CN110218475A - A kind of dedicated blocked polyisocyanates curing agent of electrophoretic paint and preparation method thereof - Google Patents
A kind of dedicated blocked polyisocyanates curing agent of electrophoretic paint and preparation method thereof Download PDFInfo
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- CN110218475A CN110218475A CN201910511515.0A CN201910511515A CN110218475A CN 110218475 A CN110218475 A CN 110218475A CN 201910511515 A CN201910511515 A CN 201910511515A CN 110218475 A CN110218475 A CN 110218475A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
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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
- C09D5/08—Anti-corrosive paints
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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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- 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
- C09D5/4476—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications comprising polymerisation in situ
-
- 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
- C09D5/4496—Cathodic paints characterised by the nature of the curing agents
Abstract
A kind of dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint, comprising: in the reactor equipped with reflux condensation mode, constant pressure funnel and blender, polyisocyanates and organic diluent is added, it is stand-by to heat to predetermined temperature；Quantitative end-capping reagent is packed into the constant pressure funnel, is at the uniform velocity added drop-wise in the reactor, control reaction temperature is 45~75 DEG C, after being added dropwise to complete, keeps the temperature 30 minutes under the conditions of this temperature；Under stirring, the reactor is cooled to 30~60 DEG C, under the conditions of this temperature, by the addition of the quantitative compound that can provide active hydrogen at the uniform velocity, and stir evenly in time, after the completion of charging, keep the temperature 20 minutes, the colorless and transparent thick liquid with certain viscosity is obtained, the synthesis of the dedicated blocked polyisocyanates curing agent of electrophoretic paint is completed.The invention also discloses a kind of dedicated blocked polyisocyanates curing agent of electrophoretic paint.It is low-temperature fast-curing that curing agent prepared by the present invention can be such that the film of electrophoretic paint has the effect of.
Description
Technical field
The present invention relates to a kind of curing agent, more particularly, to a kind of electrophoretic paint for the single-component water-based baking vanish of low-temperature setting
Dedicated blocked polyisocyanates curing agent and preparation method thereof.
Background technique
Electrophoretic coating is a kind of anticorrosion water-soluble coating of environment-friendly type, has smooth coating smooth, water resistance and chemical resistance
The advantages that good, especially with the cathode electrophoresis dope of high antiseptic property, largely as primer applications in automobile, electromechanical household electrical appliances etc.
The field that high anti-corrosive properties require；In terms of the decorative paintings such as hardware, lamps and lanterns, label, conventionally employed plating, vacuum coating and molten
The field of the industries coating such as dosage form coating, is gradually substituted by electrophoretic painting.
Electrophoretic coating is as one of widely used water paint kind, in recent years, with cathode electrophoresis dope skill
The progress and development of art, functional, decorative, economy and application range are greatly improved, are mainly reflected in
The Corrosion Protection of electrophoretic coating, dicoration, environmental-protecting performance, weatherability, energy saving etc..By reducing cathode electrophoresis dope
Baking temperature, to reach energy-saving, it has also become the main direction of development of electrophoretic coating.
Electrophoretic coating is general to solidify usually with the blocked polyisocyanates curing agent of single structure in film forming procedure
Temperature seriously constrains the application range of electrophoretic paint at 160 DEG C or more.Reduce the main method of cathode electrophoresis dope baking temperature
It is the deblocking temperature for effectively reducing blocked polyisocyanate, it is made to release-NCO at low temperature, realizes the friendship with-OH
Connection solidification, thus achieve the purpose that it is energy-saving, meanwhile, avoid part-metallic surface because of the tendency of high temperature discoloration, expand
Application of the electrophoretic paint in terms of decorating with protection field.
The Fang Jixiang etc. of CNOOC Changzhou Paint & Coatings Industry Research Institute is delivered in " coatings industry " periodical the 5th phase in 2010
" curing action of low-temperature curing cathode electrophoresis coating is studied ".This article has investigated blocked polyisocyanate in low-temperature setting cathode
Curing action and its influence factor in electrophoretic coating, discuss the synthetic method of 2 kinds of low-temperature curing cathode electrophoresis coatings, emphasis
Have studied the storage stability and construction technology stability of low-temperature curing cathode electrophoresis coating.Tongji University's Materials Science and Engineering
The Liu Lin etc. of institute has delivered the " conjunction of Blocked Polyisocyanates in " Journal of Building Materials " periodical the 5th phase in 2005
At ".This article is using methyl ethyl ketoxime as sealer, with trimethylolpropane and 2,4- toluenediisocyanate addition product (TDI-
TMP) raw material has prepared the Blocked Polyisocyanates of deblocking temperature lower (110~120 DEG C), synthesized solidification
Although agent has lower deblocking temperature, its stability in electrophoretic paint is difficult to meet the requirements！CNOOC Changzhou coating
Graduate Zhang Hanqing of work etc. has delivered " 3,5- dimethyl pyrazole-blocked type water in " coatings industry " periodical the 10th phase in 2012
The synthesis and application of property isocyanate curing agent ".This article use first isocyanate trimer and dihydromethyl propionic acid (DMPA) into
Row chain extending reaction, then closed remaining isocyanate group with 3,5- dimethyl pyrazole (DMP), finally use dimethylethanolamine
(DMEA) it is neutralized into salt, water dispersible type blocked isocyanate curing agent, the deblocking temperature (130~150 of the curing agent is made
DEG C) lower, deblocking temperature still has 15 DEG C to 20 DEG C of gap with solidification temperature, it is difficult to meet the requirement of low-temperature setting.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of electrophoretic paint dedicated blocked polyisocyanates curing agent preparation sides
Method realizes the low-temperature fast-curing of electrophoretic paint.
The technical solution of the invention is as follows:
A kind of dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint, wherein comprising:
Polyisocyanates is added in the reactor equipped with reflux condensation mode, constant pressure funnel and blender in step 1,
And 10%~65% organic diluent of polyisocyanates total amount is added, it is stand-by to heat to predetermined temperature；
The organic diluent is butanone, ethyl acetate, butyl acetate, glycol dimethyl ether, glycol methyl ether acetate
With the mixture of the one or more of them of propylene glycol methyl ether acetate；
Quantitative end-capping reagent is packed into the constant pressure funnel, is at the uniform velocity added drop-wise in the reactor, controlled by step 2
Reaction temperature is 45~75 DEG C, the used time 40 ± 10 minutes, after being added dropwise to complete, keep the temperature 30 minutes under the conditions of this temperature, completion the
One step end capping reaction；
The reactor is cooled to 30~60 DEG C under stirring by step 3, under the conditions of this temperature, will be quantified
The compound that active hydrogen can be provided addition at the uniform velocity, the used time 15 ± 5 minutes, and stir evenly in time, after the completion of charging, protect
Temperature 20 minutes completes second step end capping reaction, obtains the colorless and transparent thick liquid with certain viscosity, and it is dedicated to complete electrophoretic paint
The synthesis of blocked polyisocyanates curing agent；
The polyisocyanates includes: diisocyanate monomer, the tripolymer of diisocyanate or diisocyanate and three
The mixture of hydroxy propane addition product one or more of them.
The present invention also provides a kind of dedicated blocked polyisocyanates curing agent of electrophoretic paint, wherein it is using as above
Polyisocyanate curing agent made of the method.
It is learnt by described above, the present invention has the advantage that really
The purpose of the present invention is to provide one kind can be in the dedicated end-sealed type polyisocyanic acid of electrophoretic paint of 120 DEG C of low-temperature settings
The preparation method of ester curing agent, the curing agent are to be blocked by mixing polyisocyanates component through two-step reaction chemistry, can be with
Hydroxy resin is particularly suitable for the ability cathode electrophoresis with decorative and anti-corrosion dual function with the use of one-component baking vanish is prepared
Paint.The electrophoretic paint prepared using the curing agent, the characteristic with good decorative painting, meanwhile, having can be in lower solidification
At a temperature of (120 DEG C, 0.5 hour) realization film thorough solidification, expanded electrophoretic paint in copper material, the decoration of aluminium workpiece surface
Property coating.
Detailed description of the invention
Fig. 1 is the step schematic diagram of the dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint of the invention.
Specific embodiment
For a clearer understanding of the technical characteristics, objects and effects of the present invention, this hair of Detailed description of the invention is now compareed
Bright specific embodiment.
A kind of dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint of the invention, it is shown referring to Fig.1, compared with
In good embodiment, the dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint includes:
Polyisocyanates is added in the reactor equipped with reflux condensation mode, constant pressure funnel and blender in step 1,
And 10%~65% organic diluent of polyisocyanates total amount is added, it is stand-by to heat to predetermined temperature；
The organic diluent is butanone, ethyl acetate, butyl acetate, glycol dimethyl ether, glycol methyl ether acetate
With the mixture of the one or more of them of propylene glycol methyl ether acetate；
Quantitative end-capping reagent is packed into the constant pressure funnel, is at the uniform velocity added drop-wise in the reactor, controlled by step 2
Reaction temperature is 45~75 DEG C, the used time 40 ± 10 minutes, after being added dropwise to complete, keep the temperature 30 minutes under the conditions of this temperature, completion the
One step end capping reaction；
The reactor is cooled to 30~60 DEG C under stirring by step 3, under the conditions of this temperature, will be quantified
The compound that active hydrogen can be provided addition at the uniform velocity, the used time 15 ± 5 minutes, and stir evenly in time, after the completion of charging, protect
Temperature 20 minutes completes second step end capping reaction, obtains the colorless and transparent thick liquid with certain viscosity, and it is dedicated to complete electrophoretic paint
The synthesis of blocked polyisocyanates curing agent；
The polyisocyanates includes: diisocyanate monomer, the tripolymer of diisocyanate or diisocyanate and three
The mixture of hydroxy propane addition product one or more of them.
The dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint present invention as described above, it is preferably real
It applies in mode, the polyisocyanates includes isophorone type polyisocyanates and/or toluene class polyisocyanates, the different fluorine
Your ketone polyisocyanates includes: isophorone diisocyanate, isophorone diisocyanate trimer, two isocyanide of isophorone
One of Glycerin addition product of acid esters or in which two kinds of mixtures, the total polyisocyanates quality of Zhan 60~
100%；The 0~40% of the total polyisocyanates quality of toluene class polyisocyanates Zhan.
The dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint present invention as described above, it is preferably real
It applies in mode, end-capping reagent described in step 2 is diisobutyl ketone oxime, and reaction temperature is 55 ± 10 DEG C；Reaction temperature is in step 3
50±10℃.Diisobutyl ketone oxime is directlyed adopt in present embodiment as end-capping reagent, is carried out the end capping reaction of first time, can be made
Resulting curing agent has reached low-temperature setting and quick-setting purpose.
Since there are two exposed methyl on molecular structure for diisobutyl ketone oxime, and roll into a ball with oximido across a methylene
Distance, have very large space steric effect, this leads to 30 DEG C lower than methyl ethyl ketoxime of deblocking temperature of diisobutyl ketone oxime or more,
Methyl ethyl ketoxime only only one exposed methyl group, steric effect is smaller, and existing Isocyanates curing agent is generally
Carried out by methyl ethyl ketoxime it is closed, unseal temperature at 120 DEG C, solidification temperature is at 150 DEG C, and curing time is about 1~2 small
When, however with the closed isocyanate curing agent of diisobutyl ketone oxime can 120 DEG C of low temperature when and acrylic resin into
Row solidification, and curing time only needs 20~30 minutes.This is because one differed with methyl ethyl ketoxime of diisobutyl ketone oxime
Exposed methyl group, the essential distinction of caused solidification temperature and curing time.
The dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint present invention as described above, it is preferably real
It applies in mode, using diisobutyl ketone oxime as end-capping reagent, the diisobutyl ketone oxime rubs with the compound that can provide active hydrogen
The range of your ratio is 0.2:0.8~0.8:0.2.Certainly we are also an option that optimal molar ratio is 0.5:0.5 herein.
The dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint present invention as described above, it is another preferable
Embodiment in, end-capping reagent described in step 1 is that beta-dicarbonyl compound and can provide the mixing of active hydrogen compounds
Object；The organic diluent includes butanone, and 10/10000 sodium alkoxide of polyisocyanates total amount is added；It is sealed described in step 2
End agent is beta-dicarbonyl compound, and reaction temperature is 65 ± 10 DEG C；Reaction temperature is 40 ± 10 DEG C in step 3.The embodiment
In, by the end-capping reagent containing beta-dicarbonyl compound and the mixture that active hydrogen compounds can be provided with containing the dilute of butanone
It releases agent to be reacted in the environment of sodium alkoxide, to generate the diisobutyl ketone oxime that low temperature can be brought to tell solidification effect.
The preferable reality of the dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint present invention as described above
It applies in mode, addition 50g isophorone diisocyanate in the step 1, isophorone diisocyanate trimer 150g,
Toluene-2,4-diisocyanate, 4- diisocyanate 50g, ethyl acetate 80g, sodium methoxide 0.125g and sodium ethoxide 0.125g；Open reflux condenser
And stirring, it is heated to 65 DEG C；65 DEG C are kept in the step 2,40 minutes used times at the uniform velocity completed diethyl malonate 124.8g's
After dropwise addition, 30 minutes are kept the temperature, completes the polyisocyanate blocked reaction of the first step；It adjusts temperature and is maintained at 40 DEG C, in stirring
Under, after at the uniform velocity 3,5- dimethyl pyrazole 74.6g was added in 15 minutes used times, 20 minutes are kept the temperature, obtains thick liquid 525g.The implementation
Mode is that one of which prepares curing agent by the way of the butanone and blocking agent reaction acquisition diisobutyl ketone oxime in diluent
Mode.
The dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint present invention as described above, it is preferably real
It applies in mode, 170g isophorone diisocyanate, the trihydroxy third of isophorone diisocyanate is added in the step 1
Alkane addition product 200g, methyl ethyl ketone 162g, sodium methoxide 0.135g and sodium ethoxide 0.135g；Open reflux condenser and stirring, heating
To 75 DEG C；75 DEG C, after 50 minutes used times at the uniform velocity completed the dropwise addition of dimethyl malenate 146.5g are kept in the step 2, heat preservation
30 minutes, complete the polyisocyanate blocked reaction of the first step；It adjusts temperature and is maintained at 50 DEG C, under stirring, the used time 20 divides
After at the uniform velocity 2-methylimidazole 39g is added in clock, 20 minutes are kept the temperature, obtains thick liquid 614.5g.The embodiment is adopted for another kind
The mode of curing agent is prepared with the mode of butanone and blocking agent reaction acquisition diisobutyl ketone oxime in diluent.
The dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint present invention as described above, it is preferably real
It applies in mode, isophorone diisocyanate trimer 80g, three hydroxyls of isophorone diisocyanate is added in the step 1
Base propane addition product 40g, Toluene-2,4-diisocyanate, 4- diisocyanate Glycerin addition product 80g, glycol methyl ether acetate 20g, first
Sodium alkoxide 0.1g and sodium ethoxide 0.1g；Reflux condenser and stirring are opened, is heated to 55 DEG C；55 DEG C are kept in the step 2, are used
When at the uniform velocity complete within 30 minutes the dropwise addition of ethyl acetoacetate 36g after, keep the temperature 30 minutes, it is polyisocyanate blocked anti-to complete the first step
It answers；It adjusts temperature and is maintained at 30 DEG C, under stirring, after at the uniform velocity methyl ethyl ketoxime 57g was added in 10 minutes used times, keep the temperature 20 points
Clock obtains thick liquid 310g.The embodiment be another using in diluent butanone and blocking agent reaction acquisition two it is different
The mode of diacetylmonoxime prepares the mode of curing agent.
The dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint present invention as described above, it is preferably real
It applies in mode, isophorone diisocyanate trimer 328g, butyl acetate 80g, sodium methoxide is added in the step 1
0.328g and sodium ethoxide 0.328g；Reflux condenser and stirring are opened, is heated to 70 DEG C；70 DEG C are kept in the step 2, are used
When 40 minutes at the uniform velocity complete dimethyl malenate 129.6g dropwise addition after, keep the temperature 30 minutes, complete the first step polyisocyanates envelope
End reaction；It adjusts temperature and is maintained at 35 DEG C, under stirring, after at the uniform velocity 3,5- methylimidazole 57g was added in 20 minutes used times,
Heat preservation 20 minutes obtains thick liquid 611g.The embodiment is another using the butanone and blocking agent reaction in diluent
The mode of diisobutyl ketone oxime is obtained to prepare the mode of curing agent.
The end capping reaction of the dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint of the invention mainly divides two
Step is completed.In directlying adopt embodiment of the diisobutyl ketone oxime as end-capping reagent, be equipped with polyisocyanate mixtures and
In the reaction flask of solvent, makees end-capping reagent with diisobutyl ketone oxime first in the form of dropwise addition and end capping reaction is carried out to polyisocyanates,
To after the reaction was completed, then " other can provide the compound of active hydrogen " is slowly added and carries out secondary sealing end.
55 ± 10 DEG C of first step reaction temperature, optimal reaction temperature is 55 DEG C.
The first step reaction time is 40 ± 10 minutes, and optimum reacting time is 40 minutes.
Second step reaction temperature is 50 ± 10 DEG C, and optimal reaction temperature is 50 DEG C.
The second step reaction time is 15 ± 5 minutes, and optimum reacting time is 15 minutes.
The reactive group (- NCO) and the total molar ratio of end-capping reagent for mixing polyisocyanates are 1.0:1.05~1.15, most
Good molar ratio is 1.0:1.1.
Certainly, further, the present invention is additionally provided with end capping reaction three times, and third time end capping reaction is different to be directly added into two
Diacetylmonoxime carries out the end capping reaction at a temperature of 60 ± 10 DEG C, by the amount that 50% end-capping reagent in an end capping reaction is once added
Diisobutyl ketone oxime, then cooperate 40 ± 10 minutes time uniformly instill other 50% diisobutyl ketone oxime mode, complete most
The preparation of whole curing agent.There is more preferably stable low temperature and quick-setting effect by the curing agent of end capping reaction three times,
And liquid is more preferably dense, is conducive to the coating and solidification of electrophoretic paint.
The present invention also provides a kind of dedicated blocked polyisocyanates curing agent of electrophoretic paint, in preferred embodiment,
The dedicated blocked polyisocyanates curing agent of the electrophoretic paint is using polyisocyanate curing agent made of method as described above.
Specifically, curing agent of the invention is by the trimerization of dicyanate monomer, dicyanate with polar structure
Body and dicyanate and Glycerin addition product are primary raw material, and the compound that selection can provide active hydrogen is blocked,
It is prepared under lower reaction temperature.
The present invention can be with different in the dedicated blocked polyisocyanates curing agent of 120 DEG C of low-temperature fast-curing electrophoretic paints
Based on phorone class polyisocyanates, it is equipped with the toluene class polyisocyanates that mass fraction is 0.0~40.0%, polyisocyanic acid
The ratio of ester function group (- NCO) total mole number and end-capping reagent molal quantity is 1.0:1.05~1.15, most preferably 1.0:1.1.Together
When, end-capping reagent is by living two kinds of hydrogen nitrogenous compound and the active methylene compound dialled of band at being grouped as, molar ratio between the two
Example is 0.3:0.7~0.7:0.3, and optimal molar ratio is 0.5:0.5, in such a way that two steps block, realizes " 120 DEG C of low temperature
Solidify the dedicated blocked polyisocyanates curing agent of electrophoretic paint " preparation.
Preparation process of the invention is specific as follows:
1. being quantitatively adding different Buddhist equipped in reflux condensation mode, constant pressure funnel and the reactor of stirring with certain proportion
That ketone type polyisocyanates and toluene class polyisocyanates, and 10%~65% organic dilution of polyisocyanates total amount is added
Agent (ethyl acetate, butyl acetate, butanone, glycol dimethyl ether, glycol methyl ether acetate, propylene glycol methyl ether acetate), adds
Entering the 10/10000 of polyisocyanates total amount is sodium alkoxide (sodium methoxide, sodium ethoxide), and it is stand-by to heat to predetermined temperature；
2. quantitative beta-dicarbonyl compound end-capping reagent is packed into constant pressure funnel, at the uniform velocity it is added drop-wise in 1., control is anti-
65 ± 10 DEG C of temperature are answered, the used time 40 ± 10 minutes, after being added dropwise to complete, keeps the temperature 30 minutes under the conditions of this temperature, completes at this time
One step end capping reaction；
3. will 1. be cooled to 40 ± 10 DEG C, and under the conditions of this temperature under stirring, " other can be with by quantitative
The compound of active hydrogen is provided " used time 15 ± 5 minutes, the addition of average rate, and stir evenly in time, after the completion of charging, heat preservation 20
Minute, second step end capping reaction is completed, the colourless transparent liquid with certain viscosity is obtained, that is, realizes 120 DEG C of low-temperature settings
The synthesis of the dedicated blocked polyisocyanates curing agent of electrophoretic paint.
The above invention isophorone type polyisocyanates can be one in IPDI, IPDI tripolymer, IPDI-TMP
Kind, or in which two kinds be used in mixed way, the 60~100% of the total polyisocyanates gross mass of usage amount, most preferably 80%；
The above invention toluene class polyisocyanates can be one of TDI, TDI tripolymer, TDI-TMP, make
The 0.0~40.0% of the total polyisocyanates gross mass of dosage, most preferably 20%；
" beta-dicarbonyl compound " in the above invention end-capping reagent be diethyl malonate, dimethyl malenate,
One of in ethyl acetoacetate, dosage is the 30%~70% of end-capping reagent integral molar quantity, most preferably 50%；
" other can provide the compound of active hydrogen " in the above invention end-capping reagent is 2-methylimidazole, 3,5-
One of in dimethyl pyrazole, methyl ethyl ketoxime, dosage is the 70%~30% of end-capping reagent integral molar quantity, most preferably 50%；
The above invention end capping reaction is realized by two step end capping reactions, first in 65 ± 10 DEG C of completion " β-
Dicarbonyl compound " is to the end capping reaction of polyisocyanates, and thereafter under the conditions of 40 ± 10 DEG C, " other can provide work for completion
Sprinkle the compound of hydrogen " to the end capping reaction of polyisocyanates；
Described " beta-dicarbonyl compound " and " other can provide the compound of the active hydrogen " end-capping reagent two of the above invention
The molar ratio of person is 0.3:0.7~0.7:0.3, most preferably 0.5:0.5；
The above invention " sodium alkoxide " is the two mixture of sodium methoxide, sodium ethoxide, the two mass ratio be 0.3:0.7~
The optimal mass ratio of 0.7:0.3 is 0.5:0.5；
The ratio of the above invention polyisocyanates functional group (- NCO) total mole number and end-capping reagent total mole number
For 1.0:1.05~1.15, most preferably 1.0:1.1.
The beta-dicarbonyl compound that can provide active hydrogen in present invention as described above is diethyl malonate, the third two
Dimethyl phthalate, ethyl acetoacetate.
Other compounds that can provide active hydrogen in present invention as described above are 2-methylimidazole, 3,5- dimethyl
Pyrazoles, methyl ethyl ketoxime.
The sodium alkoxide as catalyst in present invention as described above is sodium methoxide, sodium ethoxide.
Present invention as described above in sodium alkoxide dosage be isocyanate (1-20)/10000, best 10/
10000。
Sodium methoxide in present invention as described above: the optimal mass ratio of sodium ethoxide=0.3:0.7~0.7:0.3 is 0.5:
0.5。
Beta-dicarbonyl compound in present invention as described above: other can provide compound=0.2 of active hydrogen:
The optimal molar ratio of 0.8~0.8:0.2 is 0.5:0.5.
Contain butanone below to use in the dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint of the invention
Diluent and sealer reaction obtain diisobutyl ketone oxime mode prepare 4 preferred embodiments of curing agent for, explanation
Preparation method specific example of the invention, wherein the weight amount in embodiment is mainly for example, be not used to limit this
Invention specific weight number, can be used for limiting its use ratio.
Involved dicyanate monomer, the tripolymer of dicyanate and dicyanate and three hydroxyls in the embodiment of the present invention
Base propane addition product, in terms of 100% effective component, below by specific embodiment, invention is further described in detail.
Embodiment 1
Equipped in reflux condenser, constant pressure funnel, thermometer and the 1000L of stirring four-hole boiling flask, it is added
IPDI50g (NCO=0.45mol), IPDI tripolymer 150g (NCO=0.676mol), 50gTDI tripolymer (NCO=
0.287mol), 80g ethyl acetate and 0.125g sodium methoxide, 0.125g sodium ethoxide, open reflux condenser and stirring, and heating rises
Temperature is to 65 DEG C (the total isocyano of reaction system is 1.413mol at this time).
Constant pressure funnel is added in 124.8g (molal quantity=0.78mol) diethyl malonate, in stirring and 65 DEG C of shapes
Under state, the used time 40 minutes, the dropwise addition of diethyl malonate is at the uniform velocity completed, and under the conditions of this temperature, keeps the temperature 30 minutes, completes the
The polyisocyanate blocked reaction of one step.
After completing first step sealing end, temperature of reaction system is down to 40 DEG C, under stirring, the used time 15 minutes, by powder
Reaction system is at the uniform velocity added in shape 3,5- dimethyl pyrazole 74..6g (molal quantity=0.78mol), and stirs well in time even, and charging finishes
Afterwards, 20 minutes are kept the temperature under the conditions of reaction temperature, obtains a kind of thick liquid of near colorless with certain viscosity at this time
525g, solid content 85%, the deblocking with differential scanning calorimeter (DSC) measurement product is 112 DEG C, by itself and hydroxyl value 80,
The acrylic acid of amine value 50 is configured to the cathode electrodip painting that solid content is 18%, the electrophoretic painting under the conditions of 50V, 30 DEG C, and in temperature
Degree is realized for 120 DEG C of bakings and is fully cured for 30 minutes, and gloss of film degree is 96, pencil hardness 3H.
Embodiment 2
In the device of embodiment 1, IPDI70g (NCO=0.63mol), IPDI-TMP200g (NCO=is added
0.75mol) and 162g methyl ethyl ketone and 0.135g sodium methoxide, 0.135g sodium ethoxide, being heated to 75 DEG C, (reaction system is total at this time
Isocyano is 1.38mol).146.5g (molal quantity=1.11mol) dimethyl malenate is being stirred under 75 DEG C of states, is being used
When 50 minutes, at the uniform velocity complete be added dropwise, thereafter keep the temperature 30 minutes, at this time complete the first step reaction.
After completing first step sealing end, temperature of reaction system is down to 50 DEG C, under stirring, with 20 minutes, at the uniform velocity will
Reaction system is at the uniform velocity added in 39g powdery 2-methylimidazole (molal quantity=0.48mol), and stir well in time it is even, after charging,
20 minutes are kept the temperature under conditions of reaction temperature, obtains a kind of thick liquid of near colorless with certain viscosity at this time
614.5g, solid content 84%, the deblocking that differential scanning calorimeter (DSC) measures product is 110 DEG C, same as Example 1
Condition electrophoretic painting coating, 120 DEG C are toasted 30 minutes, and gloss of film degree is 94, pencil hardness 3H.
Embodiment 3
In the device of embodiment 1,80gIPDI tripolymer (NCO=0.36mol), 40gIPDI-TMP (NCO=is added
0.15mol), 80gTDI-TMP (NCO=0.37mol), 20g glycol methyl ether acetate and 0.10g sodium methoxide, 0.10g ethyl alcohol
Sodium is heated to 55 DEG C (the total isocyano of reaction system is 0.88mol at this time).By 36g (molal quantity=0.28mol) acetyl
Ethyl acetate is being stirred under 55 DEG C of states, the used time 30 minutes, is at the uniform velocity added dropwise, is kept the temperature 30 minutes after the completion, complete first at this time
Step reaction.
Temperature of reaction system is down to 30 DEG C, under stirring, with 10 minutes, at the uniform velocity 57g powdery methyl ethyl ketoxime (rubs
Your number=0.65mol) reaction system is at the uniform velocity added, and stir well in time even, after charging, 20 minutes are kept the temperature, obtains one at this time
Kind has the thick liquid-and product of the present invention 310g of the near colorless of certain viscosity, solid content 94%, differential scanning
The deblocking that calorimeter (DSC) measures product is 114 DEG C, and condition electrophoretic painting same as Example 1,120 DEG C are toasted 30 minutes,
Gloss of film degree is 92, pencil hardness 4H.
Embodiment 4
In the device of embodiment 1, be added 328gIPDI tripolymer (isocyano 1.48mol), 80g butyl acetate and
0.328g sodium methoxide, 0.328g sodium ethoxide, are heated to 70 DEG C.By 129.6g (molal quantity=0.81mol) malonic acid diethyl
It the ester used time 40 minutes, is at the uniform velocity added dropwise, keeps the temperature 30 minutes after the completion.Thereafter, temperature of reaction system is down to 35 DEG C, in stirring
Under, with 20 minutes, at the uniform velocity by 77.8g powdery 3,5- dimethyl pyrazole (molal quantity=0.81mol) was at the uniform velocity added reaction system, adds
After material, 20 minutes are kept the temperature, thick liquid-product of the present invention 611g of the near colorless with certain viscosity is both obtained,
Solid content is 87%, and the deblocking that differential scanning calorimeter (DSC) measures product is 110 DEG C, and condition electrophoresis same as Example 1 applies
Dress, 120 DEG C are toasted 30 minutes, and gloss of film degree is 96, pencil hardness 3H.
It is of the present invention above to consolidate in 120 DEG C of dedicated blocked polyisocyanates of low-temperature fast-curing electrophoretic paint
Agent is a kind of thick liquid that the near colorless with certain viscosity is transparent, suitable for low with the single group that hydroxy resin is prepared
Warm baking vanish, especially suitable for decorating the preparation with protective low temperature electrophoretic paint, the low temperature (120 of electrophoretic paint is can be achieved in the present invention
DEG C) rapid curing, the application range of electrophoretic paint has effectively been expanded, has expanded protectiveness and decorative electronic electrophoresis painting dressing in copper, aluminium
And the application of the high temperature such as aluminium alloy surface substrate workpiece easy to change, wide market.
The foregoing is merely the schematical specific embodiment of the present invention, the range being not intended to limit the invention.It is any
Those skilled in the art, made equivalent changes and modifications under the premise of not departing from design and the principle of the present invention,
It should belong to the scope of protection of the invention.
Claims (10)
1. a kind of dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint, characterized in that it comprises:
In the reactor equipped with reflux condensation mode, constant pressure funnel and blender polyisocyanates is added, and add in step 1
10%~65% organic diluent for entering polyisocyanates total amount, it is stand-by to heat to predetermined temperature；
The organic diluent is butanone, ethyl acetate, butyl acetate, glycol dimethyl ether, glycol methyl ether acetate and third
The mixture of the one or more of them of glycol methyl ether acetate；
Quantitative end-capping reagent is packed into the constant pressure funnel, is at the uniform velocity added drop-wise in the reactor by step 2, control reaction
Temperature is 45~75 DEG C, the used time 40 ± 10 minutes, after being added dropwise to complete, keeps the temperature 30 minutes under the conditions of this temperature, completes the first step
End capping reaction；
The reactor is cooled to 30~60 DEG C under stirring by step 3, can by quantitative under the conditions of this temperature
To provide the addition of the compound of active hydrogen at the uniform velocity, the used time 15 ± 5 minutes, and stir evenly in time, after the completion of charging, heat preservation 20
Minute, second step end capping reaction is completed, the colorless and transparent thick liquid with certain viscosity is obtained, completes the dedicated sealing end of electrophoretic paint
The synthesis of type polyisocyanate curing agent；
The polyisocyanates includes: diisocyanate monomer, the tripolymer of diisocyanate or diisocyanate and trihydroxy
The mixture of propane addition product one or more of them.
2. the dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint as described in claim 1, which is characterized in that institute
Stating polyisocyanates includes isophorone type polyisocyanates and/or toluene class polyisocyanates, the isophorone polyisocyanate cyanogen
Acid esters includes: three hydroxyls of isophorone diisocyanate, isophorone diisocyanate trimer, isophorone diisocyanate
One of base propane addition product or in which two kinds of mixtures, the 60~100% of the total polyisocyanates quality of Zhan；The first
The 0~40% of the total polyisocyanates quality of benzene class polyisocyanates Zhan.
3. the dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint as claimed in claim 2, which is characterized in that step
End-capping reagent described in rapid two is diisobutyl ketone oxime, and reaction temperature is 55 ± 10 DEG C；Reaction temperature is 50 ± 10 DEG C in step 3.
4. the dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint as claimed in claim 3, which is characterized in that institute
The range for stating diisobutyl ketone oxime and the molar ratio for the compound that can provide active hydrogen is 0.2:0.8~0.8:0.2.
5. the dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint as claimed in claim 2, which is characterized in that step
End-capping reagent described in rapid one is beta-dicarbonyl compound and can provide the mixture of active hydrogen compounds；The organic diluent
Including butanone, and 10/10000 sodium alkoxide of polyisocyanates total amount is added；End-capping reagent described in step 2 is beta-dicarbonyl
Object is closed, reaction temperature is 65 ± 10 DEG C；Reaction temperature is 40 ± 10 DEG C in step 3.
6. the dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint as claimed in claim 5, which is characterized in that institute
State addition 50g isophorone diisocyanate, isophorone diisocyanate trimer 150g, Toluene-2,4-diisocyanate, 4- bis- in step 1
Isocyanates 50g, ethyl acetate 80g, sodium methoxide 0.125g and sodium ethoxide 0.125g；Open reflux condenser and stirring, heating
To 65 DEG C；
65 DEG C, after 40 minutes used times at the uniform velocity completed the dropwise addition of diethyl malonate 124.8g are kept in the step 2, heat preservation 30
Minute, complete the polyisocyanate blocked reaction of the first step；
It adjusts temperature and is maintained at 40 DEG C, under stirring, after at the uniform velocity 3,5- dimethyl pyrazole 74.6g was added in 15 minutes used times,
Heat preservation 20 minutes obtains thick liquid 525g.
7. the dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint as claimed in claim 6, which is characterized in that institute
State addition 170g isophorone diisocyanate, the Glycerin addition product of isophorone diisocyanate in step 1
200g, methyl ethyl ketone 162g, sodium methoxide 0.135g and sodium ethoxide 0.135g；Reflux condenser and stirring are opened, is heated to 75 DEG C；
75 DEG C, after 50 minutes used times at the uniform velocity completed the dropwise addition of dimethyl malenate 146.5g are kept in the step 2, heat preservation 30
Minute, complete the polyisocyanate blocked reaction of the first step；
It adjusts temperature and is maintained at 50 DEG C, under stirring, after at the uniform velocity 2-methylimidazole 39g was added in 20 minutes used times, heat preservation 20
Minute, obtain thick liquid 614.5g.
8. the dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint as claimed in claim 6, which is characterized in that institute
State addition isophorone diisocyanate trimer 80g, the Glycerin addition of isophorone diisocyanate in step 1
Object 40g, Toluene-2,4-diisocyanate, 4- diisocyanate Glycerin addition product 80g, glycol methyl ether acetate 20g, sodium methoxide 0.1g and
Sodium ethoxide 0.1g；Reflux condenser and stirring are opened, is heated to 55 DEG C；
55 DEG C, after 30 minutes used times at the uniform velocity completed the dropwise addition of ethyl acetoacetate 36g are kept in the step 2, keep the temperature 30 points
Clock completes the polyisocyanate blocked reaction of the first step；
It adjusts temperature and is maintained at 30 DEG C, under stirring, after at the uniform velocity methyl ethyl ketoxime 57g was added in 10 minutes used times, keep the temperature 20 points
Clock obtains thick liquid 310g.
9. the dedicated blocked polyisocyanates curing agent preparation method of electrophoretic paint as claimed in claim 6, which is characterized in that institute
State addition isophorone diisocyanate trimer 328g, butyl acetate 80g, sodium methoxide 0.328g and sodium ethoxide in step 1
0.328g；Reflux condenser and stirring are opened, is heated to 70 DEG C；
70 DEG C, after 40 minutes used times at the uniform velocity completed the dropwise addition of dimethyl malenate 129.6g are kept in the step 2, heat preservation 30
Minute, complete the polyisocyanate blocked reaction of the first step；
It adjusts temperature and is maintained at 35 DEG C, under stirring, after at the uniform velocity 3,5- methylimidazole 57g was added in 20 minutes used times, protect
Temperature 20 minutes obtains thick liquid 611g.
10. a kind of dedicated blocked polyisocyanates curing agent of electrophoretic paint, which is characterized in that it is using such as claim 1 to 9
Polyisocyanate curing agent made of the method.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940558A (en) * | 2021-01-13 | 2021-06-11 | 浙江潘季新材料股份有限公司 | Electrophoretic paint curing agent with good water solubility and application thereof |
| CN114853970A (en) * | 2022-06-15 | 2022-08-05 | 佛山市精信汇明科技有限公司 | Closed cationic waterborne polyurethane curing agent and preparation method and application thereof |
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| CN105778047A (en) * | 2014-12-22 | 2016-07-20 | 深圳市志邦科技有限公司 | Preparation method of terminated polyisocyanate curing agent specially used for 120DEG C low temperature-curable electrophoresis paint |
| CN108929427A (en) * | 2018-06-12 | 2018-12-04 | 湖南大学 | Improve the preparation method of the blocked isocyanate of cathode electrophoresis dope filming performance |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101792419A (en) * | 2010-02-10 | 2010-08-04 | 武汉材料保护研究所 | Synthetic method of compound blocked polyisocyanates by using multiple sealants to compound and block terminal groups |
| CN105778047A (en) * | 2014-12-22 | 2016-07-20 | 深圳市志邦科技有限公司 | Preparation method of terminated polyisocyanate curing agent specially used for 120DEG C low temperature-curable electrophoresis paint |
| CN108929427A (en) * | 2018-06-12 | 2018-12-04 | 湖南大学 | Improve the preparation method of the blocked isocyanate of cathode electrophoresis dope filming performance |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112940558A (en) * | 2021-01-13 | 2021-06-11 | 浙江潘季新材料股份有限公司 | Electrophoretic paint curing agent with good water solubility and application thereof |
| CN114853970A (en) * | 2022-06-15 | 2022-08-05 | 佛山市精信汇明科技有限公司 | Closed cationic waterborne polyurethane curing agent and preparation method and application thereof |
| CN114853970B (en) * | 2022-06-15 | 2023-07-21 | 佛山市精信汇明科技有限公司 | Enclosed type cationic waterborne polyurethane curing agent and preparation method and application thereof |
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