CN103694880B - The preparation method of waterborne one-component polyurethane paint with low viscosity - Google Patents
The preparation method of waterborne one-component polyurethane paint with low viscosity Download PDFInfo
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Abstract
A kind of preparation method of low viscosity aqueous polyurethane paint.First polymerized polyalcohol and polyisocyanates are generated isocyanate-terminated oligopolymer (a) with the reaction of 1:1.8 ~ 3.4 proportioning, secondly low molecular polylol and polyisocyanates are reacted with 1:0.3 ~ 0.5 proportioning and generate hydroxy-end capped oligopolymer (b), the polylactic acid low polymer being 800 ~ 1200g/mol by oligopolymer (a), (b) and molecular weight again reacts with the ratio of 1:0.78 ~ 0.92:0.02 ~ 0.95, obtain waterborne polyurethane resin (c), obtain finally by self-emulsifying.Waterborne polyurethane resin paint prepared by method provided by the invention, its viscosity is less than 60s, and the shelf lives is greater than 3 months, and solid content is higher than 40%, cured article water tolerance is strong, insulativity is high, mechanical strength, can be used as the surface insulating paint of transformer, charger and motor coil.
Description
Technical field
The present invention relates to a kind of method producing urethane resin, particularly relate to that excellent insulation performance under a kind of high-voltage, thermotolerance are high, stable storing and the good modified epoxy solvent impregnated resin of consistency, be specially adapted to the vacuum pressure varnished insulation technique of the coil of the big-and-middle-sized high-voltage motor of F and H level, wind power motor and other High-Voltage Electrical Appliances.
Background technology
Aqueous polyurethane paint take water as the water-miscible paint of dispersion medium, due to its not containing or only containing a small amount of VOC, and nontoxic, pollution-free, safe and reliable, because of but a kind of environmental-friendly aqueous paint.Resin matrix contained in aqueous polyurethane paint is urethane, and sticking power, the snappiness of thus giving cured paint film excellence are high, wear-resisting, oil resistant, soft durometer can be in harmonious proportion the advantages such as operative weldability is good, and these qualities are all that other water-miscible paint is difficult to surmount.But aqueous polyurethane according to a conventional method preparation process need use a large amount of material containing hydrophilic radical, as: dimethylol propionic acid and dimethylolpropionic acid etc., to realize good self-emulsifying effect, will certainly weaken the water tolerance of paint film, intensity and insulativity like this.Meanwhile, hydrophilic radical increases molecular chain hydrogen bond action also can be made to strengthen, and therefore system viscosity is also higher, and then limits the raising of solid content, also makes troubles to production application.And the content reduced containing hydrophilic group material can make resin particle diameter comparatively large, thus affect stability of emulsion.
Chinese invention patent ZL201010105129.0 discloses a kind of water-and acrylate-ester-polyurethane resin emulsion, is formed through letex polymerization by aqueous polyurethane emulsion and Acrylic Acid Monomer.Change the needs that aqueous dispersion performance that coating in the past contains single urethane (PU) structure or single acrylic ester emulsion (PA) is difficult to meet practical application, in abrasion-resistant and resistance to fingerprint, achieve superperformance.
Chinese invention patent application ZL201010135336.0 discloses a kind of nucleator for the preparation of poly(lactic acid), the Whitfield's ointment disodium that this nucleator comprises any one or a few the mixed emulsion in epoxy resin latex, ester-polyurethane resin emulsion and is dissolved in this resin emulsion, respective mass ratio is 1: 1 ~ 1: 4, to produce poly(lactic acid).
Chinese invention patent application 201310315348.5 discloses a kind of magnet ring epoxy non-isocyanate polyurethane insullac, is made up of low-molecular-weight epoxy resin, non-isocyanate polyurethane performed polymer, thinner, solidifying agent, flow agent, silicon powder, goth black 4A, silane coupling agent, silicon-dioxide, environment-friendly type bromide fire retardant and toughner.Epoxy resin and Amino End Group non-isocyanate polyurethane are reacted and forms interpenetrating polymer networks, increase the cross-linking density of polymkeric substance, the film formed thus is comparatively even and hardness is higher, and the strong adhesion of this material, water-tolerant, shock-resistance is strong, excellent insulating property, snappiness is good, and resistance toheat is strong, is applicable to magnet ring as insullac.
Chinese invention patent ZL200880118491.2 discloses a kind of waterborne polyurethane resin, hydrophilic resin and film, is reacted modulate waterborne polyurethane resin by isocyanate-terminated prepolymer and the chainextender containing polyamines.
Chinese invention patent application 201080050635.2 discloses and a kind ofly can be used in manufacturing the aqueous polyurethane resin dispersion of film with high rigidity, resistance to acidity of oil, solvent resistance, be make (a) polyol compound, (b) polyisocyanate compound, urethane resin that (c) carries out reacting containing polyol compound and (d) chain extension agent of acidic-group and obtain is dispersed in the aqueous polyurethane resin dispersion obtained in water-medium.
Chinese invention patent application 201210139908.1 discloses a kind of isocyanate-modified Synolac and preparation method thereof, is to adopt isocyanic ester to carry out modification to Synolac, the Synolac of synthesis containing ammonia ester structure.By weight percentage, its basic recipe is: vegetables oil 20% ~ 33%, polyvalent alcohol 5% ~ 8%, organic acid anhydride 2% ~ 8%, isocyanic ester 5% ~ 10%, catalyzer 0.02% ~ 0.5%, solvent 35% ~ 50% and terminator 3% ~ 8%.This isocyanate-modified Synolac, for the preparation of varnish and enamel paint time be all better than in routine in dryness, hardness, water tolerance etc., long oil alkyd paint; But in toxicity, application property and smell etc., be obviously better than bicomponent polyurethane paint, the surface of the goods such as timber, metal, plastics can be widely used in, play protection and decorative effect.
Summary of the invention
An object of the present invention is to provide the preparation method of the single-component water-based urethane resin of a kind of low viscosity, with its for insullac that base-material is made have that solid content is high, the feature of good stability and insulativity excellence.
Another object of the present invention is to provide that a kind of solid content is high, the preparation method of the waterborne one-component polyurethane paint with low viscosity of good stability and insulativity excellence.
Another object of the present invention is to provide a kind of waterborne one-component polyurethane paint with low viscosity, to flood, to spray and the coating method such as brushing is applied to the materials such as metal, timber and plastics.
The gordian technique that the present invention adopts is, low molecular weight containing hydrophilic radical is introduced the urethane end of the chain, realize the wetting ability of the free end group of polymer molecular chain, because polymer molecular chain is mutually wound around in moving process, and the end of the chain is usually sudden and violent in outside, so its wetting ability greatly improves, good aqueous solubility and the stability of polymer molecule can be ensured like this while the content reducing the inner carboxyl of molecular chain.
A kind of method preparing waterborne polyurethane resin provided by the invention, by isocyanate-terminated oligopolymer, hydroxy-end capped oligopolymer and molecular weight be the polylactic acid low polymer of 800g/mol ~ 1200g/mol with the molar ratio reaction of 1: 0.78-0.92: 0.02-0.95, obtain waterborne polyurethane resin.Wherein, polymerized polyalcohol and polyisocyanates are reacted obtained isocyanate-terminated oligopolymer with the starting molar proportioning 1: 1.8-3.4 of total OH group and total isocyanate group (also claiming: NCO group), and low molecular polylol and polyisocyanates are reacted obtained hydroxy-end capped oligopolymer with the starting molar proportioning 1: 0.3-0.5 of total OH group and total NCO group.
Another kind provided by the invention prepares the method for aqueous polyurethane, its step is as follows: in reaction vessel (can select reflux is housed), add isocyanate-terminated oligopolymer and hydroxy-end capped oligopolymer, in acetone after back flow reaction, when NCO group content is 0.8%-1.2%, add the poly(lactic acid) that molecular weight is 800g/mol-1200g/mol again, make isocyanate-terminated oligopolymer, it is 1: 0.78 ~ 0.92: 0.02 ~ 0.95 that hydroxy-end capped oligopolymer and poly(lactic acid) three react mol ratio, when lower than theoretical value 1.05 times of total isocyanate group (NCO) content, obtain waterborne polyurethane resin.
The isocyanate-terminated oligopolymer that the inventive method uses obtains as follows:
Reaction vessel (logical nitrogen protection can be selected and with reflux), add polymerized polyalcohol (can in advance through 120 DEG C of vaccum dewatering process), then add a small amount of methylethylketone, after being warming up to 50 DEG C-60 DEG C, stop heating.Drip polyisocyanates (slowly drip and be advisable), make the initial molar ratio of system total OH group and total NCO be 1: 1.8-3.4.Dropwise rear placement 0.5 hour-1.5 hours, then 65 DEG C of-75 DEG C of insulation reaction 0.5 hour-1 hour.Add the catalyzer of total amount 0.03wt%-0.05wt%, when 75 DEG C of insulations are to lower than theoretical value 1.02 times of NCO content, adjusting viscosity to 4000mPas-5000mPas(as: add proper amount of acetone), obtain isocyanate-terminated oligopolymer.
The hydroxy-end capped oligopolymer that the inventive method uses obtains as follows:
Reaction vessel (logical nitrogen protection can be selected and with reflux); add the low molecular polylol after vaccum dewatering process; add a small amount of methylethylketone again; 70 DEG C of heating make dissolution of solid; be cooled to 40 DEG C-50 DEG C; drip polyisocyanates (slowly drip and be advisable), make the initial molar ratio of system total OH group and total NCO group be 1: 0.3-0.5.Dropwise rear placement 1.5 hours-2 hours, then 60 DEG C of-70 DEG C of insulation reaction 1 hour-2 hours.
Various method provided by the invention, prepared waterborne polyurethane resin, then add required auxiliary agent through self-emulsifying and regulate solid content to be more than 40%, obtain waterborne one-component polyurethane paint with low viscosity.A kind of self-emulsifying prepares waterborne one-component polyurethane paint with low viscosity, and the waterborne polyurethane resin that neutralization is obtained makes degree of neutralization be 95%-110%.Resin after neutralization is joined in water (deionized water), at 800rmp rotating speed emulsified dispersion 30min.After a small amount of solvent of removed under reduced pressure, the auxiliary agent needed for interpolation, as: defoamer, flow agent and pigment etc., the solid content regulating emulsion was more than 40% (as: adding appropriate deionized water), to obtain final product.
The polymerized polyalcohol being applicable to above-mentioned reaction is hydroxyl value is the various polyester polyols (as: but being not limited only to poly-diprotic acid binary alcohol esters polyvalent alcohol, poly-second lactone polyols and polycarbonate polyol) of 50mgKOH/g-150mgKOH/g and one or more of polyether glycol.
Wherein, poly-diprotic acid binary alcohol esters polyvalent alcohol is that the dibasic alcohol (as: but being not limited only to ethylene glycol, 1,3-PD, neopentyl glycol and glycol ether etc.) of 60-160 is by polycondensation or ester-interchange method gained by the diprotic acid such as phthalic acid, phthalic anhydride, halogeno-benzene dicarboxylic anhydride and hexanodioic acid and molecular weight.The polyester polyol of prioritizing selection as: but be not limited only to polycaprolactone polyol, polycarbonate polyol, and the dibasic alcohol being 60-160 by phthalic acid, phthalic anhydride, halogeno-benzene dicarboxylic anhydride, hexanodioic acid and molecular weight (as: but is not limited only to ethylene glycol, 1, ammediol, neopentyl glycol and glycol ether etc.) by the poly-diprotic acid binary alcohol esters polyvalent alcohol of polycondensation or ester-interchange method gained, more preferably hydroxyl value is polycaprolactone polyol and the benzoic anhydride polyester polyol of 100mgKOH/g-120mgKOH/g.
Polyether glycol as: but be not limited only to polypropylene glycol, polyoxyethylene glycol and PTMG dibasic alcohol.These polyether glycols can separately or mixing be applied to the present invention.
The polyisocyanates that is applicable to above-mentioned reaction is as aliphatics, aromatic series, Zhi Huan race two functionality isocyanic ester and tripolymer thereof and three-functionality-degree isocyanic ester.Concrete, as: but be not limited only to tolylene diisocyanate (comprising TDI-65, TDI-80 and the TDI-100 by commercially available acquisition), diphenylmethanediisocyanate (pure MDI and liquefied mdi), isophorone diisocyanate, hexamethylene diisocyanate, tetramethyl xylylene diisocyanate, toluene diisocyanate trimer, triphenylmethane triisocyanate and Lysine triisocyanate.Prioritizing selection tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate and toluene diisocyanate trimer.These polyisocyanates kinds or cited compound can separately or mixing be applied to the present invention.
Be applicable to the low molecular polylol of above-mentioned reaction as chainextender, it comprises the dibasic alcohol (also claiming: hydrophilic dibasic alcohol) containing hydrophilic radical, and consumption is hydroxy-end capped oligopolymer 8w/w%-13w/w%.Especially the dibasic alcohol containing at least one carboxyl, as: but be not limited only to dimethylol propionic acid or dimethylolpropionic acid.
Be applicable to the low molecular polylol of above-mentioned reaction as chainextender, also comprise the polyalcohols of molecular weight at 60-1100, concrete as: but be not limited only to ethylene glycol, 1,2-propylene glycol, 1,4-butyleneglycol, positive pentanediol, neopentyl glycol, 1,4-cyclohexanediol, glycol ether, glycerine, Viscotrol C, TriMethylolPropane(TMP) and ethoxylated pentaerythritol etc., prioritizing selection molecular weight is the polyvalent alcohol of 75-950.These polyvalent alcohols can separately or mixing be applied to the present invention.
Neutralization reaction neutralizing agent used as: but be not limited only to triethylamine, dimethylethanolamine and ANP95.These neutralizing agents can separately or mixing be applied to the present invention.
The reagent that the catalyzer being applicable to produce isocyanate-terminated oligopolymer is understood for those skilled in the art, these concrete catalyzer as: but be not limited only to stannous octoate, dibutyl tin laurate, can separately or mixing be applied to the present invention.
Translucent and slightly floodlight pool under waterborne one-component polyurethane paint room temperature prepared by the present invention, range of viscosities is 40s-60s(4# agar diffusion method, 23 ± 1 DEG C), solid content is higher than 40%, and pot life at room temperature is greater than 3 months.Film curing temperature is 120-160 DEG C, and set time is 15-50min.Through solidification test, paint film has the advantages such as high strength, enhanced water resistance, insulativity are good, low VOC, and due to acid number low, so without copper corrosion phenomenon.
Waterborne one-component polyurethane paint prepared by the present invention can be applicable to the numerous areas such as metal, timber, plastics, and especially in metal-insulator paint, application is good.Its operation is extensive, applies simple and efficient, can adopt the coating methods such as dipping, spraying and brushing.
The beneficial effect that technical solution of the present invention realizes:
Various method provided by the invention, prepared aqueous polyurethane viscosity is less than 60s, and the shelf lives is greater than 3 months, and solid content is higher than 40%, cured article water tolerance is strong, insulativity is high, mechanical strength, can be used as the surface insulating paint of transformer, charger and motor coil.
Various method provided by the invention, obtained aqueous polyurethane paint overcomes that common water borne polyurethane paint viscosity is high, solid content is low, solubility promoter content is high and the shortcoming such as poor storage stability.Be applicable to the coating methods such as dipping, spraying and brushing, and be widely used in the surface of the materials such as metal, timber and plastics, there is good water tolerance, intensity and insulativity, be especially applied to metallic surface as insullac.
Embodiment
Below describe technical scheme of the present invention in detail.The embodiment of the present invention is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to the technical scheme of invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in right of the present invention.
In the following embodiment of the present invention, its NCO group mass percentage, according to acetone-Di-n-Butyl Amine method, is obtained by titration test.
The reaction product provided and the viscosity of intermediate adopt rotational viscosimeter, in 23 ± 1 DEG C of mensuration.The viscosity of final aqueous polyurethane paint adopts to be coated with 4# agar diffusion method, in 23 ± 1 DEG C of mensuration.
Solids content be paint by taking about 1g in 45mm × 45mm aluminium box, after being dried to constant weight in 130 degree, by calculating.
Embodiment 1
In logical nitrogen protection and with in the reaction flask of reflux, adding the hydroxyl value after 120 DEG C of vaccum dewaterings is 112mgKOH/g polyphenyl acid anhydride glycol ether ester polyol 201.92g(0.40 mole of OH), then add 5g methylethylketone, stop heating after being warming up to 50 DEG C.MDI-50144.38g(1.15 mole of NCO is slowly dripped with dropping funnel), within 1.5 hours, dropwise rear system automatic heat evolution 1 hour, then with 65 DEG C of insulation reaction 0.5 hour.After system is steady, add dibutyl tin laurate 0.18g, when 75 DEG C of insulation to mensuration NCO content are 9.08%, add proper amount of acetone adjusting viscosity to 4720mPas, obtain isocyanate-terminated oligopolymer.
In logical nitrogen protection and with in the reaction flask of reflux; add the glycol ether 42.4g(0.8 mole OH after 120 DEG C of vaccum dewatering process), dimethylol propionic acid 16.75g(0.25 mole OH) and glycerine 13.8g(0.45 mole OH); add 5g methylethylketone again; 70 DEG C of heating make dissolution of solid; be cooled to 45 DEG C, slowly drip MDI-5065.7g(0.525 mole of NCO).Within 1.5 hours, dropwise rear automatic heat evolution 2 hours, then 65 DEG C of insulation reaction 1.5 hours, obtain hydroxy-end capped oligopolymer.
Get synthetic hydroxy-end capped oligopolymer 95.7g, join in pre-synthesis isocyanate-terminated oligopolymer, add proper amount of acetone, in 60 degree of back flow reaction, stopped reaction when residue NCO content is 1.02%, adds the poly(lactic acid) 25g(0.025 mole of OH that molecular weight is 1000g/mol), 75 DEG C of reactions, when NCO content is 0.69%, obtain pale yellow transparent shape waterborne polyurethane resin, acid number is 18.7mgKOH/g.
In urethane resin, add 13.9g triethylamine (0.138 mole) neutralize, then join in deionized water, at 800rpm rotating speed emulsified dispersion 30min.After 50 DEG C of a small amount of solvents of removed under reduced pressure, add 0.1%BYK024 and 0.2%AFCONA3570, obtaining solid content is 44%, and viscosity is the waterborne one-component polyurethane paint of 58s.
Embodiment 2
In logical nitrogen protection and with in the reaction flask of reflux; adding the hydroxyl value after 120 DEG C of vaccum dewaterings is 120mgKOH/g polycaprolactone polyol 140.25g(0.3 mole of OH) and hydroxyl value be the polypropylene glycol 150g(0.3 mole OH of 110mgKOH/g); add 6g methylethylketone again, after being warming up to 50 DEG C, stop heating.TDI130.62g(1.5 mole of NCO is slowly dripped with dropping funnel), within 1.5 hours, dropwise rear system automatic heat evolution 1 hour, then with 65 DEG C of insulation reaction 0.5 hour.After system is steady, add dibutyl tin laurate 0.2g, when 75 DEG C of insulation to mensuration NCO content are 8.97%, add proper amount of acetone adjusting viscosity to 4290mPas, obtain isocyanate-terminated oligopolymer.
In logical nitrogen protection and with in the reaction flask of reflux; add the propylene glycol 45.6g(1.2 mole OH after 120 DEG C of vaccum dewatering process), dimethylol propionic acid 20.1g(0.3 mole OH) and trimethylolethane 20g(0.5 mole OH); add 6g methylethylketone again; 70 DEG C of heating make dissolution of solid; be cooled to 50 DEG C, slowly drip IPDI93.32g(0.84 mole of NCO).Within 1.5 hours, dropwise rear automatic heat evolution 2 hours, then 70 DEG C of insulation reaction 1.5 hours, obtain hydroxy-end capped oligopolymer.
Get synthetic hydroxy-end capped oligopolymer 124g, join in pre-synthesis isocyanate-terminated oligopolymer, add proper amount of acetone, in 60 degree of back flow reaction, stopped reaction when residue NCO content is 1.13%, adds the poly(lactic acid) 68g(0.08 mole of OH that molecular weight is 850g/mol), 75 DEG C of reactions, when NCO content is 0.41%, obtain pale yellow transparent shape waterborne polyurethane resin, recording acid number is 17.3mgKOH/g.
In urethane resin, add 18.2g triethylamine (0.18 mole) neutralize, then join in deionized water, at 800rmp rotating speed emulsified dispersion 30min.After 50 DEG C of a small amount of solvents of removed under reduced pressure, add 0.1%BYK024 and 0.2%AFCONA3570, obtaining solid content is 41%, and viscosity is the waterborne one-component polyurethane paint of 52s.
Embodiment 3
In logical nitrogen protection and with in the reaction flask of reflux; adding the hydroxyl value after 120 DEG C of vaccum dewaterings is 112mgKOH/g polyphenyl acid anhydride glycol ether ester polyol 201.92g(0.40 mole of OH); add 10g methyl-2-pyrrolidone again, after being warming up to 50 DEG C, stop heating.MDI-50144.38g(1.15 mole of NCO is slowly dripped with dropping funnel), within 1.5 hours, dropwise rear system automatic heat evolution 1 hour, then with 65 DEG C of insulation reaction 0.5 hour.After system is steady, adds propylene glycol, dimethylol propionic acid and glycerine, add dibutyl tin laurate 0.18g, 75 DEG C of reactions, this process reduces system viscosity by adding acetone.When NCO content is 0.51%, obtain waterborne polyurethane resin, recording acid number is 29mgKOH/g.
In above-mentioned resin, add triethylamine neutralize, then join in deionized water, at 800rpm rotating speed emulsified dispersion 30min.After 50 DEG C of a small amount of solvents of removed under reduced pressure, add 0.1%BYK024,0.2%AFCONA3570 and butyl glycol ether, obtaining solid content is 25%, and viscosity is the waterborne one-component polyurethane paint of 79s.
Embodiment of the present invention sample and comparative example performance index are contrasted, see the following form:
Claims (13)
1. prepare a method for aqueous polyurethane, it is characterized in that its step is as follows:
Add isocyanate-terminated oligopolymer and hydroxy-end capped oligopolymer, in acetone after back flow reaction, when NCO group content is 0.8%-1.2%, add the poly(lactic acid) that molecular weight is 800g/mol-1200g/mol again, described isocyanate-terminated oligopolymer, described hydroxy-end capped oligopolymer and described poly(lactic acid) is made to be 1: 0.78 ~ 0.92: 0.02 ~ 0.95 by reaction mol ratio, when NCO content is lower than theoretical value 1.05 times, to obtain final product;
The preparation method of described isocyanate-terminated oligopolymer is: in reaction vessel, add polymerized polyalcohol and a small amount of methylethylketone, heating is stopped after being warming up to 50 DEG C-60 DEG C, slow dropping polyisocyanates, the initial molar ratio of system total OH group and total NCO group is made to be 1: 1.8-3.4, dropwise rear placement 0.5 hour-1.5 hours, then 65 DEG C of-75 DEG C of insulation reaction 0.5 hour-1 hour, add the catalyzer of total amount 0.03wt%-0.05wt%, 75 DEG C of insulations are to lower than theoretical value 1.02 times of NCO content, adjusting viscosity is to 4000mPas-5000mPas, obtain,
The preparation method of described hydroxy-end capped oligopolymer is: in reaction vessel, add low molecular polylol and a small amount of methylethylketone, 70 DEG C of heating make dissolution of solid, be cooled to 40 DEG C-50 DEG C, slow dropping polyisocyanates, the initial molar ratio making system total OH group and total NCO group is 1: 0.3-0.5, dropwises rear placement 1.5 hours-2 hours, then 60 DEG C of-70 DEG C of insulation reaction 1 hour-2 hours, to obtain final product.
2. the method preparing aqueous polyurethane according to claim 1, is characterized in that described low molecular polylol is the polyalcohols of molecular weight at 60-1100.
3. the method preparing aqueous polyurethane according to claim 1, it is characterized in that described low molecular polylol comprises and be selected from ethylene glycol, 1,2-propylene glycol, 1,4-butyleneglycol, positive pentanediol, neopentyl glycol, 1, one or more of 4-cyclohexanediol, glycol ether, glycerine, Viscotrol C, TriMethylolPropane(TMP) and ethoxylated pentaerythritol, and the dibasic alcohol containing hydrophilic radical of one or more being selected from dimethylol propionic acid and dimethylolpropionic acid; The consumption of the described dibasic alcohol containing hydrophilic radical is the 8w/w%-13w/w% of described low molecular polylol and described polyisocyanates total amount.
4. the method preparing aqueous polyurethane according to claim 1, is characterized in that described polymerized polyalcohol to be hydroxyl value is that the polyester polyol of 50mgKOH/g-150mgKOH/g and hydroxyl value are one or more of the polyether glycol of 50mgKOH/g-150mgKOH/g.
5. the method preparing aqueous polyurethane according to claim 1, is characterized in that described polymerized polyalcohol is polyester polyol, is selected from poly-diprotic acid binary alcohol esters polyvalent alcohol and polycarbonate polyol one or more.
6. the method preparing aqueous polyurethane according to claim 5, it is characterized in that described poly-diprotic acid binary alcohol esters polyvalent alcohol is is that the dibasic alcohol of 60-160 is by polycondensation or ester-interchange method gained by one or more diprotic acid of phthalic acid, phthalic anhydride, halogeno-benzene dicarboxylic anhydride and hexanodioic acid and molecular weight.
7. the method preparing aqueous polyurethane according to claim 6, is characterized in that described dibasic alcohol is selected from one or more of ethylene glycol, 1,3-PD, neopentyl glycol and glycol ether.
8. the method preparing aqueous polyurethane according to claim 1, it is characterized in that described polymerized polyalcohol is selected from polycaprolactone polyol that hydroxyl value is 100mgKOH/g-120mgKOH/g and hydroxyl value is one or more of the benzoic anhydride polyester polyol of 100mgKOH/g-120mgKOH/g.
9. the method preparing aqueous polyurethane according to claim 1, is characterized in that described polymerized polyalcohol is polyether glycol, is selected from polypropylene glycol, polyoxyethylene glycol and PTMG dibasic alcohol one or more.
10. the method preparing aqueous polyurethane according to claim 1, is characterized in that described polyisocyanates is selected from one or more of tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, tetramethyl xylylene diisocyanate, toluene diisocyanate trimer, triphenylmethane triisocyanate and Lysine triisocyanate.
11. 1 kinds of methods preparing aqueous polyurethane paint, it is characterized in that by after the obtained waterborne polyurethane resin self-emulsifying of the method preparing aqueous polyurethane one of claim 1-10 Suo Shu, after a small amount of solvent of removed under reduced pressure, the auxiliary agent needed for interpolation, regulates solid content to be more than 40%.
12. methods preparing aqueous polyurethane paint according to claim 11, it is characterized in that described self-emulsification approach is: the waterborne polyurethane resin that neutralization is obtained, make degree of neutralization be 95%-110%, the resin after neutralization is added to the water, at 800rpm rotating speed emulsified dispersion 30min.
13. methods preparing aqueous polyurethane paint according to claim 12, is characterized in that described N-process uses one or more neutralizing agents of triethylamine, dimethylethanolamine and ANP95.
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