CN105778046A - Waterborne polyurethane as well as preparation method and application thereof - Google Patents
Waterborne polyurethane as well as preparation method and application thereof Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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Abstract
The invention provides waterborne polyurethane. The waterborne polyurethane provided by the invention contains an R2 structure, so that when a membrane-forming agent prepared by utilizing waterborne polyurethane as a raw material is applied to preparation of an anticorrosive paint, a membrane of the obtained anticorrosive paint has relatively high pencil hardness and is relatively compact, so that the non-corrosibility is improved.
Description
Technical field
The present invention relates to anticorrosive paint field, particularly relate to a kind of aqueous polyurethane and its preparation method and application.
Background technology
Metal erosion problem, throughout all departments of national economy, causes significant damage to the national economic development.Countries in the world all carry out corrosion protection in the actively various technology of searching.Polyaniline is a kind of high-tech new material with specific function, since DeBerry in 1985 finds that the polyaniline film synthesized by electrochemical process in acid medium can make stainless steel surfaces active passivation have antiseptic property, blended to itself and film-forming resin composite coating of preparing into, as a kind of important anti-corrosion material, has been become the focus of anticorrosive paint research field by polyaniline.
Increasingly serious now with environmental problem, the research of environment-friendly coating is paid attention to, and the clearer production technology of environment-friendly coating is also increasingly subject to the favor of people.Ultraviolet-heat dual curing coating is a kind of brand-new environmental type coating of the exploitation sixties in 20th century, has efficient, energy-conservation advantage.The preparation method that patent 200810051576.5 discloses a kind of ultraviolet-heat dual curing polyaniline anti-corrosive paint, its core technology is as anti-corrosion material additive using polyaniline, join in ultraviolet-heat dual curing resin system and be prepared from, but, this coating system to use the substantial amounts of reactive diluent with intense stimulus, human body skin can be caused damage by the process of construction, environment is brought pollution.Patent 201210192961.8 discloses a kind of waterborne ultraviolet-heat dual curing coating composite and preparation method thereof.This coating is using aqueous polyurethane acrylate and the waterborne polyurethane resin containing hydroxyl as the film-forming resin component of polyaniline anti-corrosive paint, add aqueous polyisocyanate curing agent component, aqueous polyanion is as anti-corrosion material additive, wherein aqueous polyurethane acrylate component completes ultraviolet light polymerization through ultraviolet light polymerization, aqueous polyurethane containing hydroxyl and aqueous polyisocyanate curing agent are under heating state, complete curing process, thus being finally completed waterborne ultraviolet-heat dual curing process, owing to being Waterborne Polyaniline Corrosion Protection Coatings system, thus, without any volatile organic solvent and reactive diluent monomer, decrease environmental pollution, it it is a kind of real environmental protection ultraviolet-heat polyaniline anti-corrosive paint.But, the aqueous film-forming resin used in this patent is aqueous polyurethane acrylate and the aqueous polyurethane containing hydroxyl, thus, both water-base resins are in carrying out ultraviolet light polymerization and curing process, and both film forming matters cannot really become a phase, it may occur that microphase-separated, define the two-layer paint film that cannot merge, add the roughness of paint film so that the compactness of anticorrosion paint film declines, and reduces the antiseptic property of paint film.Therefore, seek a kind of not only environmental friendliness but also polyaniline anti-corrosive paint that antiseptic property is good is to be presently required to solve the technical problem that.And, in these two patents of invention above-mentioned, the raw material of the film-forming resin of use is both from petrochemical, thus, anticorrosive paint preparation still depends critically upon fossil resources, does not have sustainable development.
Summary of the invention
In view of this, the technical problem to be solved is in that to provide a kind of aqueous polyurethane and its preparation method and application, the anticorrosive paint that aqueous polyurethane provided by the invention prepares not only environmental friendliness, and antiseptic property is good.
The invention provides a kind of aqueous polyurethane, there is formula (II) structure,
Wherein, described R1Alkylidene for the arlydene of C6～C35, the cycloalkylidene of C5～C30 or C3～C12；
Described H-R2-H has formula (I) structure,
Wherein, 1≤m≤30,1≤n≤35,1≤x≤30,1≤y≤35；
Described R3For halogen or the structure with formula (b),
Wherein, described RbHaloalkyl for the alkyl of C1～C5 or C1～C5；
Described z is 2～10.
Preferably, described R1Alkylidene for the arlydene of C10～C20, the cycloalkylidene of C10～C20 or C4～C8.
Preferably, described R1For propylidene, sub-normal-butyl, sub-n-pentyl, sub-n-hexyl, sub-n-heptyl, sub-n-octyl, formula (a-1), formula (a-2), formula (a-3) or formula (a-4),
Preferably, described R3For fluorine, chlorine, formula (b-1), formula (b-2) or formula (b-3),
The preparation method that present invention also offers a kind of aqueous polyurethane, including:
1) will have the H-R of formula (I) structure2-H、ONC-R1-CNO and solvent hybrid reaction, obtain the first reactant mixture；
Wherein, 1≤m≤30,1≤n≤35,1≤x≤30,1≤y≤35；
Described R1Alkylidene for the arlydene of C6～C35, the cycloalkylidene of C5～C30 or C3～C12；
2) by the first reactant mixture, hydrophilic chain extender and catalyst reaction, the second reactant mixture is obtained,
Described hydrophilic chain extender is N methyldiethanol amine；
3) glycol of the second reactant mixture with C2～C10 is reacted, use R3-H neutralizes, and obtains the aqueous polyurethane with formula (II) structure,
Described R3R in-H3For halogen or the structure with formula (b),
Wherein, described RbHaloalkyl for the alkyl of C1～C5 or C1～C5；
Preferably, described step 1) in solvent be one or more in acetone, butanone or pentanone.
Preferably, described step 2) in catalyst be one or more in dibutyl tin laurate, stannous octoate or organic carboxyl acid bismuth.
Preferably, described step 2) temperature reacted is 30～40 DEG C.
Preferably, the H-R of described formula (I) structure2-H prepares in accordance with the following methods:
By reacting containing the expoxy propane of maleic anhydride, carbon dioxide and catalyst mix, obtain the H-R with formula (I) structure1-H。
Present invention also offers a kind of optical and thermal dual curing polyaniline anticorrosive paint, including: waterborne conductive polyaniline, aqueous film-forming resin and adjuvant, wherein, described aqueous film-forming resin is aqueous polyurethane provided by the invention.
Compared with prior art, the invention provides a kind of aqueous polyurethane, containing R in aqueous polyurethane provided by the invention2Structure, and then when making preparation that the aqueous polyurethane prepared using it for raw material is applied to anticorrosive paint as membrane-forming agent, the paint film of the anticorrosive paint obtained has higher pencil hardness, it was shown that paint film is finer and close, thus, improve anti-corrosive properties.Test result indicate that, anticorrosive paint of the present invention is when film thickness is 80 microns, anti-smog is up to more than 550h, and the impact strength of film, pliability and pencil hardness are all relatively good, in addition, film-forming resin in anticorrosive paint of the present invention is using poly-(carbonic ester-ether) dihydroxylic alcohols as raw material, it is not necessary to relying on fossil resources, raw material sources are extensive.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the aqueous polyurethane that the embodiment of the present invention 1 prepares.
Detailed description of the invention
Present invention also offers a kind of aqueous polyurethane, there is formula (II) structure,
Wherein, described R1Alkylidene for the arlydene of C6～C35, the cycloalkylidene of C5～C30 or C3～C12；
Described H-R2-H has formula (I) structure,
Wherein, 1≤m≤30,1≤n≤35,1≤x≤30,1≤y≤35,
Described R3For halogen or the structure with formula (b),
Wherein, described RbHaloalkyl for the alkyl of C1～C5 or C1～C5；
Described z is 2～10.
According to the present invention, described R1It is preferably the alkylidene of the arlydene of C10～C20, the cycloalkylidene of C10～C20 or C4～C8, more preferably the alkylidene of the arlydene of C13～C18, the cycloalkylidene of C13～C18 or C6～C7, more specifically, described R1For propylidene, sub-normal-butyl, sub-n-pentyl, sub-n-hexyl, sub-n-heptyl, sub-n-octyl, formula (a-1), formula (a-2), formula (a-3) or formula (a-4),
According to the present invention, described H-R2In-H, described m is preferably 10≤m≤20, and described n is preferably 10≤n≤25, and described x is preferably 10≤x≤20, and described y is preferably 10≤y≤25.
According to the present invention, described R3It is preferably fluorine, chlorine, formula (b-1), formula (b-2) or formula (b-3),
According to the present invention, described z is preferably 2～8, more preferably 4～6.
Wherein, x, y, z, m and n are the degree of polymerization.
The preparation method that present invention also offers a kind of aqueous polyurethane, including:
1) will have the H-R of formula (I) structure2-H、ONC-R1-CNO and solvent hybrid reaction, obtain the first reactant mixture；
Wherein, 1≤m≤30,1≤n≤35,1≤x≤30,1≤y≤35；
Described R1Alkylidene for the arlydene of C6～C35, the cycloalkylidene of C5～C30 or C3～C12；
2) by the first reactant mixture, hydrophilic chain extender N methyldiethanol amine and catalyst reaction, the second reactant mixture is obtained；
3) the second reactant mixture is reacted with glycol, use R3-H neutralizes, and obtains the aqueous polyurethane with formula (II) structure；
Described R3R in-H3For halogen or the structure with formula (b),
Wherein, described RbHaloalkyl for the alkyl of C1～C5 or C1～C5；
According to the present invention, the present invention will have the H-R of formula (I) structure2-H、ONC-R1-CNO and solvent hybrid reaction, obtain the first reactant mixture；Wherein, described H-R2R in-H2In, described m is preferably 10≤m≤20, and described n is preferably 10≤n≤25, and described x is preferably 10≤x≤20, and described y is preferably 10≤y≤25；Described ONC-R1R in-CNO1It is preferably the alkylidene of the arlydene of C10～C20, the cycloalkylidene of C10～C20 or C4～C8, more preferably the alkylidene of the arlydene of C13～C18, the cycloalkylidene of C13～C18 or C6～C7, more specifically, described R1For propylidene, sub-normal-butyl, sub-n-pentyl, sub-n-hexyl, sub-n-heptyl, sub-n-octyl, formula (a-1), formula (a-2), formula (a-3) or formula (a-4),
Described solvent is preferably one or more in acetone, butanone or pentanone, more preferably butanone；The temperature of described reaction is preferably 65～85 DEG C, more preferably 70～75 DEG C；The time of described reaction is preferably 1～5h, more preferably 2～3 hours；The described H-R with formula (I) structure2-H and described ONC-R1The mass ratio of-CNO is preferably (950～1400): (380～600).
According to the present invention, by the first reactant mixture, hydrophilic chain extender N methyldiethanol amine and catalyst reaction, obtain the second reactant mixture；Described catalyst is preferably one or more in dibutyl tin laurate, stannous octoate or organic carboxyl acid bismuth, being more preferably as one or more in organic carboxyl acid bismuth that dibutyl tin laurate, stannous octoate or model are DY-20, the mass ratio of described catalyst and described N methyldiethanol amine is preferably (0.073～0.115): (70～220)；Described reaction temperature is preferably 30～40 DEG C, and the response time is preferably 1～2 hour；And in order to make reaction be easier to control, described N methyldiethanol amine is preferably dividedly in some parts in mixed liquor by the present invention.
According to the present invention, the second reactant mixture is also reacted by the present invention with glycol, uses R3-H neutralizes, obtain the aqueous polyurethane with formula (II) structure, wherein, described glycol is preferably the glycol of C2～C10, it is more preferably the glycol of C2～C6, more specifically, described glycol is one or more in ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol and heptandiol；Described R3-H is preferably one or more in halogen acids, trifluoroacetic acid, trichloroacetic acid or acetic acid；The temperature of described reaction is preferably 65～75 DEG C；The time of described reaction is preferably 1.5～2 hours；Concrete, first the second reactant mixture is preferably reacted by the present invention with glycol, after completion of the reaction, uses R3-H neutralizes, and obtains the aqueous polyurethane with formula (II) structure；Wherein, the pH value of the system after neutralization is 6～7；After neutralization, the present invention also adds distilled water mix and blend in reactant liquor, and then decompression is distilled off the solvent in reaction, and described mixing speed is preferably 1200～1800rpm；The time of described stirring is preferably 0.5～2h.
Wherein, there is described in the H-R of formula (I) structure2-H preferably prepares in accordance with the following methods:
By reacting containing the expoxy propane of maleic anhydride, chain-transferring agent, carbon dioxide and catalyst mix, obtain the H-R with formula (I) structure1-H.Wherein, described catalyst is preferably Zn3[Co(CN)6]2Bimetallic catalyst；Described chain-transferring agent is preferably p-phthalic acid；The pressure of described reaction is preferably 2～3MPa；The temperature of described reaction is preferably 45～60 DEG C, more preferably 55～55 DEG C；The time of described reaction is preferably 5～30 hours, more preferably 15～24 hours.Present invention also offers a kind of optical and thermal dual curing polyaniline anti-corrosion material, including: waterborne conductive polyaniline, aqueous film-forming resin and adjuvant, wherein, described aqueous film-forming resin is the aqueous polyurethane with formula (II) structure of the present invention；Described adjuvant is preferably waterborne curing agent, light trigger, aqueous defoamer or aqueous levelling agent；Wherein, described waterborne curing agent is one or more in Bayhydur3100, BayhydurVPLS2306, BayhydurVPLS2319, BayhydurXP2570 and BayhydurXP2451；Described light trigger is one or more in Irfacure184 (1-hydroxycyclohexylphenylketone), Irfacure2959 (2-hydroxyl-4 '-(2 hydroxy ethoxy)-2-methyl phenyl ketone), Darocur1173 (2-hydroxy-2-methyl-1-phenyl-1-acetone)；Described defoamer is one or more in BYK-019, BYK-024 and BYK-028；Described levelling agent is the mixing of one or more in BYK-380N, BYK-307, BYK-341 and BYK-381.
The invention provides a kind of aqueous polyurethane, containing R in aqueous polyurethane provided by the invention2Structure, and then when making preparation that the aqueous polyurethane prepared using it for raw material is applied to anticorrosive paint as membrane-forming agent, the antiseptic property of the anticorrosive paint obtained is good, test result indicate that, anticorrosive paint of the present invention is when film thickness is 80 microns, anti-smog is up to more than 550h, and the impact strength of film, pliability and pencil hardness are all relatively good, in addition, film-forming resin in anticorrosive paint of the present invention is using poly-(carbonic ester-ether) dihydroxylic alcohols as raw material, needing not rely on fossil resources, raw material sources are extensive.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention.
Prepared by embodiment 1 aqueous polyurethane
1) prepared by poly-(carbonic ester-ether) dihydroxylic alcohols
Zn3 [Co (CN) 6] 2 bimetallic catalysts of 0.12g p-phthalic acid chain-transferring agent Yu 0.015g are joined in autoclave, the 16g expoxy propane containing 5.5g maleic anhydride is added in still, then in still, it is filled with 5.8g carbon dioxide, react 24 hours at 2MPa pressure and temperature 55 DEG C, gathered (carbonic ester-ether) dihydroxylic alcohols.
2) prepared by aqueous polyurethane:
nullAdding 120 grams of molecular weight prepared in there-necked flask is 1500 daltonian poly-(carbonic ester-ether) dihydroxylic alcohols，It is heated to 100 DEG C，Dehydration 1 hour under-0.98MPa，It is cooled to 75 DEG C，Under nitrogen protection，Add 200 grams of butanone and 62 grams of methyl diphenylene diisocyanates，React 2 hours，Then 30 DEG C it are cooled to，Drip 0.0018 gram of dibutyltin dilaurate catalyst，Add 9.5 grams of N methyldiethanol amines in three batches，React 1 hour after addition，Then heat to 70 DEG C，Add 4.8 grams of butanediols，React 2 hours，Add in glacial acetic acid and pH to 7，It is subsequently adding 170 grams of deionized waters，1200rpm stirs 1 hour，Decompression removes butanone，Namely the structure obtaining having the aqueous polyurethane of formula (II) structure detects，Result is shown in Fig. 1，Fig. 1 is the infrared spectrum of the aqueous polyurethane that the embodiment of the present invention 1 prepares，As can be seen from the figure，This waterborne polyurethane resin is at 1645cm-1And 1750cm-1Occur in that the characteristic peak of double bond and carbonic ester respectively.
Embodiment 2
Aqueous polyurethane, the 3 grams of aqueous polyanion powder (preparing according to patent 201210215967.2 embodiment 2) 139 grams of embodiments 1 prepared are put in sand mill tank, and the rotating speed of 900 revs/min stirs 2 hours；Then to add 6.9 grams of Irfacure184 of light trigger, 2 grams of levelling agent BYK-380N, 3 grams of defoamer BYK-019 under the speed of 1300 revs/min, continue stirring 2 hours, 100 grams of Bayhydur3100 of waterborne curing agent are added under the mixing speed of 1000 revs/min, continue stirring 2 minutes, obtain optical and thermal dual curing polyaniline anticorrosive paint, be designated as WP1.
The waterborne ultraviolet-heat dual curing polyaniline paint WP1 obtained is sprayed on the metal foil of polishing, oil removing, rust cleaning in advance, levelling 3 minutes at 50 DEG C, with mono-ultra violet lamp of 3kw, 20 seconds hardening times, then baking 3 minutes at 55 DEG C, obtain WP1 corrosion-inhibiting coating.Coating is carried out paint film property test, and test result is in Table 1.
Embodiment 3
Aqueous polyurethane, the 8 grams of aqueous polyanion powder (preparing according to patent 201210215967.2 embodiment 2) 223 grams of embodiments 1 prepared are put in sand mill tank, and the rotating speed of 800 revs/min stirs 2 hours；Then to add 8.5 grams of light trigger Irfacure2959,8.5 grams of levelling agent BYK-341,5.9 grams of defoamer BYK-028 under the speed of 1200 revs/min, continue stirring 2 hours, 125 grams of waterborne curing agent BayhydurVPLS2306 are added under the mixing speed of 1000 revs/min, continue stirring 2 minutes, obtain waterborne ultraviolet-heat dual curing polyaniline anti-corrosive paint WP2.
The waterborne ultraviolet-heat dual curing polyaniline paint WP2 obtained is sprayed on the metal foil of polishing, oil removing, rust cleaning in advance, levelling 3 minutes at 50 DEG C, with mono-ultra violet lamp of 3kw, 25 seconds hardening times, then baking 5 minutes at 45 DEG C, obtain WP2 corrosion-inhibiting coating.Coating is carried out paint film property test, and test result is in Table 1.
Embodiment 4
Aqueous polyurethane, the 14 grams of aqueous polyanion powder (preparing according to patent 201210215967.2 embodiment 2) 274 grams of embodiments 1 prepared are put in sand mill tank, and the rotating speed of 800 revs/min stirs 2 hours；Then to add 11.5 grams of light trigger Darocur1173,6.7 grams of levelling agent BYK-307 and 1.6 grams of levelling agent BYK-381,6.7 grams of defoamer BYK-028 under the speed of 1300 revs/min, continue stirring 2 hours, 157 grams of waterborne curing agent BayhydurVPLS2319 are added under the mixing speed of 1100 revs/min, continue stirring 2 minutes, obtain waterborne ultraviolet-heat dual curing polyaniline anti-corrosive paint WP3.
The waterborne ultraviolet-heat dual curing polyaniline paint WP3 obtained is sprayed on the metal foil of polishing, oil removing, rust cleaning in advance, levelling 3 minutes at 50 DEG C, with mono-ultra violet lamp of 3kw, 30 seconds hardening times, then baking 4 minutes at 50 DEG C, obtain WP3 corrosion-inhibiting coating.Coating is carried out paint film property test, and test result is in Table 1.
Embodiment 5
Aqueous polyurethane, the 4.5 grams of aqueous polyanion powder (preparing according to patent 201210215967.2 embodiment 2) 105 grams of embodiments 1 prepared are put in sand mill tank, and the rotating speed of 900 revs/min stirs 2 hours；Then to add 2.3 light trigger Irfacure184 and 5 grams of light trigger Irfacure2959,1.8 grams of levelling agent BYK-307,1.1 grams of defoamer BYK-024 and 1 gram of defoamer BYK-028 under the speed of 1300 revs/min, continue stirring 2 hours, 26.6 grams of waterborne curing agent BayhydurVPLS2306 and 20 grams of waterborne curing agent BayhydurXP2570 are added under the mixing speed of 1100 revs/min, continue stirring 2 minutes, obtain waterborne ultraviolet-heat dual curing polyaniline anti-corrosive paint WP4.
The waterborne ultraviolet-heat dual curing polyaniline paint WP4 obtained is sprayed on the metal foil of polishing, oil removing, rust cleaning in advance, levelling 3 minutes at 50 DEG C, with mono-ultra violet lamp of 3kw, 40 seconds hardening times, then baking 5 minutes at 45 DEG C, obtain WP4 corrosion-inhibiting coating.Coating is carried out paint film property test, and test result is in Table 1.
Embodiment 6
Aqueous polyurethane, the 7.8 grams of aqueous polyanion powder (preparing according to patent 201210215967.2 embodiment 2) 126 grams of embodiments 1 prepared are put in sand mill tank, and the rotating speed of 1000 revs/min stirs 2 hours；Then to add 4.2 grams of light trigger Irfacure2959,1.0 grams of levelling agent BYK-341 and 2.0 grams of levelling agent BYK-381,1 gram of defoamer BYK-019 and 0.6 gram of defoamer BYK-028 under the speed of 1300 revs/min, continue stirring 2 hours, under the mixing speed of 900 revs/min, add 65.6 grams of waterborne curing agent BayhydurVPLS2319, continue stirring 3 minutes, obtain waterborne ultraviolet-heat dual curing polyaniline anti-corrosive paint WP5.
The waterborne ultraviolet-heat dual curing polyaniline paint WP5 obtained is sprayed on the metal foil of polishing, oil removing, rust cleaning in advance, levelling 3 minutes at 50 DEG C, with mono-ultra violet lamp of 3kw, 30 seconds hardening times, then baking 4 minutes at 50 DEG C, obtain WP5 corrosion-inhibiting coating.Coating is carried out paint film property test, and test result is in Table 1.
Embodiment 7
Aqueous polyurethane, the 6.5 grams of aqueous polyanion powder (preparing according to patent 201210215967.2 embodiment 2) 119 grams of embodiments 1 prepared are put in sand mill tank, and the rotating speed of 800 revs/min stirs 2 hours；Then to add 9.5 grams of light trigger Irfacure184,1.6 grams of levelling agent BYK-341,1.8 grams of defoamer BYK-024 under the speed of 1300 revs/min, continue stirring 2 hours, 33.6 grams of waterborne curing agent BayhydurXP2451 are added under the mixing speed of 1100 revs/min, continue stirring 2 minutes, obtain waterborne ultraviolet-heat dual curing polyaniline anti-corrosive paint WP6.
The waterborne ultraviolet-heat dual curing polyaniline paint WP6 obtained is sprayed on the metal foil of polishing, oil removing, rust cleaning in advance, levelling 3 minutes at 50 DEG C, with mono-ultra violet lamp of 3kw, 35 seconds hardening times, then baking 3 minutes at 60 DEG C, obtain WP6 corrosion-inhibiting coating.Coating is carried out paint film property test, and test result is in Table 1.
Comparative example 1
Prepare water-base resin according to the waterborne polyurethane resin method in embodiment 1, be only that poly adipate succinic acid ester dihydroxylic alcohols (molecular weight 1500 dalton) replaces poly-(carbonic ester-ether) dihydroxylic alcohols.The water-base resin obtained is prepared polyaniline aqueous anticorrosive paint DB1 according to embodiment 2, and tests according to the method for embodiment 2, and test result is in Table 1.
Table 1
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention carries out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (10)
1. an aqueous polyurethane, has formula (II) structure,
Wherein, described R1Alkylidene for the arlydene of C6～C35, the cycloalkylidene of C5～C30 or C3～C12；
Described H-R2-H has formula (I) structure,
Wherein, 1≤m≤30,1≤n≤35,1≤x≤30,1≤y≤35；
Described R3For halogen or the structure with formula (b),
Wherein, described RbHaloalkyl for the alkyl of C1～C5 or C1～C5；
Described z is 2～10.
2. aqueous polyurethane according to claim 1, it is characterised in that described R1Alkylidene for the arlydene of C10～C20, the cycloalkylidene of C10～C20 or C4～C8.
3. aqueous polyurethane according to claim 1, it is characterised in that described R1For propylidene, sub-normal-butyl, sub-n-pentyl, sub-n-hexyl, sub-n-heptyl, sub-n-octyl, formula (a-1), formula (a-2), formula (a-3) or formula (a-4),
4. aqueous polyurethane according to claim 1, it is characterised in that described R3For fluorine, chlorine, formula (b-1), formula (b-2) or formula (b-3),
5. a preparation method for aqueous polyurethane, including:
1) will have the H-R of formula (I) structure2-H、ONC-R1-CNO and solvent hybrid reaction, obtain the first reactant mixture；
Wherein, 1≤m≤30,1≤n≤35,1≤x≤30,1≤y≤35；
Described R1Alkylidene for the arlydene of C6～C35, the cycloalkylidene of C5～C30 or C3～C12；
2) by the first reactant mixture, hydrophilic chain extender and catalyst reaction, the second reactant mixture is obtained,
Described hydrophilic chain extender is N methyldiethanol amine；
3) glycol of the second reactant mixture with C2～C10 is reacted, use R3-H neutralizes, and obtains the aqueous polyurethane with formula (II) structure,
Described R3R in-H3For halogen or the structure with formula (b),
Wherein, described RbHaloalkyl for the alkyl of C1～C5 or C1～C5；
6. preparation method according to claim 5, it is characterised in that described step 1) in solvent be one or more in acetone, butanone or pentanone.
7. preparation method according to claim 5, it is characterised in that described step 2) in catalyst be one or more in dibutyl tin laurate, stannous octoate or organic carboxyl acid bismuth.
8. preparation method according to claim 5, it is characterised in that described step 2) temperature reacted is 30～40 DEG C.
9. preparation method according to claim 5, it is characterised in that the H-R of described formula (I) structure2-H prepares in accordance with the following methods:
By reacting containing the expoxy propane of maleic anhydride, carbon dioxide and catalyst mix, obtain the H-R with formula (I) structure1-H。
10. an optical and thermal dual curing polyaniline anticorrosive paint, including: waterborne conductive polyaniline, aqueous film-forming resin and adjuvant, wherein, the aqueous polyurethane that described aqueous film-forming resin is the aqueous polyurethane with formula (II) structure described in Claims 1 to 4 any one or prepared by the preparation method described in claim 5～9 any one.
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