhesive is 2000m~28000mPas；Thixotropic index is 1.2~12.
5. the ultraviolet cured adhesive of doped nano titanium dioxide as claimed in claim 1 sticks agent and preparation method thereof, its feature It is：
It is made up of the raw material of following parts by weight：Make 40 parts of bifunctionality polyurethane acrylate prepolymer, the poly- ammonia of polyfunctionality by oneself 10 parts of ester acrylate prepolymer body, 8 parts of polyester acrylate performed polymer, 12 parts of reactive amine compounding ingredient, acrylics activity 20 parts of diluent, 2 parts of levelling wetting agent, 2 parts of light trigger, titanium dioxide receive 2 parts of powder, 4 parts of aerosil；
The self-control bifunctionality polyurethane acrylate prepolymer follows the steps below：
By polyether Glycols temperature be 110 DEG C, pressure be -0.098MPa under conditions of be dehydrated 1.5 hours；Add two isocyanic acids Ester temperature be 60 DEG C, pressure be -0.098 under conditions of, stir 0.6h, add catalyst, temperature be 75 DEG C, pressure for - 2h is reacted under conditions of 0.098MPa；Sequentially add the acrylate of polymerization inhibitor and hydroxyl and temperature be 70 DEG C, pressure for- 2h is stirred under conditions of 0.098MPa, the content of NCO group is analyzed with infrared spectrometer every 30min samplings, when NCO peak is complete When totally disappeared mistake, stop heating response, produce bifunctionality polyurethane acrylate prepolymer；The polyether Glycols, two isocyanides The acrylate mol ratio of acid esters and hydroxyl is 1:1.8:1.8, catalyst and polymerization inhibitor respectively account for self-control bifunctionality polyurethane The 0.2 ‰ of acrylate prepolymer body weight；The PTMEG is polyethylene glycol, and its molecular weight is 800；The diisocyanate It is toluene di-isocyanate(TDI), hexamethylene diisocyanate and IPDI according to mass ratio 1:2:3 combination Thing；The acrylate of the hydroxyl is hydroxy-ethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate according to quality Than 3:2:1 composition；The catalyst is dibutyl tin laurate；The polymerization inhibitor is hydroquinones and para hydroxybenzene first Ether is according to mass ratio 2:1 composition；
The nano TiO 2 powder follows the steps below：
1) precursors are prepared：10mL tetra-n-butyl titanates are added in the container for filling 250mL ethylene glycol, and at 30 DEG C
Under the conditions of stir 8h, gained colourless transparent solution is precursors；
2) Ti0 is prepared2Powder：1mL glacial acetic acid is added in the container for filling 500mL acetone, is 200~300r/ in rotating speed min
Under conditions of precursors are poured into the container for filling acetone, stir 30min, be aged 30min, obtain white Ti02 Suspension, by suspension centrifugal filtration, and with water and the washed screening of ethanol, by filtrate under the conditions of 60 DEG C freeze-day with constant temperature 12h, obtain Ti02Powder；
3）Prepare Ti02Nano-powder：By TiO2Powder is positioned in Muffle furnace, and 2h is calcined under the conditions of 500 DEG C, grinding, with 400 The screen cloth sieving of mesh specification, obtains Ti02Nano-powder;
The ultraviolet cured adhesive follows the steps below：
Will 40 parts of self-control bifunctionality polyurethane acrylate prepolymer, 10 parts of polyfunctionality polyurethane acrylate prepolymer, 8 parts of polyester acrylate performed polymer, 12 parts of reactive amine compounding ingredient, 20 parts of acrylics reactive diluent, levelling wetting agent 2 2 parts of part and nano TiO 2 powder, are sequentially added into double-planet power mixing kettle, and unlatching revolution is stirred and disperseed at a high speed, 1h is persistently stirred, is well mixed system, adds 2 parts of light trigger, continues to stir 1h, adds 5 parts of aerosil, stirring 1h, deaeration under the conditions of being -0.098 in pressure, discharging, produce the ultraviolet cured adhesive for protecting temporarily and stick agent；The revolution Speed of agitator is 20r/min, and scattered rotating speed is 600r/min at a high speed；The polyester acrylate performed polymer is Sartomer C3108；
The acrylics reactive diluent includes tetrahydrofuran methyl acrylate and isodecyl acrylate according to quality Than 1:1 composition；The polyfunctionality polyurethane acrylate prepolymer is the CN975 of Sartomer；The reactivity Amine compounding ingredient be state refine learn limited company GC1100W；The levelling wetting agent is TEGO-4000；It is described light-initiated Agent is that 2- hydroxyls -2- methyl isophthalic acids-phenylacetone and phenyl are double（2,4,6- trimethylbenzoyls）Phosphorous oxide, 2,2- bis- Methoxyl group -2- phenyl acetophenones are according to mass ratio 1:1 composition；The fumed silica is the TS- of Cabot Co., Ltd 720。
CN201710658396.2A 2017-08-04 2017-08-04 Nano-titanium dioxide doped ultraviolet curing adhesive and preparation method thereof Active CN107502272B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108913070A (en) * 2018-05-21 2018-11-30 南京林业大学 The preparation method and applications method of thermosetting property watersoluble melamine formaldehyde resin nano-powder adhesive
CN111440586A (en) * 2020-03-09 2020-07-24 王凤艳 Environment-friendly high-strength ultraviolet-curing acrylate pressure-sensitive adhesive and preparation method thereof

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CN105925238A (en) * 2016-06-28 2016-09-07 烟台信友新材料股份有限公司 UV-curing adhesive with low Tg point and high permeability and preparation method thereof

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CN105925238A (en) * 2016-06-28 2016-09-07 烟台信友新材料股份有限公司 UV-curing adhesive with low Tg point and high permeability and preparation method thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108913070A (en) * 2018-05-21 2018-11-30 南京林业大学 The preparation method and applications method of thermosetting property watersoluble melamine formaldehyde resin nano-powder adhesive
CN111440586A (en) * 2020-03-09 2020-07-24 王凤艳 Environment-friendly high-strength ultraviolet-curing acrylate pressure-sensitive adhesive and preparation method thereof
CN111440586B (en) * 2020-03-09 2022-03-29 王凤艳 Environment-friendly high-strength ultraviolet-curing acrylate pressure-sensitive adhesive and preparation method thereof

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