CN107987716A - A kind of phenyl compound and UV type cathode electrophoresis dope and its preparation and application - Google Patents

A kind of phenyl compound and UV type cathode electrophoresis dope and its preparation and application Download PDF

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CN107987716A
CN107987716A CN201711147163.2A CN201711147163A CN107987716A CN 107987716 A CN107987716 A CN 107987716A CN 201711147163 A CN201711147163 A CN 201711147163A CN 107987716 A CN107987716 A CN 107987716A
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parts
product
catalyst
electrophoresis
cathode electrophoresis
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CN107987716B (en
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涂伟萍
陈君华
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/4465—Polyurethanes
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
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    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
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    • 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
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    • 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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4488—Cathodic paints
    • C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/04—Electrophoretic coating characterised by the process with organic material
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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Abstract

The invention belongs to the technical field of electrophoretic coating, discloses a kind of phenyl compound and UV type cathode electrophoresis dope and its preparation and application.The structural formula of the phenyl compound is Formulas I.The UV types cathode electrophoresis dope is made of following component by weight：10~25 parts of dimethylaminoethyl methacrylate, 15~30 parts of methyl methacrylate, 4~20 parts of hydroxy-ethyl acrylate, 15~30 parts of butyl acrylate, 5~20 parts of styrene, 5~20 parts of diisocyanate, 0.2~1 part of catalyst, 1~2 part of polymerization inhibitor, 1~10 part of radical initiator, 2~8 parts of dispersant, 2~8 parts of photoinitiator, 5~30 parts of phenyl compound, 3~10 parts of neutralizer, 102~210 parts of organic solvent, 100~1500 parts of water.The UV types cathode electrophoresis dope has preferable heat resistance, hardness and glossiness；It is used to prepare electrophoresis product.

Description

A kind of phenyl compound and UV type cathode electrophoresis dope and its preparation and application
Technical field
The invention belongs to the technical field of electrophoretic coating, and in particular to a kind of phenyl compound and UV type cathode electrophoresis dope And preparation method and application.
Background technology
Electrophoretic coating is main because having the advantages that paint film is homogeneous, hardness is high, the transparency is good, efficient and energy saving and low stain To apply and be applied in automobile production.Compared with anode electrophoresis dope, there is more excellent anti-corrosion after cathode electrophoresis dope application Ability, throwing power are high and because its utilization efficiency of coatings is high, film is uniformly from the influence of coated article shape, good decorating effect, environment Polluting the advantages that small is not only widely used in painting dressing automobiles field, and in metal surfaces such as building materials, furniture, hardware and craftworks Anti-corrosion and furnishing fields are also widely used.
What the curing mode of conventional electrophoretic paint was generally taken is to be heating and curing, and required solidification temperature is very high, cures temperature Degree limits the application in heatsensitive substrates such as plastics, timber generally at 140~180 DEG C, and hardening time is longer.It is purple Outer photocuring technology be using apply film resin occurs under ultraviolet light polymerization bridging reaction, the short time under conditions of low temperature The interior curing process that can just complete.And ultraviolet light cures electrophoretic coating except because its solidification temperature is relatively low, curing rate is fast, no Common electrophoretic painting is only applicable to, is additionally suitable for other products.Therefore comprehensive UV cures and electrophoretic painting advantage Ultraviolet light (UV) Curable Cationic Electrodeposition Coatings have great application development prospect.
But it is few suitable for the species of the photoinitiator of UV Curable Cationic Electrodeposition Coatings at present, new photoinitiator but still In the laboratory research stage, there is a distance from actual industrial production application, need further to be studied；Coated solidified mistake Influence and flash process application problem of the journey to paint film property also need to further study.There is also hardness of paint film, heat-resisting at the same time Property and low in glossiness problem.
Ultraviolet light curing cathodic electrophoretic coating common at present is there are poor heat resistance, and hardness is low, and glossiness is low, and pliability is poor The problems such as.Therefore it is highly desirable to provide and a kind of has hardness and the high cathode electrophoresis dope of glossiness concurrently with UV type heat resistances.
The content of the invention
The shortcomings that in order to solve the prior art and shortcoming, primary and foremost purpose of the invention are synthesizing a kind of rigid structure Heat-resistant monomer (i.e. phenyl compound) and preparation method thereof.
Another object of the present invention is to provide a kind of UV type cathode electrophoresis dopes prepared using above-mentioned phenyl compound And its method.By using phenyl compound, the present invention solves UV type cathode electrophoresis dope poor heat resistances, and hardness is low, gloss Spend low, the technical problem such as pliability difference.
It is still another object of the present invention to provide the application using above-mentioned UV types cathode electrophoresis dope.The UV types cathode electricity It is electrophoretic paint used in preparing electrophoresis product.
The purpose of the present invention is achieved through the following technical solutions：
A kind of phenyl compound, its structural formula are
The preparation method of the phenyl compound be using organic solvent as reaction medium, using benzaldehyde and methyl acrylate as Reaction raw materials, reaction raw materials are reacted under the action of catalyst, and purifying, obtains phenyl compound.The benzaldehyde and third The molar ratio of e pioic acid methyl ester is (2~10) mol：(3~15) mol.
The amount ratio of the benzaldehyde and catalyst is (2~10) mol：(2~12) mol；The benzaldehyde with it is organic molten The amount ratio of agent is (2~10) mol：(50~200) ml.
The catalyst is triethylamine, triethylene diamine, tetrabutyl Ammonium hydrogen sulfate, four butyl bromation amine, triethylbenzyl One or more of ammonium chloride, 4-dimethylaminopyridine；The organic solvent is tetrahydrofuran, ethyl acetate, methanol, dimethyl One or more of sulfoxide, dimethylformamide.
The temperature of the reaction is room temperature, and whether the reaction is completed by thin-layered chromatography TLC monitoring reactions.
The purifying refers to wash the product after reaction with saturated aqueous ammonium chloride, is then extracted, had with extract Machine mutually uses desiccant dryness, filters, and revolving, silica gel column chromatography, revolving, obtains phenyl compound.
The extract is one or more of carbon tetrachloride, alcohol, ethyl acetate；The drier is anhydrous slufuric acid One or more of magnesium, anhydrous sodium sulfate, natrium carbonicum calcinatum.
The temperature of the revolving is 30~60 DEG C；The time of desiccant dryness is 6~10h.
50~the 300ml of saturated aqueous ammonium chloride, extract dosage are 10~50ml, drier dosage be 5~ 10g。
The phenyl compound is used to prepare UV type cathode electrophoresis dopes.
A kind of UV type cathode electrophoresis dopes prepared using above-mentioned phenyl compound, by following component group by weight Into：10~25 parts of dimethylaminoethyl methacrylate (DMAEMA), 15~30 parts of methyl methacrylate (MMA), acrylic acid 4~20 parts of hydroxyl ethyl ester (HEA), 15~30 parts of butyl acrylate (BA), 5~20 parts of styrene (St), diisocyanate 5~20 Part, 0.2~1 part of catalyst, 1~2 part of polymerization inhibitor, 1~10 part of radical initiator, 2~8 parts of dispersant, photoinitiator 2~8 Part, 5~30 parts of phenyl compound, 3~10 parts of neutralizer, 102~210 parts of organic solvent, 100~1500 parts of water.
The diisocyanate is isophorone diisocyanate (IPDI).
The catalyst is triethylamine, dibutyl tin laurate, triethylene diamine, tetrabutyl Ammonium hydrogen sulfate, the tetrabutyl One or more of amine bromide, triethylbenzyl ammonium chloride, 4-dimethylaminopyridine.
The polymerization inhibitor for hydroquinone, 1,4-benzoquinone, 2,6- toluene di-tert-butyl phenols, beta-phenyl naphthylamines, to the tert-butyl group One or more of catechol.
The radical initiator is one in azodiisobutyronitrile, azo-bis-iso-dimethyl, benzoyl peroxide More than kind.
The dispersant is ethylene glycol monobutyl ether, in propyleneglycoles monobutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether More than one.
The photoinitiator is 1- hydroxycyclohexyl phenyl ketones, 2- hydroxy-2-methyl -1- phenylacetones, 2,4,6- tri- One in methyl benzoyl-diphenyl phosphine oxide, 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) phenyl] -1- acetone More than kind.
The neutralizer is one or more of lactic acid, glacial acetic acid, nitric acid, bishydroxymethyl propionic acid.
The organic solvent is propylene glycol methyl ether acetate, ethyl acetate, methanol, dimethyl sulfoxide (DMSO), methyl iso-butyl ketone (MIBK) One or more of.
The preparation method of the UV types cathode electrophoresis dope, comprises the following steps：
(1) by 10~25 parts of dimethylaminoethyl methacrylate (DMAEMA), methyl methacrylate (MMA) 15~30 Part, 2~10 parts of hydroxy-ethyl acrylate (HEA), 15~30 parts of butyl acrylate (BA), 5~20 parts of styrene (St), free radical draw Send out 1~10 part of agent and 50~100 parts of organic solvent is uniformly mixed, obtain mixed monomer solution；(stirring turns under conditions of stirring Speed is 120~200r/min), in 70 DEG C~90 DEG C, into 50~100 parts of organic solvents, mixed monomer solution is added dropwise, drips 4~6h is kept the temperature after finishing, it is 50wt%~70wt% to be evaporated under reduced pressure to solid content, obtains product A；
(2) 0.5~1 part of 5~20 parts of diisocyanate and polymerization inhibitor are uniformly mixed, then at 40~70 DEG C, are added dropwise By 2~10 parts of hydroxy-ethyl acrylate (HEA) and 0.1~0.5 part of mixture mixed of catalyst, after dripping, continue anti- Should, when the content of the theoretical value after the content of-NCO in reaction system reaches semiclosed, reaction is terminated, obtains product B；
(3) 0.1~0.5 part of catalyst, 0.5~1 part of polymerization inhibitor are dissolved in 2~10 parts of organic solvents, obtain catalyst With the mixed solution of polymerization inhibitor；The mixed solution of catalyst and polymerization inhibitor is uniformly mixed with the product B of step (2), is mixed Compound；Under conditions of stirring (speed of agitator is 100~150r/min), in 40 DEG C~70 DEG C, into the product A of step (1) Mixture is added dropwise, is added dropwise, keeps the temperature 3~4h, obtains resin product；
(4) in 40 DEG C~70 DEG C, 3~10 parts of neutralizer is added to the resin product of step (3), stirs evenly, is down to room Temperature, adds 2~8 parts of dispersant, 5~30 parts of 2~8 parts of photoinitiator and phenyl compound, is uniformly dispersed, it is gradually added 100~ 1500 parts of water make it that solid content is 10~20%, and high speed emulsion dispersion, curing, obtaining UV types cathode electrophoresis dope, (i.e. UV light is consolidated Change the acids cathode electrophoresis dope of modified propylene).
The condition of high speed emulsion dispersion described in step (4) is to disperse 20~60min under 3000~6000r/min rotating speeds, The condition of curing is to cure 24~48h with 150~250r/min.
Stirred evenly described in step (4) and refer to stir 20~60min with the speed of 120~200r/min；It is described scattered Uniformly refer to stir 5~10min with 180~250r/min rotating speeds.
The temperature being evaporated under reduced pressure described in step (1) is 40 DEG C~70 DEG C；Need to cool down before vacuum distillation；The dropwise addition need to be It is added dropwise in 2-3h；
The content of-NCO di-n-butylamine method titration determination in the reaction system of step (2)；
Being added dropwise described in step (2) need to be added dropwise in 1~2h；
Being added dropwise described in step (3) needs to be added dropwise in 1~2h.
The UV types cathode electrophoresis dope is used to prepare electrophoresis product.
The electrophoresis product includes substrate pole plate and is deposited on the UV types cathode electrophoresis dope deposition of substrate polar board surface Layer.The substrate pole plate is the iron plate that phosphorating treatment is crossed.
The specific preparation method of the electrophoresis product is：Using UV types cathode electrophoresis dope as working solution, made with aluminium alloy plate For anode, using substrate pole plate as cathode, electrophoretic process is carried out, is cleaned, dry, UV lamp irradiation, obtains electrophoresis product.The cathode Spacing with anode is 8~15cm；100~150V of supply voltage of the electrophoresis, the time of electrophoresis is 60~180s；It is described clear Wash and refer to clean cathode plate surface supernatant liquid with deionized water, the drying is in 60~100 DEG C of dry 2~3min, the UV lamp The condition of irradiation is that 10~60s is irradiated under the UV lamp of 1000W~2000W.
The deposit thickness is 10~15 μm.
The beneficial effects of the invention are as follows：The phenyl compound of the present invention has the phenyl ring for stablizing rigid structure, while has again There is reactive group；Phenyl compound is prepared UV type cathode electrophoresis dopes by the present invention together with other monomers so that UV cathodes electricity Heat resistance, hardness and the glossiness of swimming coating all obtained lifting.Therefore modified UV cathode electrophoresis dopes have wide answer Use prospect.
Brief description of the drawings
Fig. 1 is (right for acrylic ester prepolymer in embodiment 1 (corresponding is product A prepared by step (2)), photosensitive resin What is answered is resin product prepared by step (4)) and semiclosed IPDI prepolymers (product B prepared by step (3)) infrared absorption light Spectrogram.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, however, the present invention is not limited thereto. Thin-layered chromatography TLC is that suitable stationary phase is coated on glass plate, into a thin uniform layer；After point sample, expansion after, according to than Shifting value (Rf) with raw material by the same method gained chromatogram Rf value (Rf) compare, to monitor whether reaction is completed；When occur with When raw material point compares polarity larger point, reaction terminates.
The TLC eluents refer to respectively ethyl acetate and n-hexane.
Embodiment 1
(1) by benzaldehyde (2mol), methyl acrylate (4mol), 4-dimethylaminopyridine (3mol) and organic solvent four Whether hydrogen furans (50ml) is uniformly mixed, and is stirred at normal temperatures, completed by thin-layered chromatography TLC monitoring reactions, reaction terminates Afterwards, washed and dissolved with saturated aqueous ammonium chloride (50ml), extracted with ethyl acetate (10ml), anhydrous slufuric acid is added to by organic Magnesium (5g) dries 6h, filters, and vacuum rotary steam goes out solvent at 30 DEG C, and silica gel column chromatography, 30 DEG C of revolvings, obtain phenyl compound；
(2) by 10 parts of dimethylaminoethyl methacrylate (DMAEMA), 15 parts of methyl methacrylate (MMA), propylene Sour 4 parts of hydroxyl ethyl ester (HEA), 15 parts of butyl acrylate (BA), 5 parts of styrene (St), 2 parts of azo-bis-iso-dimethyl and organic 50 parts of solvent propylene glycol methyl ether acetate is uniformly mixed, and obtains mixed monomer solution；(the speed of agitator under conditions of stirring For 120r/min), in 75 DEG C, into 50 parts of organic solvent propylene glycol methyl ether acetates, mixed monomer solution is added dropwise, control is wriggled Pump drop speed 10rpm, is added dropwise in 2h, keeps the temperature 4h, cooling discharging, and 40 DEG C of vacuum distillations to solid content are 50wt% or so, Obtain product A；
(3) 0.5 part of 5 parts of isophorone diisocyanate (IPDI) and hydroquinone are uniformly mixed, then in stirring and Under the conditions of 40 DEG C, it is added dropwise by 2 parts of hydroxy-ethyl acrylate (HEA) and 0.1 part of mixture mixed of triethylamine, passes through wriggling Pump, control drop speed 4rpm, is added dropwise in 2h；It is added dropwise after rear 5min that (method refers to state with di-n-butylamine method titration Mark GBT 18446-2009) in measure reaction system-NCO content, until the content of-NCO reach semiclosed after theoretical value (- NCO, 9.18%) content, terminates reaction, obtains product B；
(4) 0.1 part of triethylamine, 0.5 part of hydroquinone are dissolved in 2 parts of organic solvent propylene glycol methyl ether acetates, obtained The mixed solution of catalyst and polymerization inhibitor；The mixed solution of catalyst and polymerization inhibitor is uniformly mixed with the product B of step (3), Obtain mixture；Under conditions of stirring (speed of agitator 100r/min), in 40 DEG C, it is added dropwise into the product A of step (2) mixed Compound, is added dropwise using peristaltic pump, is added dropwise in control drop speed 5rpm, 2h, insulation 3h (is characterized using Fourier infrared spectrograph Analysis, it is ensured that isocyano and hydroxyl reaction are complete), obtain resin product；
(5) in 40 DEG C, 3 parts of lactic acid is added to the resin product of step (4), is stirred with the mixing speed of 120r/min 20min；Then room temperature is down to, adds 3 parts of ethylene glycol monobutyl ether, 3 parts of 1- hydroxycyclohexyl phenyl ketones and phenyl compound 5 Part, 10min is stirred with 180r/min rotating speeds, so as to be uniformly dispersed；Deionized water to solid content is gradually added into three times to be reduced to 20% (mass percent), carries out emulsion dispersion (disperseing 60min under 3000r/min rotating speeds), with 150r/ with high speed dispersor Min cures 48h, obtains the acids cathode electrophoresis dope working solution of UV types cathode electrophoresis dope i.e. UV photocurings modified propylene；
(6) using above-mentioned UV types cathode electrophoresis dope as working solution (ability cathode electrophoresis working solution), ability cathode electrophoresis working solution is added Enter in electrophoresis tank, be stirred with 150r/min rotating speeds；By the use of clean aluminium alloy plate as anode, after being cleaned with ethanol and acetone 5 × 7.5cm phosphatizations plate (parkerized iron plate) be used as cathode, both are equally immersed in working solution, between adjustment plate Away from for 8cm；After regulating power source voltage 100V, deenergization after electrophoresis 180s；Cathode plate surface supernatant liquid is cleaned using deionized water, Drain and be placed on air dry oven in 70 DEG C of dry 3min, removal surface moisture；After pole plate cooling, 1000W is placed on UV lamp under irradiate 20s, obtain the smooth electrophoresis product in surface.
Acrylic ester prepolymer (corresponding is product A prepared by step (2)), photosensitive resin are (corresponding in the present embodiment It is resin product prepared by step (4)) and semiclosed IPDI prepolymers (product B prepared by step (3)) infrared absorpting light spectra As shown in Figure 1.
Electrophoretic deposition layer thickness is 10 μm, pencil hardness 3H in the electrophoresis product, and heat resistance is 100 DEG C of retention properties Constant, glossiness 70, it is 100 that resistance to butanone, which wipes number, and adhesive force is 0 grade.
Embodiment 2
(1) by benzaldehyde (5mol), methyl acrylate (7mol), triethylene diamine (6mol) and organic solvent acetic acid second Whether ester (100ml) is uniformly mixed, and is stirred at normal temperatures, completed by thin-layered chromatography TLC monitoring reactions, after reaction, Washed and dissolved with saturated aqueous ammonium chloride (100ml), extracted with ethyl acetate (30ml), anhydrous sodium sulfate is added to by organic (6g) dries 8h, filters, and vacuum rotary steam goes out solvent at 40 DEG C, and silica gel column chromatography, 40 DEG C of revolvings, obtain phenyl compound；
(2) by 15 parts of dimethylaminoethyl methacrylate (DMAEMA), 20 parts of methyl methacrylate (MMA), propylene Sour 6 parts of hydroxyl ethyl ester (HEA), 20 parts of butyl acrylate (BA), 8 parts of styrene (St), 4 parts of azodiisobutyronitrile and there is ethyl acetate 80 parts are uniformly mixed, and obtain mixed monomer solution；Under conditions of stirring (speed of agitator 175r/min), in 80 DEG C, Into 80 parts of organic solvent ethyl acetate, mixed monomer solution is added dropwise, control peristaltic pump drop speed 12rpm, drips in 2.5h Finish, keep the temperature 5h, cooling discharging, 50 DEG C of vacuum distillations to solid content are 60wt% or so, obtain product A；
(3) 10 parts of isophorone diisocyanate (IPDI) and 0.7 part of 2,6- toluene di-tert-butyl phenol are uniformly mixed, Then under the conditions of stirring with 50 DEG C, it is added dropwise by the 0.3 part of mixing of 5 parts of hydroxy-ethyl acrylate (HEA) and dibutyl tin laurate The mixture formed, by peristaltic pump, control drop speed 6rpm, is added dropwise in 1.5h；It is added dropwise after rear 10min with two just In butylamine method titration (method refers to national standard GBT18446-2009) measure reaction system-NCO content, until the content of-NCO The content of theoretical value (- NCO, 9.18%) after reaching semiclosed, terminates reaction, obtains product B；
(4) 0.3 part of dibutyl tin laurate, 0.6 part of 2,6- toluene di-tert-butyl phenols are dissolved in 5 parts of organic solvent second In acetoacetic ester, the mixed solution of catalyst and polymerization inhibitor is obtained；By the production of the mixed solution of catalyst and polymerization inhibitor and step (3) Thing B is uniformly mixed, and obtains mixture；Under conditions of stirring (speed of agitator 120r/min), in 60 DEG C, to step (2) Mixture is added dropwise in product A, is added dropwise using peristaltic pump, is added dropwise in control drop speed 6rpm, 1.5h, insulation 4h (uses Fourier Leaf infrared spectrometer phenetic analysis, it is ensured that isocyano and hydroxyl reaction are complete), obtain resin product；
(5) in 50 DEG C, 5 parts of glacial acetic acid is added to the resin product of step (4), is stirred with the mixing speed of 150r/min 30min；Then room temperature is down to, adds 4 parts of ethylene glycol monobutyl ether, 4 parts of 2- hydroxy-2-methyl -1- phenylacetones and phenyl chemical combination 10 parts of thing, stirs 8min with 200r/min rotating speeds, is uniformly dispersed；Deionized water to solid content is gradually added into three times to be reduced to 15%, emulsion dispersion (disperseing 50min under 4000r/min rotating speeds) is carried out with high speed dispersor, 40h is cured with 200r/min, is obtained To the acids cathode electrophoresis dope working solution of UV types cathode electrophoresis dope, that is, UV photocuring modified propylenes；
(6) using above-mentioned UV types cathode electrophoresis dope as working solution (ability cathode electrophoresis working solution), ability cathode electrophoresis working solution is added Enter in electrophoresis tank, be stirred with 180r/min rotating speeds；By the use of clean aluminium alloy plate as anode, after being cleaned with ethanol and acetone 5 × 7.5cm phosphatizations plate (parkerized iron plate) be used as cathode, both are equally immersed in working solution, between adjustment plate Away from for 10cm；After regulating power source voltage 120V, deenergization after electrophoresis 100s；Floated using deionized water cleaning cathode plate surface Liquid, drains and is placed on air dry oven in 80 DEG C of dry 3min, removal surface moisture；After pole plate cooling, it is placed on 30s is irradiated under the UV lamp of 1000W, obtains the smooth electrophoresis product in surface.
Electrophoretic deposition layer thickness is 12 μm, pencil hardness 6H in the electrophoresis product, and heat resistance is 120 DEG C of retention properties Constant, glossiness 80, it is 300 that resistance to butanone, which wipes number, and adhesive force is 0 grade.
Embodiment 3
(1) by benzaldehyde (7mol), methyl acrylate (10mol), tetrabutyl Ammonium hydrogen sulfate (8mol) and organic solvent Whether methanol (150ml) is uniformly mixed, and is stirred at normal temperatures, completed by thin-layered chromatography TLC monitoring reactions, reaction terminates Afterwards, washed and dissolved with saturated aqueous ammonium chloride (200ml), extracted with ethyl acetate (40ml), anhydrous sulphur is added to by organic Filtered after the dry 9h of sour sodium (8g), vacuum rotary steam goes out solvent at 50 DEG C, and silica gel column chromatography, 50 DEG C of revolvings, obtain phenyl compound；
(2) by 20 parts of dimethylaminoethyl methacrylate (DMAEMA), 25 parts of methyl methacrylate (MMA), propylene Sour 8 parts of hydroxyl ethyl ester (HEA), 25 parts of butyl acrylate (BA), 10 parts of styrene (St), 5 parts of azodiisobutyronitrile and organic solvent 90 parts of methanol is uniformly mixed, and obtains mixed monomer solution；Under conditions of stirring (speed of agitator 180r/min), in 85 DEG C, into 90 parts of organic solvent methanol, mixed monomer solution is added dropwise, control peristaltic pump drop speed 14rpm, drips in 2.5h Finish, keep the temperature 5h, discharge after cooling, 65 DEG C of vacuum distillations to solid content are 65%, obtain product A；
(3) 0.8 part of 15 parts of isophorone diisocyanate (IPDI) and 1,4-benzoquinone are uniformly mixed, then in stirring and 60 Under the conditions of DEG C, it is added dropwise by 8 parts of hydroxy-ethyl acrylate (HEA) and 0.4 part of mixture mixed of tetrabutyl Ammonium hydrogen sulfate, passes through Peristaltic pump, control drop speed 8rpm, is added dropwise in 1h；Di-n-butylamine method titration (method ginseng is used after rear 10min is added dropwise Examine national standard GBT 18446-2009)-NCO content is measured in reaction system, the theory after the content of-NCO reaches semiclosed It is worth the content of (- NCO, 9.18%), terminates reaction, obtain product B；
(4) 0.4 part of tetrabutyl Ammonium hydrogen sulfate, 0.8 part of 1,4-benzoquinone are dissolved in 8 parts of organic solvent methanol, obtain catalyst With the mixed solution of polymerization inhibitor；The mixed solution of catalyst and polymerization inhibitor is uniformly mixed with the product B of step (3), is mixed Compound；Under conditions of stirring (speed of agitator 140r/min), in 50 DEG C, mixture is added dropwise into the product A of step (2), It is added dropwise, is added dropwise in control drop speed 7rpm, 1.2h, insulation 3h (uses Fourier infrared spectrograph characterization point using peristaltic pump Analysis, it is ensured that isocyano and hydroxyl reaction are complete), obtain resin product；
(5) in 60 DEG C, 8 parts of nitric acid is added to the resin product of step (4), is stirred with the mixing speed of 180r/min 50min；Then room temperature is down to, adds 6 parts of propyleneglycoles monobutyl ether, 2,4,6- trimethylbenzoy-dipheny phosphine oxides 6 20 parts of part and phenyl compound, stir 6min with 220r/min, it is uniformly dispersed；Deionized water is gradually added into three times to admittedly Content is reduced to 10%, emulsion dispersion (disperseing 30min under 5000r/min rotating speeds) is carried out with high speed dispersor, with 180r/min 30h is cured, obtains the acids cathode electrophoresis dope working solution of UV types cathode electrophoresis dope i.e. UV photocurings modified propylene；
(6) using above-mentioned UV types cathode electrophoresis dope as working solution (ability cathode electrophoresis working solution), ability cathode electrophoresis working solution is added Enter in electrophoresis tank, be stirred with 200r/min rotating speeds；By the use of clean aluminium alloy plate as anode, after being cleaned with ethanol and acetone 5 × 7.5cm phosphatizations plate (parkerized iron plate) be used as cathode, both are equally immersed in working solution, between adjustment plate Away from for 12cm；After regulating power source voltage 100V, deenergization after electrophoresis 180s；Floated using deionized water cleaning cathode plate surface Liquid, drains and is placed on air dry oven in 90 DEG C of dry 3min, removal surface moisture；After pole plate cooling, it is placed on 50s is irradiated under the UV lamp of 2000W, obtains the smooth electrophoresis product in surface.
Electrophoretic deposition layer thickness is 14 μm, pencil hardness 5H in the electrophoresis product, and heat resistance is 110 DEG C of retention properties Constant, glossiness 60, it is 120 that resistance to butanone, which wipes number, and adhesive force is 0 grade.
Embodiment 4
(1) by benzaldehyde (10mol), methyl acrylate (15mol), 4-dimethylaminopyridine (12mol) and organic molten Whether agent dimethylformamide (200ml) is uniformly mixed, and is stirred at normal temperatures, completed by thin-layered chromatography TLC monitoring reactions, After reaction, washed and dissolved with saturated aqueous ammonium chloride (300ml), extracted with ethyl acetate (50ml), by organic addition Filtered after entering the dry 9h of natrium carbonicum calcinatum (10g), 60 DEG C of vacuum rotary steams go out solvent, and silica gel column chromatography, 60 DEG C of revolvings, obtain phenyl Compound；
(2) by 25 parts of dimethylaminoethyl methacrylate (DMAEMA), 30 parts of methyl methacrylate (MMA), propylene Sour 10 parts of hydroxyl ethyl ester (HEA), 30 parts of butyl acrylate (BA), 15 parts of styrene (St), 7 parts of benzoyl peroxide and organic solvent 100 parts of methyl iso-butyl ketone (MIBK) is uniformly mixed, and obtains mixed monomer solution；(the speed of agitator 200r/ under conditions of stirring Min), in 85 DEG C, into 100 parts of organic solvent methyl iso-butyl ketone (MIBK)s, mixed monomer solution, control peristaltic pump drop speed is added dropwise 15rpm, is added dropwise in 3h, keeps the temperature 6h, discharges after cooling, and 40 DEG C of vacuum distillations to solid content are 70%, obtain product A；
(3) 1 part of 20 parts of isophorone diisocyanate (IPDI) and beta-phenyl naphthylamines are uniformly mixed, then in stirring and Under the conditions of 70 DEG C, it is added dropwise by 10 parts of hydroxy-ethyl acrylate (HEA) and 0.5 part of mixture mixed of 4-dimethylaminopyridine, By peristaltic pump, control drop speed 8rpm, is added dropwise in 1h；Di-n-butylamine method titration (side is used after rear 20min is added dropwise Method refers to national standard GBT 18446-2009)-NCO content is measured in reaction system, until after the content of-NCO reaches semiclosed The content of theoretical value (- NCO, 9.18%), terminates reaction, obtains product B；
(4) 0.5 part of 4-dimethylaminopyridine, 1 part of beta-phenyl naphthylamines are dissolved in 10 parts of organic solvent methyl iso-butyl ketone (MIBK)s, Obtain the mixed solution of catalyst and polymerization inhibitor；The mixed solution of catalyst and polymerization inhibitor is mixed with the product B of step (3) It is even, obtain mixture；Under conditions of stirring (speed of agitator 150r/min), in 50 DEG C, dripped into the product A of step (2) Add mixture, be added dropwise using peristaltic pump, is added dropwise in control drop speed 8rpm, 1h, insulation 4h (uses Fourier infrared spectrograph Phenetic analysis, it is ensured that isocyano and hydroxyl reaction are complete), obtain resin product；
(5) in 70 DEG C, 10 parts of bishydroxymethyl propionic acid is added to the resin product of step (4), with the stirring of 200r/min Speed stirs 60min；Then room temperature is down to, adds 8 parts of propylene glycol monopropyl ether, 2- hydroxy-2-methyls -1- [4- (2- '-hydroxyethoxies Base) phenyl] 30 parts of 8 parts of -1- acetone and phenyl compound, stir 5min with 250r/min, it is uniformly dispersed；It is gradual in three times Add deionized water to solid content and be reduced to 10%, carry out emulsion dispersion with high speed dispersor (disperses under 6000r/min rotating speeds 20min), 24h is cured with 150r/min, obtains the UV types cathode electrophoresis dope i.e. acids ability cathode electrophoresis of UV photocurings modified propylene Coating working solution；
(6) using above-mentioned UV types cathode electrophoresis dope as working solution (ability cathode electrophoresis working solution), ability cathode electrophoresis working solution is added Enter in electrophoresis tank, be stirred with 250r/min rotating speeds；By the use of clean aluminium alloy plate as anode, after being cleaned with ethanol and acetone 5 × 7.5cm phosphatizations plate (parkerized iron plate) be used as cathode, both are equally immersed in working solution, between adjustment plate Away from for 15cm；After regulating power source voltage 100V, deenergization after electrophoresis 180s；Floated using deionized water cleaning cathode plate surface Liquid, drains and is placed on air dry oven in 100 DEG C of dry 3min, removal surface moisture；After pole plate cooling, it is placed on 10s is irradiated under the UV lamp of 2000W, obtains the smooth electrophoresis product in surface.
Electrophoretic deposition layer thickness is 15 μm in the electrophoresis product；Pencil hardness is 4H；Heat resistance is 100 DEG C of retention properties It is constant；Glossiness is 65；It is 90 that resistance to butanone, which wipes number,；Adhesive force is 0 grade.
Comparative example 5
1. the preparation of acrylic resin
The azodiisobutyronitrile for accounting for monomer gross mass 3% is mixed with monomer, wherein monomers methyl methacrylate, benzene second Alkene, butyl methacrylate and methacrylic acid -2-2 hydroxyl ethyl esters, dosage are respectively 79,21,22 and 44.4g, methacrylic acid The dosage of diethylamine ethyl ester is 16.8g；Monomer is slowly dropped into the container equipped with solvent butanone at 75 DEG C, its dosage is monomer 1.5 times of gross mass, when reaction 4 is small, makes monomer conversion reach more than 98%, obtain acrylic resin product；
2. acrylic resin modified preparation
0.5wt% (the 0.5% of acrylic resin product quality) catalyst dibutyltin osmanthus is added into acrylic resin product Sour dibutyl tin, is slowly added dropwise isopropenyl-alpha, alpha-dimethylbenzyl isocyanates between 42.4g at 60 DEG C, when reaction 3 is small, Appropriate absolute ethyl alcohol is added, removes the isocyanates for failing reaction, vacuum extracts solvent, obtains acrylic resin modified；
3. ultraviolet light cures the preparation of cathod coating
It is 1 in acrylic resin modified middle addition mass ratio:1 2- hydroxy-2-methyls propiophenone and 1- hexahydrotoluenes Benzophenone photoinitiator, its dosage are the 1.5wt% of resin, and it is 6.0 to be neutralized with lactic acid to pH value, and is diluted with deionized water It is 15% to solid content, ultraviolet light curing cathodic electrophoretic coating is configured to through high speed dispersion；
4. ultraviolet light curing cathodic electrophoretic coating performance detection
Using the ultraviolet light curing cathodic electrophoretic coating of preparation as electrophoresis groove liquid, under 25 DEG C of temperature, voltage 20V, to not Steel surface of becoming rusty carries out electrophoretic painting.Stainless steel plate after application flashes 10 minutes at 60 DEG C, in room temperature, 1kW high pressure Hg lamp spokes Cure crosslinking 55 seconds according to lower.Coating thickness is measured as 25 μm, pencil hardness 3H, is not decomposed at 90 DEG C, glossiness 60.
The above 1~4 is only the embodiment of the present invention, and 5 be comparative example, from embodiment 1~4 and comparative example In 5 performance comparison, the heat resistance and glossiness of the compound modified UV cathode electrophoresis dopes of synthesis of phenyl are obviously improved, right In not thereby limiting the scope of the invention for pressure electrophoretic coating, every equivalent structure using present specification Or equivalent process transformation, other related technical areas are directly or indirectly used in, are similarly included in the guarantor of the present invention In the range of shield.

Claims (10)

  1. A kind of 1. phenyl compound, it is characterised in that：Its structural formula is Formulas I
  2. 2. the preparation method of phenyl compound according to claim 1, it is characterised in that：To be situated between by reaction of organic solvent Matter, using benzaldehyde and methyl acrylate as reaction raw materials, reaction raw materials are reacted under the action of catalyst, and purifying, obtains Phenyl compound.
  3. 3. the preparation method of phenyl compound according to claim 2, it is characterised in that：
    The catalyst is triethylamine, triethylene diamine, tetrabutyl Ammonium hydrogen sulfate, four butyl bromation amine, triethylbenzyl chlorination One or more of amine, 4-dimethylaminopyridine；The organic solvent is tetrahydrofuran, ethyl acetate, methanol, dimethyl are sub- One or more of sulfone, dimethylformamide；
    The molar ratio of the benzaldehyde and methyl acrylate is (2~10) mol：(3~15) mol；
    The amount ratio of the benzaldehyde and catalyst is (2~10) mol：(2~12) mol；The benzaldehyde and organic solvent Amount ratio is (2~10) mol：(50~200) ml；
    The temperature of the reaction is room temperature, and whether the reaction is completed by thin-layered chromatography TLC monitoring reactions.
  4. 4. a kind of UV types cathode electrophoresis dope is prepared using phenyl compound described in claim 1.
  5. 5. UV types cathode electrophoresis dope according to claim 4, it is characterised in that：It is made of following component by weight： 10~25 parts of dimethylaminoethyl methacrylate, 15~30 parts of methyl methacrylate, 4~20 parts of hydroxy-ethyl acrylate, third 15~30 parts of olefin(e) acid butyl ester, 5~20 parts of styrene, 5~20 parts of diisocyanate, 0.2~1 part of catalyst, 1~2 part of polymerization inhibitor, 1~10 part of radical initiator, 2~8 parts of dispersant, 2~8 parts of photoinitiator, 5~30 parts of phenyl compound, neutralizer 3~10 Part, 102~210 parts of organic solvent, 100~1500 parts of water.
  6. 6. UV types cathode electrophoresis dope according to claim 5, it is characterised in that：The diisocyanate is isophorone two Isocyanates；The catalyst is triethylamine, dibutyl tin laurate, triethylene diamine, tetrabutyl Ammonium hydrogen sulfate, the tetrabutyl One or more of amine bromide, triethylbenzyl ammonium chloride, 4-dimethylaminopyridine；
    The polymerization inhibitor for hydroquinone, 1,4-benzoquinone, 2,6- toluene di-tert-butyl phenols, beta-phenyl naphthylamines, to tert-butyl o benzene One or more of diphenol；
    The radical initiator is azodiisobutyronitrile, azo-bis-iso-dimethyl, in benzoyl peroxide it is a kind of with On；
    The dispersant is one in ethylene glycol monobutyl ether, propyleneglycoles monobutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether More than kind；
    The photoinitiator is 1- hydroxycyclohexyl phenyl ketones, 2- hydroxy-2-methyl -1- phenylacetones, 2,4,6- trimethyls In benzoyl-diphenyl phosphine oxide, 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) phenyl] -1- acetone it is a kind of with On；
    The neutralizer is one or more of lactic acid, glacial acetic acid, nitric acid, bishydroxymethyl propionic acid；
    The organic solvent is propylene glycol methyl ether acetate, ethyl acetate, methanol, dimethyl sulfoxide (DMSO), methyl iso-butyl ketone (MIBK) it is mixed One or more of compound.
  7. 7. according to the preparation method of the UV types cathode electrophoresis dope of claim 5 or 6, it is characterised in that：Comprise the following steps：
    (1) by 10~25 parts of dimethylaminoethyl methacrylate, 15~30 parts of methyl methacrylate, hydroxy-ethyl acrylate 2 ~10 parts, 15~30 parts of butyl acrylate, 5~20 parts of styrene, 1~10 part of radical initiator and organic solvent 50~100 Part is uniformly mixed, and obtains mixed monomer solution；Under conditions of stirring, in 70 DEG C~90 DEG C, to 50~100 parts of organic solvents In, mixed monomer solution is added dropwise, 4~6h is kept the temperature after being added dropwise, it is 50wt%~70wt% to be evaporated under reduced pressure to solid content, is obtained Product A；
    (2) 0.5~1 part of 5~20 parts of diisocyanate and polymerization inhibitor are uniformly mixed, then at 40~70 DEG C, are added dropwise by third 2~10 parts of olefin(e) acid hydroxyl ethyl ester and 0.1~0.5 part of mixture mixed of catalyst, after dripping, sustained response, works as reaction During the content of the theoretical value after the content of-NCO reaches semiclosed in system, reaction is terminated, obtains product B；
    (3) 0.1~0.5 part of catalyst, 0.5~1 part of polymerization inhibitor are dissolved in 2~10 parts of organic solvents, obtain catalyst and resistance The mixed solution of poly- agent；The mixed solution of catalyst and polymerization inhibitor is uniformly mixed with the product B of step (2), obtains mixture； Under conditions of stirring, in 40 DEG C~70 DEG C, mixture is added dropwise into the product A of step (1), is added dropwise, keep the temperature 3~4h, Obtain resin product；
    (4) in 40 DEG C~70 DEG C, 3~10 parts of neutralizer is added to the resin product of step (3), stirs evenly, is down to room temperature, add Enter 5~30 parts of 2~8 parts of dispersant, 2~8 parts of photoinitiator and phenyl compound, be uniformly dispersed, be gradually added 100~1500 parts Water make it that solid content is 10~20%, and high speed emulsion dispersion, curing, obtains UV type cathode electrophoresis dopes.
  8. 8. the preparation method of UV types cathode electrophoresis dope according to claim 7, it is characterised in that：It is high described in step (4) The condition of fast emulsion dispersion is to disperse 20~60min under 3000~6000r/min rotating speeds, and the condition of curing is with 150~250r/ Min cures 24~48h.
  9. 9. according to the application of any one of the claim 4~6 UV types cathode electrophoresis dope, it is characterised in that：The UV types are cloudy Pole electrophoretic coating is used to prepare electrophoresis product.
  10. 10. application according to claim 9, it is characterised in that：The specific preparation method of the electrophoresis product is：With UV types Cathode electrophoresis dope is working solution, using aluminium alloy plate as anode, using substrate pole plate as cathode, carries out electrophoretic process, cleans, do Dry, UV lamp irradiation, obtains electrophoresis product；
    The spacing of the cathode and anode is 8~15cm；100~150V of supply voltage of the electrophoresis, the time of electrophoresis is 60 ~180s；The condition of the UV lamp irradiation is that 10~60s is irradiated under the UV lamp of 1000W~2000W.
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CN114316660A (en) * 2021-12-17 2022-04-12 广东工业大学 Water-based ultraviolet-curing cathode electrophoretic coating and preparation method thereof

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CN107163664A (en) * 2017-06-14 2017-09-15 深圳市天泽科技实业有限公司 Ultraviolet light solidifies the preparation method of cathode electrodip painting

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CN114316660A (en) * 2021-12-17 2022-04-12 广东工业大学 Water-based ultraviolet-curing cathode electrophoretic coating and preparation method thereof
WO2023109123A1 (en) * 2021-12-17 2023-06-22 广东深展实业有限公司 Water-based ultraviolet curing cathode electrophoretic coating and preparation method therefor

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