CN102702467B - Waterborne polyurethane resin, waterborne polyaniline anticorrosive paint and preparation methods thereof - Google Patents
Waterborne polyurethane resin, waterborne polyaniline anticorrosive paint and preparation methods thereof Download PDFInfo
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Abstract
The invention discloses a waterborne polyurethane resin and a preparation method of the waterborne polyurethane resin. Correspondingly, the invention also provides a single-constituent waterborne polyaniline anticorrosive paint and a preparation method of the single-constituent waterborne polyaniline anticorrosive paint. The single-constituent waterborne polyaniline anticorrosive paint comprises the following constituents: waterborne polyurethane resin, waterborne film-forming cosolvent, deionized water, water-based conductive polyaniline, filler, paint, a defoaming agent and a water-based dispersing agent. The waterborne polyurethane resin adopted by the method takes polyethylene glycol adipate or poly(butylene succinate) as a soft segment, and an inner crosslinking agent trimethylolpropane is introduced, so that the waterborne polyurethane and the waterborne polyaniline form an interpenetrating network structure through hydrogen bonds, and the antiseptic property of the polyaniline is fully played. More importantly, a single-constituent self-supporting film with excellent performance can be formed without double-constituent curing due to introducing of the inner crosslinking agent trimethylolpropane, so that excellent preservative effect of the single-constituent waterborne polyaniline anticorrosive paint system is ensured.
Description
Technical field
The present invention relates to protective system technical field, more particularly, relate to a kind of waterborne polyurethane resin, Waterborne Polyaniline Corrosion Protection Coatings and preparation method thereof.
Background technology
At present, protective system field seriously relies on the poisonous and harmful such as heavy metal or lead, the chromium metallic elements such as zinc powder, but global zinc reserves are only 2.2 hundred million tons, wherein within 2007, consumed 1,157 ten thousand tons (China 3,170,000 tons), thereby global reserves only can use 19 years (domestic only can use 10 years).On the other hand, the protective system that coating contains poisonous and harmful metallic element is very big to environmental hazard, once and coating have slightly and to scratch, its preservative effect reduces greatly.Therefore, development does not rely on zinc powder and becomes protective system a kind of development trend in future without the protective system of poisonous and harmful metallic element.
Polyaniline anti-corrosive paint does not rely on zinc powder and poisonous and harmful metal, is the coating of a class antiseptic property excellence.Abroad, German Ormecon company and Panipol company of Finland etc. have developed Corrpassiv in succession
tM, Ormecon
tMand Versicon
tMetc. business-like polyaniline anti-corrosive paint.In addition, " intrinsic safety " board polyaniline anti-corrosive paint of the large novel material of the Hunan Ben Anya company limited of domestic Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences's technical support has 5000 tonnes of coating production lines, indicates the scale operation of domestic polyaniline anti-corrosive paint.But above-mentioned wide coverage the polyaniline anti-corrosive paint of producing are solvent based coating, contain a large amount of organic solvents such as benzene, dimethylbenzene, in use can cause great bodily injury to operator ' s health, environment are brought to huge pollution simultaneously.
Compared with traditional organic solvent, environment-friendly type aqueous polyaniline anti-corrosive paint, taking water as thinner, has been eliminated organic discharge, is expected to become the desirable protective system of a class.At present, the polyaniline anti-corrosive paint of reporting is mostly two-pack, for example, application number is that 01138153.1,200710047366.4,200610029482.9 and 98116978.3 Chinese patent literature has been reported respectively polyaniline anti-corrosive paint, taking the epoxy resin that contains polyaniline additive as A component, taking polymeric amide or phenolic aldehyde amine as solidifying agent B component, before construction, two kinds of components are mixed and constructed.But there is short shortcoming construction working life in two-component coating, the long-time problems such as coating gel and inefficacy that are prone to of placing.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is, a kind of waterborne polyurethane resin and preparation method thereof is provided, the present invention also provides a kind of single-component water-based polyaniline anti-corrosive paint that contains waterborne polyurethane resin and preparation method thereof, and the preservative effect of this Waterborne Polyaniline Corrosion Protection Coatings is good.
In order to solve above technical problem, the invention provides a kind of formula 1) shown in waterborne polyurethane resin:
Formula 1)
R is the one in following structure:
Formula 2) formula 3) formula 4)
Formula 5) formula 6) formula 7)
R ' is suc as formula 8) or formula 9) shown in,
formula 8)
formula 9)
Wherein, n is that 1 ~ 50, m is 1 ~ 50.
Accordingly, the present invention also provides a kind of preparation method of waterborne polyurethane resin, comprises the following steps:
Under nitrogen protection, by the first compound and the second compound, after reaction, obtain the first product, described the first compound has formula 10) structure, described the second compound is 2,4-toluene diisocyanate, diphenylmethanediisocyanate, benzene two methylene vulcabond, hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexyl methane diisocyanate;
H-R '-H formula 10)
R ' is suc as formula 8) or formula 9) shown in,
formula 8)
formula 9)
N is that 1 ~ 50, m is 1 ~ 50;
Under the katalysis of dibutyl tin laurate, described the first product, TriMethylolPropane(TMP) are reacted in solvent, obtain the second product;
Described the second product is reacted in solvent with N methyldiethanol amine, obtain third product;
By third product and glycol reaction, add trifluoroacetic acid after adding deionized water emulsification, after reaction, obtain waterborne polyurethane resin.
Preferably, described the first compound is that molecular weight is that 232 ~ 8660 daltonian polyethylene glycol adipates or molecular weight are 260 ~ 8690 daltonian poly butylene succinates.
The present invention also provides a kind of Waterborne Polyaniline Corrosion Protection Coatings, comprises following composition:
Waterborne polyurethane resin 12 ~ 25 weight parts claimed in claim 1;
Waterborne film-forming solubility promoter 1 ~ 5 weight part;
Deionized water 20 ~ 30 weight parts;
Waterborne conductive polyaniline 0.2 ~ 3 weight part;
Filler 5 ~ 25 weight parts;
Pigment 26 ~ 45 weight parts;
Defoamer 0.5 ~ 2 weight part;
Aqueous dispersant 0.2 ~ 3 weight part.
Preferably, described waterborne conductive polyaniline is suc as formula 11) shown in:
formula 11)
Wherein, y is that 0 ~ 1, p is 1 ~ 500.
Accordingly, the present invention also provides a kind of preparation method of Waterborne Polyaniline Corrosion Protection Coatings, comprises the following steps:
Step a) is mixed the waterborne conductive polyaniline of the deionized water of the waterborne film-forming solubility promoter of the waterborne polyurethane resin claimed in claim 1 of 12 ~ 25 weight parts, 1 ~ 5 weight part, 20 ~ 30 weight parts and 0.2 ~ 3 weight part, sand milling 1.5 ~ 3 hours after stirring;
Step b), under agitation condition, adds the filler of 5 ~ 25 weight parts, pigment, the defoamer of 0.5 ~ 2 weight part and the aqueous dispersant of 0.2 ~ 3 weight part of 26 ~ 45 weight parts, and sand milling filtered after 3 ~ 5 hours, obtained water-based anticorrosive paint.
Preferably, described waterborne film-forming solubility promoter is butyl glycol ether, Diethylene Glycol butyl ether or propylene glycol.
Preferably, described waterborne conductive polyaniline is suc as formula 11) shown in:
formula 11)
Wherein, y is that 0 ~ 1, p is 1 ~ 500.
Preferably, described filler is one or more in talcum powder, process white and calcium carbonate; Described pigment is aluminium dihydrogen tripolyphosphate and/or iron mica.
The invention provides waterborne polyurethane resin and preparation method thereof, this waterborne polyurethane resin is using polyethylene glycol adipate or poly butylene succinate as soft section, and introduce internal crosslinker TriMethylolPropane(TMP), thereby utilize this waterborne polyurethane resin to form after water-based anticorrosive paint, can form inierpeneirating network structure by hydrogen bond and aqueous polyanion, be conducive to give full play to the antiseptic property of polyaniline.What is more important, due to the introducing of internal crosslinker TriMethylolPropane(TMP) in waterborne polyurethane resin, just need not two-pack solidify can forming property excellence single component self-supported membrane, be conducive to form mono-component aqueous polyaniline anti-corrosive paint system.
Accordingly, the present invention also provides a kind of single-component water-based polyaniline anti-corrosive paint and preparation method thereof, comprises following composition: waterborne polyurethane resin, waterborne film-forming solubility promoter, deionized water, waterborne conductive polyaniline, filler, pigment, defoamer and aqueous dispersant.Wherein, the redox potential of waterborne conductive polyaniline is far away higher than the redox potential of iron, the surface of iron and steel is oxidized, between steel surface and electrically conductive polyaniline, generate one deck compact metal oxide film, make the electropotential of iron in passivation region, prevented the further corrosion of iron and steel.
Compared with prior art, the waterborne polyurethane resin that the present invention adopts is using polyethylene glycol adipate or poly butylene succinate as soft section, and introduce internal crosslinker TriMethylolPropane(TMP), make this aqueous polyurethane and aqueous polyanion form inierpeneirating network structure by hydrogen bond, be conducive to give full play to the antiseptic property of polyaniline.What is more important, due to the introducing of internal crosslinker TriMethylolPropane(TMP), just need not two-pack solidify can forming property excellence single component self-supported membrane, ensured to have formed mono-component aqueous polyaniline anti-corrosive paint system and there is good preservative effect.
Brief description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum of the waterborne polyurethane resin prepared of the embodiment of the present invention 1.
Embodiment
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Of the present inventionly provide a kind of formula 1) shown in waterborne polyurethane resin:
Formula 1)
R is the one in following structure:
Formula 2) formula 3) formula 4)
Formula 5) formula 6) formula 7)
R ' is suc as formula 8) or formula 9) shown in,
formula 8)
formula 9)
Wherein, n is that 1 ~ 50, m is 1 ~ 50.
Accordingly, the present invention also provides a kind of preparation method of above-mentioned waterborne polyurethane resin, comprise the following steps: under nitrogen protection, by the first compound and the second compound, after reaction, obtain the first product, described the first compound has formula 10) structure, described the second compound is 2,4-toluene diisocyanate, diphenylmethanediisocyanate, benzene two methylene vulcabond, hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexyl methane diisocyanate;
H-R '-H formula 10)
R ' is suc as formula 8) or formula 9) shown in,
formula 8)
formula 9)
N is that 1 ~ 50, m is 1 ~ 50;
Under the katalysis of dibutyl tin laurate, described the first product, TriMethylolPropane(TMP) are reacted in solvent, obtain the second product; Described the second product is reacted in solvent with N methyldiethanol amine, obtain third product; By third product and glycol reaction, add trifluoroacetic acid after adding deionized water emulsification, after reaction, obtain waterborne polyurethane resin.
In the preparation process of waterborne polyurethane resin, it is that 232 ~ 8660 daltonian polyethylene glycol adipates or molecular weight are 260 ~ 8690 daltonian poly butylene succinates that the first compound of employing is preferably molecular weight; More preferably molecular weight is that 1000 ~ 5000 daltonian polyethylene glycol adipates or molecular weight are 1000 ~ 5000 daltonian poly butylene succinates; More preferably molecular weight is that 2000 daltonian polyethylene glycol adipates or molecular weight are 2000 daltonian poly butylene succinates.
As preferred version; the step of preparing the first product is specially: under nitrogen protection; the first compound is warming up to 80 ~ 100 DEG C; more preferably 90 DEG C, the second compound is dropped in the first compound, after reaction, obtain the first product; rate of addition is preferably 10 ~ 30ml/min; more preferably 15 ~ 20ml/min, the reaction times is preferably 1 ~ 5 hour, more preferably 2 ~ 3 hours.
Prepare after the first product, preferably described the first product is cooled to 70 DEG C, then react in solvent with TriMethylolPropane(TMP).As preferred version, the step that obtains the second product is specially: in the first product, add successively butanone, TriMethylolPropane(TMP) and dibutyl tin laurate, obtain the second product after reaction, the reaction times is preferably 1 ~ 2 hour, more preferably 1.5 hours.Wherein, the effect of butanone is to reduce reaction system viscosity, is convenient to react completely and carries out.
In above-mentioned steps, using polyethylene glycol adipate or poly butylene succinate as soft section, and introduce internal crosslinker TriMethylolPropane(TMP), thereby utilize this waterborne polyurethane resin to form after water-based anticorrosive paint, can form inierpeneirating network structure by hydrogen bond and aqueous polyanion, be conducive to give full play to the antiseptic property of polyaniline.What is more important, due to the introducing of internal crosslinker TriMethylolPropane(TMP), just need not two-pack solidify can forming property excellence single component self-supported membrane, be conducive to form mono-component aqueous polyaniline anti-corrosive paint system.
Obtain after the second product, described the second product is reacted in solvent with N methyldiethanol amine, introduce hydrophilic radical, obtain third product, described solvent is preferably butanone, its role is to reduce reaction system viscosity, is convenient to react completely and carries out.Concrete, the step that obtains third product is specially: will in the second product, add butanone, be cooled to 20 ~ 40 DEG C, be preferably 30 DEG C, drip N methyldiethanol amine, rate of addition is preferably 3 ~ 8ml/mim, more preferably 5ml/mim, after reaction, obtain third product, preferably 0.5 ~ 2 hour reaction times, more preferably 0.5 hour.
The step that finally obtains waterborne polyurethane resin is specially: third product is warming up to 60 ~ 70 DEG C, be preferably 65 DEG C, add glycol chain extender, react 1 ~ 3 hour, after adding deionized water emulsification, add trifluoroacetic acid, in carrying out with the amino of hydrophilic radical and salify, after reaction, obtain waterborne polyurethane resin, described emulsification times is preferably 1 ~ 3 hour, more preferably 2 hours.
Can find out from such scheme, the invention provides a kind of waterborne polyurethane resin and preparation method thereof, this waterborne polyurethane resin is using polyethylene glycol adipate or poly butylene succinate as soft section, and introduce internal crosslinker TriMethylolPropane(TMP), thereby utilize this waterborne polyurethane resin to form after water-based anticorrosive paint, can form inierpeneirating network structure by hydrogen bond and aqueous polyanion, be conducive to give full play to the antiseptic property of polyaniline.What is more important, due to the introducing of internal crosslinker TriMethylolPropane(TMP) in waterborne polyurethane resin, just need not two-pack solidify can forming property excellence single component self-supported membrane, be conducive to form mono-component aqueous polyaniline anti-corrosive paint system.
Accordingly, the present invention also provides a kind of Waterborne Polyaniline Corrosion Protection Coatings, comprises following composition: waterborne polyurethane resin 12 ~ 25 weight parts described in technique scheme; Waterborne film-forming solubility promoter 1 ~ 5 weight part; Deionized water 20 ~ 30 weight parts; Waterborne conductive polyaniline 0.2 ~ 3 weight part; Filler 5 ~ 25 weight parts; Pigment 26 ~ 45 weight parts; Defoamer 0.5 ~ 2 weight part; Aqueous dispersant 0.2 ~ 3 weight part.
Waterborne polyurethane resin is preferably suc as formula 1) shown in:
Formula 1)
R is the one in following structure:
Formula 2) formula 3) formula 4)
Formula 5) formula 6) formula 7)
R ' is suc as formula 8) or formula 9) shown in,
formula 8)
formula 9)
Wherein, n is that 1 ~ 50, m is 1 ~ 50.
Described waterborne conductive polyaniline is preferably suc as formula 11) shown in:
formula 11)
Wherein, y is that 0 ~ 1, p is 1 ~ 500.
The aqueous polyanion particle diameter that the present invention adopts is preferably 35 ~ 100nm, more preferably 50 ~ 80nm.Wherein, the gegenion phosphoric acid ester in aqueous polyanion can with iron in Fe
2+form insoluble mixture protective layer, make metal surface passivation, further strengthen preservative property.In addition, the redox potential (0.5 ~ 0.7V vs.SCE) of waterborne conductive polyaniline, far away higher than the redox potential (0.64V vs.SCE) of iron, the surface of iron and steel is oxidized, between steel surface and electrically conductive polyaniline, generate one deck compact metal oxide film, thereby make the electropotential of iron in passivation region, prevented the further corrosion of iron and steel.
The aqueous polyanion that the present invention adopts is preferably prepared as follows: by formula 12) the polyaniline in eigenstate powder of structure mixes with phosphoric acid ester doping agent, after reaction, obtain aqueous polyanion, described phosphoric acid ester doping agent is formula 13) and formula 14) shown in compound.To the manufacturer of described phosphoric acid ester doping agent, there is no particular restriction in the present invention, can adopt method preparation well known to those skilled in the art, or adopt the product of knowing producer.
Formula 12)
Formula 13) formula 14).
According to the present invention, described waterborne film-forming solubility promoter is preferably butyl glycol ether, Diethylene Glycol butyl ether or propylene glycol; Described filler is preferably one or more in talcum powder, process white and calcium carbonate; Described pigment optimization is aluminium dihydrogen tripolyphosphate and/or iron mica.
Accordingly, the present invention also provides a kind of preparation method of Waterborne Polyaniline Corrosion Protection Coatings, comprise the following steps: step a) is mixed the waterborne conductive polyaniline of the deionized water of the waterborne film-forming solubility promoter of the waterborne polyurethane resin described in the technique scheme of 12 ~ 25 weight parts, 1 ~ 5 weight part, 20 ~ 30 weight parts and 0.2 ~ 3 weight part sand milling 1.5 ~ 3 hours after stirring; Step b), under agitation condition, adds the filler of 5 ~ 25 weight parts, pigment, the defoamer of 0.5 ~ 2 weight part and the aqueous dispersant of 0.2 ~ 3 weight part of 26 ~ 45 weight parts, and sand milling filtered after 3 ~ 5 hours, obtained Waterborne Polyaniline Corrosion Protection Coatings.
As preferred version, described step a) is specially: the deionized water of the waterborne film-forming solubility promoter of the urethane resin described in the technique scheme of 12 ~ 25 weight parts, 1 ~ 5 weight part and 20 ~ 30 weight parts is added in sand mill tank, under agitation condition, add the waterborne conductive polyaniline of 0.2 ~ 3 weight part, continue to stir 0.5 ~ 1 hour, sand milling 1.5 ~ 3 hours, wherein, the speed of stirring is preferably 1500 ~ 3000rpm, more preferably 2000rpm.
Aqueous polyurethane in the present invention uses soft section as aqueous polyurethane of crystallinity polyethylene glycol adipate, and introduce internal crosslinker TriMethylolPropane(TMP), make this aqueous polyurethane to form hydrogen bond with aqueous polyanion, make the two can form well inierpeneirating network structure, be conducive to give full play to the antiseptic property of polyaniline.In addition, the preparation of waterborne polyurethane resin adopts the trifluoroacetic acid that contains fluorine atom as neutralizing agent, has utilized the inertia of fluorine atom, makes to have more excellent antiseptic property; What is more important, due to the introducing of internal crosslinker, just need not two-pack solidify can forming property excellence single component self-supported membrane, thereby formed mono-component aqueous polyaniline anti-corrosive paint system.
Described step b) is specially: under agitation condition, add the filler of 5 ~ 25 weight parts, pigment, the defoamer of 0.5 ~ 2 weight part and the aqueous dispersant of 0.2 ~ 3 weight part of 26 ~ 45 weight parts, sand milling 3 ~ 5 hours, utilize 200 object filter-cloth filterings, obtain water-based anticorrosive paint, described stirring velocity is preferably 1500 ~ 3000rpm, more preferably 2500rpm.
Described waterborne conductive polyaniline is suc as formula 11) shown in:
formula 11)
Wherein, y is that 0 ~ 1, p is 1 ~ 500.
Waterborne conductive polyaniline is preferably the form of nano-dispersed aqueous polyanion powder, can be dispersed in waterborne polyurethane resin, because waterborne polyurethane resin is resin cation (R.C.), thereby can not cause the particle of aqueous polyanion to become large, thereby form the Waterborne Polyaniline Corrosion Protection Coatings of nano-dispersed.In addition, the gegenion phosphoric acid ester in aqueous polyanion can with iron in Fe
2+form insoluble mixture protective layer, make metal surface passivation, further strengthened preservative property.
According to the present invention, described waterborne film-forming solubility promoter is butyl glycol ether, Diethylene Glycol butyl ether or propylene glycol; Described filler is one or more in talcum powder, process white and calcium carbonate; Described pigment is aluminium dihydrogen tripolyphosphate and/or iron mica.
As preferred version, the present invention prepares the raw material adopting in Waterborne Polyaniline Corrosion Protection Coatings and is preferably: waterborne polyurethane resin 15 ~ 20 weight parts described in technique scheme; Waterborne film-forming solubility promoter 1 ~ 3 weight part; Deionized water 25 ~ 30 weight parts; Waterborne conductive polyaniline 0.2 ~ 2 weight part; Filler 10 ~ 20 weight parts; Pigment 30 ~ 42 weight parts; Defoamer 0.5 ~ 1.5 weight part; Aqueous dispersant 0.2 ~ 2 weight part.
Prepare after Waterborne Polyaniline Corrosion Protection Coatings, Waterborne Polyaniline Corrosion Protection Coatings is sprayed on the metal foil of polishing, oil removing, rust cleaning, levelling 3 minutes at 60 DEG C, drying at room temperature 5 days, surveys its performance after film curing.
Waterborne Polyaniline Corrosion Protection Coatings provided by the invention has following features: (1) mono-component aqueous polyaniline anti-corrosive paint provided by the invention, there is not the problem of working life, and there is the construction time long, feature easy to use.(2) compared with traditional protective system, the present invention is nano-dispersed type polyaniline anti-corrosive paint, and polyaniline consumption is few, and addition is only 0.2 ~ 3wt%, greatly reduces the cost of protective system in having excellent preservative effect.(3) compared with traditional solvent-borne type protective system, aqueous polyanion protective system of the present invention makes it have eco-friendly feature, is a kind of environmental type coating.
In order to further illustrate technical scheme of the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The chemical reagent that the embodiment of the present invention and comparative example adopt is commercial.
BYK163 described in embodiment and comparative example and BYKP 105 are the dispersion agent of Bi Ke company, and BYK055, BYK088 and BYK067A are the defoamer of Bi Ke company.Described polyaniline in eigenstate is the product that the large novel material of Hunan Ben Anya company limited produces, and polyaniline in eigenstate molecular weight is 110000 dalton.
Embodiment 1
Under drying nitrogen protection, the 2000 dalton's polyethylene glycol adipates of the 200g molecular weight after vacuum hydro-extraction to be put in there-necked flask, temperature rises to 90 DEG C, speed with 15ml/min drips 2 of 87g, and 4-toluene diisocyanate, after dropwising, continue reaction 2h, obtain the first product;
The first product is cooled to 70 DEG C, adds the butanone of 150ml, then add the dibutyl tin laurate of 13.4g TriMethylolPropane(TMP) and 0.0001g, continue reaction 1.5h, obtain the second product;
To in the second product, add 100ml butanone, cool to 30 DEG C, drip the N methyldiethanol amine of 8.7g with the speed of 5ml/mim, continue reaction 0.5h, obtain the 3rd intermediate product;
Third product is warmed up to 65 DEG C, adds 20.5g ethylene glycol, reaction 2h, adds 200ml deionized water to carry out emulsification 20min, then, adds the trifluoroacetic acid of 6.7g, last, and butanone is removed in decompression, obtains waterborne polyurethane resin.
Aqueous polyurethane tree prepared by the present embodiment carries out nucleus magnetic hydrogen spectrum analysis, and as shown in Figure 1, result is: H NMR(d-DMSO): 1.0ppm, 1.09ppm, 1.52ppm, 1.60ppm, 2.12ppm, 2.17ppm, 2.28ppm, 2.50ppm, 2.64ppm, 3.34ppm, 3.47ppm, 4.02ppm, 4.21ppm, 4.58ppm, 7.06ppm, 7.17ppm, 7.49ppm, 8.78ppm, 9.51ppm.
The preparation of embodiment 2 waterborne conductive polyaniline powders
Formula 13) structure phosphoric acid ester doping agent preferably in accordance with the following methods preparation:
42g Vanadium Pentoxide in FLAKES is added to the 150ml tetracol phenixin that is dissolved with 36g ethylene glycol monomethyl ether, for adding in 1h, be warmed up to 60 DEG C of reaction 4h, add 10g water and 21g gac, after 80 DEG C of reaction 1h, filter, reduce pressure away after organic reagent, obtain formula 13) the phosphoric acid ester doping agent of structure.
Formula 14) structure phosphoric acid ester doping agent preferably in accordance with the following methods preparation:
56g Vanadium Pentoxide in FLAKES is added in the 300ml tetracol phenixin that is dissolved with 145g ethylene glycol monomethyl ether, in 2h, add, be warmed up to 70 DEG C of reaction 5h, add 32g water and 41g gac, after 90 DEG C of reaction 2h, filter, reduce pressure away after organic reagent, obtain formula 14) the phosphoric acid ester doping agent of structure.
By the formula of the above-mentioned preparation of 100g 13) the phosphoric acid ester doping agent of structure, the formula 14 of the above-mentioned preparation of 100g) phosphoric acid ester doping agent, the 100g formula 12 of structure) the polyaniline in eigenstate powder (y=0.5 of structure, p=140) and the deionized water of 6000g mix, at room temperature stir 72h, obtain waterborne conductive polyaniline dispersion liquid;
Utilize supercentrifuge to carry out the aqueous polyanion dispersion liquid obtaining centrifugal, centrifugal with the speed of 5000 revs/min, by the powder obtaining in vacuum drying oven 45 DEG C dry 72 hours, obtain waterborne conductive polyaniline powder.
Embodiment 3
Waterborne polyurethane resin prepared by 12 grams of embodiment 1,1 gram of propylene glycol and 20 grams of deionized waters join in sand mill tank, under stirring with the speed of 2000rpm, the waterborne conductive polyaniline powder that adds 0.2 gram of embodiment 2 to prepare, continues to stir 0.5 hour then sand milling 1.5 hours.
Then, under stirring with the speed of 2500rpm, add 3 grams of talcum powder, 1.5 grams of process whites and 0.5 gram of calcium carbonate, 26 grams of aluminium dihydrogen tripolyphosphates and 19 grams of iron micas, 0.5 gram of BYK055 and 0.2 gram of BYK163, continue sand milling 3 hours, with 200 object filter-cloth filterings, obtain aqueous polyanion coating.
By paint spay-coating on the metal foil through polishing, oil removing, rust cleaning, levelling 3 minutes at 60 DEG C, drying at room temperature 5 days, surveys its performance after film curing, performance is in table 1.
Embodiment 4
Waterborne polyurethane resin prepared by 25 grams of embodiment 1,5 grams of butyl glycol ethers and 30 grams of deionized waters join in sand mill tank, under stirring with the speed of 2000rpm, the waterborne conductive polyaniline powder that adds 3 grams of embodiment 2 to prepare, continues to stir 1 hour then sand milling 3 hours.
Then, under stirring with the speed of 2500rpm, add 13 grams of talcum powder, 10 grams of process whites and 2 grams of calcium carbonate, 16 grams of aluminium dihydrogen tripolyphosphates and 10 grams of iron micas, 2 grams of BYK088 and 3 grams of BYKP 105, continue sand milling 5 hours, with 200 object filter-cloth filterings, obtain aqueous polyanion coating.
By paint spay-coating on the metal foil through polishing, oil removing, rust cleaning, levelling 3 minutes at 60 DEG C, drying at room temperature 5 days, surveys its performance after film curing, performance is in table 1.
Embodiment 5
Waterborne polyurethane resin prepared by 21 grams of embodiment 1,3 grams of Diethylene Glycol butyl ether and 25 grams of deionized waters join in sand mill tank, under stirring with the speed of 2000rpm, the waterborne conductive polyaniline powder that adds 0.8 gram of embodiment 2 to prepare, continues to stir 0.5 hour then sand milling 2.5 hours.
Then, under stirring with the speed of 2500rpm, add 5 grams of talcum powder, 2.5 grams of process whites and 1.5 grams of calcium carbonate, 6 grams of aluminium dihydrogen tripolyphosphates and 22 grams of iron micas, 1.5 grams of BYK055 and 1.2 grams of BYK163, continue sand milling 4 hours, with 200 object filter-cloth filterings, obtain aqueous polyanion coating.
By paint spay-coating on the metal foil through polishing, oil removing, rust cleaning, levelling 3 minutes at 60 DEG C, drying at room temperature 5 days, surveys its performance after film curing, performance is in table 1.
Embodiment 6
Waterborne polyurethane resin prepared by 18 grams of embodiment 1,3 grams of propylene glycol and 23 grams of deionized waters join in sand mill tank, under stirring with the speed of 2000rpm, the waterborne conductive polyaniline powder that adds 1.5 grams of embodiment 2 to prepare, continues to stir 1 hour then sand milling 2 hours.
Then, under stirring with the speed of 2500rpm, add 13 grams of talcum powder, 0.5 gram of process white and 1.5 grams of calcium carbonate, 12 grams of aluminium dihydrogen tripolyphosphates and 15 grams of iron micas, 1 gram of BYK067A and 2 grams of BYKP 105, continue sand milling 3 hours, with 200 object filter-cloth filterings, obtain aqueous polyanion coating.
By paint spay-coating on the metal foil through polishing, oil removing, rust cleaning, levelling 3 minutes at 60 DEG C, drying at room temperature 5 days, surveys its performance after film curing, performance is in table 1.
Embodiment 7
Waterborne polyurethane resin prepared by 23 grams of embodiment 1,4 grams of butyl glycol ethers and 25 grams of deionized waters join in sand mill tank, under stirring with the speed of 2000rpm, the waterborne conductive polyaniline powder that adds 1.8 grams of embodiment 2 to prepare, continues to stir 1 hour then sand milling 3 hours.
Then, under stirring with the speed of 2500rpm, add 9 grams of talcum powder, 2.5 grams of process whites and 6.5 grams of calcium carbonate, 15 grams of aluminium dihydrogen tripolyphosphates and 22 grams of iron micas, 1.5 grams of BYK055 and 2.2 grams of BYK163, continue sand milling 5 hours, with 200 object filter-cloth filterings, obtain aqueous polyanion coating.
By paint spay-coating on the metal foil through polishing, oil removing, rust cleaning, levelling 3 minutes at 60 DEG C, drying at room temperature 5 days, surveys its performance after film curing, performance is in table 1.
Comparative example 1
Waterborne polyurethane resin prepared by 15 grams of embodiment 1,1.5 grams of butyl glycol ethers and 25 grams of deionized waters join in sand mill tank, under stirring with the speed of 2500rpm, add 3.5 grams of talcum powder, 1 gram of process white and 0.5 gram of calcium carbonate, 25 grams of aluminium dihydrogen tripolyphosphates, 18 grams of iron micas, 0.7 gram of BYK055 and 0.3 gram of BYK163, continue sand milling 3 hours, with 200 object filter-cloth filterings, obtain water-based anticorrosive paint.
By paint spay-coating on the metal foil through polishing, oil removing, rust cleaning, levelling 3 minutes at 60 DEG C, drying at room temperature 5 days, surveys its performance after film curing, performance is in table 1.
The paint film property test result that water-based anticorrosive paint prepared by table 1 embodiment and comparative example forms
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiment, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (9)
1. a waterborne polyurethane resin, preparation in accordance with the following methods: under nitrogen protection, by the first compound and the second compound, after reaction, obtain the first product, described the first compound has formula 10) structure, described the second compound is 2,4-toluene diisocyanate, diphenylmethanediisocyanate, benzene two methylene vulcabond, hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexyl methane diisocyanate;
H-R '-H formula 10)
R ' is suc as formula 8) or formula 9) shown in,
formula 8)
formula 9)
N is that 1～50, m is 1～50;
Under the katalysis of dibutyl tin laurate, described the first product, TriMethylolPropane(TMP) are reacted in solvent, obtain the second product;
Described the second product is reacted in solvent with N methyldiethanol amine, obtain third product;
By third product and glycol reaction, add trifluoroacetic acid after adding deionized water emulsification, after reaction, obtain described waterborne polyurethane resin.
2. a preparation method for waterborne polyurethane resin, comprises the following steps:
Under nitrogen protection, by the first compound and the second compound, after reaction, obtain the first product, described the first compound has formula 10) structure, described the second compound is 2,4-toluene diisocyanate, diphenylmethanediisocyanate, benzene two methylene vulcabond, hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexyl methane diisocyanate;
H-R '-H formula 10)
R ' is suc as formula 8) or formula 9) shown in,
formula 8)
formula 9)
N is that 1～50, m is 1～50;
Under the katalysis of dibutyl tin laurate, described the first product, TriMethylolPropane(TMP) are reacted in solvent, obtain the second product;
Described the second product is reacted in solvent with N methyldiethanol amine, obtain third product;
By third product and glycol reaction, add trifluoroacetic acid after adding deionized water emulsification, after reaction, obtain waterborne polyurethane resin.
3. preparation method according to claim 2, is characterized in that, described the first compound is that molecular weight is that 232～8660 daltonian polyethylene glycol adipates or molecular weight are 260～8690 daltonian poly butylene succinates.
4. a Waterborne Polyaniline Corrosion Protection Coatings, comprises following composition:
5. Waterborne Polyaniline Corrosion Protection Coatings according to claim 4, is characterized in that, described waterborne conductive polyaniline is suc as formula 11) shown in:
formula 11)
Wherein, y is that 0～1, p is 1～500.
6. a preparation method for Waterborne Polyaniline Corrosion Protection Coatings, comprises the following steps:
Step a) is mixed the waterborne conductive polyaniline of the deionized water of the waterborne film-forming solubility promoter of the waterborne polyurethane resin claimed in claim 1 of 12～25 weight parts, 1～5 weight part, 20～30 weight parts and 0.2～3 weight part, sand milling 1.5～3 hours after stirring;
Step b), under agitation condition, adds the filler of 5～25 weight parts, pigment, the defoamer of 0.5～2 weight part and the aqueous dispersant of 0.2～3 weight part of 26～45 weight parts, and sand milling filtered after 3～5 hours, obtained Waterborne Polyaniline Corrosion Protection Coatings.
7. preparation method according to claim 6, is characterized in that, described waterborne film-forming solubility promoter is butyl glycol ether, Diethylene Glycol butyl ether or propylene glycol.
8. preparation method according to claim 6, is characterized in that, described waterborne conductive polyaniline is suc as formula 11) shown in:
formula 11)
Wherein, y is that 0～1, p is 1～500.
9. preparation method according to claim 6, is characterized in that,
Described filler is one or more in talcum powder, process white and calcium carbonate;
Described pigment is aluminium dihydrogen tripolyphosphate and/or iron mica.
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| CN103193957B (en) * | 2013-03-20 | 2015-05-20 | 中国科学院长春应用化学研究所 | Waterborne polyurethane, waterborne antistatic coating composition and preparation method thereof |
| CN105576285B (en) * | 2015-10-15 | 2018-04-03 | 安徽大学 | A kind of lithium ion battery anode glue size and its aqueous polyurethane/polyaniline bonding agent |
| CN107201158B (en) * | 2017-06-16 | 2019-05-24 | 邢台学院 | A kind of nano-material modified aqueous polyurethane anticorrosive paint and preparation method thereof |
| CN107325702B (en) * | 2017-07-24 | 2020-05-15 | 安徽省炫科新材料科技有限公司 | Single-component high-corrosion-resistance waterborne polyurethane coating and preparation method thereof |
| CN112625591B (en) * | 2020-10-20 | 2022-02-11 | 兰州理工大学 | High-stability multifunctional conductive super-hydrophobic anticorrosive coating, preparation method and application |
| CN116042073B (en) * | 2023-02-10 | 2024-03-26 | 中国科学院长春应用化学研究所 | Carbon dioxide-based waterborne polyurethane rust conversion resin and preparation method thereof |
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| CN1215744A (en) * | 1997-10-25 | 1999-05-05 | 中国科学院长春应用化学研究所 | Method for preparing conductive antifouling corrosion-resistant poly-aniline paint |
| CN101407650A (en) * | 2008-11-24 | 2009-04-15 | 中国科学院长春应用化学研究所 | UV curing polyaniline anti-corrosive paint and preparation thereof |
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| CN1215744A (en) * | 1997-10-25 | 1999-05-05 | 中国科学院长春应用化学研究所 | Method for preparing conductive antifouling corrosion-resistant poly-aniline paint |
| CN101407650A (en) * | 2008-11-24 | 2009-04-15 | 中国科学院长春应用化学研究所 | UV curing polyaniline anti-corrosive paint and preparation thereof |
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