CN106634384A - Preparation method of cation acrylate resin of cathode electrophoresis coating - Google Patents
Preparation method of cation acrylate resin of cathode electrophoresis coating Download PDFInfo
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- CN106634384A CN106634384A CN201610873377.7A CN201610873377A CN106634384A CN 106634384 A CN106634384 A CN 106634384A CN 201610873377 A CN201610873377 A CN 201610873377A CN 106634384 A CN106634384 A CN 106634384A
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- 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
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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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
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4407—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 by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
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- 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
- C09D5/448—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications characterised by the additives used
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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
- C09D5/44—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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Abstract
The invention discloses a preparation method of a cation acrylate resin of a cathode electrophoresis coating. The method includes steps of preparing cation fluorine modified acrylate resin and semi-closed type polyisocyanates crosslinking agent; and then reacting the cation fluorine modified acrylate resin with semi-closed type polyisocyanates crosslinking agent; preparing and acquiring a single-component grafted self-crosslinking type acrylate resin; after adding organic acid to acidize; finally, adding deionized water to disperse and prepare the cation acrylate resin of cathode electrophoresis coating. The method perfectly combines acrylate with epoxy resin; acrylate makes up the shortcoming that the epoxy resin is only suitable for primer for the acrylate has excellent weather resistance and good color retaining and light retaining properties; the acrylate resin is used as the main resin, and hydrophobicity aluminium oxide particle is used as the coating modifying agent; the components are extremely good in weather resistance, and good in delustering effect, good in performance, and long in service life; the cation acrylate resin can be applied to various high-quality hardware products.
Description
Technical field
The present invention relates to a kind of preparation technology of new material, is a kind of cathode electrophoresis dope cationic acrylamide specifically
The preparation method of acid ester resin.
Background technology
Electrophoretic painting (electro-coating) is to make pigment and resin for being suspended in electrophoresis liquid etc. using extra electric field
Particulate directional migration and be deposited on one of electrode substrate surface coating process.The principle invention of electrophoretic painting then 20th century
The end of the thirties, but it is that after 1963, electrophoretic painting has been developed over nearly 30 years to develop this technology and obtain commercial Application
A kind of special coating film-forming methods for coming, are the construction technologies being most of practical significance to water paint.With water-soluble, nothing
Poison, the features such as be easy to Automated condtrol, it is widely used in industries such as automobile, building materials, five metals, household electrical appliances rapidly.
The most basic physical principle of electrophoretic painting is attracting with its electrically charged contrary electrode by charged coating particle.
Using dc source, metal works are dipped in Electrophoretic Paints.After energization, cation paint particle to cathode-workpiece is moved, it is cloudy from
Sub- coating particle to anode workpiece is moved, and is deposited on then on workpiece, and in surface of the work uniform, continuous film is formed.Work as painting
Film reaches certain thickness (paint film resistance is big to a certain extent), and surface of the work forms insulating barrier, and " heteropole is attracting " stops, and electrophoresis is applied
Dress process terminates.Cathode electro-coating, metal works are negative electrode, attract coating particle positively charged in paint liquid, due to being applied
Workpiece is negative electrode rather than anode, and the metal ion into film greatly reduces, so as to improve paint film property.Film is excellent, tool
There is excellent corrosion resisting property.
Cathode electrophoresis dope originates from 20 century 70s, and PPG companies of the U.S. succeed in developing first 1st generation negative electrode within 1971
Electrophoretic coating.The Car Body Painting line of industrially developed country has been changed to cathodic electrophoretic coating line, and cathode electrophoresis dope
Kind constantly update.Early 1990s, the country started the research work of cathode electrodip painting, and progress is also quickly.Due to
It is a kind of water paint, with anticorrosive property is excellent, application high degree of automation, it is low in the pollution of the environment the features such as, current negative electrode
Electrophoretic coating is widely used to many such as automobile, light industry, agricultural machinery, household electrical appliances, instrument, school supply and stationery, handicraft, military project, building materials
Department, and it is well received.At present, world's cathode electrophoresis dope is broadly divided into PPG and the big systems of Hoechst two, and the former is by U.S.
Bi-component, the low viscosity emulsion type electrophoretic paint of Flat Glass Co., Ltd of Pittsburgh of state exploitation；The latter be by German Hoechst groups and
One pack system, high viscosity, the Soluble Electrophoretic Paint of Austrian Stolllack companies exploitation.
Electrophoretic coating matrix resin often selects various of monomer to be combined, and makes to make the characteristics of mainly comprehensively utilize respective
Resin have best suit ideal and can meet each side requirement performance.Current application mainly has crylic acid resin, a ring
Several matrix resins such as oxygen tree lipid, polybutadiene and polyurethanes.Wherein cathode electrophoresis dope introduces the in the majority of nitrogen.
It is poor often to there is weatherability in conventional cathode electrophoretic coating, heats easy xanthochromia, and solidification temperature is high, it is difficult to the problems such as coloured silkization, acrylic acid
Cathode electrophoresis dope is the coating new varieties grown up after the 1950's, because of its film to the main absworption peak of light in the sun
Outside spectral region, and there is particularly excellent light resistance and resistance to outdoor aging, it is strong to protect color gloss retention, its outward appearance smooth coating
It is smooth, plentiful, fine and close, ornamental strong.Thus can be widely used in fields such as car, light industry, household electrical appliances, buildings.
In recent years, especially light fixture, fittings of bathroom, metal handicrafts are developed rapidly and electrophoresis high-performance hardware
The continuous development and progress of application techniques, to the performance of coating especially hydrophobicity, weatherability and dicoration propose it is higher
Require.Traditional aqueous cathode electrophoresis dope, its hydrophobicity, weatherability and dicoration be not good enough, it is impossible to meets high-grade five metals system
The new demand that product are proposed to aqueous cathode electrophoresis dope.
The content of the invention
The present invention is exactly for various weak points present in prior art, there is provided a kind of cathode electrophoresis dope sun from
The preparation method of sub- acrylate.
The present invention is realized to reach above-mentioned purpose by such technical scheme：
The invention discloses a kind of preparation method of cathode electrophoresis dope cationic acrylate resin, prepares cation fluorine
The type semienclosed polyisocyanate crosslinker of modified acrylic ester resin, then seals cation fluorine modified acrylic ester resin and half
After the reaction of closed form polyisocyanate crosslinker, one pack system grafting self-crosslinking acrylate resin is prepared, added organic
After acid acidifying, it is eventually adding deionized water dispersion and prepares cathode electrophoresis dope cationic acrylate resin.
Used as further improving, the concrete preparation process of the present invention is as follows：In a kettle., solvent and part is added to draw
Send out agent, at 70-100 DEG C by crylic acid ester mixture monomer and epoxide function monomer and fluorinated acrylate monomer mixture and
Partial initiator solution is added drop-wise in reactor, is dripped off in 2-4 hours, continues insulation reaction 2-4 hour, is subsequently adding polynary
Amine carries out ring-opening reaction, continues insulation reaction 2-4h, is eventually adding organic acid stirring 20-60 minutes, and cation is obtained after cooling
Fluorin modified crylic acid ester resin；In a kettle., add IPDI, under agitation, delay at 50-70 DEG C
Slowly sealer is added drop-wise in reactor, is dripped within 50 minutes to 70 minutes, be heated to 60-80 DEG C, react 2-4 hours, determined
Free NCO content, when closed stratum is 50-70%, cooling discharge makes type semienclosed polyisocyanate crosslinker；Will be a certain amount of
Cation fluorine modified acrylic ester resin, type semienclosed polyisocyanate crosslinker are added in reactor, anti-at 60-80 DEG C
2-4 hours are answered, organic acid is added and 1-2 hours is acidified at 50-70 DEG C, cooling discharge is subsequently adding a certain amount of deionization
Water, under high-speed stirred, disperses 15-30min, and it is 5.0-6.5 to control pH, is obtained with hydrophobic fluorine-containing cationic acrylate
Resin cathode electrophoresis dope.
As further improving, the described fluorinated acrylate monomer of the present invention be Hexafluorobutyl mathacrylate,
Hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate, the trifluoro monooctyl ester of methacrylic acid ten, perluorooctyl acrylate and complete
One or more in fluoroalkyl ethylmethyl acrylate.
As further improving, the described epoxide function monomer of the present invention be GMA, third
It is a kind of or many in olefin(e) acid ethylene oxidic ester, allyl glycidyl ether and glycidyl ether blocked allyl alcohol atactic polyether
The mixture planted.
As further improving, the described crylic acid ester mixture monomer of the present invention, including styrene, methacrylic acid
Methyl esters, EMA, butyl acrylate, isopropyl acrylate, 2-Hydroxy ethyl acrylate, methacrylic acid -2- hydroxyls
One or more in base ethyl ester and methacrylic acid -2- hydroxy propyl esters；Polyamine be diethanol amine, triethanolamine, ethylenediamine,
One or more mixture in propane diamine, butanediamine.
As further improving, the organic acid of the present invention for formic acid, acetic acid, lactic acid and sulfamic acid one kind or
It is various.
As further improving, in cation fluorine modified acrylic ester resin of the present invention, esters of acrylic acid list
Body 25-50 weight portions, fluorinated acrylate monomer 10-20 weight portions, epoxide function monomer 15-30 weight portions, polyamine 5-10
Weight portion, initiator 0.5-2 weight portions.
Used as further improving, sealer of the present invention is butyl, methyl ethyl ketoxime, n-butanol and different
One or more of octanol.
Used as further improving, cathode electrophoresis dope cationic acrylate resin each group of the present invention is divided into sun
Ion fluorin modified crylic acid ester resin 50-60 weight portions, type semienclosed polyisocyanate crosslinker 20-25 weight portions.
Used as further improving, after varnish film forming, film connects the cathode electrophoresis dope obtained by the present invention with water
Feeler is 130-150 degree.
Beneficial effects of the present invention are as follows：
1st, the invention provides a kind of have hydrophobic cathode electrophoresis dope cationic acrylate resin and its preparation
Method.Conventional propylene acid resin cathode electrophoresis dope does not have hydrophobic performance, and the present invention introduces fluorin modified crylic acid ester monomer
In acrylate cathode electrophoresis dope, using the excellent chemical resistance and low-surface-energy of fluorine resin, so as to be effectively improved
The hydrophobic performance of film.
2nd, the present invention gets up acrylate and epoxy resin perfect adaptation, and acrylate is because of its excellent weather resisteant and good
Good guarantor's color, gloss retention, and compensate for epoxy resin and be only suitable for doing the deficiency of priming paint；Acrylate is employed as main body
Resin, and hydrophobic silica aluminium particulate is used as modified paint agent, they have splendid weather resistance, and with excellent
Extinction effect, function admirable, life-span length can be widely used for all kinds of high-quality hardwares.
3rd, the hydroxyl obtained using after alkylpolyamines open loop is present invention employs as crosslinking points, the crosslinking needed for making up is close
Degree.While acrylate polarity is reduced, hardener dose is also reduced, it is good to obtain application Stability of Bath Solution, decorative coating film
The excellent cathode electrophoresis dope of property.
4th, acrylic cathodic electrophoretic coating technique conventional at present is by Eudragit RL and enclosed type isocyanide
Acid esters curing agent, although process is simple, is difficult to avoid that electrophoresis painting film component and proportioning not according to certain ratio mechanical blending
Stable, electrophoresis groove liquid stability is not good, the problems such as be easily layered.Present invention employs and preparing cationic acrylic hydroxy resin
On the basis of type semienclosed isocyanate crosslinking, left by type semienclosed isocyanate crosslinking-NCO group with
The reaction of hydroxyl on acrylic resin, type semienclosed isocyanate crosslinking is grafted on acrylic resin, prepares one pack system
Self-cross linking type acrylic acid ability cathode electrophoresis varnish, so as to overcome the problem that curing agent comes with resin alloy process bands.
Specific embodiment
The invention discloses a kind of cathode electrophoresis dope cationic acrylate resin and preparation method thereof, the present invention is below
Make detailed description further to technical scheme in conjunction with specific embodiments, but the scope of the present invention is not limited to
Embodiment.
Embodiment 1
(1) preparation of cation fluorine modified acrylic ester resin
In the reactor equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
The weight portion of butyl acetate 10 and the weight portion of initiator azodiisobutyronitrile 0.2, by crylic acid ester mixture monomer (methyl at 70 DEG C
The weight portion of methyl acrylate 10, the weight portion of butyl acrylate 15), the weight portion of glycidyl ether blocked allyl alcohol atactic polyether 15
With the weight portion of fluorinated acrylate monomer perfluor alkyl ethide methacrylate 10 and the weight of initiator azodiisobutyronitrile 0.3
Amount part solution is added drop-wise in reactor, is dripped off in 2 hours, continues insulation reaction 2 hours.It is subsequently adding polyamine triethanolamine 5
Weight portion carries out ring-opening reaction, continues insulation reaction 4h, is eventually adding organic acid acetic acid and stirs 30 minutes, obtain after cooling sun from
Sub- fluorin modified crylic acid ester resin.
(2) preparation of type semienclosed polyisocyanate crosslinker
In the reactor equipped with agitating device, constant pressure funnel and reflux condensing tube, the isocyanide of isophorone two is added
The weight portion of acid esters 50, under agitation, slowly reaction is added drop-wise at 60 DEG C by the weight portion of sealer butyl about 50
In kettle, drip within 1 hour.70 DEG C are heated to, are reacted 4 hours, determine free NCO content, when closed stratum is 50%, is lowered the temperature and
Material.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 50 weight portions, the type semienclosed multi isocyanate crosslinking of 20 weight portions
Agent is added in reactor, is reacted 2 hours at 70 DEG C, is added quantitative organic acid acetic acid and is acidified 2 hours at 50 DEG C.Drop
Temperature discharging, is subsequently adding the deionized water of 30 weight portions, under high-speed stirred, disperses 15-30min, and it is 5.0 to control pH, is had
There is hydrophobic cationic acrylate resin cathode electrophoresis dope.
With electrophoresis emulsion obtained in the present embodiment, cathode electro-coating, electrophoretic voltage 150V, electrophoresis temperature 30 are directly carried out
DEG C, electrophoresis time 3 minutes.Gained film is toasted 30 minutes at 170 DEG C, and gained appearance of film uniform ground, film connects with water
Feeler is 130 °, and film other performances meet product standard.
Embodiment 2
(1) preparation of cation fluorine modified acrylic ester resin
In the reactor equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
The weight portion of propylene glycol methyl ether acetate 30 and the weight portion of initiator benzoyl peroxide 1, by crylic acid ester mixture list at 100 DEG C
Body (weight portion of EMA 20, the weight portion of isopropyl acrylate 30), the weight portion of allyl glycidyl ether 30 and contain
The weight portion of fluoroacrylate monomers hexafluorobutyl acrylate 20 and the parts by weight solution of initiator benzoyl peroxide 1 are added drop-wise to instead
In answering kettle, drip off in 4 hours, continue insulation reaction 2 hours.Being subsequently adding the weight portion of polyamine diethanol amine 10, to carry out open loop anti-
Should, continue insulation reaction 2h, it is eventually adding organic acid lactic acid and stirs 30 minutes, cation fluorine modification acrylate is obtained after cooling
Resin.
(2) preparation of type semienclosed polyisocyanate crosslinker
In the reactor equipped with agitating device, constant pressure funnel and reflux condensing tube, the isocyanide of isophorone two is added
The weight portion of acid esters 50, under agitation, is slowly added drop-wise to sealer methyl ethyl ketoxime in reactor at 60 DEG C, is added dropwise within 1 hour
It is complete.70 DEG C are heated to, are reacted 2 hours, determine free NCO content, when closed stratum is 70%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 60 weight portions and the type semienclosed polyisocyanates of 25 weight portions
Crosslinking agent is added in reactor, is reacted 2 hours at 70 DEG C, and adding quantitative organic acid lactic acid, that 1 is acidified at 70 DEG C is little
When, cooling discharge.The deionized water of 40 weight portions is subsequently adding, under high-speed stirred, disperses 15-30min, it is 6.5 to control pH, is obtained
To with hydrophobic cationic acrylate resin cathode electrophoresis dope.
With electrophoresis emulsion obtained in the present embodiment, cathode electro-coating, electrophoretic voltage 150V, electrophoresis temperature 30 are directly carried out
DEG C, electrophoresis time 3 minutes.Gained film is toasted 30 minutes at 170 DEG C, and gained appearance of film uniform ground, film connects with water
Feeler is 150 °, and film other performances meet product standard.
Embodiment 3
(1) preparation of cation fluorine modified acrylic ester resin
In the reactor equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
The weight portion of MEK 20 and the weight portion of initiator azodiisobutyronitrile 0.5, by crylic acid ester mixture monomer (methyl-prop at 95 DEG C
The weight portion of olefin(e) acid ethyl ester 10, the weight portion of isopropyl acrylate 20, the weight portion of methacrylic acid -2- hydroxy methacrylates 10), epoxide function
20 parts of monomer methacrylic acid ethylene oxidic ester and the weight portion of ten trifluoro monooctyl ester of fluorinated acrylate monomer methacrylic acid 20 with
And the parts by weight solution of initiator azodiisobutyronitrile 0.5 is added drop-wise in reactor, is dripped off in 3 hours, continue insulation reaction 2 little
When.Being subsequently adding the weight portion of polyamine propane diamine 7 carries out ring-opening reaction, continues insulation reaction 2h, is eventually adding organic acid formic acid
Stirring 30 minutes, obtains cation fluorine modified acrylic ester resin after cooling.
(2) preparation of type semienclosed polyisocyanate crosslinker
In the reactor equipped with agitating device, constant pressure funnel and reflux condensing tube, the isocyanide of isophorone two is added
The weight portion of acid esters 50, under agitation, is slowly added drop-wise to sealer n-butanol in reactor at 60 DEG C, drips within 1 hour.
70 DEG C are heated to, are reacted 3 hours, determine free NCO content, when closed stratum is 60%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 55 weight portions and the type semienclosed polyisocyanates of 23 weight portions
Crosslinking agent is added in reactor, is reacted 2 hours at 70 DEG C, adds quantitative formic acid, is well mixed, and at 50 DEG C 1 is acidified
Hour, cooling discharge.The deionized water of 50 weight portions is subsequently adding, under high-speed stirred, disperses 15-30min, it is 5.5 to control pH,
Obtain with hydrophobic cationic acrylate resin cathode electrophoresis dope.
With electrophoresis emulsion obtained in the present embodiment, cathode electro-coating, electrophoretic voltage 150V, electrophoresis temperature 30 are directly carried out
DEG C, electrophoresis time 3 minutes.Gained film is toasted 30 minutes at 170 DEG C, and gained appearance of film uniform ground, film connects with water
Feeler is 138 °, and film other performances meet product standard.
Embodiment 4
(1) preparation of cation fluorine modified acrylic ester resin
In the reactor equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
The weight portion of cyclohexanone 20 and the weight portion of initiator azodiisobutyronitrile 1, by crylic acid ester mixture monomer (metering system at 85 DEG C
The weight portion of sour methyl esters 10, the weight portion of butyl acrylate 20, the weight portion of 2-Hydroxy ethyl acrylate 5), epoxide function monomer propylene
25 parts of acid glycidyl ester and the weight portion of fluorinated acrylate monomer Hexafluorobutyl mathacrylate 10 and initiator azo two
The parts by weight solution of isobutyronitrile 1 is added drop-wise in reactor, is dripped off in 2 hours, continues insulation reaction 2 hours.It is subsequently adding polyamine
The weight portion of ethylenediamine 8 carries out ring-opening reaction, continues insulation reaction 2h, is eventually adding organic acid sulfamic acid and stirs 30 minutes, drop
Cation fluorine modified acrylic ester resin is obtained after temperature.
(2) preparation of type semienclosed polyisocyanate crosslinker
In the reactor equipped with agitating device, constant pressure funnel and reflux condensing tube, the isocyanide of isophorone two is added
The weight portion of acid esters 50, under agitation, is slowly added drop-wise to sealer isooctanol in reactor at 60 DEG C, drips within 1 hour.
70 DEG C are heated to, are reacted 4 hours, determine free NCO content, when closed stratum is 65%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 50 weight portions and the type semienclosed polyisocyanates of 20 weight portions
Crosslinking agent is added in reactor, is reacted 2 hours at 70 DEG C, adds quantitative sulfamic acid, is well mixed, acid at 50 DEG C
Change 2 hours, cooling discharge.The deionized water of 40 weight portions is subsequently adding, under high-speed stirred, disperses 15-30min, controlling pH is
6.0, obtain with hydrophobic cationic acrylate resin cathode electrophoresis dope.
With electrophoresis emulsion obtained in the present embodiment, cathode electro-coating, electrophoretic voltage 150V, electrophoresis temperature 30 are directly carried out
DEG C, electrophoresis time 3 minutes.Gained film is toasted 30 minutes at 170 DEG C, and gained appearance of film uniform ground, film connects with water
Feeler is 141 °, and film other performances meet product standard.
Embodiment 5
(1) preparation of cation fluorine modified acrylic ester resin
In the reactor equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
The weight portion of methyl iso-butyl ketone (MIBK) 20 and the weight portion of initiator azodiisobutyronitrile 0.5, by crylic acid ester mixture monomer at 100 DEG C
(weight portion of EMA 20, the weight portion of isopropyl acrylate 30), epoxide function monomeric diglycidyl glycerine ether block alkene
The weight portion of propyl alcohol atactic polyether 15 and the weight portion of fluorinated acrylate monomer dodecafluoroheptyl methacrylate 30 and initiator
The parts by weight solution of azodiisobutyronitrile 1 is added drop-wise in reactor, is dripped off in 4 hours, continues insulation reaction 2 hours.It is subsequently adding
The weight portion of polyamine butanediamine 5 carries out ring-opening reaction, continues insulation reaction 2h, is eventually adding organic acid acetic acid and stirs 30 minutes,
Cation fluorine modified acrylic ester resin is obtained after cooling.
(2) preparation of type semienclosed polyisocyanate crosslinker
In the reactor equipped with agitating device, constant pressure funnel and reflux condensing tube, the isocyanide of isophorone two is added
The weight portion of acid esters 50, under agitation, is slowly added drop-wise to sealer n-butanol in reactor at 60 DEG C, drips within 1 hour.
70 DEG C are heated to, are reacted 2 hours, determine free NCO content, when closed stratum is 60%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 60 weight portions and the type semienclosed polyisocyanates of 25 weight portions
Crosslinking agent is added in reactor, is reacted 2 hours at 70 DEG C, adds quantitative acetic acid, is well mixed, and at 50 DEG C 1 is acidified
Hour, cooling discharge.The deionized water of 50 weight portions is subsequently adding, under high-speed stirred, disperses 15-30min, it is 5.5 to control pH,
Obtain with hydrophobic cationic acrylate resin cathode electrophoresis dope.
With electrophoresis emulsion obtained in the present embodiment, cathode electro-coating, electrophoretic voltage 150V, electrophoresis temperature 30 are directly carried out
DEG C, electrophoresis time 3 minutes.Gained film is toasted 30 minutes at 170 DEG C, and gained appearance of film uniform ground, film connects with water
Feeler is 134 °, and film other performances meet product standard.
Embodiment 6
(1) preparation of cation fluorine modified acrylic ester resin
In the reactor equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
The weight portion of butyl acetate 10 and the weight portion of initiator azodiisobutyronitrile 0.5, by crylic acid ester mixture monomer (methyl at 85 DEG C
The weight portion of methyl acrylate 10, the weight portion of butyl acrylate 20, the weight portion of 2-Hydroxy ethyl acrylate 10), epoxide function monomer
The weight portion of glycidyl ether blocked allyl alcohol atactic polyether 15 and the weight of fluorinated acrylate monomer perluorooctyl acrylate 10
Amount part and the parts by weight solution of initiator azodiisobutyronitrile 0.5 are added drop-wise in reactor, are dripped off in 2 hours, continue to be incubated instead
Answer 2 hours.Being subsequently adding the weight portion of polyamine triethanolamine 5 carries out ring-opening reaction, continues insulation reaction 4h, is eventually adding organic
Sour acetic acid is stirred 30 minutes, and cation fluorine modified acrylic ester resin is obtained after cooling.
(2) preparation of type semienclosed polyisocyanate crosslinker
In the reactor equipped with agitating device, constant pressure funnel and reflux condensing tube, the isocyanide of isophorone two is added
The weight portion of acid esters 50, under agitation, is slowly added drop-wise to sealer butyl in reactor at 60 DEG C, 1 hour
Drip.70 DEG C are heated to, are reacted 4 hours, determine free NCO content, when closed stratum is 63%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 50 weight portions and the type semienclosed polyisocyanates of 20 weight portions
Crosslinking agent is added in reactor, is reacted 2 hours at 70 DEG C, adds quantitative acetic acid, is well mixed, and at 50 DEG C 2 are acidified
Hour, cooling discharge.The deionized water of 40 weight portions is subsequently adding, under high-speed stirred, disperses 15-30min, it is 5.5 to control pH,
Obtain with hydrophobic cationic acrylate resin cathode electrophoresis dope.
With electrophoresis emulsion obtained in the present embodiment, cathode electro-coating, electrophoretic voltage 150V, electrophoresis temperature 30 are directly carried out
DEG C, electrophoresis time 3 minutes.Gained film is toasted 30 minutes at 170 DEG C, and gained appearance of film uniform ground, film connects with water
Feeler is 142 °, and film other performances meet product standard.
Finally, in addition it is also necessary to it is noted that listed above is only that the present invention is embodied as example.Obviously, the present invention not
It is limited to above example, there can also be many deformations.One of ordinary skill in the art can be straight from present disclosure
The all deformations derived or associate are connect, protection scope of the present invention is considered as.
Claims (10)
1. a kind of preparation method of cathode electrophoresis dope cationic acrylate resin, it is characterised in that first prepare cation fluorine
The type semienclosed polyisocyanate crosslinker of modified acrylic ester resin, then seals cation fluorine modified acrylic ester resin and half
After the reaction of closed form polyisocyanate crosslinker, one pack system grafting self-crosslinking acrylate resin is prepared, added organic
After acid acidifying, it is eventually adding deionized water dispersion and prepares cathode electrophoresis dope cationic acrylate resin.
2. the preparation method of electrophoretic coating cationic acrylate resin in pole according to claim 1, it is characterised in that tool
Preparation step is as follows：In a kettle., solvent and part initiator are added, by crylic acid ester mixture monomer at 70-100 DEG C
It is added drop-wise in reactor with epoxide function monomer and fluorinated acrylate monomer mixture and partial initiator solution, 2-4
Drip off in hour, continue insulation reaction 2-4 hour, being subsequently adding polyamine carries out ring-opening reaction, continues insulation reaction 2-4h, most
Organic acid stirring 20-60 minutes are added afterwards, and cation fluorine modified acrylic ester resin is obtained after cooling；In a kettle., add
IPDI, under agitation, is slowly added drop-wise to sealer in reactor at 50-70 DEG C, and 50 minutes extremely
Drip within 70 minutes, be heated to 60-80 DEG C, react 2-4 hours, determine free NCO content, when closed stratum is 50-70%, cooling
Type semienclosed polyisocyanate crosslinker is made in discharging；By a certain amount of cation fluorine modified acrylic ester resin, type semienclosed
Polyisocyanate crosslinker is added in reactor, and 2-4 hours are reacted at 60-80 DEG C, adds organic acid at 50-70 DEG C
Acidifying 1-2 hours, cooling discharge is subsequently adding a certain amount of deionized water, under high-speed stirred, disperses 15-30min, controls pH
For 5.0-6.5, obtain with hydrophobic fluorine-containing cationic acrylate cathode electrophoresis dope.
3. the preparation method of cathode electrophoresis dope cationic acrylate resin according to claim 2, it is characterised in that
Described fluorinated acrylate monomer is Hexafluorobutyl mathacrylate, hexafluorobutyl acrylate, methacrylic acid ten difluoro heptan
One kind in ester, the trifluoro monooctyl ester of methacrylic acid ten, perluorooctyl acrylate and perfluor alkyl ethide methacrylate or
It is various.
4. the preparation method of cathode electrophoresis dope cationic acrylate resin according to claim 2, it is characterised in that
Described epoxide function monomer be GMA, glycidyl acrylate, allyl glycidyl ether and
One or more mixture in glycidyl ether blocked allyl alcohol atactic polyether.
5. the preparation method of the cathode electrophoresis dope cationic acrylate resin according to Claims 2 or 3 or 4, it is special
Levy and be, crylic acid ester mixture monomer, including styrene, methyl methacrylate, EMA, butyl acrylate,
In isopropyl acrylate, 2-Hydroxy ethyl acrylate, methacrylic acid -2- hydroxy methacrylates and methacrylic acid -2- hydroxy propyl esters
One or more；Described polyamine be diethanol amine, triethanolamine, ethylenediamine, propane diamine, butanediamine in one kind or
Various mixtures.
6. the preparation method of cathode electrophoresis dope cationic acrylate resin according to claim 5, it is characterised in that
The organic acid is one or more of formic acid, acetic acid, lactic acid and sulfamic acid.
7. the preparation side of the cathode electrophoresis dope cationic acrylate resin according to claim 1 or 2 or 3 or 4 or 6
Method, it is characterised in that in described cation fluorine modified acrylic ester resin, it is acrylic ester monomer 25-50 weight portions, fluorine-containing
Acrylate monomer 10-20 weight portions, epoxide function monomer 15-30 weight portions, polyamine 5-10 weight portions, initiator 0.5-2
Weight portion.
8. the preparation method of cathode electrophoresis dope cationic acrylate resin according to claim 2, it is characterised in that
The sealer is one or more of butyl, methyl ethyl ketoxime, n-butanol and isooctanol.
9. the preparation of the cathode electrophoresis dope cationic acrylate resin according to claim 1 or 2 or 3 or 4 or 6 or 8
Method, it is characterised in that described cathode electrophoresis dope cationic acrylate resin each group is divided into cation fluorine modified propylene
Acid ester resin 50-60 weight portions, type semienclosed polyisocyanate crosslinker 20-25 weight portions.
10. the preparation method of cathode electrophoresis dope cationic acrylate resin according to claim 9, its feature exists
In after varnish film forming, film is 130-150 degree with the contact angle of water to obtained cathode electrophoresis dope.
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