CN106479338B - A kind of preparation method with hydrophobic cationic acrylate resin cathode electrophoresis dope - Google Patents
A kind of preparation method with hydrophobic cationic acrylate resin cathode electrophoresis dope Download PDFInfo
- Publication number
- CN106479338B CN106479338B CN201610872247.1A CN201610872247A CN106479338B CN 106479338 B CN106479338 B CN 106479338B CN 201610872247 A CN201610872247 A CN 201610872247A CN 106479338 B CN106479338 B CN 106479338B
- Authority
- CN
- China
- Prior art keywords
- weight
- parts
- hydrophobic
- cathode electrophoresis
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- 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
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
-
- 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
-
- 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
- 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
- C08F220/1803—C3-(meth)acrylate, e.g. (iso)propyl (meth)acrylate
-
- 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
- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Abstract
The invention discloses a kind of preparation methods with hydrophobic cationic acrylate resin cathode electrophoresis dope, first prepare the preparation of cation fluorine modified acrylic ester resin and Totally-enclosed-type polyisocyanate crosslinker, it will be acidified after cation fluorine modified acrylic ester resin and the reaction of Totally-enclosed-type polyisocyanate crosslinker, it is carried out after being sufficiently mixed preparation with hydrophobic oxide particle, is eventually adding deionized water dispersion and cathode electrophoresis dope is prepared.Fluorin modified crylic acid ester monomer is introduced into acrylate cathode electrophoresis dope by the present invention, utilize the excellent chemical resistance and low-surface-energy of fluorine resin, to be effectively improved the hydrophobic performance of film, meanwhile acrylate and epoxy resin perfect combination getting up, acrylate is because of its excellent weatherability and good guarantor's color, gloss retention, it is only suitable for doing the deficiency of priming paint to compensate for epoxy resin, properties of product are excellent, and the service life is long, can be widely used for all kinds of high-quality hardwares.
Description
Technical field
The present invention relates to a kind of preparation processes of new material, specifically, being a kind of with hydrophobic cationic acrylamide
The preparation method of acid ester resin cathode electrophoresis dope.
Background technique
In recent years, super-hydrophobic (contact angle is greater than 150 °) in nature causes the research of people emerging with self-cleaning phenomenon
Interest.Manually preparing super hydrophobic surface can be used for the antifouling of automotive window, the windowpane of building and glass outer wall, be used for thunder
Reach, signal is decayed caused by antenna surface can be prevented due to precipitation adhesion, the surface super hydrophobic of material can inhibit micro- life
Object inhibits the blood coagulation phenomenon of polymer surfaces in the adherency of body surface, can reduce fluid resistance for water delivery, oil transportation inner tubal wall
Deng.The research of super hydrophobic surface has become hot subject, is related to botany, chemistry, materialogy, engineering mechanics etc. more
Section.
Cathodic Electrophoretic Painting Technology, due to its coating uniformity and excellent corrosion resistance and low pollution the advantages that,
Application field is growing, it has also become one of indispensable method of field of coating.Since first generation cathode electrophoresis dope is developed
Since succeeding and being applied, by development in more than 40 years, the research of domestic and international cathode electrophoresis dope and application field occurred
Very big variation, has researched and developed the 6th generation, the 7th generation or even eighth generation product.Cathode electrophoresis dope belongs to environment friend
Good type water paint, from now on, during cathode electro-coating new technology development, coating process should be towards the saving energy, reduction
Labor intensity and production cost, reduce environmental pollution, heavy metal free, low VOC, VOC, reduce solidification temperature,
The directions such as high performance are developed.
Since 1971, PPG company, the U.S. developed first generation cathode electrophoresis dope, and electrophoretic coating enters one quickly
The track of development, especially cathode electrophoresis dope, because corrosion resistance is 3-4 times high compared with anode electrophoresis dope for it, permeability ratio is high
1.3-1.5 times, and metal surface is not easy to be ionized and eluted when electro-deposition, solves workpiece surface etching problem, thus obtain
Be widely applied, gradually comprehensively instead of anode electrophoresis dope, cathode electrophoresis dope shows several major sects at present: i.e. with
PPG company, the U.S. is the anti-corrosion cation electrophoretic coating at beginning；It is used with German Hocehst company for the car truck of pioneer
Cation electrophoretic coating；Using the western paint company in day Benshen Dongguan as the modified cation electrophoretic coating of representative.Some skills
The leading cathode electrophoresis dope company of art has developed corner rust-proof type, yin of weather-proof and the 5th generation of low temperature curing type forth generation
Pole electrophoretic coating, while in the six, the seven generations, also developed in laboratory research.The May 4th research institute, weapons portion (five or nine institute) at home,
Shanghai coating research institute and coating research institute, the Ministry of Chemical Industry develop cathode electrophoresis dope the eighties in succession, and some Paint Factories are also confused
The confused Introduced from Japan Northwest, Austrian Stollack, U.S. PPG, the technologies such as German BASF carry out the production of electrophoretic coating, and
The matrix resin generally used has epoxy resin, polyester resin, epoxy-polyurethane etc..But it is poor often to there is weatherability, and heating is easy
Xanthochromia, solidification temperature are high, it is difficult to the problems such as coloured silkization.And acrylic cathodic electrophoretic coating is because of its excellent guarantor's light, weather-proof, uvioresistant
The performances such as line aging, high decoration and be widely used in bottom surface unification electrophoretic painting.
In recent years, high-performance hardware especially lamps and lanterns, fittings of bathroom, the rapid development of metal handicrafts and electrophoresis
The continuous development and progress of application techniques propose performance especially hydrophobicity, weatherability and the dicoration of coating higher
It is required that.After traditional aqueous cathode electrophoresis dope film forming, the comprehensive performance of film especially hydrophobicity, weatherability and dicoration are owed
It is good, it is not able to satisfy the new demand that high-grade hardware proposes aqueous cathode electrophoresis dope.CN101993576 provides one kind
Hydrophobicity cathode electrophoresis dope resin emulsion and preparation method thereof.The resin emulsion is by cation fluorine carbon resin and contains active hydrogen
Organic compound is to be acidified after the Totally-enclosed-type polyisocyanate crosslinker of sealer reacts, and deionized water dispersion preparation is added
Obtain, the resin emulsion of the invention after being configured to cathode electrophoresis dope varnish film forming, the contact angle 100 of film and water~
120 °, the biggish hydrophobicity for improving aqueous cathode electrophoresis dope, weatherability and dicoration.CN103333596A has registered one
Kind fluorinated silicone modified acrylic cathodic electrophoretic coating of automatically cleaning and preparation method thereof, it is modified to use semiclosed aliphatic isocyanates
Fluorine silicon acrylic cationic resin and nano-titanium dioxide modified mill base are prepared, and the contact angle of film coated surface and water reaches
130°。
Although having there is many progress in hydrophobicity, the comprehensive performance of existing film especially hydrophobicity,
Weatherability and the decorative new demand for being not met by high-grade hardware and aqueous cathode electrophoresis dope being proposed, it is especially super
The requirement of hydrophobic performance.Therefore further the cathode electrophoresis dope of development function type is current research hotspot.
Summary of the invention
The present invention is exactly directed to various shortcomings existing in the prior art, provide it is a kind of have hydrophobic sun from
The preparation method of sub- acrylate cathode electrophoresis dope.
The present invention is technical solution in this way to realize in order to achieve the above objectives:
The invention discloses a kind of preparation method with hydrophobic cationic acrylate resin cathode electrophoresis dope,
The preparation for first preparing cation fluorine modified acrylic ester resin and Totally-enclosed-type polyisocyanate crosslinker, cation fluorine is modified
It is acidified, is carried out with hydrophobic oxide particle sufficiently mixed after acrylate and the reaction of Totally-enclosed-type polyisocyanate crosslinker
It closes after preparing, is eventually adding deionized water dispersion and cathode electrophoresis dope is prepared.
As a further improvement, of the present invention, specific preparation process is as follows: in a kettle, solvent and part is added
Initiator azodiisobutyronitrile, at 85-100 DEG C by crylic acid ester mixture monomer and fluorinated acrylate monomer mixture and
Partial initiator azodiisobutyronitrile solution is added drop-wise in reaction kettle, is dripped off in 2-4 hours, is continued insulation reaction 2 hours, drop
Cation fluorine modified acrylic ester resin is obtained after temperature；Prepare Totally-enclosed-type polyisocyanate crosslinker, by it is a certain amount of sun from
Sub- fluorin modified crylic acid ester resin, Totally-enclosed-type polyisocyanate crosslinker and ethylene glycol monobutyl ether, organic acid and hydrophobicity oxygen
Compound particle is uniformly mixed, and be acidified 1-2 hours at 50-70 DEG C, is then added a certain amount of deionized water, under high-speed stirred, is divided
Scattered 15-30min obtains having hydrophobic cationic acrylate resin cathode electrophoresis dope, and control pH is 5.0-6.5.
As a further improvement, of the present invention there is hydrophobic cationic acrylate resin ability cathode electrophoresis to apply
The preparation method of material, which is characterized in that the preparation method of the Totally-enclosed-type polyisocyanate crosslinker be in a kettle,
Isophorone diisocyanate is added slowly butyl is added drop-wise in reaction kettle under agitation, drip within 1 hour
It adds, is heated to 70 DEG C, react 2-4 hours, when measurement free NCO content is lower than 0.5%, cooling discharge.
As a further improvement, fluorinated acrylate monomer of the present invention is Hexafluorobutyl mathacrylate, third
Olefin(e) acid hexafluoro butyl ester, dodecafluoroheptyl methacrylate, ten trifluoro monooctyl ester of methacrylic acid, perluorooctyl acrylate and perfluor
One of alkyl ethylmethyl acrylate is a variety of.
As a further improvement, crylic acid ester mixture monomer of the present invention includes tertiary amino acrylic ester monomer
With general acrylic ester monomer, wherein tertiary amino acrylic ester monomer includes dimethylaminoethyl methacrylate, acrylic acid two
Ethylamino propyl ester, dimethylaminoethyl acrylate, dimethylaminoethyl propyl ester, methacrylic acid lignocaine propyl ester,
One of dimethylaminoethyl methacrylate, dimethylaminoethyl propyl ester are a variety of；General esters of acrylic acid list
Body includes styrene, methyl methacrylate, ethyl methacrylate, butyl acrylate, isopropyl acrylate, acrylic acid -2-
One of hydroxy methacrylate, methacrylic acid -2- hydroxy methacrylate and methacrylic acid -2- hydroxy propyl ester are a variety of.
As a further improvement, in cation fluorine modified acrylic ester resin of the present invention, tertiary amino acrylic acid
Esters monomer 10-20 parts by weight, general acrylic ester monomer 40-70 parts by weight, fluorinated acrylate monomer 10-30 weight
Part, initiator azodiisobutyronitrile 0.5-2 parts by weight and solvent 10-30 parts by weight, organic acid are formic acid, acetic acid, lactic acid and ammonia
Base sulfonic acid it is one or more.
As a further improvement, hydrophobic oxide particle of the present invention is hydrophobic silica, it is primary flat
Equal partial size is 3-100nm, and the specific surface area measured with BET method is 50-300 m2/g。
As a further improvement, having trimethylsilyl on its surface of hydrophobic silica of the present invention.
As a further improvement, cathode electrophoresis dope each group of the present invention is divided into cation fluorine modification acrylate
Resin 50-60 parts by weight, Totally-enclosed-type polyisocyanate crosslinker 20-25 parts by weight, hydrophobic oxide particle 2-10 weight
Part.
As a further improvement, cathode electrophoresis dope obtained by the present invention is after varnish film forming, film and water are connect
Feeler is 145-160 degree.
Beneficial effects of the present invention are as follows:
1, the present invention provides one kind to 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, to be effectively improved
The hydrophobic performance of film.
Specific embodiment
The invention discloses one kind to have hydrophobic cationic acrylate resin cathode electrophoresis dope and its preparation side
Method, the present invention make detailed description further to technical solution of the present invention combined with specific embodiments below, but of the invention
Range is not limited to embodiment.
Embodiment 1
(1) preparation of cation fluorine modified acrylic ester resin
In the reaction kettle equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
0.2 parts by weight of 10 parts by weight of butyl acetate and initiator azodiisobutyronitrile, by crylic acid ester mixture monomer (propylene at 85 DEG C
Sour 10 parts by weight of dimethylamino propyl ester, 10 parts by weight of methyl methacrylate, 20 parts by weight of butyl acrylate, acrylic acid -2- hydroxyl
10 parts by weight of base ethyl ester) and 10 parts by weight of fluorinated acrylate monomer perfluor alkyl ethide methacrylate and initiator it is even
0.3 parts by weight solution of nitrogen bis-isobutyronitrile is added drop-wise in reaction kettle, is dripped off in 2 hours, is continued insulation reaction 2 hours.After cooling
To cation fluorine modified acrylic ester resin.
(2) preparation of Totally-enclosed-type polyisocyanate crosslinker
In the reaction kettle equipped with agitating device, constant pressure funnel and reflux condensing tube, two isocyanide of isophorone is added
About 75 parts by weight of butyl are slowly added drop-wise in reaction kettle by 50 parts by weight of acid esters under agitation, are dripped within 1 hour
It adds.70 DEG C are heated to, is reacted 4 hours, when measurement free NCO content is lower than 0.5%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 50 parts by weight, 20 parts of Totally-enclosed-type polyisocyanate crosslinker
With the hydrophobic silicas of 20 parts by weight of ethylene glycol monobutyl ether, quantitative acetic acid and 2 parts by weight (average grain diameter is 3nm,
The specific surface area measured with BET method has trimethylsilyl for 300 m2/g on its surface of hydrophobic silica), mixing
Uniformly, it is acidified 2 hours at 50 DEG C.Then it is added the deionized water of 40 parts by weight, under high-speed stirred, dispersion 15-30min is had
There is hydrophobic cationic acrylate resin cathode electrophoresis dope, control pH is 5.0.
The electrophoresis lotion made from the present embodiment, directly progress cathode electro-coating, electrophoretic voltage 250V, electrophoresis temperature 30
DEG C, electrophoresis time 5 minutes.Gained film toasts 30 minutes at 160 DEG C, gained appearance of film uniform ground, film and water
Contact angle is 145 °, other performances of film meet product standard.
Embodiment 2
(1) preparation of cation fluorine modified acrylic ester resin
In the reaction kettle equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
1 parts by weight of 30 parts by weight of butyl acetate and initiator azodiisobutyronitrile, by crylic acid ester mixture monomer (methyl at 100 DEG C
20 parts by weight of dimethylaminoethyl methacrylate, 20 parts by weight of ethyl methacrylate, 30 parts by weight of isopropyl acrylate, methyl-prop
20 parts by weight of olefin(e) acid -2- hydroxy propyl ester) and 30 parts by weight of fluorinated acrylate monomer hexafluorobutyl acrylate and initiator it is even
1 parts by weight solution of nitrogen bis-isobutyronitrile is added drop-wise in reaction kettle, is dripped off in 4 hours, is continued insulation reaction 2 hours.It is obtained after cooling
Cation fluorine modified acrylic ester resin.
(2) preparation of Totally-enclosed-type polyisocyanate crosslinker
In the reaction kettle equipped with agitating device, constant pressure funnel and reflux condensing tube, two isocyanide of isophorone is added
About 75 parts by weight of butyl are slowly added drop-wise in reaction kettle by 50 parts by weight of acid esters under agitation, are dripped within 1 hour
It adds.70 DEG C are heated to, is reacted 2 hours, when measurement free NCO content is lower than 0.5%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 60 parts by weight, 25 parts of Totally-enclosed-type polyisocyanate crosslinker
(average grain diameter is with the hydrophobic silicas of 20 parts by weight of ethylene glycol monobutyl ether, quantitative lactic acid and 10 parts by weight
100nm, the specific surface area measured with BET method have trimethylsilyl for 50 m2/g on its surface of hydrophobic silica),
It is uniformly mixed, is acidified 1 hour at 70 DEG C.Then it is added the deionized water of 60 parts by weight, under high-speed stirred, dispersion 15-30min is obtained
To with hydrophobic cationic acrylate resin cathode electrophoresis dope, controlling pH is 6.5.
The electrophoresis lotion made from the present embodiment, directly progress cathode electro-coating, electrophoretic voltage 250V, electrophoresis temperature 30
DEG C, electrophoresis time 5 minutes.Gained film toasts 30 minutes at 160 DEG C, gained appearance of film uniform ground, film and water
Contact angle is 155 °, other performances of film meet product standard.
Embodiment 3
(1) preparation of cation fluorine modified acrylic ester resin
In the reaction kettle equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
0.5 parts by weight of 20 parts by weight of butyl acetate and initiator azodiisobutyronitrile, by crylic acid ester mixture monomer (propylene at 95 DEG C
Sour 15 parts by weight of dimethylaminoethyl, 5 parts by weight of styrene, 10 parts by weight of ethyl methacrylate, 30 weight of isopropyl acrylate
Measure part, 15 parts by weight of methacrylic acid -2- hydroxy methacrylate) and ten trifluoro monooctyl ester of fluorinated acrylate monomer methacrylic acid, 20 weight
Amount part and 0.5 parts by weight solution of initiator azodiisobutyronitrile are added drop-wise in reaction kettle, are dripped off in 3 hours, and it is anti-to continue heat preservation
It answers 2 hours.Cation fluorine modified acrylic ester resin is obtained after cooling.
(2) preparation of Totally-enclosed-type polyisocyanate crosslinker
In the reaction kettle equipped with agitating device, constant pressure funnel and reflux condensing tube, two isocyanide of isophorone is added
About 75 parts by weight of butyl are slowly added drop-wise in reaction kettle by 50 parts by weight of acid esters under agitation, are dripped within 1 hour
It adds.70 DEG C are heated to, is reacted 3 hours, when measurement free NCO content is lower than 0.5%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 55 parts by weight, 23 parts of Totally-enclosed-type polyisocyanate crosslinker
With the hydrophobic silicas of 20 parts by weight of ethylene glycol monobutyl ether, quantitative formic acid and 6 parts by weight (average grain diameter is 7nm,
The specific surface area measured with BET method has trimethylsilyl for 220 m2/g on its surface of hydrophobic silica), mixing
Uniformly, it is acidified 1 hour at 70 DEG C.Then it is added the deionized water of 50 parts by weight, under high-speed stirred, dispersion 15-30min is had
There is hydrophobic cationic acrylate resin cathode electrophoresis dope, control pH is 5.5.
The electrophoresis lotion made from the present embodiment, directly progress cathode electro-coating, electrophoretic voltage 250V, electrophoresis temperature 30
DEG C, electrophoresis time 5 minutes.Gained film toasts 30 minutes at 160 DEG C, gained appearance of film uniform ground, film and water
Contact angle is 160 °, other performances of film meet product standard.
Embodiment 4
(1) preparation of cation fluorine modified acrylic ester resin
In the reaction kettle equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
1 parts by weight of 20 parts by weight of butyl acetate and initiator azodiisobutyronitrile, by crylic acid ester mixture monomer (methyl-prop at 85 DEG C
10 parts by weight of olefin(e) acid dimethylaminoethyl, 10 parts by weight of methyl methacrylate, 20 parts by weight of butyl acrylate, acrylic acid -2-
10 parts by weight of hydroxy methacrylate) and 10 parts by weight of fluorinated acrylate monomer Hexafluorobutyl mathacrylate and initiator azo two
1 parts by weight solution of isobutyronitrile is added drop-wise in reaction kettle, is dripped off in 2 hours, is continued insulation reaction 2 hours.Obtained after cooling sun from
Sub- fluorin modified crylic acid ester resin.
(2) preparation of Totally-enclosed-type polyisocyanate crosslinker
In the reaction kettle equipped with agitating device, constant pressure funnel and reflux condensing tube, two isocyanide of isophorone is added
About 75 parts by weight of butyl are slowly added drop-wise in reaction kettle by 50 parts by weight of acid esters under agitation, are dripped within 1 hour
It adds.70 DEG C are heated to, is reacted 4 hours, when measurement free NCO content is lower than 0.5%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 50 parts by weight, 20 parts of Totally-enclosed-type polyisocyanate crosslinker
(average grain diameter is with the hydrophobic silicas of 20 parts by weight of ethylene glycol monobutyl ether, quantitative sulfamic acid and 8 parts by weight
12nm, the specific surface area measured with BET method have trimethylsilyl for 180 m2/g on its surface of hydrophobic silica),
It is uniformly mixed, is acidified 2 hours at 50 DEG C.Then it is added the deionized water of 40 parts by weight, under high-speed stirred, dispersion 15-30min is obtained
To with hydrophobic cationic acrylate resin cathode electrophoresis dope, controlling pH is 6.0.
The electrophoresis lotion made from the present embodiment, directly progress cathode electro-coating, electrophoretic voltage 250V, electrophoresis temperature 30
DEG C, electrophoresis time 5 minutes.Gained film toasts 30 minutes at 160 DEG C, gained appearance of film uniform ground, film and water
Contact angle is 158 °, other performances of film meet product standard.
Embodiment 5
(1) preparation of cation fluorine modified acrylic ester resin
In the reaction kettle equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
0.5 parts by weight of 20 parts by weight of butyl acetate and initiator azodiisobutyronitrile, by crylic acid ester mixture monomer (third at 100 DEG C
20 parts by weight of olefin(e) acid lignocaine propyl ester, 20 parts by weight of ethyl methacrylate, 30 parts by weight of isopropyl acrylate, metering system
20 parts by weight of acid -2- hydroxy propyl ester) and 30 parts by weight of fluorinated acrylate monomer dodecafluoroheptyl methacrylate and initiation
1 parts by weight solution of agent azodiisobutyronitrile is added drop-wise in reaction kettle, is dripped off in 4 hours, is continued insulation reaction 2 hours.After cooling
Obtain cation fluorine modified acrylic ester resin.
(2) preparation of Totally-enclosed-type polyisocyanate crosslinker
In the reaction kettle equipped with agitating device, constant pressure funnel and reflux condensing tube, two isocyanide of isophorone is added
About 75 parts by weight of butyl are slowly added drop-wise in reaction kettle by 50 parts by weight of acid esters under agitation, are dripped within 1 hour
It adds.70 DEG C are heated to, is reacted 2 hours, when measurement free NCO content is lower than 0.5%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 60 parts by weight, 25 parts of Totally-enclosed-type polyisocyanate crosslinker
(average grain diameter is with the hydrophobic silicas of 20 parts by weight of ethylene glycol monobutyl ether, quantitative acetic acid and 4 parts by weight
20nm, the specific surface area measured with BET method have trimethylsilyl for 150 m2/g on its surface of hydrophobic silica),
It is uniformly mixed, is acidified 1 hour at 70 DEG C.Then it is added the deionized water of 60 parts by weight, under high-speed stirred, dispersion 15-30min is obtained
To with hydrophobic cationic acrylate resin cathode electrophoresis dope, controlling pH is 5.5.
The electrophoresis lotion made from the present embodiment, directly progress cathode electro-coating, electrophoretic voltage 250V, electrophoresis temperature 30
DEG C, electrophoresis time 5 minutes.Gained film toasts 30 minutes at 160 DEG C, gained appearance of film uniform ground, film and water
Contact angle is 153 °, other performances of film meet product standard.
Embodiment 6
(1) preparation of cation fluorine modified acrylic ester resin
In the reaction kettle equipped with mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube, solvent is added
0.5 parts by weight of 10 parts by weight of butyl acetate and initiator azodiisobutyronitrile, by crylic acid ester mixture monomer (methyl at 85 DEG C
10 parts by weight of dimethylaminoethyl methacrylate, 10 parts by weight of methyl methacrylate, 20 parts by weight of butyl acrylate, acrylic acid-
10 parts by weight of 2- hydroxy methacrylate) and 10 parts by weight of fluorinated acrylate monomer perluorooctyl acrylate and initiator azo two
0.5 parts by weight solution of isobutyronitrile is added drop-wise in reaction kettle, is dripped off in 2 hours, is continued insulation reaction 2 hours.Sun is obtained after cooling
Ion fluorin modified crylic acid ester resin.
(2) preparation of Totally-enclosed-type polyisocyanate crosslinker
In the reaction kettle equipped with agitating device, constant pressure funnel and reflux condensing tube, two isocyanide of isophorone is added
About 75 parts by weight of butyl are slowly added drop-wise in reaction kettle by 50 parts by weight of acid esters under agitation, are dripped within 1 hour
It adds.70 DEG C are heated to, is reacted 4 hours, when measurement free NCO content is lower than 0.5%, cooling discharge.
(3) preparation of cathodic electrophoretic emulsion
By the cation fluorine modified acrylic ester resin of 50 parts by weight, 20 parts of Totally-enclosed-type polyisocyanate crosslinker
With the hydrophobic silicas of 20 parts by weight of ethylene glycol monobutyl ether, quantitative acetic acid and 5 parts by weight (average grain diameter is 7nm,
The specific surface area measured with BET method has trimethylsilyl for 220 m2/g on its surface of hydrophobic silica), mixing
Uniformly, it is acidified 2 hours at 50 DEG C.Then it is added the deionized water of 40 parts by weight, under high-speed stirred, dispersion 15-30min is had
There is hydrophobic cationic acrylate resin cathode electrophoresis dope, control pH is 5.5.
The electrophoresis lotion made from the present embodiment, directly progress cathode electro-coating, electrophoretic voltage 250V, electrophoresis temperature 30
DEG C, electrophoresis time 5 minutes.Gained film toasts 30 minutes at 160 DEG C, gained appearance of film uniform ground, film and water
Contact angle is 160 °, other performances of film meet product standard.
Finally, it should also be noted that the above enumerated are only specific embodiments of the present invention son.Obviously, the present invention is not
It is limited to above embodiment, acceptable there are many deformations.Those skilled in the art can be straight from present disclosure
All deformations for connecing export or associating, are considered as protection scope of the present invention.
Claims (7)
1. a kind of preparation method with hydrophobic cationic acrylate resin cathode electrophoresis dope, which is characterized in that first
Cation fluorine modified acrylic ester resin and Totally-enclosed-type polyisocyanate crosslinker are prepared, by cation fluorine modification acrylate
Resin and Totally-enclosed-type polyisocyanate crosslinker are acidified after being sufficiently mixed with hydrophobic oxide particle, are eventually adding
Cathode electrophoresis dope is prepared in ion water dispersion, and specific preparation process is as follows:
In a kettle, solvent and part initiator azodiisobutyronitrile is added, by crylic acid ester mixture list at 85-100 DEG C
Body and fluorinated acrylate monomer mixture and partial initiator azodiisobutyronitrile solution are added drop-wise in reaction kettle, 2-4
It is dripped off in hour, continues insulation reaction 2-4 hours, cation fluorine modified acrylic ester resin is obtained after cooling；Wherein, acrylic acid
Ester mix monomer includes tertiary amino acrylic ester monomer and general acrylic ester monomer, the general esters of acrylic acid list
Body includes styrene, methyl methacrylate, ethyl methacrylate, butyl acrylate, isopropyl acrylate, acrylic acid -2-
One of hydroxy methacrylate, methacrylic acid -2- hydroxy methacrylate and methacrylic acid -2- hydroxy propyl ester are a variety of；
Totally-enclosed-type polyisocyanate crosslinker is prepared, in a kettle, isophorone diisocyanate is added, in stirring condition
Under, slowly butyl is added drop-wise in reaction kettle, is dripped within 1 hour, is heated to 70 DEG C, is reacted 2-4 hours, measurement trip
When being lower than 0.5% from NCO content, cooling discharge obtains Totally-enclosed-type polyisocyanate crosslinker；
By a certain amount of cation fluorine modified acrylic ester resin, Totally-enclosed-type polyisocyanate crosslinker and ethylene glycol only son
Ether, organic acid and hydrophobic oxide particle are uniformly mixed, and are acidified 1-2 hours at 50-70 DEG C, be then added it is a certain amount of go from
Sub- water, under high-speed stirred, dispersion 15-30min obtains having hydrophobic cationic acrylate resin cathode electrophoresis dope, controls
PH processed is 5.0-6.5；Wherein, hydrophobic oxide particle is the hydrophobic silica with trimethylsilyl.
2. the preparation side according to claim 1 with hydrophobic cationic acrylate resin cathode electrophoresis dope
Method, which is characterized in that the fluorinated acrylate monomer is Hexafluorobutyl mathacrylate, hexafluorobutyl acrylate, methyl
Dodecafluorhe-ptylacrylate, ten trifluoro monooctyl ester of methacrylic acid, perluorooctyl acrylate and perfluor alkyl ethide metering system
One of acid esters is a variety of.
3. the preparation side according to claim 2 with hydrophobic cationic acrylate resin cathode electrophoresis dope
Method, which is characterized in that the tertiary amino acrylic ester monomer includes dimethylaminoethyl methacrylate, acrylic acid lignocaine
Propyl ester, dimethylaminoethyl acrylate, dimethylaminoethyl propyl ester, methacrylic acid lignocaine propyl ester, methyl-prop
One of olefin(e) acid dimethylaminoethyl is a variety of.
4. the system according to claim 1 or 2 or 3 with hydrophobic cationic acrylate resin cathode electrophoresis dope
Preparation Method, which is characterized in that in the cation fluorine modified acrylic ester resin, tertiary amino acrylic ester monomer 10-20
Parts by weight, general acrylic ester monomer 40-70 parts by weight, fluorinated acrylate monomer 10-30 parts by weight, initiator azo two
Isobutyronitrile 0.5-2 parts by weight and solvent 10-30 parts by weight, the organic acid are one kind of formic acid, acetic acid, lactic acid and sulfamic acid
Or it is a variety of.
5. the system according to claim 1 or 2 or 3 with hydrophobic cationic acrylate resin cathode electrophoresis dope
Preparation Method a, which is characterized in that average grain diameter of the hydrophobic silica is 3-100nm, the ratio measured with BET method
Surface area is 50-300m2/g。
6. the system according to claim 1 or 2 or 3 with hydrophobic cationic acrylate resin cathode electrophoresis dope
Preparation Method, which is characterized in that the cathode electrophoresis dope each group is divided into cation fluorine modified acrylic ester resin 50-60 weight
Part, Totally-enclosed-type polyisocyanate crosslinker 20-25 parts by weight, hydrophobic oxide particle 2-10 parts by weight.
7. the preparation side according to claim 6 with hydrophobic cationic acrylate resin cathode electrophoresis dope
Method, which is characterized in that for obtained cathode electrophoresis dope after varnish film forming, the contact angle of film and water is 145-160 degree.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610872247.1A CN106479338B (en) | 2016-10-01 | 2016-10-01 | A kind of preparation method with hydrophobic cationic acrylate resin cathode electrophoresis dope |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610872247.1A CN106479338B (en) | 2016-10-01 | 2016-10-01 | A kind of preparation method with hydrophobic cationic acrylate resin cathode electrophoresis dope |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106479338A CN106479338A (en) | 2017-03-08 |
| CN106479338B true CN106479338B (en) | 2019-07-12 |
Family
ID=58268423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610872247.1A Active CN106479338B (en) | 2016-10-01 | 2016-10-01 | A kind of preparation method with hydrophobic cationic acrylate resin cathode electrophoresis dope |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106479338B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987657A (en) * | 2017-12-07 | 2018-05-04 | 安徽省华腾农业科技有限公司 | A kind of preparation method of water-repellent paint |
| CN109970928B (en) * | 2019-04-17 | 2021-08-27 | 广州希森美克新材料科技有限公司 | High-performance resin for electrophoretic paint and synthetic method thereof |
| CN109988497B (en) * | 2019-04-17 | 2021-02-12 | 广州希森美克新材料科技股份有限公司 | High-wear-resistance high-hardness easy-to-clean electrophoretic color nano coating and preparation method thereof |
| CN111041440B (en) * | 2019-12-20 | 2021-08-31 | 浙江中杭新材料科技有限公司 | Surface protection method of neodymium iron boron permanent magnet |
| CN112662104B (en) * | 2020-12-10 | 2022-04-15 | 中电保力（北京）科技有限公司 | Composite test material based on graphene oxide and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993576A (en) * | 2010-11-04 | 2011-03-30 | 安吉万国涂料有限公司 | Resin emulsion for hydrophobic cathode electrophoretic coating as well as preparation method and application thereof |
| CN103333596A (en) * | 2013-06-24 | 2013-10-02 | 浩力森涂料（上海）有限公司 | Self-cleaning fluorosilicone-modified acrylic acid cathode electrophoresis paint and preparation method thereof |
| CN103601838A (en) * | 2013-11-13 | 2014-02-26 | 深圳市志邦科技有限公司 | Method for preparing special fluorocarbon resin for fluorinated electrophoretic paint |
| CN104725554A (en) * | 2015-03-25 | 2015-06-24 | 安吉万国涂料有限公司 | High-solid-content fluorine-modified acrylate cationic resin and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014053268A1 (en) * | 2012-10-04 | 2014-04-10 | Basf Coatings Gmbh | Fluorine-containing non-aqueous coating composition, coating process, and the use of the coating composition |
-
2016
- 2016-10-01 CN CN201610872247.1A patent/CN106479338B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993576A (en) * | 2010-11-04 | 2011-03-30 | 安吉万国涂料有限公司 | Resin emulsion for hydrophobic cathode electrophoretic coating as well as preparation method and application thereof |
| CN103333596A (en) * | 2013-06-24 | 2013-10-02 | 浩力森涂料（上海）有限公司 | Self-cleaning fluorosilicone-modified acrylic acid cathode electrophoresis paint and preparation method thereof |
| CN103601838A (en) * | 2013-11-13 | 2014-02-26 | 深圳市志邦科技有限公司 | Method for preparing special fluorocarbon resin for fluorinated electrophoretic paint |
| CN104725554A (en) * | 2015-03-25 | 2015-06-24 | 安吉万国涂料有限公司 | High-solid-content fluorine-modified acrylate cationic resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 纳米SiO2改性阴极电泳漆的制备及耐蚀性研究;黄娇等;《电镀与精饰》;20120215;第34卷(第2期);第43-46页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106479338A (en) | 2017-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106479338B (en) | A kind of preparation method with hydrophobic cationic acrylate resin cathode electrophoresis dope | |
| CN103333314B (en) | A kind of cationic photo-cured fluorine-containing urethane resin and preparation method thereof | |
| CN106632882B (en) | The preparation method of fluorine-containing cationic acrylate cathode electrophoresis dope | |
| CN103333596A (en) | Self-cleaning fluorosilicone-modified acrylic acid cathode electrophoresis paint and preparation method thereof | |
| CN108165151A (en) | A kind of watersoluble fluorine-carbon modified acrylic polyurethane finish paint and preparation method thereof | |
| CN104592850A (en) | Preparation method of super hydrophilic transparent anti-fog coating | |
| CN102337073B (en) | Water-soluble nonluminous anionic electrophoretic coating and preparation method and application thereof | |
| CN104497736A (en) | Double-component transparent glass thermal-insulating coating and preparation method thereof | |
| CN108129967A (en) | A kind of aqueous polyurethane anticorrosive paint | |
| CN111793421B (en) | Environment-friendly chromium-free insulating coating liquid for surface treatment of oriented silicon steel and preparation method and application thereof | |
| CN104419226A (en) | Stabilized coating for surface rust layer of weatherproof steel | |
| CN111808505B (en) | Heat-reflection high-corrosion-resistance weather-resistant steel plate coil metal coating and preparation method thereof | |
| CN111303741A (en) | High-film-thickness waterborne polyurethane long-acting anticorrosive paint for wind power and petrochemical equipment and preparation method thereof | |
| CN104672366A (en) | High-solid low-viscosity acrylic resin and preparation method thereof | |
| CN109206996A (en) | A kind of bloom one-component plain color finishing coat of aqueous solvent-free bottom surface unification and its preparation | |
| CN111073459A (en) | Energy-saving and environment-friendly cathode electrophoretic coating | |
| CN103555081A (en) | Super-hydrophobic composite water-based finish varnish, and preparation method thereof | |
| CN108531066B (en) | Preparation method and application of water-based strippable film coating | |
| CN102492100B (en) | Water-dispersed fluorine-containing hydroxyl acrylic-epoxy ester heterozygous body resin and coating thereof | |
| CN104559591B (en) | Environment-friendly water-based paint for aluminum profile production and preparation method thereof | |
| CN106894009B (en) | A kind of epoxy group POSS modified metal surface pretreating reagent and preparation method thereof, application | |
| CN106634384A (en) | Preparation method of cation acrylate resin of cathode electrophoresis coating | |
| CN104974611A (en) | Cold spraying zinc coating and preparation method thereof | |
| CN105238175A (en) | Hydrophobic self-cleaning coating | |
| CN111909301B (en) | Tertiary carbonate resin and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210913 Address after: 528000 401-2, 402, 403, 404-2, 405, 406, 407-2, 408, building 1, Guoteng intelligent manufacturing center, No. 7, Xinhui Road, Wusha community, Daliang street, Shunde District, Foshan City, Guangdong Province Patentee after: Foshan Feiyang Environmental Protection Technology Co.,Ltd. Address before: 310023, Hangzhou, Zhejiang, Xihu District, leaving town stay and Road No. 318 Patentee before: ZHEJIANG University OF SCIENCE AND TECHNOLOGY |