CN102115526A - Extinction acrylic resin for anodic electrophoresis and preparation method thereof - Google Patents
Extinction acrylic resin for anodic electrophoresis and preparation method thereof Download PDFInfo
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- CN102115526A CN102115526A CN 201110000272 CN201110000272A CN102115526A CN 102115526 A CN102115526 A CN 102115526A CN 201110000272 CN201110000272 CN 201110000272 CN 201110000272 A CN201110000272 A CN 201110000272A CN 102115526 A CN102115526 A CN 102115526A
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Abstract
The invention discloses an extinction acrylic resin for anodic electrophoresis and a preparation method thereof. The preparation method of the extinction acrylic resin for anodic electrophoresis comprises the following steps: (1) preparing mixed acrylate monomers; and (2) thoroughly mixing water, a chain-transfer agent, part of the mixed acrylate monomers, an anionic polyurethane surfactant and a blocked isocyanate crosslinking agent, heating to 70-90 DEG C, adding an initiator, reacting for 0.5-1 hour, dropwisely adding the rest of the mixed acrylate monomers, adding the rest of the initiator in batches, keeping the temperature for 1-3 hours after finishing the dropwise addition, and adding a basic compound to regulate the pH value to 8.5-9.5, thereby obtaining the extinction acrylic resin for anodic electrophoresis. The extinction acrylic resin for anodic electrophoresis has low curing temperature, and overcomes the defect of high curing temperature of the anionic extinction electrophoresis paint in the prior art.
Description
Technical field
The present invention relates to a kind of metallic surface Decorative tree fat, be specifically related to anodic electrophoresis anionic acrylic matting resin and preparation method thereof.
Background technology
The aluminium alloy light weight, intensity and stainless steel are suitable, fields such as widespread use and building, furniture, industry.For satisfying the demand in market, decorating generally needs surface treatment with aluminium section bar.Electrophoretic painting is because its utilization ratio height, and technology is suitable for automatic assembly line, and throwing power is good, can handle complex-shaped workpiece and becomes the most potential process for treating surface.Because the transparent light of common electrophoretic layer of aluminium section bar is easy to amplify the flaw of anodized aluminum layer, thereby cause that fraction defective raises, the production cost height, and the top layer light is used under multiple occasion also and is influenced its visual effect.The aluminium section bar of employing delustring electrophoretic process can be covered the trickle flaw of lower floor's anodic oxide coating, improves yield rate, and the outward appearance top grade.
In order to obtain extinction effect, a kind of way is to add matting agent in coating, as silicon oxide, organic particle etc.But, the chemical proofing of matting agent superfine silicon dioxide, particularly alkali resistance is poor, can not obtain filming of good transparency, for the coated article of coating decoration complexity, superfine silicon dioxide can deposit on coated article, thereby in the coated article subregion, particularly vertical surface etc. is located, and can produce shortcomings such as gloss difference.Organic particle is dispersed in method in the coating (special public clear 51-8975 communique), because the organic fine particles electrophoresis is poor, organic particle can come off during washing, and is not suitable for electrophoretic paint.In addition, use contains the easy yellowing of coating of the matting agent that encircles the amidine class and is that baking property is poor.
Another kind method is synthetic matting resin, and this method can avoid using matting agent, reduces the coating cost.At present, import the alcoxyl silyl in binder resin, by the condensation reaction of alcoxyl silyl, microgel is one of method of using always in the insoluble particle of formation in copolymer resin.For example special open clear 59-67396 communique, spy open clear 64-14281 communique, spy open flat 05-263296 communique, with reference to special open flat 2-255871 communique, referring to the spy open flat 11-315254 communique, the spy opens the similar technique of reporting in the flat 2001-131494 communique, but when the time by change application condition variation gloss, be subjected to the influence of matting behind the electrophoresis easily, can become the condition of restriction coating decoration.
Additive method has the carboxyl that utilizes in the resin, and cooperation can form the method for microgel with the functional group of this carboxyl reaction.(spy opens clear 59-138278 communique, special open 2-12511 communique, CN 1307270C), oxazolinyl (spy opens flat 6-25568 communique) etc. to this class functional group just like epoxy group(ing).In these class methods, in order to obtain stable low gloss, all must form the particle inner gel, thereby on making, bother by reacting by heating.
Solution polymerization is adopted in the Vinylite manufacturing mostly in the above-mentioned method of mentioning, need to use a large amount of organic solvents in the manufacturing processed, after making water dispersible vinyl copolymer resin, need add linking agent, other additives, basic cpd at once, obtain the emulsion that the extinction anion electrophoresis coating is used by water-dispersion, thus, become emulsion must pass through a series of operation from making resin to water-dispersion.The negatively charged ion delustring electrophoretic paint of gained exists that storage property is poor, solidification value height (180 ℃), finishability and mold-mart disguise are insufficient.
Summary of the invention
The objective of the invention is to overcome the problem that is run in the current electrocoating paint preparation, a kind of anodic electrophoresis of solidified at a lower temperature mat acrylic resin is provided.
Another object of the present invention is to provide the preparation method of above-mentioned anodic electrophoresis with the mat acrylic resin.
Purpose of the present invention is achieved through the following technical solutions:
A kind of anodic electrophoresis mat acrylic resin is that the feedstock production by following massfraction obtains:
The acrylic ester monomer of hydroxyl: 1.2～2.5%
Free-radical polymerised acrylic ester monomer: 18.4～19.7%
Anionic polyurethane tensio-active agent: 0.6～1.8%
Blocked isocyanate linking agent: 0.6～1.9%
Basic cpd: 0.2～0.4%
Chain-transfer agent: 0.1%
Initiator: 0.1%
Water: 74.8～76.5%
The acrylic ester monomer of hydroxyl is hydroxyethyl (methyl) acrylate, hydroxypropyl (methyl) acrylate, hydroxyl butyl (methyl) acrylate, (gathering) glycol monomethyl (methyl) acrylate or (gathering) propylene glycol list (methyl) acrylate.
Free-radical polymerised acrylic ester monomer is (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, acrylic acid C1-C18 alkyl ester, (methyl) acrylic acid amides, N-methyl (methyl) acrylamide or (methyl) vinyl cyanide.
These monomeric cooperation ratios, with respect to the acrylic ester monomer that contains hydroxyl (a), the solid composition sum total metering of other free-radical polymerised unsaturated monomers (b), the acrylic ester monomer (a) that contains hydroxyl is 88-94 weight % for 6-12 weight %, other free-radical polymerised acrylic ester monomers (b);
The anionic polyurethane tensio-active agent can contain the urethane that the addition polymerization of carboxyl chainextender obtains for aromatics, fats, alicyclic ring kind isocyanate, polyethers, polyester polyols are pure and mild, its end group is the alkyl of C1-C18, the urethane of preferred fat class and alicyclic ring class, carboxyl-content is 5-20%, the pH value is 6.5-7.5, and molecular weight is 2000-10000; Compound shown in the special preferred formula I:
(formula I)
The urethane that the sealing polyurethane cross-linking agent can contain the addition polymerization of carboxyl chainextender for aromatics, fats, alicyclic ring kind isocyanate, polyethers, polyester polyols are pure and mild, be obtained by the methyl ethyl ketoxime end-blocking, the urethane of preferred fat class and alicyclic ring class, carboxyl-content is 5-20%, the pH value is 6.5-7.5, and molecular weight is 3000-7000; Compound shown in the special preferred formula II:
(formula II)
Compound shown in formula I and the II can be obtained by common polyaddition reaction, and its molecular weight can be controlled by regulating isocyano and hydroxyl ratio, promptly controls NCO: the OH value.
In reactor, add isocyanic ester, polyoxyethylene glycol (400～2000), 80 ℃ of following stirring reactions 2 hours, then adding dimethylol propionic acid continues to react to NCO: the OH value arrives default scope, add alkyl alcohol or methyl ethyl ketoxime and carry out end-blocking, after reaction finishes, add triethylamine and neutralize, obtain polyurethane surfactant and sealing polyurethane cross-linking agent respectively.
The infared spectrum measurement result of polyurethane surfactant and sealing polyurethane cross-linking agent: 3407.60cm
-1The broad peak that the place occurs is in the carboxylamine ester structure-stretching vibration (v of NH
N-H); 1956cm
-1C-H stretching vibration (v appears in the place
CH2, CH3); 1710.55cm
-1Strong and wide C=O stretching vibration (v appears in the place
C=O); 1540cm
-1N-H flexural vibration (the δ of secondary amide appears in the place
N-H) and C-N stretching vibration (v
C-N); 1465.63cm
-1Flexural vibration (the δ of methylene radical appears in the place
CH2); 1388.50cm
-1Flexural vibration (the δ that methyl occurs
CH3); 1357.64cm
-1, 1307.50cm
-1, 1245.79cm
-1And 1043.40cm
-1The C-O-C symmetry and the asymmetrical stretching vibration (v of ester class appears in the place
C-O-C); 1122.37cm
-1C-O stretching vibration (the v of polyoxyethylene glycol component appears in the place
C-O); 836.95cm
-1, 777.17cm
-1, 53.75cm
-1The outer formation vibration absorption peak (δ of N-H face appears in the place
N-H); 2200～2280cm
-1Between-NCO absorbs characteristic peak and disappears, illustrate in the raw material-the NCO base all reacts.
The nuclear magnetic resonance hydrogen spectruming determining result of polyurethane surfactant and sealing polyurethane cross-linking agent: the strong absorption peak in 7.24ppm place comes from the N-H key in the carbamate, and the 3.61ppm place is in the polyoxyethylene segment-CH
2CH
2The hydrogen of O-spectrum, 2.86～3.038ppm and 0.823～1.659ppm are on the IPDI ring and hold CH on the alkyl chain
3And CH
2Characteristic peak.
The molecular weight of polyurethane surfactant and sealing polyurethane cross-linking agent can be obtained by gel permeation chromatography.
The basic cpd that is used to regulate ph value of emulsion is the unary primary amine of ammonia, sodium hydroxide, potassium hydroxide, ethamine, propylamine, butylamine, benzylamine, monoethanolamine, neopentyl alcohol amine, 2-aminopropanol, 3-aminopropanol etc.; Monobasic secondary amine such as diethylin diethanolamine, N-Mono Methyl Ethanol Amine, N-ehtylethanolamine; Monobasic tertiary amines such as dimethylethanolamine, Trimethylamine 99, triethylamine, trolamine, methyldiethanolamine, dimethylaminoethanol; Polyamines triethylamines such as diethylenetriamine, hydroxyethyl aminoethyl, ethylamino ethylamine, methylamino propyl group amine.
Described initiator is Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, hydrogen peroxide, benzoyl peroxide, t-butyl hydroperoxide, di-tert-butyl hydroperoxide, Three methyl Benzene superoxide or isopropyl benzene hydroperoxide.
Described chain-transfer agent is lauryl mercaptan, list-n-dodecane sulfenyl sodium sulfate, acetic acid n-dodecyl mercaptan ester, Succinic Acid list-n-dodecyl mercaptan ester, oxalic acid two-n-dodecyl mercaptan ester.Chain-transfer agent is in order to the molecular weight of controlling polymers.
The above-mentioned anodic electrophoresis preparation method of mat acrylic resin may further comprise the steps:
(1) acrylic ester monomer of 1.2～2.5% hydroxyls is mixed with 18.4～19.7% free-radical polymerised acrylic ester monomers, obtain mixing acrylate monomer;
(2) with 74.8～76.5% water, 0.1% chain-transfer agent, mix 40% of acrylate monomer quality, 0.6～1.8% anionic polyurethane tensio-active agent mixes with 0.6～1.9% blocked isocyanate linking agent, fully stir, be warming up to 70-90 ℃, add 0.02～0.04% initiator, reacted 0.5-1 hour, drip remaining mixing acrylate monomer, dropwise in 1-4 hour, in the meantime remaining initiator is divided into 2-4 and criticizes adding, dropwise back insulation 1-3 hour, add 0.2～0.4% basic cpd and regulate the pH value, obtain anodic electrophoresis mat acrylic resin to 8.5-9.5;
Described per-cent is mass percent.
The solution that described initiator is mixed with massfraction 1～2% uses.
Characteristics of the present invention are that described anodic electrophoresis is to adopt single stage method to prepare by letex polymerization with mat acrylic resin synthetic implementation method, the emulsifying agent that uses in the letex polymerization is the anion polyurethane tensio-active agent, linking agent is a methyl ethyl ketoxime sealing polyurethane cross-linking agent, the acrylic resin for preparing is for having nuclear shell structure nano level latex particle, can solidify at a lower temperature, temperature is controlled at 110-120 ℃, this matting resin need not to add aminoresin or matting agent, can reach the effect of delustring, regulate the glossiness of resin by the content of regulating polyurethane surfactant.
Anodic electrophoresis of the present invention is mainly used in the high-grade anode electro-coating of decorating with aluminium section bar with the mat acrylic resin.
The present invention has following advantage and effect with respect to prior art:
Anodic electrophoresis of the present invention adopts single stage method to prepare with the delustring polyurethane acrylic resin, simplified operation, in the process of producing and using, there is not volatilization, pollution-free, and solidification value is lower, can economize on resources to reduce and consume, the aluminium section bar yield rate is improved greatly, and expenses such as reduction equipment, cost, manufacturing belong to environmental protection and energy saving water-based emulsion product.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
8g hydroxyethyl meth acrylate, 50g methyl methacrylate, 30g n-BMA, 10g ethyl propenoate, 2g Isooctyl methacrylate mixed obtain mixing acrylate monomer, standby.
Anion polyurethane tensio-active agent (compound shown in the formula I with 9g, molecular weight is 3000) and 9g sealing polyurethane cross-linking agent (compound shown in the formula II, molecular weight is 3000) be dissolved in the 357g deionized water, add then agitator is housed, reflux condensing tube, temperature is taken into account in the four-hole round-bottomed flask of separating funnel, add 40g mixing acrylate monomer and 0.5g lauryl mercaptan, stirred 30 minutes fast, stir down elevated temperature to 80 ℃, the initiator potassium persulfate solution 8g of adding 2%, react after 0.5 hour, from dropping funnel, drip 60g mixing acrylate monomer, drip off in 2 hours, add 2% initiator potassium persulfate solution 17g during this time in three batches, keep temperature to continue reaction 1.5 hours.Reaction finishes the back and adds the 1.5g triethylamine and regulate pH value to 8.5, can obtain with the white solid content of blue light at 23.6% anodic electrophoresis acrylic ester emulsion.
Embodiment 2
6g hydroxyethyl meth acrylate, 52g methyl methacrylate, 30g n-BMA, 10g ethyl propenoate, 2g Isooctyl methacrylate mixed obtain mixing acrylate monomer, standby.
Anion polyurethane tensio-active agent (compound shown in the formula I with 5g, molecular weight is 2000) and 5g sealing polyurethane cross-linking agent (compound shown in the formula II, molecular weight is 6000) be dissolved in the 365g deionized water, add then agitator is housed, reflux condensing tube, temperature is taken into account in the four-hole round-bottomed flask of separating funnel, the mixing acrylate monomer and the 0.5g lauryl mercaptan that add 40g, stirred 30 minutes fast, stir down elevated temperature to 75 ℃, the initiator potassium persulfate solution 10g of adding 2%, react after 1 hour, from dropping funnel, drip 60g mixing acrylate monomer, drip off in 4 hours, the initiator potassium persulfate solution 15g that divides two batches of addings 2% during this time keeps temperature to continue reaction 3 hours.Reaction finishes the back and adds 1g sodium hydroxide and regulate pH value to 9, can obtain with the white solid content of blue light at 22% anodic electrophoresis acrylic ester emulsion.
Embodiment 3
12g hydroxyethyl meth acrylate, 56g methyl methacrylate, 22g n-BMA, 8g ethyl propenoate, 2g Isooctyl methacrylate mixed obtain mixing acrylate monomer, standby.
Anion polyurethane tensio-active agent (compound shown in the formula I with 7g, molecular weight is 10000) and 3g sealing polyurethane cross-linking agent (compound shown in the formula II, molecular weight is 3000) be dissolved in the 365g deionized water, add then agitator is housed, reflux condensing tube, temperature is taken into account in the four-hole round-bottomed flask of separating funnel, the mixing acrylate monomer and the 0.5g lauryl mercaptan that add 40g, stirred 30 minutes fast, stir down elevated temperature to 85 ℃, the initiator potassium persulfate solution 5g of adding 2%, react after 0.5 hour, from dropping funnel, drip 60g mixing acrylate monomer, drip off in 1 hour, add 2% initiator potassium persulfate solution 20g during this time in four batches, keep temperature to continue reaction 1 hour.Reaction finishes the back and adds the 2g trolamine and regulate pH value to 9.5, can obtain with the white solid content of blue light at 22% anodic electrophoresis acrylic ester emulsion.
Embodiment 4
10g hydroxypropylmethyl acrylate, 42g methyl methacrylate, 40g n-BMA, 6g ethyl propenoate, 2g Isooctyl methacrylate mixed obtain mixing acrylate monomer, standby.
Anion polyurethane tensio-active agent (compound shown in the formula I with 3g, molecular weight is 6000) and 9g sealing polyurethane cross-linking agent (compound shown in the formula II, molecular weight is 7000) be dissolved in the 363g deionized water, add then agitator is housed, reflux condensing tube, temperature is taken into account in the four-hole round-bottomed flask of separating funnel, the mixing acrylate monomer and the 0.5g list-n-dodecane sulfenyl sodium sulfate that add 40g, stirred 30 minutes fast, stir down elevated temperature to 80 ℃, the initiator potassium persulfate solution 8g of adding 2%, react after 0.5 hour, from dropping funnel, drip 60g mixing acrylate monomer, 2.5 drip off in hour, add 2% initiator potassium persulfate solution 17g during this time in three batches, keep temperature to continue reaction 2 hours.Reaction finishes the back and adds the 1.8g methyldiethanolamine and regulate pH value to 9, can obtain with the white solid content of blue light at 22.4% anodic electrophoresis acrylic ester emulsion.
With deionized water the above-mentioned acrylic ester emulsion that obtains is diluted to 10%, makes negative electrode, carry out the anodic electrophoresis test as anode with aluminium sheet with insoluble conductor.Voltage is 90V, and electrophoresis time is 2min.
The insoluble paint film that obtains solidifies under 120 ℃ * 30min condition after washing is dried.Film and have following performance: being coated with thickness is 12 μ m, pencil hardness 4H, resistance to impact shock 50cm, salt fog resistance＞400h, 30 days no changes of water tolerance, 7 days no changes of alkali resistance (3%NaOH), 7 days no changes of acid resistance (hydrochloric acid soln of pH=4), abrasion resistance 〉=10000 time, glossiness (60 °) is respectively 23%, 35%, 32%, 28%.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. anodic electrophoresis mat acrylic resin is characterized in that it being that feedstock production by following massfraction obtains:
The acrylic ester monomer of hydroxyl: 1.2～2.5%
Free-radical polymerised acrylic ester monomer: 18.4～19.7%
Anionic polyurethane tensio-active agent: 0.6～1.8%
Blocked isocyanate linking agent: 0.6～1.9%
Basic cpd: 0.2～0.4%
Chain-transfer agent: 0.1%
Initiator: 0.1%
Water: 74.8～76.5%.
2. according to the described a kind of anodic electrophoresis mat acrylic resin of claim 1, it is characterized in that:
The acrylic ester monomer of described hydroxyl is hydroxyethyl (methyl) acrylate, hydroxypropyl (methyl) acrylate, hydroxyl butyl (methyl) acrylate, (gathering) glycol monomethyl (methyl) acrylate or (gathering) propylene glycol list (methyl) acrylate;
Described free-radical polymerised acrylic ester monomer is (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, acrylic acid C1-C18 alkyl ester, (methyl) acrylic acid amides, N-methyl (methyl) acrylamide or (methyl) vinyl cyanide.
3. according to the described a kind of anodic electrophoresis mat acrylic resin of claim 1, it is characterized in that: described anionic polyurethane tensio-active agent is the compound shown in the formula I:
(formula I)
Its molecular weight is 2000-10000.
4. according to the described a kind of anodic electrophoresis mat acrylic resin of claim 1, it is characterized in that: described sealing polyurethane cross-linking agent is the compound shown in the formula II:
(formula II)
Its molecular weight is 3000-7000.
5. according to the described a kind of anodic electrophoresis mat acrylic resin of claim 1, it is characterized in that:
Described basic cpd is ammonia, sodium hydroxide, potassium hydroxide, ethamine, propylamine, butylamine, benzylamine, monoethanolamine, neopentyl alcohol amine, 2-aminopropanol, 3-aminopropanol, diethylin diethanolamine, N-Mono Methyl Ethanol Amine, N-ehtylethanolamine, dimethylethanolamine, Trimethylamine 99, triethylamine, trolamine, methyldiethanolamine, dimethylaminoethanol, diethylenetriamine, hydroxyethyl aminoethyl, ethylamino ethylamine, methylamino propyl group amine;
Described initiator is Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, hydrogen peroxide, benzoyl peroxide, t-butyl hydroperoxide, di-tert-butyl hydroperoxide, Three methyl Benzene superoxide or isopropyl benzene hydroperoxide;
Described chain-transfer agent is lauryl mercaptan, list-n-dodecane sulfenyl sodium sulfate, acetic acid n-dodecyl mercaptan ester, Succinic Acid list-n-dodecyl mercaptan ester, oxalic acid two-n-dodecyl mercaptan ester.
6. according to claim 1 or 2 described a kind of anodic electrophoresis mat acrylic resins, it is characterized in that:
The acrylic ester monomer of described hydroxyl is hydroxyethyl meth acrylate, hydroxypropylmethyl acrylate;
Described free-radical polymerised acrylic ester monomer is methyl methacrylate, ethyl propenoate, n-BMA, Isooctyl methacrylate.
7. according to claim 1 or 5 described a kind of anodic electrophoresis mat acrylic resins, it is characterized in that:
Described basic cpd is sodium hydroxide, triethylamine, trolamine, methyldiethanolamine;
Described initiator is a Potassium Persulphate;
Described chain-transfer agent is lauryl mercaptan, list-n-dodecane sulfenyl sodium sulfate.
8. the described a kind of anodic electrophoresis of claim 1 is characterized in that may further comprise the steps with the preparation method of mat acrylic resin:
(1) acrylic ester monomer of 1.2～2.5% hydroxyls is mixed with 18.4～19.7% free-radical polymerised acrylic ester monomers, obtain mixing acrylate monomer;
(2) with 74.8～76.5% water, 0.1% chain-transfer agent, mix 40% of acrylate monomer quality, 0.6～1.8% anionic polyurethane tensio-active agent mixes with 0.6～1.9% blocked isocyanate linking agent, fully stir, be warming up to 70-90 ℃, add 0.02～0.04% initiator, reacted 0.5-1 hour, drip remaining mixing acrylate monomer, dropwise in 1-4 hour, in the meantime remaining initiator is divided into 2-4 and criticizes adding, dropwise back insulation 1-3 hour, add 0.2～0.4% basic cpd and regulate the pH value, obtain anodic electrophoresis mat acrylic resin to 8.5-9.5;
Described per-cent is mass percent.
9. described according to Claim 8 a kind of anodic electrophoresis preparation method of mat acrylic resin is characterized in that: the solution that described initiator is mixed with massfraction 1～2% uses.
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| CN102337073A (en) * | 2011-08-18 | 2012-02-01 | 中科院广州化学有限公司 | Water-soluble nonluminous anionic electrophoretic coating and preparation method and application thereof |
| CN103613702A (en) * | 2013-12-04 | 2014-03-05 | 中科院广州化学有限公司 | Aqueous multi-functional crylic acid extinction resin and preparation method thereof |
| CN103626930A (en) * | 2013-11-27 | 2014-03-12 | 中科院广州化学有限公司 | Preparation method of water-based acrylic acid polyurethane extinction resin with phase separation structure |
| CN104130375A (en) * | 2014-07-31 | 2014-11-05 | 中国海洋石油总公司 | Polyacrylate modified water-based enclosed isocyanate curing agent and preparation method thereof |
| CN104250507A (en) * | 2013-06-25 | 2014-12-31 | 郎溪县鑫泽涂料有限公司 | Acrylic anodic electrophoresis coating and its production method |
| CN105694651A (en) * | 2014-11-28 | 2016-06-22 | 合众（佛山）化工有限公司 | A preparing method of water-based self-crosslinking acrylic acid modified polyurethane matte resin |
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| CN109912766A (en) * | 2019-03-04 | 2019-06-21 | 江西省龙海化工有限公司 | It is a kind of aqueous from ester modified polyurethane resin of mat acrylic and preparation method thereof |
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| CN102337073B (en) * | 2011-08-18 | 2013-12-25 | 中科院广州化学有限公司 | Water-soluble nonluminous anionic electrophoretic coating and preparation method and application thereof |
| CN102337073A (en) * | 2011-08-18 | 2012-02-01 | 中科院广州化学有限公司 | Water-soluble nonluminous anionic electrophoretic coating and preparation method and application thereof |
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