CN102702467A - 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 the 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; The protective system field seriously relies on heavy metal or poisonous and harmful metallic elements such as lead, chromium such as zinc powder; But global zinc reserves are merely 2.2 hundred million tons, wherein consumed 1,157 ten thousand tons (3,170,000 tons in China) in 2007, thereby global reserves only can use 19 years (domestic only can the use 10 years).On the other hand, it is very big to environmental hazard to apply the protective system contain the poisonous and harmful metallic element, in case and coating have slightly and scratch, its preservative effect then reduces greatly.Therefore, the development protective system that do not rely on zinc powder and do not have a poisonous and harmful metallic element becomes following a kind of development trend of protective system.
Polyaniline anti-corrosive paint does not rely on zinc powder and poisonous and harmful metal, is the excellent coating of one type of antiseptic property.Abroad, German Ormecon company and Finland Panipol company 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 big novel material of the Hunan Ben Anya ltd of domestic Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences's technical support has 5000 tonnes of coating material production lines, indicates the scale operation of domestic polyaniline anti-corrosive paint.Yet above-mentioned wide coverage and the polyaniline anti-corrosive paint of producing are solvent based coating, contain organic solvents such as a large amount of benzene, YLENE, in use can cause great bodily injury to operator ' s health, simultaneously environment are brought huge pollution.
Compare with traditional organic solvent, environment-friendly type aqueous polyaniline anti-corrosive paint is a thinner with water, has eliminated organic discharging, is expected to become one type of ideal protective system.At present; The polyaniline anti-corrosive paint of being reported is mostly for two-pack, and for example, application number is that 01138153.1,200710047366.4,200610029482.9 and 98116978.3 Chinese patent document has been reported polyaniline anti-corrosive paint respectively; With the epoxy resin that contains the polyaniline additive is the A component; With polymeric amide or phenolic aldehyde amine is solidifying agent B component, before the construction, two kinds of components mixing is constructed.But there is construction short shortcoming 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 that the present invention will solve 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 present invention provides a kind of formula 1) shown in waterborne polyurethane resin:
Formula 1)
R is a kind of in the 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,
Wherein, n is 1 ~ 50, and m is 1 ~ 50.
Accordingly, the present invention also provides a kind of preparation method of waterborne polyurethane resin, may further comprise the steps:
Under nitrogen protection; With first compound and second compound; Obtain first product after the reaction; Said first compound has formula 10) structure, said 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,
N is 1 ~ 50, and m is 1 ~ 50;
Under the katalysis of dibutyl tin laurate, said first product, TriMethylolPropane(TMP) are reacted in solvent, obtain second product;
Said second product and N methyldiethanol amine are reacted in solvent, obtain third product;
With third product and glycol reaction, add trifluoroacetic acid after the emulsification of adding deionized water, obtain waterborne polyurethane resin after the reaction.
Preferably, said 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:
Described waterborne polyurethane resin 12 ~ 25 weight parts of 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;
Skimmer 0.5 ~ 2 weight part;
Aqueous dispersant 0.2 ~ 3 weight part.
Preferably, said waterborne conductive polyaniline is suc as formula 11) shown in:
Wherein, y is 0 ~ 1, and p is 1 ~ 500.
Accordingly, the present invention also provides a kind of preparation method of Waterborne Polyaniline Corrosion Protection Coatings, may further comprise the steps:
Step a) is mixed the waterborne film-forming solubility promoter of the described waterborne polyurethane resin of the claim 1 of 12 ~ 25 weight parts, 1 ~ 5 weight part, the deionized water of 20 ~ 30 weight parts and the waterborne conductive polyaniline of 0.2 ~ 3 weight part, stirs the back sand milling 1.5 ~ 3 hours;
Step b) adds filler, the pigment of 26 ~ 45 weight parts, the skimmer of 0.5 ~ 2 weight part and the aqueous dispersant of 0.2 ~ 3 weight part of 5 ~ 25 weight parts under agitation condition, 3 ~ 5 hours after-filtration of sand milling obtain water-based anticorrosive paint.
Preferably, said waterborne film-forming solubility promoter is butyl glycol ether, Diethylene Glycol butyl ether or Ucar 35.
Preferably, said waterborne conductive polyaniline is suc as formula 11) shown in:
Wherein, y is 0 ~ 1, and p is 1 ~ 500.
Preferably, said filler is one or more in talcum powder, process white and the lime carbonate; Said pigment is aluminium dihydrogen tripolyphosphate and/or iron mica.
The invention provides waterborne polyurethane resin and preparation method thereof; This waterborne polyurethane resin with polyethylene glycol adipate or poly butylene succinate as soft section; And introduce the internal crosslinker TriMethylolPropane(TMP); Thereby after utilizing this waterborne polyurethane resin to form water-based anticorrosive paint, can form inierpeneirating network structure, help giving full play to the antiseptic property of polyaniline through hydrogen bond and aqueous polyanion.What is more important because the introducing of internal crosslinker TriMethylolPropane(TMP) in the waterborne polyurethane resin need not two-pack be solidified the single component self-supported membrane that just can form excellent performance, helps having formed 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, skimmer and aqueous dispersant.Wherein, The redox potential of waterborne conductive polyaniline is higher than the redox potential of iron far away; Make the surface of iron and steel that oxidation take place; Between steel surface and electrically conductive polyaniline, generate one deck compact metal sull, make the electropotential of iron be in passivation region, prevented the further corrosion of iron and steel.
Compared with prior art; The waterborne polyurethane resin that the present invention adopts with polyethylene glycol adipate or poly butylene succinate as soft section; And introduce the internal crosslinker TriMethylolPropane(TMP); Make this aqueous polyurethane and aqueous polyanion form inierpeneirating network structure, help giving full play to the antiseptic property of polyaniline through hydrogen bond.What is more important because the introducing of internal crosslinker TriMethylolPropane(TMP) need not two-pack be solidified the single component self-supported membrane that just can form excellent performance, has guaranteed to have formed mono-component aqueous polyaniline anti-corrosive paint system and has had good preservative effect.
Description of drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum of the waterborne polyurethane resin of the embodiment of the invention 1 preparation.
Embodiment
Carry out clear, intactly description in the face of the technical scheme in the embodiment of the invention down, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
Of the present invention a kind of formula 1 is provided) shown in waterborne polyurethane resin:
Formula 1)
R is a kind of in the 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,
Wherein, n is 1 ~ 50, and m is 1 ~ 50.
Accordingly; The present invention also provides a kind of preparation method of above-mentioned waterborne polyurethane resin, may further comprise the steps: under nitrogen protection, with first compound and second compound; Obtain first product after the reaction; Said first compound has formula 10) structure, said 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,
N is 1 ~ 50, and m is 1 ~ 50;
Under the katalysis of dibutyl tin laurate, said first product, TriMethylolPropane(TMP) are reacted in solvent, obtain second product; Said second product and N methyldiethanol amine are reacted in solvent, obtain third product; With third product and glycol reaction, add trifluoroacetic acid after the emulsification of adding deionized water, obtain waterborne polyurethane resin after the reaction.
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 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 for preparing first product is specially: under nitrogen protection, first compound is warming up to 80 ~ 100 ℃; More preferably 90 ℃, second compound is dropped in first compound, obtain first product after the reaction; Rate of addition is preferably 10 ~ 30ml/min; 15 ~ 20ml/min more preferably, the reaction times is preferably 1 ~ 5 hour, more preferably 2 ~ 3 hours.
After preparing first product, preferably said first product is cooled to 70 ℃, reacts in solvent with TriMethylolPropane(TMP) then.As preferred version, the step that obtains second product is specially: in first product, add butanone, TriMethylolPropane(TMP) and dibutyl tin laurate successively, obtain second product after the 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; With polyethylene glycol adipate or poly butylene succinate as soft section; And introduce the internal crosslinker TriMethylolPropane(TMP); Thereby after utilizing this waterborne polyurethane resin to form water-based anticorrosive paint, can form inierpeneirating network structure, help giving full play to the antiseptic property of polyaniline through hydrogen bond and aqueous polyanion.What is more important because the introducing of internal crosslinker TriMethylolPropane(TMP) need not two-pack be solidified the single component self-supported membrane that just can form excellent performance, helps having formed mono-component aqueous polyaniline anti-corrosive paint system.
After obtaining second product, said second product and N methyldiethanol amine are reacted in solvent, introduce hydrophilic radical, obtain third product, said 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: with adding butanone in second product, be cooled to 20 ~ 40 ℃; Be preferably 30 ℃, drip N methyldiethanol amine, rate of addition is preferably 3 ~ 8ml/mim; 5ml/mim more preferably; Obtain third product after the reaction, preferred 0.5 ~ 2 hour of reaction times, more preferably 0.5 hour.
The step that obtains waterborne polyurethane resin at last is specially: third product is warming up to 60 ~ 70 ℃, is preferably 65 ℃, add chainextender terepthaloyl moietie; Reacted 1 ~ 3 hour; Add trifluoroacetic acid after adding deionized water emulsification, be used for amino with hydrophilic radical carry out in and salify, obtain waterborne polyurethane resin after the reaction; Said 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 as soft section, and is introduced the internal crosslinker TriMethylolPropane(TMP) with polyethylene glycol adipate or poly butylene succinate, thereby after utilizing this waterborne polyurethane resin to form water-based anticorrosive paint; Can form inierpeneirating network structure through hydrogen bond and aqueous polyanion, help giving full play to the antiseptic property of polyaniline.What is more important because the introducing of internal crosslinker TriMethylolPropane(TMP) in the waterborne polyurethane resin need not two-pack be solidified the single component self-supported membrane that just can form excellent performance, helps having formed 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: described waterborne polyurethane resin 12 ~ 25 weight parts of 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; Skimmer 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 a kind of in the 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,
Wherein, n is 1 ~ 50, and m is 1 ~ 50.
Said waterborne conductive polyaniline is preferably suc as formula 11) shown in:
Wherein, y is 0 ~ 1, and 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 SULPHOSUCCINIC ACID ESTER in the aqueous polyanion can with the Fe in the iron
2+Form insoluble mixture resist, make metal surface passivation, further strengthen preservative property.In addition; The redox potential of waterborne conductive polyaniline (0.5 ~ 0.7V vs.SCE); The redox potential (0.64V vs.SCE) that is higher than iron far away makes the surface of iron and steel that oxidation take place, and between steel surface and electrically conductive polyaniline, generates one deck compact metal sull; Thereby make the electropotential of iron be in passivation region, prevented the further corrosion of iron and steel.
The aqueous polyanion that the present invention adopts is preferably according to following method preparation: with formula 12) the polyaniline in eigenstate powder of structure mixes with the SULPHOSUCCINIC ACID ESTER doping agent; After the reaction; Obtain aqueous polyanion, said SULPHOSUCCINIC ACID ESTER doping agent is a formula 13) and formula 14) shown in compound.The present invention does not have special restriction to the manufacturer of said SULPHOSUCCINIC ACID ESTER doping agent, can adopt method preparation well known to those skilled in the art, perhaps adopts the product of knowing producer.
Formula 12)
Formula 13) formula 14).
According to the present invention, said waterborne film-forming solubility promoter is preferably butyl glycol ether, Diethylene Glycol butyl ether or Ucar 35; Said filler is preferably one or more in talcum powder, process white and the lime carbonate; Said 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; May further comprise the steps: step a) is mixed the waterborne film-forming solubility promoter of the described waterborne polyurethane resin of the technique scheme of 12 ~ 25 weight parts, 1 ~ 5 weight part, the deionized water of 20 ~ 30 weight parts and the waterborne conductive polyaniline of 0.2 ~ 3 weight part, stirs the back sand milling 1.5 ~ 3 hours; Step b) adds filler, the pigment of 26 ~ 45 weight parts, the skimmer of 0.5 ~ 2 weight part and the aqueous dispersant of 0.2 ~ 3 weight part of 5 ~ 25 weight parts under agitation condition, 3 ~ 5 hours after-filtration of sand milling obtain Waterborne Polyaniline Corrosion Protection Coatings.
As preferred version; Said step a) is specially: the waterborne film-forming solubility promoter of the described urethane resin of the technique scheme of 12 ~ 25 weight parts, 1 ~ 5 weight part and the deionized water of 20 ~ 30 weight parts are added in the sand mill jar, 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 among the present invention uses crystallinity polyethylene glycol adipate soft section as aqueous polyurethane; And introduced the internal crosslinker TriMethylolPropane(TMP); Make this aqueous polyurethane to form hydrogen bond with aqueous polyanion; Make the two to form inierpeneirating network structure well, help giving 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 is because the introducing of internal crosslinker need not two-pack curing just can form the single component self-supported membrane of excellent performance, thereby form mono-component aqueous polyaniline anti-corrosive paint system.
Said step b) is specially: under agitation condition; The filler, the pigment of 26 ~ 45 weight parts, the skimmer of 0.5 ~ 2 weight part and the aqueous dispersant of 0.2 ~ 3 weight part that add 5 ~ 25 weight parts; Sand milling 3 ~ 5 hours utilizes 200 purpose filter clothes to filter, and obtains water-based anticorrosive paint; Said stirring velocity is preferably 1500 ~ 3000rpm, more preferably 2500rpm.
Said waterborne conductive polyaniline is suc as formula 11) shown in:
Wherein, y is 0 ~ 1, and p is 1 ~ 500.
The waterborne conductive polyaniline is preferably the form of nano-dispersed aqueous polyanion powder; Can be dispersed in the waterborne polyurethane resin; Because waterborne polyurethane resin is a resin cation(R.C.), thereby can not cause the particle of aqueous polyanion to become big, thereby form the Waterborne Polyaniline Corrosion Protection Coatings of nano-dispersed.In addition, the gegenion SULPHOSUCCINIC ACID ESTER in the aqueous polyanion can with the Fe in the iron
2+Form insoluble mixture resist, make metal surface passivation, further strengthened preservative property.
According to the present invention, said waterborne film-forming solubility promoter is butyl glycol ether, Diethylene Glycol butyl ether or Ucar 35; Said filler is one or more in talcum powder, process white and the lime carbonate; Said pigment is aluminium dihydrogen tripolyphosphate and/or iron mica.
As preferred version, the present invention prepares the raw material that adopts in the Waterborne Polyaniline Corrosion Protection Coatings and is preferably: described waterborne polyurethane resin 15 ~ 20 weight parts of 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; Skimmer 0.5 ~ 1.5 weight part; Aqueous dispersant 0.2 ~ 2 weight part.
After preparing Waterborne Polyaniline Corrosion Protection Coatings, Waterborne Polyaniline Corrosion Protection Coatings is sprayed on the metal foil of polishing, oil removing, rust cleaning, 60 ℃ of following levellings 3 minutes, drying at room temperature 5 days is surveyed its performance behind the film curing.
Waterborne Polyaniline Corrosion Protection Coatings provided by the invention has following characteristics: (1) mono-component aqueous polyaniline anti-corrosive paint provided by the invention, there is not the problem of working life, and have long, easy to use characteristics of construction time.(2) compare with traditional protective system, the present invention is a nano-dispersed type polyaniline anti-corrosive paint, and the polyaniline consumption is few, and addition is merely 0.2 ~ 3wt%, when having excellent preservative effect, greatly reduces the cost of protective system.(3) compare with traditional solvent-borne type protective system, aqueous polyanion protective system of the present invention makes it have eco-friendly characteristics, is a kind of environmental type coating.
In order to further specify technical scheme of the present invention; Below in conjunction with embodiment the preferred embodiment of the invention is described; Describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The chemical reagent that the embodiment of the invention and comparative example adopt is commercial.
BYK163 described in embodiment and the comparative example and BYKP 105 are the dispersion agent of Bi Ke company, and BYK055, BYK088 and BYK067A are the skimmer of Bi Ke company.Said polyaniline in eigenstate is the product that the big novel material of Hunan Ben Anya ltd produces, and the polyaniline in eigenstate molecular weight is 110000 dalton.
Embodiment 1
Under the drying nitrogen protection, the 2000 dalton's polyethylene glycol adipates of the 200g molecular weight after the vacuum hydro-extraction to be put in the there-necked flask, temperature rises to 90 ℃; Speed with 15ml/min drips 2 of 87g, and the 4-toluene diisocyanate is after dropwising; Continue reaction 2h, obtain first product;
First product is cooled to 70 ℃, adds the butanone of 150ml, add the dibutyl tin laurate of 13.4g TriMethylolPropane(TMP) and 0.0001g then, continue reaction 1.5h, obtain second product;
With adding the 100ml butanone in second product, cool to 30 ℃, 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 ℃, adds 20.5g terepthaloyl moietie, reaction 2h adds the 200ml deionized water and carries out emulsification 20min, then, adds the trifluoroacetic acid of 6.7g, and last, butanone is removed in decompression, obtains waterborne polyurethane resin.
Aqueous polyurethane tree to the present embodiment preparation carries out the nucleus magnetic hydrogen spectrum analysis, and as shown in Figure 1, the 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) the SULPHOSUCCINIC ACID ESTER doping agent of structure is preferably according to following method preparation:
The 42g Vanadium Pentoxide in FLAKES is added the 150ml tetracol phenixin that is dissolved with the 36g ethylene glycol monomethyl ether,, be warmed up to 60 ℃ of reaction 4h for adding in the 1h; Add 10g water and 21g gac, behind 80 ℃ of reaction 1h, filter; Reduce pressure away after the organic reagent, obtain formula 13) the SULPHOSUCCINIC ACID ESTER doping agent of structure.
Formula 14) the SULPHOSUCCINIC ACID ESTER doping agent of structure is preferably according to following method preparation:
The adding of 56g Vanadium Pentoxide in FLAKES is dissolved with in the 300ml tetracol phenixin of 145g ethylene glycol monomethyl ether, adds in the 2h, be warmed up to 70 ℃ of reaction 5h; Add 32g water and 41g gac, behind 90 ℃ of reaction 2h, filter; Reduce pressure away after the organic reagent, obtain formula 14) the SULPHOSUCCINIC ACID ESTER doping agent of structure.
Formula 13 with the above-mentioned preparation of 100g) formula 14 of the SULPHOSUCCINIC ACID ESTER doping agent of structure, the above-mentioned preparation of 100g) SULPHOSUCCINIC 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;
It is centrifugal to utilize supercentrifuge that the aqueous polyanion dispersion liquid that obtains is carried out, centrifugal with 5000 rev/mins speed, with the powder that obtains 45 ℃ of dryings 72 hours in vacuum drying oven, obtains the waterborne conductive polyaniline powder.
Embodiment 3
Waterborne polyurethane resin, 1 gram Ucar 35 and the 20 gram deionized waters of 12 gram embodiment, 1 preparation are joined in the sand mill jar; Speed with 2000rpm stirs down; Add the waterborne conductive polyaniline powder of 0.2 gram embodiment, 2 preparations, continue to stir 0.5 hour, sand milling is 1.5 hours then.
Then; Speed with 2500rpm stirs down; Add 3 gram talcum powder, 1.5 gram process whites and 0.5 gram lime carbonate, 26 gram aluminium dihydrogen tripolyphosphates and 19 gram iron micas, 0.5 gram BYK055 and 0.2 gram BYK163; Continued sand milling 3 hours, and filtered, obtain aqueous polyanion coating with 200 purpose filter clothes.
With paint spay-coating on the metal foil of polishing, oil removing, rust cleaning, 60 ℃ of following levellings 3 minutes, drying at room temperature 5 days is surveyed its performance behind the film curing, performance is seen table 1.
Waterborne polyurethane resin, 5 gram butyl glycol ethers and the 30 gram deionized waters of 25 gram embodiment, 1 preparation are joined in the sand mill jar; Speed with 2000rpm stirs down; Add the waterborne conductive polyaniline powder of 3 gram embodiment, 2 preparations, continue to stir 1 hour, sand milling is 3 hours then.
Then; Speed with 2500rpm stirs down; Add 13 gram talcum powder, 10 gram process whites and 2 gram lime carbonate, 16 gram aluminium dihydrogen tripolyphosphates and 10 gram iron micas, 2 gram BYK088 and 3 gram BYKP 105; Continued sand milling 5 hours, and filtered, obtain aqueous polyanion coating with 200 purpose filter clothes.
With paint spay-coating on the metal foil of polishing, oil removing, rust cleaning, 60 ℃ of following levellings 3 minutes, drying at room temperature 5 days is surveyed its performance behind the film curing, performance is seen table 1.
Embodiment 5
Waterborne polyurethane resin, 3 gram Diethylene Glycol butyl ether and the 25 gram deionized waters of 21 gram embodiment, 1 preparation are joined in the sand mill jar; Speed with 2000rpm stirs down; Add the waterborne conductive polyaniline powder of 0.8 gram embodiment, 2 preparations, continue to stir 0.5 hour, sand milling is 2.5 hours then.
Then; Speed with 2500rpm stirs down; Add 5 gram talcum powder, 2.5 gram process whites and 1.5 gram lime carbonate, 6 gram aluminium dihydrogen tripolyphosphates and 22 gram iron micas, 1.5 gram BYK055 and 1.2 gram BYK163; Continued sand milling 4 hours, and filtered, obtain aqueous polyanion coating with 200 purpose filter clothes.
With paint spay-coating on the metal foil of polishing, oil removing, rust cleaning, 60 ℃ of following levellings 3 minutes, drying at room temperature 5 days is surveyed its performance behind the film curing, performance is seen table 1.
Waterborne polyurethane resin, 3 gram Ucar 35 and the 23 gram deionized waters of 18 gram embodiment, 1 preparation are joined in the sand mill jar; Speed with 2000rpm stirs down; Add the waterborne conductive polyaniline powder of 1.5 gram embodiment, 2 preparations, continue to stir 1 hour, sand milling is 2 hours then.
Then; Speed with 2500rpm stirs down; Add 13 gram talcum powder, 0.5 gram process white and 1.5 gram lime carbonate, 12 gram aluminium dihydrogen tripolyphosphates and 15 gram iron micas, 1 gram BYK067A and 2 gram BYKP 105; Continued sand milling 3 hours, and filtered, obtain aqueous polyanion coating with 200 purpose filter clothes.
With paint spay-coating on the metal foil of polishing, oil removing, rust cleaning, 60 ℃ of following levellings 3 minutes, drying at room temperature 5 days is surveyed its performance behind the film curing, performance is seen table 1.
Embodiment 7
Waterborne polyurethane resin, 4 gram butyl glycol ethers and the 25 gram deionized waters of 23 gram embodiment, 1 preparation are joined in the sand mill jar; Speed with 2000rpm stirs down; Add the waterborne conductive polyaniline powder of 1.8 gram embodiment, 2 preparations, continue to stir 1 hour, sand milling is 3 hours then.
Then; Speed with 2500rpm stirs down; Add 9 gram talcum powder, 2.5 gram process whites and 6.5 gram lime carbonate, 15 gram aluminium dihydrogen tripolyphosphates and 22 gram iron micas, 1.5 gram BYK055 and 2.2 gram BYK163; Continued sand milling 5 hours, and filtered, obtain aqueous polyanion coating with 200 purpose filter clothes.
With paint spay-coating on the metal foil of polishing, oil removing, rust cleaning, 60 ℃ of following levellings 3 minutes, drying at room temperature 5 days is surveyed its performance behind the film curing, performance is seen table 1.
Comparative example 1
Waterborne polyurethane resin, 1.5 gram butyl glycol ethers and the 25 gram deionized waters of 15 gram embodiment, 1 preparation are joined in the sand mill jar; Speed with 2500rpm stirs down; Add 3.5 gram talcum powder, 1 gram process white and 0.5 gram lime carbonate, 25 gram aluminium dihydrogen tripolyphosphates, 18 gram iron micas, 0.7 gram BYK055 and 0.3 gram BYK163; Continued sand milling 3 hours, and filtered, obtain water-based anticorrosive paint with 200 purpose filter clothes.
With paint spay-coating on the metal foil of polishing, oil removing, rust cleaning, 60 ℃ of following levellings 3 minutes, drying at room temperature 5 days is surveyed its performance behind the film curing, performance is seen table 1.
The paint film property test result that the water-based anticorrosive paint of table 1 embodiment and comparative example preparation forms
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (9)
1. the waterborne polyurethane resin formula 1):
Formula 1)
R is a kind of in the 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)
Wherein, n is 1 ~ 50, and m is 1 ~ 50.
2. the preparation method of a waterborne polyurethane resin may further comprise the steps:
Under nitrogen protection; With first compound and second compound; Obtain first product after the reaction; Said first compound has formula 10) structure, said 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 9)
N is 1 ~ 50, and m is 1 ~ 50;
Under the katalysis of dibutyl tin laurate, said first product, TriMethylolPropane(TMP) are reacted in solvent, obtain second product;
Said second product and N methyldiethanol amine are reacted in solvent, obtain third product;
With third product and glycol reaction, add trifluoroacetic acid after the emulsification of adding deionized water, obtain waterborne polyurethane resin after the reaction.
3. preparation method according to claim 2 is characterized in that, said 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. Waterborne Polyaniline Corrosion Protection Coatings comprises following composition:
Described waterborne polyurethane resin 12 ~ 25 weight parts of 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;
Skimmer 0.5 ~ 2 weight part;
Aqueous dispersant 0.2 ~ 3 weight part.
5. Waterborne Polyaniline Corrosion Protection Coatings according to claim 4 is characterized in that, said waterborne conductive polyaniline is suc as formula 11) shown in:
Wherein, y is 0 ~ 1, and p is 1 ~ 500.
6. the preparation method of a Waterborne Polyaniline Corrosion Protection Coatings may further comprise the steps:
Step a) is mixed the waterborne film-forming solubility promoter of the described waterborne polyurethane resin of the claim 1 of 12 ~ 25 weight parts, 1 ~ 5 weight part, the deionized water of 20 ~ 30 weight parts and the waterborne conductive polyaniline of 0.2 ~ 3 weight part, stirs the back sand milling 1.5 ~ 3 hours;
Step b) adds filler, the pigment of 26 ~ 45 weight parts, the skimmer of 0.5 ~ 2 weight part and the aqueous dispersant of 0.2 ~ 3 weight part of 5 ~ 25 weight parts under agitation condition, 3 ~ 5 hours after-filtration of sand milling obtain Waterborne Polyaniline Corrosion Protection Coatings.
7. preparation method according to claim 6 is characterized in that, said waterborne film-forming solubility promoter is butyl glycol ether, Diethylene Glycol butyl ether or Ucar 35.
8. preparation method according to claim 6 is characterized in that, said waterborne conductive polyaniline is suc as formula 11) shown in:
Wherein, y is 0 ~ 1, and p is 1 ~ 500.
9. preparation method according to claim 6 is characterized in that,
Said filler is one or more in talcum powder, process white and the lime carbonate;
Said pigment is aluminium dihydrogen tripolyphosphate and/or iron mica.
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| CN103193957A (en) * | 2013-03-20 | 2013-07-10 | 中国科学院长春应用化学研究所 | Waterborne polyurethane, waterborne antistatic coating composition and preparation method thereof |
| CN105576285A (en) * | 2015-10-15 | 2016-05-11 | 安徽大学 | Lithium ion battery positive electrode paste and waterborne polyurethane/polyaniline adhesive thereof |
| CN107201158A (en) * | 2017-06-16 | 2017-09-26 | 邢台学院 | A kind of nano-material modified aqueous polyurethane anticorrosive paint and preparation method thereof |
| CN107325702A (en) * | 2017-07-24 | 2017-11-07 | 合肥思敬齐化工材料有限责任公司 | A kind of high anticorrosion water-soluble polyurethane coating of one-component and preparation method thereof |
| CN112625591A (en) * | 2020-10-20 | 2021-04-09 | 兰州理工大学 | High-stability multifunctional conductive super-hydrophobic anticorrosive coating, preparation method and application |
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| CN103193957A (en) * | 2013-03-20 | 2013-07-10 | 中国科学院长春应用化学研究所 | Waterborne polyurethane, waterborne antistatic coating composition and preparation method thereof |
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| CN107201158A (en) * | 2017-06-16 | 2017-09-26 | 邢台学院 | A kind of nano-material modified aqueous polyurethane anticorrosive paint and preparation method thereof |
| 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 |
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| CN112625591A (en) * | 2020-10-20 | 2021-04-09 | 兰州理工大学 | High-stability multifunctional conductive super-hydrophobic anticorrosive coating, preparation method and application |
| CN116042073A (en) * | 2023-02-10 | 2023-05-02 | 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 |
| 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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