CN103626930A - Preparation method of water-based acrylic acid polyurethane extinction resin with phase separation structure - Google Patents
Preparation method of water-based acrylic acid polyurethane extinction resin with phase separation structure Download PDFInfo
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Abstract
The invention discloses a preparation method of water-based acrylic acid polyurethane extinction resin with a phase separation structure, and belongs to the field of water-based flat paint. The water-based acrylic acid polyurethane extinction resin with the phase separation structure comprises the following components in parts by weight: 30-68 parts of acrylate, 10-34 parts of ionic type closed polyurethane, 5-17 parts of non-ionic polyurethane, 0.18-0.41 part of initiating agent, 0.03-0.068 part of chain transfer agent, 4.2-11.7 parts of alkaline compound and 90-204 parts of water. The water-based acrylic acid polyurethane extinction resin with the phase separation structure, prepared by the method, has the advantages of low-temperature solidification, excellent mold mark masking, high extinction efficiency, water resistance, acid resistance, alkali resistance, good wear resistance and the like. The anionic closed polyurethane and hydroxide radicals in acrylic resin are introduced so as to carry out cross-linking reaction, so that the crosslinking density between resins is increased, and the mechanical strength and the surface erasibility of the extinction resin are improved.
Description
Technical field
The invention belongs to water-based Flat paint field, particularly a kind of preparation method with the water soluble acrylic acid urethane matting resin of phase separation structure.
Background technology
Widespread demand water-based Flat paint in recent years, but this Flat paint great majority are all to manufacture water-based Flat paint by adding matting agent or flatting silica.As this preparation method's water-based Flat paint, for example, silica flatting agent is dispersed in to the method (CN101186773A) in self-crosslinking acrylic resin; Add matting agent to aqueous mono-component matte varnish (CN102363702) in acrylic acid modified polyurethane system; Add matting agent to polyacrylic acid polyvalent alcohol the inside and form component A, then component A and the anion-modified HDI polyisocyanates of B component are mixed in proportion to the aqueous double-component dull finishing type finish paint (CN102363696A) of making; Flatting silica is added to the method (CN102533079A) that forms extinction type use for synthetic leather finishing agent in water-latex type anionic polyurethane resin and water-borne acrylic resin.
Yet also there is some shortcoming in current technology, need to be by macromolecule dispersing agent in the dispersion process of matting agent, wetting agent, the various auxiliary agents such as anti-settling agent, cause the preparation process of coating loaded down with trivial details and complicated; In addition, matting agent is along with the increase of storage period can produce precipitation, thereby the application of water-based Flat paint is exerted an influence.
And as the water-based Flat paint of resin type, have and utilize two kinds of different acrylic resins of solubility parameter and the anion electrophoresis coating " Unexamined Patent 10-46065 communique " that does not have the melamine resin of consistency to be dispersed in water with these resins; In addition, in addition the resin that possesses water dispersible is mixed with melamine resin, utilize the poor unglazed coating " JP 2001-131494 communique " that obtains of the SP value of resin.But the coating of above-mentioned two inventions must be 170 ℃ of above bakings, and easily making to film produces be full of cracks, and film performance is exerted an influence; Its consumed energy increases in addition, can cause loss economically.
In addition, there is the resin using containing carboxyl and hydroxyl, the water-based electrophoretic paint that blocked polyisocyanates compound is manufactured, has low the filming of excellent performance, gloss that obtains 140 ℃ of baking-curings, but its covering property of mould scar inadequate " Unexamined Patent 8-41380 communique ".
In the above-mentioned method medium vinyl resin manufacture process of mentioning, mostly adopt solution polymerization process, in manufacturing processed, need in a large number with an organic solvent, coating is easily subject to the impact of solvent, and contain a large amount of volatile organic compoundss (Volatile organic compounds, VOC), contaminate environment, produces harm to human body.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, primary and foremost purpose of the present invention is to provide a kind of water soluble acrylic acid urethane matting resin with phase separation structure, this acroleic acid polyurethane matting resin can solidify at low temperatures, stability in storage is good, covering property of mold-mart is good, flatting efficiency is high,, containing organic solvent, 60 ° of lower gloss do not reach below 20.
Another object of the present invention is to provide the above-mentioned preparation method with the water soluble acrylic acid urethane matting resin of phase separation structure.
A further object of the present invention is to provide the above-mentioned application with the water soluble acrylic acid urethane matting resin of phase separation structure.
Object of the present invention is achieved through the following technical solutions: a kind of water soluble acrylic acid urethane matting resin with phase separation structure, and the component that comprises following weight part meter:
Described acrylate is mixed and is formed by carboxylic unsaturated acrylic ester monomer, the unsaturated acrylic ester monomer of hydroxyl and free-radical polymerised acrylic ester monomer;
The acid number of described acrylate is 15-150mg KOH/g, preferably 40-100mg KOH/g; Hydroxyl value is 30-150mg KOH/g, preferably 40-100mg KOH/g; Second-order transition temperature is 20-60 ℃, preferably 30-50 ℃; Molecular weight is 10000-100000, preferably the scope of 20000-60000; Molecular weight distribution is 1～5;
Described carboxylic unsaturated acrylic ester monomer is preferably one or both in methacrylic acid or vinylformic acid;
The unsaturated acrylic ester monomer of described hydroxyl is preferably at least one in (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, polypropylene glycol monomethacrylate or polypropylene glycol mono acrylic ester;
Described free-radical polymerised acrylic ester monomer is preferably the two or more monomers in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, vinyl cyanide, acrylamide, lauryl methacrylate(LMA), N methacrylamide etc. or vinylbenzene;
The cooperation ratio of the mix monomer in described acrylate, more preferably the one-tenth by following weight part meter is grouped into:
Described anionic sealing urethane is that aromatics, fatty compounds, alicyclic ring kind isocyanate and polyester polyol are under catalyst action, through small molecule alcohol and the urethane that obtains containing the addition polymerization of carboxyl chainextender; Described polyester polyol content (referring to account for the massfraction of synthetic urethane) is 10-50%, preferably 25-45%; Polyester polyol number-average molecular weight used is 200-5000, preferably 400-1000; Synthesis of polyurethane molecular weight is 1000～7000, preferably 2000～5000; Preferably alicyclic ring kind isocyanate and polyester polyol be under catalyst action, through small molecule alcohol and the urethane that obtains containing the addition polymerization of carboxyl chainextender;
Described anionic sealing polyurethane molecular amount can be by regulating polyester polyol molecular weight to control;
Described anionic sealing urethane is prepared by following steps: 0.10mol isophorone diisocyanate mixes with 0.025mol polyoxyethylene glycol, add 1-2 to drip catalyzer dibutyl tin laurate, 50ml acetone, stir, back flow reaction 1.5h in 80 ℃ of waters bath with thermostatic control, under stirring, add 0.0125mol1, 4-butyleneglycol continues reaction 1h, add again 0.0525mol dimethylol propionic acid to continue reaction 4h, after adding 0.8mol end-capping reagent, continue back flow reaction 2h, with dibutylamine method measure in product containing free-during NCO, cooling down to 60 ℃, add 0.0525mol basic cpd to continue reaction 0.5h, under high-speed stirring, add distilled water, violent shear agitation 0.5h, cool, extract acetone, make anionic sealing urethane,
The molecular weight of described polyoxyethylene glycol is preferably 400～1000;
In the preparation of anionic sealing urethane, described end-capping reagent has phenolic compound, alcohol compound, oxime compounds, active methylene group compounds, lactam analog compound, aminated compounds, glyoxaline compound, urea compound, amino formate compounds etc.; Preferred oxime compounds; More preferably methyl ethyl ketoxime;
In the preparation of anionic sealing urethane, described basic cpd is a kind of in ethamine, propylamine, butylamine, benzylamine, monoethanolamine, neopentyl alcohol amine, 2-aminopropanol, 3-aminopropanol, diethylamine, triethylamine, Isopropylamine, Diisopropylamine, tri-isopropyl amine, diethanolamine, diisopropanolamine (DIPA), trolamine, dimethylethanolamine, diethylethanolamine, amine water, sodium hydroxide or potassium hydroxide, from over-all properties, considers to be preferably triethylamine;
Described nonionic polyurethane is prepared by following steps: get 0.05mol hexamethylene diisocyanate trimer (HDI tripolymer) and mix with 0.15mol poly glycol monomethyl ether, add 1～2 catalyzer dibutyl tin laurate, 50ml acetone, stir, back flow reaction in 80 ℃ of waters bath with thermostatic control, with dibutylamine method measure in product containing free-during NCO, under high-speed stirring, add distilled water, violent shear agitation 0.5h, cooling down, extract acetone, make nonionic polyurethane;
The molecular weight of described poly glycol monomethyl ether is 500～2000;
Described initiator is a kind of in Potassium Persulphate, Sodium Persulfate or ammonium persulphate, preferably Potassium Persulphate;
Described chain-transfer agent is sulfur alcohol compound, preferably lauryl mercaptan;
Described basic cpd is a kind of in ethamine, propylamine, butylamine, benzylamine, monoethanolamine, neopentyl alcohol amine, 2-aminopropanol, 3-aminopropanol, diethylamine, triethylamine, Isopropylamine, Diisopropylamine, tri-isopropyl amine, diethanolamine, diisopropanolamine (DIPA), trolamine, dimethylethanolamine, diethylethanolamine, amine water, sodium hydroxide or potassium hydroxide; From over-all properties, consider, select thanomin best; The neutralization ratio reaching by these alkaline matters is advisable with 30%～100%, especially better with 60%～90%;
The preferred deionized water of described water.
Of the present invention have in phase separation structure acroleic acid polyurethane matting resin, can add as required pigment, dyestuff, linking agent, defoamer, stablizer etc. to regulate, and further optimizes the performance of filming.
The above-mentioned preparation method with the water soluble acrylic acid urethane matting resin of phase separation structure, comprises the following steps:
Under the protection of nitrogen, by anionic seal urethane and nonionic polyurethane water-soluble after, add the initiator of part propylene acid esters, chain-transfer agent, part, fully mix, at 75-85 ℃ of reaction 0.5-1.5h, make seed emulsion; Then drip remaining acrylate and remaining initiator, time for adding is controlled at 3-5h, after dropwising, at 75-85 ℃ of insulation 1-3h, reduces temperature to 45 ℃, add basic cpd to regulate pH value to 8.0-9.5, obtain having the water soluble acrylic acid urethane matting resin of phase separation structure.
Described part propylene acid esters and the mass ratio of remaining acrylate are 1:3;
The initiator of described part and the mass ratio of remaining initiator are 1:3.
Described a kind of phase separation structure acroleic acid polyurethane matting resin that has, it is applied as and can, by having that phase separation structure acroleic acid polyurethane matting resin finished product is coated to woodenware or drying and forming-film above metal device, obtains the film coated surface of gloss below 20.
The preparation that the present invention has a phase separation structure acroleic acid polyurethane matting resin is that Extinction Characteristic, paint stability, curability at low temperatures, the feature of environmental protection and the physicochemical property each side from coating considers, contradiction between balance various factors, design all good products of coating performance and workability, by the ratio between soft or hard monomer, control the second-order transition temperature of polymkeric substance, by mercaptan, control polymericular weight and distribution thereof; By hydroxy radical content reasonable in design, so that suitable hydroxyl value to be provided; Introduce appropriate methacrylic acid and reach suitable acid number; Introduce styrene monomer, make coating possess resistance to crocking and water tolerance, reduce the consistency between coating.By whole design, make synthetic emulsion possess satisfactory stability and physicochemical property.
Reaction principle of the present invention is:
In the present invention, there is the 1st elementary reaction prepared by phase separation structure acroleic acid polyurethane matting resin, isophorone diisocyanate is reacted under catalyst action with polyoxyethylene glycol, then by adding 1,4-butyleneglycol, dimethylol propionic acid carries out chain extension, finally utilize end-capping reagent methyl ethyl ketoxime end-blocking, then utilize triethylamine to neutralize, make anionic sealing urethane; The 2nd stage reacted hexamethylene diisocyanate trimer (HDI tripolymer) to prepare nonionic polyurethane under catalyzer condition with poly glycol monomethyl ether; The 3rd stage carried out the unsaturated monomer that contains hydroxyl, the unsaturated monomer that contains carboxyl and other free-radical polymerised unsaturated acrylic ester monomer after letex polymerization under the condition of anionic sealing urethane and nonionic polyurethane existence, add basic cpd to regulate pH value to 8.0-9.5, obtain having phase separation structure acroleic acid polyurethane matting resin; In resin film process, anionic part seals the hydroxyl generation crosslinking reaction in urethane and acrylic resin, strengthens the cross-linking density of interlaminar resin, has improved physical strength and the surperficial erasibility of matting resin; Meanwhile, excessive negatively charged ion sealing urethane and nonionic polyurethane are non-uniformly distributed in acrylic resin, impel phase separation structure to occur, and make coating produce ununiform shrinkage when film forming, form micro-uneven surface, reach the object that reduces gloss.
The present invention compared with prior art has following features:
1. the phase separation structure acroleic acid polyurethane matting resin that has preparing is usingd water as dispersion medium, and VOC content is low, and smell is little, nontoxic pollution-free;
2. what prepare has a phase separation structure acroleic acid polyurethane matting resin, has curability at low temperatures, covering property of mold-mart is good, flatting efficiency is high, water tolerance, the advantage such as acidproof, alkali resistance outstanding, and wear resisting property is good.And by introducing the hydroxyl generation crosslinking reaction in negatively charged ion sealing urethane and acrylic resin, strengthen the cross-linking density of interlaminar resin, improved physical strength and the surperficial erasibility of matting resin.
3. non-ionic type sealing urethane is insensitive to ionogen, and the paint stability of preparation is better; Resin does not need to add matting agent, and cost is low; Raw material sources are extensive, so application prospect is extensive.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
A preparation method with phase separation structure acroleic acid polyurethane matting resin, comprises the following steps:
(1) prepare anionic sealing urethane: 0.10mol isophorone diisocyanate is mixed with 0.025mol polyoxyethylene glycol (molecular weight 400), add 1-2 to drip catalyzer dibutyl tin laurate, 50ml acetone, stir, back flow reaction 1.5h in 80 ℃ of waters bath with thermostatic control, under stirring, add 0.0125mol1, 4-butyleneglycol continues reaction 1h, add again 0.0525mol dimethylol propionic acid to continue reaction 4h, add 0.8mol methyl ethyl ketoxime to continue back flow reaction 2h, with dibutylamine method measure in product containing free-during NCO, cooling down to 60 ℃, add 0.0525mol triethylamine to continue reaction 0.5h, under high-speed stirring, add distilled water, violent shear agitation 0.5h, cool, extract acetone, make anionic sealing urethane,
(2) prepare nonionic polyurethane: in reactor, add 0.05molHDI tripolymer and 0.15mol poly glycol monomethyl ether (molecular weight 500), 1～2 catalyzer dibutyl tin laurate, 50ml acetone, stir, back flow reaction 5h in 80 ℃ of waters bath with thermostatic control, with dibutylamine method measure in product containing free-during NCO, under high-speed stirring, add distilled water, violent shear agitation 0.5h, cooling down, extract acetone, make nonionic polyurethane;
(3) 5.4 parts of methyl methacrylates, 4.5 parts of hydroxyethyl methylacrylates, 2.4 parts of methacrylic acids, 6.0 parts of butyl methacrylate, 7.2 parts of butyl acrylates, 4.4 parts of vinylbenzene are mixed and obtain acrylate mixture, standby;
(4) under the protection of nitrogen, by the anionic polyurethane of 10 parts of steps (1), the nonionic polyurethane of 5 parts of steps (2) is dissolved in 120 parts of deionized waters, then add in the four-hole round-bottomed flask that agitator, reflux condensing tube, thermometer and separating funnel are housed, add 7.5 parts of acrylate mixtures, 0.03 part of lauryl mercaptan, 5%(massfraction) 0.9 part of initiator potassium persulfate solution, in rapid stirring process, be warming up to 75 ℃, after reaction 1.5h, make seed emulsion; From dropping funnel, drip 22.5 parts of acrylate mixtures and 5%(massfraction) 2.7 parts of initiator Sodium Persulfate solution, in 5h, drip off, continuation is at 75 ℃ of insulation 3h, reduce temperature to 45 ℃, add 4.2 parts of trolamines to regulate pH to 8.5 left and right, can obtain milky, solid content at 20.8% acroleic acid polyurethane matting resin A.
Described umber is weight fraction.
Embodiment 2
A preparation method with phase separation structure acroleic acid polyurethane matting resin, comprises the following steps:
(1) preparation method of anionic polyurethane is with embodiment 1 step (1);
(2) prepare nonionic polyurethane: in reactor, add 0.05molHDI tripolymer and 0.15mol poly glycol monomethyl ether (molecular weight 1000), 1～2 catalyzer dibutyl tin laurate, 50ml acetone, stir, back flow reaction 5h in 80 ℃ of waters bath with thermostatic control, with dibutylamine method measure in product containing free-during NCO, under high-speed stirring, add distilled water, violent shear agitation 0.5h, cooling down, extract acetone, make nonionic polyurethane;
(3) 12 parts of methyl methacrylates, 7.5 parts of hydroxyethyl methylacrylates, 5.0 parts of methacrylic acids, 7.7 parts of butyl methacrylate, 10.2 parts of butyl acrylates, 7.6 parts of vinylbenzene are mixed and obtain acrylate mixture, standby;
(4) under the protection of nitrogen, by the anionic polyurethane of 25 parts of steps (1), the nonionic polyurethane of 12.5 parts of steps (2) is dissolved in 150 parts of deionized waters, then add in the four-hole round-bottomed flask that agitator, reflux condensing tube, thermometer and separating funnel are housed, add 12.5 parts of acrylate mixtures, 0.05 part of lauryl mercaptan, 5%(massfraction) 1.5 parts of initiator potassium persulfate solution, in rapid stirring process, be warming up to 80 ℃, after reaction 1h, make seed emulsion; From dropping funnel, drip 37.5 parts of acrylate mixtures and 5%(massfraction) 4.5 parts of initiator Sodium Persulfate solution, in 5h, drip off, continuation is at 80 ℃ of insulation 2h, reduce temperature to 45 ℃, add 8.7 parts of trolamines to regulate pH to 8.5 left and right, can obtain milky, solid content at 20.5% acroleic acid polyurethane matting resin B.
Described umber is weight fraction.
Embodiment 3
A preparation method with phase separation structure acroleic acid polyurethane matting resin, comprises the following steps:
(1) prepare anionic sealing urethane: 0.10mol isophorone diisocyanate is mixed with 0.025mol polyoxyethylene glycol (molecular weight 1000), add 1-2 to drip catalyzer dibutyl tin laurate, 50ml acetone, stir, back flow reaction 1.5h in 80 ℃ of waters bath with thermostatic control, under stirring, add 0.0125mol1, 4-butyleneglycol continues reaction 1h, add again 0.0525mol dimethylol propionic acid to continue reaction 4h, add 0.8mol methyl ethyl ketoxime to continue back flow reaction 2h, with dibutylamine method measure in product containing free-during NCO, cooling down to 60 ℃, add 0.0525mol triethylamine to continue reaction 0.5h, under high-speed stirring, add distilled water, violent shear agitation 0.5h, cool, extract acetone, make anionic sealing urethane,
(2) preparation method of non-type polyurethane is with embodiment 1 step (2)
(3) 17.2 parts of methyl methacrylates, 10.2 parts of hydroxyethyl methylacrylates, 6.8 parts of methacrylic acids, 10.7 parts of butyl methacrylate, 13.1 parts of butyl acrylates, 10.0 parts of vinylbenzene are mixed and obtain acrylate mixture, standby;
(4) under the protection of nitrogen, by the anionic polyurethane of 34 parts of steps (1), the nonionic polyurethane of 17 parts of steps (2) is dissolved in 204 parts of deionized waters, then add in the four-hole round-bottomed flask that agitator, reflux condensing tube, thermometer and separating funnel are housed, add 17 parts of acrylate mixtures, 0.068 part of lauryl mercaptan, 5%(massfraction) 2.04 parts of initiator potassium persulfate solution, in rapid stirring process, be warming up to 85 ℃, after reaction 0.5h, make seed emulsion; From dropping funnel, drip 51 parts of acrylate mixtures and 5%(massfraction) 6.12 parts of initiator Sodium Persulfate solution, in 3h, drip off, continuation is at 85 ℃ of insulation 1h, reduce temperature to 45 ℃, add 11.7 parts of trolamines to regulate pH to 9.0 left and right, can obtain milky, solid content at 20.2% acroleic acid polyurethane matting resin C.
Described umber is weight fraction.
The acroleic acid polyurethane matting resin of embodiment 1～3 is added to water and is made into 15%(massfraction) coating (coating A, B, C correspond respectively to embodiment 1,2,3), composition after dilution is placed in glassware seasoning five days, then is dried 24h in the baking oven of 50 ℃.Film performance is pressed coating A～C as table 1:
Table 1 acroleic acid polyurethane matting resin performance (after drying and forming-film)
Gloss detects by the standard of GB/T9754; Pencil hardness detects by the standard of GB/T6739;
Impact strength detects by the standard of GB/T1732;
Abrasion resistance detects by the standard of GB/T9266-2009;
Resistance to boiling water: will film (20 * 20 * 1mm) is placed on 30min in the boiling water of 100 ℃, takes out the film coated surface state of observing;
Water tolerance: will film (20 * 20 * 1mm) is placed in deionized water and floods after 7 days, observes the state of filming;
Acid resistance: film (20 * 20 * 1mm) is immersed in 5%H
2sO
4, after 24h, observe and be coated with membrane stage;
Alkali resistance: will film (20 * 20 * 1mm) is immersed in 3% NaOH solution after 24h, observes and is coated with membrane stage;
Covering property of mould scar: visual valuation: covering property of 〇 mould scar is good; Covering property of △ mould scar is poor; Covering property of * mould scar is very poor; Covering property of mould scar (L value): use angle spectrophotometer GCMS-4 to measure under 90 degree.Filming that L value is large is gonorrhoea look, and covering property of mould scar is good.
Stability in storage: whether the acroleic acid polyurethane matting resin of preparation is placed in to the water-bath 7 days of 50 ℃, observing container bottom has throw out.
As can be seen from Table 1, the water soluble acrylic acid urethane matting resin that the present invention has phase separation structure does not form gel or tackify in preserving or using, therefore possess good preservation stability, after drying and forming-film, can obtain opacifying property good, 60 ° of gloss smooth the filming below 20 of mould scar.
Above-described embodiment is preferably embodiment 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 principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a water soluble acrylic acid urethane matting resin with phase separation structure, is characterized in that the component that comprises following weight part meter:
2. the water soluble acrylic acid urethane matting resin with phase separation structure according to claim 1, is characterized in that: described acrylate is mixed and formed by carboxylic unsaturated acrylic ester monomer, the unsaturated acrylic ester monomer of hydroxyl and free-radical polymerised acrylic ester monomer;
The acid number of described acrylate is 15-150mg KOH/g; Hydroxyl value is 30-150mg KOH/g; Second-order transition temperature is 20-60 ℃; Molecular weight is the scope of 10000-100000; Molecular weight distribution is 1～5.
3. the water soluble acrylic acid urethane matting resin with phase separation structure according to claim 2, is characterized in that: described carboxylic unsaturated acrylic ester monomer is one or both in methacrylic acid or vinylformic acid;
The unsaturated acrylic ester monomer of described hydroxyl is at least one in (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, polypropylene glycol monomethacrylate or polypropylene glycol mono acrylic ester;
Described free-radical polymerised acrylic ester monomer is the two or more monomers in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, vinyl cyanide, acrylamide, lauryl methacrylate(LMA), N methacrylamide or vinylbenzene.
4. the water soluble acrylic acid urethane matting resin with phase separation structure according to claim 3, is characterized in that: the cooperation ratio of the mix monomer in described acrylate, and the one-tenth of the following weight part meter of serving as reasons is grouped into:
5. the water soluble acrylic acid urethane matting resin with phase separation structure according to claim 1, it is characterized in that: described anionic sealing urethane is that aromatics, fatty compounds, alicyclic ring kind isocyanate and polyester polyol are under catalyst action, through small molecule alcohol and the urethane that obtains containing the addition polymerization of carboxyl chainextender; The massfraction that described polyester polyol content accounts for synthetic urethane is 10-50%; Polyester polyol number-average molecular weight used is 200-5000; Synthesis of polyurethane molecular weight is 1000～7000.
6. the water soluble acrylic acid urethane matting resin with phase separation structure according to claim 1, it is characterized in that: described anionic sealing urethane is prepared by following steps: 0.10mol isophorone diisocyanate mixes with 0.025mol polyoxyethylene glycol, add 1-2 to drip catalyzer dibutyl tin laurate, 50ml acetone, stir, back flow reaction 1.5h in 80 ℃ of waters bath with thermostatic control, under stirring, add 0.0125mol1, 4-butyleneglycol continues reaction 1h, add again 0.0525mol dimethylol propionic acid to continue reaction 4h, after adding 0.8mol end-capping reagent, continue back flow reaction 2h, with dibutylamine method measure in product containing free-during NCO, cooling down to 60 ℃, add 0.0525mol basic cpd to continue reaction 0.5h, under high-speed stirring, add distilled water, violent shear agitation 0.5h, cool, extract acetone, make anionic sealing urethane,
The molecular weight of described polyoxyethylene glycol is 400～1000;
Described end-capping reagent has phenolic compound, alcohol compound, oxime compounds, active methylene group compounds, lactam analog compound, aminated compounds, glyoxaline compound, urea compound, amino formate compounds;
In the preparation of anionic sealing urethane, described basic cpd is a kind of in ethamine, propylamine, butylamine, benzylamine, monoethanolamine, neopentyl alcohol amine, 2-aminopropanol, 3-aminopropanol, diethylamine, triethylamine, Isopropylamine, Diisopropylamine, tri-isopropyl amine, diethanolamine, diisopropanolamine (DIPA), trolamine, dimethylethanolamine, diethylethanolamine, amine water, sodium hydroxide or potassium hydroxide.
7. the water soluble acrylic acid urethane matting resin with phase separation structure according to claim 1, it is characterized in that: described nonionic polyurethane is prepared by following steps: get 0.05mol hexamethylene diisocyanate trimer and mix with 0.15mol poly glycol monomethyl ether, add 1～2 catalyzer dibutyl tin laurate, 50ml acetone, stir, back flow reaction in 80 ℃ of waters bath with thermostatic control, with dibutylamine method measure in product containing free-during NCO, under high-speed stirring, add distilled water, violent shear agitation 0.5h, cooling down, extract acetone, make nonionic polyurethane,
The molecular weight of described poly glycol monomethyl ether is 500～2000;
Described initiator is a kind of in Potassium Persulphate, Sodium Persulfate or ammonium persulphate;
Described chain-transfer agent is sulfur alcohol compound;
Described basic cpd is a kind of in ethamine, propylamine, butylamine, benzylamine, monoethanolamine, neopentyl alcohol amine, 2-aminopropanol, 3-aminopropanol, diethylamine, triethylamine, Isopropylamine, Diisopropylamine, tri-isopropyl amine, diethanolamine, diisopropanolamine (DIPA), trolamine, dimethylethanolamine, diethylethanolamine, amine water, sodium hydroxide or potassium hydroxide; The neutralization ratio 30%～100% reaching by these alkaline matters;
Described water is deionized water.
8. the water soluble acrylic acid urethane matting resin with phase separation structure according to claim 1, is characterized in that: the described water soluble acrylic acid urethane matting resin with phase separation structure contains pigment, dyestuff, linking agent, defoamer, stablizer.
9. the preparation method of the water soluble acrylic acid urethane matting resin with phase separation structure described in claim 1～8 any one, is characterized in that comprising the following steps:
Under the protection of nitrogen, by anionic seal urethane and nonionic polyurethane water-soluble after, add the initiator of part propylene acid esters, chain-transfer agent, part, fully mix, at 75-85 ℃ of reaction 0.5-1.5h, make seed emulsion; Then drip remaining acrylate and remaining initiator, time for adding is controlled at 3-5h, after dropwising, at 75-85 ℃ of insulation 1-3h, reduces temperature to 45 ℃, add basic cpd to regulate pH value to 8.0-9.5, obtain having the water soluble acrylic acid urethane matting resin of phase separation structure;
Described part propylene acid esters and the mass ratio of remaining acrylate are 1:3;
The initiator of described part and the mass ratio of remaining initiator are 1:3.
10. the water soluble acrylic acid urethane matting resin with phase separation structure described in claim 1～8 any one is applied to be coated to woodenware or drying and forming-film above metal device, obtains the film coated surface of gloss below 20.
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| CN104263184A (en) * | 2014-09-06 | 2015-01-07 | 广东华澜浩宇科技创新有限公司 | Preparation method of water-based matte paint |
| CN104974324A (en) * | 2015-06-30 | 2015-10-14 | 中科院广州化学有限公司南雄材料生产基地 | Reactive self-delustering waterborne polyurethane resin, and preparation method and application thereof |
| 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 |
| CN106519133A (en) * | 2016-11-10 | 2017-03-22 | 万华化学集团股份有限公司 | Sulfonic acid type waterborne polyurethane-acrylate self extinction resin and preparation method and application thereof |
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| CN109535352A (en) * | 2018-11-30 | 2019-03-29 | 东莞大宝化工制品有限公司 | Hydroxyl acrylic emulsion and preparation method thereof |
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| CN104263184A (en) * | 2014-09-06 | 2015-01-07 | 广东华澜浩宇科技创新有限公司 | Preparation method of water-based matte paint |
| 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 |
| CN105694651B (en) * | 2014-11-28 | 2018-06-15 | 合众（佛山）化工有限公司 | A kind of preparation method of water-borne Self-Crosslinked Acrylic modified polyurethane dumb light resin |
| CN104974324A (en) * | 2015-06-30 | 2015-10-14 | 中科院广州化学有限公司南雄材料生产基地 | Reactive self-delustering waterborne polyurethane resin, and preparation method and application thereof |
| CN106519133A (en) * | 2016-11-10 | 2017-03-22 | 万华化学集团股份有限公司 | Sulfonic acid type waterborne polyurethane-acrylate self extinction resin and preparation method and application thereof |
| CN107459618A (en) * | 2017-08-24 | 2017-12-12 | 广州至然科技应用有限公司 | A kind of preparation method of woodcare paint water-based acrylic resin and the product of acquisition |
| CN107879453A (en) * | 2017-11-15 | 2018-04-06 | 顺德职业技术学院 | New chelant type heavy metal chelating agent and its synthetic method and its application |
| CN108676434A (en) * | 2018-04-28 | 2018-10-19 | 佛山市莱威化工科技有限公司 | Aqueous one-component with the high grade of transparency and water resistance mute coating and its preparation and application entirely |
| WO2019227803A1 (en) * | 2018-05-30 | 2019-12-05 | 广东艺都科技股份有限公司 | Surface treating agent for pearlylustre bopp film and preparation method therefor |
| CN109535352A (en) * | 2018-11-30 | 2019-03-29 | 东莞大宝化工制品有限公司 | Hydroxyl acrylic emulsion and preparation method thereof |
| CN110283575A (en) * | 2019-06-12 | 2019-09-27 | 刘国辉 | A kind of high temperature resistant salt tolerant fluid loss agent |
| CN110558685A (en) * | 2019-09-10 | 2019-12-13 | 健力粘扣带有限公司 | manufacturing method of anti-static water-resistant hot-melting nylon fastening tape |
| CN110951039A (en) * | 2019-11-24 | 2020-04-03 | 华南理工大学 | Environment-friendly self-extinction waterborne polyurethane and preparation method and application thereof |
| CN111234168A (en) * | 2020-03-05 | 2020-06-05 | 合肥安利聚氨酯新材料有限公司 | Nonionic neutralizer and preparation method thereof, waterborne polyurethane and preparation method and application thereof |
| CN114410174A (en) * | 2022-02-24 | 2022-04-29 | 郑州中科新兴产业技术研究院 | High-performance water-based acrylic polyurethane coating and preparation method thereof |
| CN114410174B (en) * | 2022-02-24 | 2023-09-29 | 郑州中科新兴产业技术研究院 | High-performance aqueous acrylic polyurethane coating and preparation method thereof |
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