CN102031057B - Anti-icing and abrasion-resistant coating suitable for blades of wind driven generator - Google Patents
Anti-icing and abrasion-resistant coating suitable for blades of wind driven generator Download PDFInfo
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Abstract
The invention discloses an anti-icing and abrasion-resistant coating for blades of a wind driven generator. The coating at least comprises two following components of: polyurethane resin and a solid additive with the anti-icing property and 3-15% by mass of the polyurethane resin. For the solid additive, the range of dielectric constant is 1 to 4, the range particle diameter is 0.5 micron to 200 microns, and the range of density is 0.8g/cm<3> to 4g/m<3>. The polyurethane resin consists of an A component and a B component by the reaction, wherein the A component at least comprises aliphatic isocyanate or aliphatic isocyanate derivates or aliphatic isocyanate polymer, and the B component at least comprises hydroxylated acrylic resin or polyester polyol or polyether polyol or polyaspartic ester or micro-molecule polyol chain extender. The invention has the anti-icing property and abrasion resistance at the same time, the adhesion force of the coating and the ice is smaller than 300N, and the abrasion is lower than 50mg; therefore, the invention is suitable for the protective coating materials of the blades of the wind driven generator.
Description
Technical field
The present invention relates to a kind of coating, be specifically related to a kind of not only anti-icing but also abrasion-resistant coating, can be used for the wind electricity blade coating.
Background technology
The resin matrix of blade of wind-driven generator (abbreviation wind electricity blade) is made up of epoxy or unsaturated polyester, and ultraviolet resistance does not lose intensity in a short time rapidly under the atmospheric aging environment.Therefore, need outside blade, apply the layer of protecting coating.But this layer supercoat not only will satisfy the demand in 20 years of anti-atmospheric aging, also needs anti-icing performance and wear resisting property.
For a long time, the spontaneous icing subject matter that troubles blade of wind-driven generator running in winter that becomes of wind-powered electricity generation blade surface under the low temperature.During winter, landlocked temperature can be low to moderate subzero below-10 ℃, and the minor amount of water branch frosting on wind electricity blade surface is frozen, and has a strong impact on the distribution of wind electricity blade weight, causes the distortion of blade shape, and wind power equipment must shut down when serious.Therefore, the inland will guarantee to greatest extent that with the wind electricity blade coating surface does not freeze.Therefore, the blade coating need have certain anti-icing performance.
Simultaneously, the open-air wind sand environment that wind energy turbine set is harsh requires blade to have excellent abrasive, to resist long dust storm invasion and attack.
Chinese patent publication number CN1556161A has introduced through in epoxy resin, adding graphite, utilizes the not wellability of graphite to water, and ice can't be frozen at coatingsurface, but not mentioned abrasion property.Chinese patent publication number CN101392144A, Chinese patent publication number CN101613564A have reported preparation method and the performance of wind-powered electricity generation with the blade coating, but equal anti-icing property of not mentioned coating.
U.S. Pat 2006281861A1 has introduced a kind of ice-phobic coating.This coating is a matrix with fluorine carbon or silicone resin, adds the siloxanes or the fluorine carbon of liquid, adds the solid additive compatible with liquid silicon again.This solid additive is: tetrafluoroethylene, graphite, this additive can significantly reduce the bonding force between coating and the ice, thereby reach anti-icing purpose, and this coating is used for aircraft, but not mentioned abrasion property ability.
The resin matrix that is commonly used to as ice-phobic coating is low-surface-energy materials such as tetrafluoroethylene or Zylox, and it is enough to guarantee can come off fast attached to the ice on the coating with the low-down bonding force of ice, thereby reaches the anti-icing effect of coating.Yet the wear resistance of tetrafluoroethylene and Zylox is relatively poor, can not satisfy the technical requirements of wind electricity blade with coating.
Summary of the invention
The present invention is exactly in order to address the above problem, and overcomes existing coating and can not have anti-icing and attrition resistant problem simultaneously, and a kind of anti-icing, wear-resistant coating that is applicable to wind electricity blade is provided.This invention is applicable to the protective coating of blade of wind-driven generator.
One aspect of the present invention makes coating have anti-icing effect through selecting the solid additive for use.On the one hand, select for use and optimized the resin matrix of urethane resin, make coating possess wear resisting property as coating.Thereby prepared a kind of ice but also abrasion-resistant coating of putting not only, can be used for the supercoat of blade of wind-driven generator.
Antiicing coating can not stop freezing of coatingsurface, but reduce to ice and coating between bonding force, thereby ice can be come off from coatingsurface under the effect of external force fast.Therefore, ice-phobic coating means low bonding force between ice and the coating.
Bonding force between ice and the coating depends on two aspects: the Van der Waals force between (1) ice and the coating; (2) electrostatic force between ice and the coating.The macro manifestations of Van der Waals force is: the contact angle between water and the coating, contact angle are big more, and coating is hydrophobic more, and the Van der Waals force between the water (ice) is more little.The macro manifestations of electrostatic force is: the specific inductivity of material surface, specific inductivity is more little, and the electrostatic force between the ice is more little.Therefore, big more with the contact angle of water, the bonding force between the material that specific inductivity is low more, itself and ice is more little.
There is a large amount of hydrogen bonds in polyurethane-polyurea material unique soft section with segment structure firmly, and making with urethane resin or polyaspartate polyurea is that the coating of matrix has good wear resistance.But, there is a large amount of hydrophilic radical (carbamate groups, ether, ester group) in the middle of the polyurethane structural, be wetting ability but not hydrophobic material.The specific inductivity of polyurethane material itself also bigger (generally greater than 4).Therefore, itself possesses wear resistance polyurethane material, but does not possess anti-icing performance.
Therefore, in the middle of polyurethane coating, add the solid additive of low-k small particle size, can significantly reduce the bonding force of polyurethane coating and ice.This solid additive must possess enough low specific inductivity, to reduce the electrostatic force between coating and the ice; Simultaneously, this solid additive must possess enough little particle diameter, with the uniformity on surface behind the assurance paint coating; At last, this solid additive must possess less density, can be suspended in coatingsurface with a considerable amount of solid additives after guaranteeing coating curing.The adding of this solid additive makes polyurethane coating possess anti-icing performance and wear resisting property simultaneously, has satisfied the technical requirements of wind electricity blade with coating.
The technical problem that will solve required for the present invention, can realize through following technical scheme:
A kind of anti-icing, wear-resistant coating that is applicable to wind electricity blade, said coating comprise following two kinds of integral parts at least:
(2) urethane resin;
(2) solid additive of the anti-icing character of 3%～15% tool of urethane resin quality.
Wherein, the solid additive that meets above-mentioned requirements mainly comprises: (1) polyethylene wax, modified polyethylene wax, Poly Propylene Wax, tetrafluoroethylene wax; (2) hollow glass micropearl, hollow ceramic microspheres, ceramic microsphere, silicon dioxide microsphere, polymer microballoon; (3) mineral dye of low-k, filler.
Said solid additive, its dielectric constant range is: 1～4, its particle size range is 0.5 μ m～200 μ m, its density is 0.8g/cm
3～4g/cm
3
Said solid additive, preferred specific inductivity is 1.05～2.5, and preferred particle diameter is 1 μ m～40 μ m, and preferred density is 0.8g/cm
3～1.5g/cm
3
The addition of said solid additive is no more than 15% of urethane resin quality.In general, be added to 5%～10%, be enough to the bonding force between coating and the ice is reduced to below the 300N.
Wherein, said urethane resin is to be formed by A, B two-part reaction.Urethane provides enough wear resistancies as resin matrix to coating.Urethane resin is formed by A, the two component reactions of B.The A component is the compound that contains NCO, and the B component can be formed with the resin of-NCO radical reaction for some have.
Said A component comprises aliphatic isocyanates or aliphatic isocyanates verivate or aliphatic isocyanates prepolymer at least.
Because the wind electricity blade coating needs long-term exposure under harsh uviolizing; Therefore the isocyanic ester of A component is necessary for aliphatic isocyanates; The available isocyanic ester comprises hexamethylene diisocyanate (HDI); Isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (H
12MDI), 1,4-cyclohexyl diisocyanate (CHDI), cyclohexanedimethyleterephthalate isocyanic ester (HXDI); Trimethylammonium-1,6-hexamethylene diisocyanate (TMHDI), tetramethyl-mphenylenedimethylim-vulcabond (TMXDI); Norbornene alkyl diisocyanate (NBDI), Methylcyclohexyl diisocyanate (HTDI), they can obtain from following supplier mostly: Degussa (Degussa); Bayer (Bayer), Japanese polyurethane (NPU), the military field of Mitsui Co., Ltd.; Sieve ground inferior (Rhodia), Du Pont (Dupont), Japanese Asahi Kasei Corporation etc.
Sometimes, in order to increase hardness or snappiness, balance rate of drying and time, directly do not use aliphatic isocyanates; And being to use isocyanate derivates, main verivate comprises: HDI tripolymer, HDI biuret, IPDI tripolymer; The HDI dimer, HDI allophanate, H
6XDI tripolymer, and the isocyanate addition product that forms of aliphatic isocyanates and small molecules polyol reaction.The main small molecules polyvalent alcohol that uses is TriMethylolPropane(TMP) and trimethylolethane, and other available small molecules polyvalent alcohols include but not limited to: 1, and 4-butyleneglycol, NSC 6366,1; The 6-pinakon, glycol ether, DPG, 1; The 4-hydroxymethyl-cyclohexane, cyclohexanediol, TCD three ring glycol, 1; 2,6-hexanetriol, tris(2-hydroxy ethyl)isocyanurate, polycaprolactonetriol and tetrol.These isocyanate derivates can obtain from following supplier, as: Degussa (Degussa), Bayer (Bayer), Japanese polyurethane (NPU), the military field of Mitsui Co., Ltd., perhaps synthetic under suitable condition.
Further, said isocyanate derivates is the isocyanic ester polymer, perhaps the affixture of isocyanic ester and small molecules polyvalent alcohol; Said small molecules polyvalent alcohol contains two or three hydroxy functional groups, and its molecular weight is less than 300g/mol.
Further, said isocyanate prepolymer is that one or more reactions in aliphatic isocyanates and polyether glycol or polyester polyol or the small molecules polyvalent alcohol form.
Sometimes, the A component need be used the performed polymer of aliphatic isocyanates.Performed polymer is that aliphatic isocyanates and polyether glycol or polyester polyol reaction are formed.Used polyvalent alcohol has the number-average molecular weight of 500g/mol～4000g/mol.Sometimes, when synthetic, also can add the small molecules polyvalent alcohol and carry out chain extension.
The B component of urethane resin is had and can be formed with the resin of-NCO radical reaction by some, and said B component comprises Hydroxylated acrylic resin at least; Perhaps polyester polyol; Perhaps polyether glycol, perhaps polyaspartate, perhaps small molecules polyvalent alcohol chainextender.
Further, said Hydroxylated acrylic resin is a polyacrylate polyol, perhaps polyether-modified polyacrylate polyol, perhaps polyester modification polyacrylate polyol, perhaps silicone-modified polyacrylate polyvalent alcohol.Said Hydroxylated acrylic resin has the number-average molecular weight of 500g/mol～4000g/mol.Said polyacrylate polyol is by the propenoate of hydroxyl and propenoate or rare propyl alcohol of hydroxyl are not raw material synthetic oligomer polyol.
Further, said polyester polyol is that hexanodioic acid is a polyester polyol, perhaps aromatic polyester polyol; Perhaps polycarbonate polyol; Perhaps polycaprolactone polyol, perhaps Viscotrol C polyester polyol, perhaps dimer polyester polyol; The polyester polyol that perhaps contains polyethers, said polyester polyol has the number-average molecular weight of 500g/mol～4000g/mol.
Polyester polyol is that main chain or side chain contain hydroxyl, the resin that is mainly formed by small molecules polyprotonic acid and small molecules polyol reaction.The polyester polyol that is used for coating, the main small molecules polyprotonic acid that uses comprises: hexanodioic acid, neck phthalic acid, terephthalic acid, dimer diacid, Viscotrol C, THIXCIN.Also comprise some polyester polyols in addition, be mainly polycaprolactone polyol and polycarbonate polyol by the transesterification reaction preparation.
No matter use polyester polyol, be to add a part or separately as the polyvalent alcohol use, all can improve the wear resistance of material.Therefore, when using polyacrylate polyol can't reach the ideal wear resistance separately, usually add polyester polyol and improve.The wear resistance of polyether glycol is relatively poor, can obtain best wear resistance but be to use polyaspartate that isocyanic ester usually is cured.
Further; Said polyether glycol is the homopolymer of propylene oxide; The perhaps multipolymer of propylene oxide and oxyethane, the perhaps homopolymer of THF, the perhaps multipolymer of THF and propylene oxide; The perhaps multipolymer of THF and oxyethane, said polyether glycol has the number-average molecular weight of 500g/mol～4000g/mol.
Further, said small molecules polyvalent alcohol chainextender contains two or three hydroxy functional groups, and its molecular weight is less than 300g/mol.
Further, the bonding force of said coating and ice is less than 300N, and abrasion are less than 50mg (1000 change for GB/T1786-2006,1000g).
In general, polyurethane material all has wear resistance preferably, has hardness and flexible balance.But, want to make the wear resistance of material to be lower than 50mg (1000 change for GB/T 1786-2006,1000g), its hard segment content should be higher than 25%.(definition of hard segment content: the quality of isocyanic ester and small molecules polyvalent alcohol accounts for the per-cent of resin total mass.) preferred hard segment content is 30%～65%, too high hard segment content will influence the snappiness of material and then influence abrasion property.
Beneficial effect of the present invention:
The present invention has anti-icing and attrition resistant performance simultaneously, and the bonding force of coating and ice is less than 300N, and abrasion are applicable to the protective coating of blade of wind-driven generator less than 50mg (1000 change for GB/T 1786-2006,1000g).
Description of drawings
Further specify the present invention below in conjunction with accompanying drawing and embodiment.
Fig. 1 is the front view of aluminium flake and mould.
Fig. 2 is the side-view of aluminium flake and mould.
Fig. 3 is the sectional view of mould.
Fig. 4 is the stereographic map of mould.
Label among the figure: 100 is aluminium flake, and 200 is mould, and 210 is groove.
Embodiment
In order to make technique means of the present invention, creation characteristic, to reach purpose and effect and be easy to understand and understand,, further set forth the present invention below in conjunction with specific embodiment.
Embodiment
The preparation method:
Polyester polyol resin or polyether polyol resin or polyaspartate resin and pigment (like titanium oxide), dispersion agent (like organic SULPHOSUCCINIC ACID ESTER, propenoate), solvent (like 1-Methoxy-2-propyl acetate) mixed grinding are prepared into mill base.To have superhigh speeds (1750rpm) such as the solid additive of anti-icing character, remaining polyol resin or polyaspartate resin, solvent (like 1-Methoxy-2-propyl acetate), catalyzer (like dibutene two LAURIC ACID 99 MIN tin), auxiliary agent disperses slowly to add in the mill base after 20 minutes.Continue the B component that high speed dispersion promptly got coating in 20 minutes.
Directly buy in supplier under some situation of A component of coating, for example the HDI tripolymer.Isocyanate derivates and isocyanic ester performed polymer are that oneself is synthetic.Synthetic method: the polyvalent alcohol of isocyanic ester and proportioning, solvent are dropped in the reaction kettle, add 0.1% organotin catalysts of reaction system quality, be warming up to 50 ℃, react and promptly got product in 6 hours.
The A component is seen table 1.
Table 1A component
The B component is seen table 2.
Table 2B component
The stock white preparation method: with titanium oxide 24kg, polyaspartate resin 9.25kg, 1-Methoxy-2-propyl acetate 6kg, organophosphate dispersion agent 0.75kg ground 40 minutes and made with sand mill after disperseing with high speed dispersor (1750rpm).
Black slurry preparation method: with carbon black 2kg, polyaspartate resin 15.2kg, 1-Methoxy-2-propyl acetate 22kg, propenoate dispersion agent 0.8kg ground 2 hours and made with sand mill after disperseing with high speed dispersor (1750rpm).
Testing method:
The test of ice bonding force: shown in Fig. 1-2, the rectangle aluminium flake 100 of a perforate, the thickness of aluminium flake 100 are 0.5cm, and width is 1.5cm, the test piece of generally testing as the tackiness agent shearing resistance (being aluminium flake 100).Adopt the method for dip-coating to be coated with layer height＞2.5cm away from an end coated of perforate.
Prepare a mould 200 in addition referring to Fig. 3-Fig. 4, mould 200 contains a long * wide * height and is the groove 210 of 2.1cm * 1.1cm * 2.5cm hollow.
Referring to Fig. 1-Fig. 2, the aluminium flake 100 that scribbles coating can be put in the middle of the groove 210 once more.With fills with water in the middle of the groove 210, on low temperature shearing resistance test machine, subzero 20 ℃ of urgency are frozen after 20 minutes and are carried out shearing force testing, draw back the bonding force that the used power of test piece is coating and ice.
Wear-resisting test: adopt the elastic grinding wheel method, meet GB: GB/T 1786-2006, the counterweight of employing 1000g changes 1000 circles, and the data that record are the loss of weight of coating, and coating abrasion performance is good more more at least.
Test result is seen table 3.
Table 3 test result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| The ice bonding force | 220N | 190N | 260N | 720N | 890N | 560N |
| Wear resistance | 23mg | 14.5mg | 39.5mg | 29mg | 18mg | 52.5mg |
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; The present invention is not restricted to the described embodiments; That describes in the foregoing description and the specification sheets just explains principle of the present invention; The present invention also has various changes and modifications under the prerequisite that does not break away from spirit and scope of the invention, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain to be defined by appending claims and equivalent thereof.
Claims (12)
1. anti-icing, wear-resistant coating that is applicable to wind electricity blade, said coating comprises following two kinds of integral parts at least:
(1) urethane resin;
(2) solid additive of the anti-icing character of 3%～15% tool of urethane resin quality;
Said solid additive mainly comprises: (1) polyethylene wax, modified polyethylene wax, Poly Propylene Wax, tetrafluoroethylene wax; (2) hollow glass micropearl, hollow ceramic microspheres, silicon dioxide microsphere, polymer microballoon; (3) mineral dye of low-k, filler;
Said solid additive, specific inductivity are 1.05～2.5, and particle diameter is 1 μ m～40 μ m, and density is 0.8g/cm
3～1.5g/cm
3
2. a kind of anti-icing, wear-resistant coating that is applicable to wind electricity blade according to claim 1 is characterized in that the addition of said solid additive is a urethane resin quality 5%～10%.
3. a kind of anti-icing, wear-resistant coating that is applicable to wind electricity blade according to claim 1 is characterized in that, said urethane resin is to be formed by A, B two-part reaction.
4. a kind of anti-icing, wear-resistant coating that is applicable to wind electricity blade according to claim 3 is characterized in that said A component comprises aliphatic isocyanates or aliphatic isocyanates verivate or aliphatic isocyanates prepolymer at least.
5. a kind of anti-icing, wear-resistant coating that is applicable to wind electricity blade according to claim 4 is characterized in that said isocyanate derivates is the isocyanic ester polymer, perhaps the affixture of isocyanic ester and small molecules polyvalent alcohol; Said small molecules polyvalent alcohol contains two or three hydroxy functional groups, and its molecular weight is less than 300g/mol.
6. a kind of anti-icing, wear-resistant coating that is applicable to wind electricity blade according to claim 4; It is characterized in that said isocyanate prepolymer is that the one or more reactions in aliphatic isocyanates and polyether glycol or polyester polyol or the small molecules polyvalent alcohol form.
7. a kind of anti-icing, wear-resistant coating that is applicable to wind electricity blade according to claim 3 is characterized in that said B component; At least comprise Hydroxylated acrylic resin, perhaps polyester polyol, perhaps polyether glycol; Perhaps polyaspartate, perhaps small molecules polyvalent alcohol chainextender.
8. a kind of anti-icing, wear-resistant coating that is applicable to wind electricity blade according to claim 7; It is characterized in that; Said Hydroxylated acrylic resin is a polyacrylate polyol; Perhaps polyether-modified polyacrylate polyol, perhaps polyester modification polyacrylate polyol, said Hydroxylated acrylic resin has the number-average molecular weight of 500g/mol～4000g/mol.
9. a kind of anti-icing, wear-resistant coating that is applicable to wind electricity blade according to claim 7 is characterized in that said polyester polyol is that hexanodioic acid is a polyester polyol; Perhaps aromatic polyester polyol, perhaps polycarbonate polyol, perhaps polycaprolactone polyol; Perhaps Viscotrol C polyester polyol; Perhaps dimer polyester polyol perhaps contains the polyester polyol of polyethers, and said polyester polyol has the number-average molecular weight of 500g/mol～4000g/mol.
10. a kind of anti-icing, wear-resistant coating that is applicable to wind electricity blade according to claim 7; It is characterized in that said polyether glycol is the homopolymer of propylene oxide, perhaps the multipolymer of propylene oxide and oxyethane; The perhaps homopolymer of THF; The perhaps multipolymer of THF and propylene oxide, the perhaps multipolymer of THF and oxyethane, said polyether glycol has the number-average molecular weight of 500g/mol～4000g/mol.
11. a kind of anti-icing, wear-resistant coating that is applicable to wind electricity blade according to claim 7 is characterized in that, said small molecules polyvalent alcohol chainextender contains two or three hydroxy functional groups, and its molecular weight is less than 300g/mol.
12. a kind of anti-icing, wear-resistant coating that is applicable to wind electricity blade according to claim 1 is characterized in that, the bonding force of said coating and ice is less than 300N, and abrasion are less than 50mg.
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| CN101665655A (en) * | 2009-10-12 | 2010-03-10 | 西北永新化工股份有限公司 | High-performance wind-power generating facility coating prepared by taking organic fluorinated silicone modified elastic polyurethane-urea resin as substrate |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101665655A (en) * | 2009-10-12 | 2010-03-10 | 西北永新化工股份有限公司 | High-performance wind-power generating facility coating prepared by taking organic fluorinated silicone modified elastic polyurethane-urea resin as substrate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796446A (en) * | 2012-08-10 | 2012-11-28 | 中山大桥化工企业集团中山智亨实业发展有限公司 | Anti-sandstorm special blade paint |
| CN102796446B (en) * | 2012-08-10 | 2014-12-17 | 中山大桥化工企业集团中山智亨实业发展有限公司 | Anti-sandstorm special blade paint |
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| CN102031057A (en) | 2011-04-27 |
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