CN101665655B - High-performance wind-power generating facility coating prepared by taking organic fluorinated silicone modified elastic polyurethane-urea resin as substrate - Google Patents
High-performance wind-power generating facility coating prepared by taking organic fluorinated silicone modified elastic polyurethane-urea resin as substrate Download PDFInfo
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Abstract
The invention discloses high-performance wind-power generating facility coating prepared by taking organic fluorinated silicone modified elastic polyurethane-urea resin as substrate. The high-performance wind-power generating facility coating is prepared from component A and component B according to proportion. The wind-power generating facility coating has toughness, attrition resistance, high elasticity, excellent mechanical property, yellowing resistance, good colour retention, high ultraviolet resistance, high weather resistance, favorable and excellent electrical insulation, chemical stability, moisture resistance and freeze resistance. In addition, the wind-power generating facility coating has high performance and moderate cost and can strongly protect the wind-power generating facility, reduce the maintenance frequency and lower the purchasing cost of the wind-power generating facility, thereby having extremely high implementation value and social and economic benefit.
Description
Technical field
The present invention relates to the wind-powered electricity generation paint field, particularly is a kind of high-performance wind-power coating of base-material preparation with the organic fluorinated silicone modified elastic polyurethane urea resin.
Background technology
In order to alleviate the imbalance between supply and demand of the energy, countries in the world all tap a new source of energy in active research, and the renewable energy resources particularly are to guarantee human power supply steady in a long-term.
Wind-power electricity generation becomes renewable energy source with the fastest developing speed in recent years, begins to develop from the direction of " replenishing the energy " court's " strategy alternatives energy ".The wind power station long-term exposure requires to carry out effective corrosionproof protection in the harsh climate environment.Wherein large-scale wind electricity equipment is because of its apparatus expensive, work under bad environment, and on-the-spot inconvenience is dismantled maintenance to main position.The protection against corrosion work of pylon just becomes important integral part of assurance wind-power electricity generation; Because it need move decades; And wind tower height degree keeps in repair relatively difficulty, so will guarantee that the long-term operation stably of large-scale wind electricity equipment reliable is the most basic requirement more than 30m; Need carry out an application to the wind tower, even wind power equipment has the long protection against corrosion life-span.The residing environment of wind tower itself is different, and desired anticorrosion grade is different, and difference is bigger.Wind power equipment wants moistureproof in the coastland, anti-salt, and waterproof etc., wind power equipment is wanted anti-dust stone in the area, Inner Mongol, and drying is tanned by the sun, the temperature difference, cold etc., thus require to be coated in the hardness of wind tower japanning, chemical property, surface-treated technology etc. are different.General requirement in work-ing life by the national standard blower fan is 20 years, all is to carry out with the standard in 20 years so be coated in all standards of wind tower japanning.
Along with Chinese wind-powered electricity generation, especially northwest wind-powered electricity generation industry is flourish, and the particular surroundings of wind-powered electricity generation industry is very strict for the requirements such as performance of coating.Present operating wind-powered electricity generation facility coating all is import or foreign brand name; Also all in design period; But the actual motion effect is unsatisfactory, and the non-irrigated Wind-sandy Area of particularly trembling with fear in the three Norths is because tower inside and outside wall corrosive environment is different; It is superfluous with the inside coating performance that the outer wall coating performance is not enough, causes dual waste; Secondly, blade wind erosion well damage; Too high painting cost and actual performance performance are not reciprocity; Wind-powered electricity generation manufacturing cost and maintenance cost are high, badly influence the development of wind-powered electricity generation industry and wind-powered electricity generation equipment manufacture.In the face of the construction in regional ten million multikilowatt bases such as Hebei, Meng Dong, Meng Xi, Jiuquan, the coating protection research and development, work such as the improvement of wind-powered electricity generation coating property, cost reduction seem particularly urgent.
Because the anti-marquis that wind-powered electricity generation coating requires, anti-ultraviolet, cold-resistant thermal cycling (80 ℃ ~-40 ℃), the windsand mill corrosion of anti-high speed the, freezing, anti-salt fog (seashore wind field) performance harshness; In addition because the inconvenience of safeguarding requires an application need reach the life-span more than 20 years.In the existing coating variety, epoxy resin has excellent cohesive force, chemical proofing, protection against corrosion and performance such as water-fast, and film adhesive is good, and thermostability and insulativity are better.Its shortcoming is that poor, the easy efflorescence of weathering resistance, the fullness ratio of filming are bad, is not suitable for doing outdoor.But its good cohesiveness can be used as priming paint and uses.
Synolac has that low price, construction are simple, less demanding to construction environment, plentiful hard, the weather resistance of filming and advantage such as weathering resistance is better, ornamental and protectiveness is all relatively good.But its drying is slow, filming is difficult for reaching higher requirement, poor water resistance, and acid and alkali-resistance not, hardness is low, and is nonelastic, not wear-resisting, and sticking power is strong inadequately, shortcomings such as easy-weathering.
Look shallow is, weather-proof, fast light, heat-resisting, good corrosion resistance because of having for acrylic resin paint, and it is strong to protect the look gloss retention, and characteristics such as paint film fullness ratio are widely used in every field.But vinyl resin is water-fast, poor solvent resistance, and is not wear-resistant, and has the phenomenon of " hot sticky cold crisp ".Its drawbacks limit its application in the wind-powered electricity generation paint field.
Urethane resin has winter hardiness preferably, good thermotolerance, wear resistance, ageing-resistant performance, and durometer level is wide, can have high hardness and snappiness concurrently, and is water-fast, corrosion-resistant good, so polyurethane coating is the main product of wind-powered electricity generation coating.But polyurethane coating is after 5 ~ 6 years, and paint film color and luster degree can reduce.
So common coating variety does not reach the requirement of wind-powered electricity generation coating.The wind-powered electricity generation top coat adopts ZGK 5 or fluorinated polyurethane resin mostly in the market.But the general wind field by the sea of using, the wind field effect is very undesirable by land, and abrasion resistance is low, and sharp wear appears in the windward side.
Summary of the invention
In order to address these problems, the object of the invention is intended to: 1, a kind of novel wind power coating cohesive strength, sticking power, polyester that wear resistance is high and preparation method thereof are provided; 2, a kind of organic fluorinated silicone modified elastic polyurethane urea resin A, organic fluorinated silicone modified elastic polyurethane urea resin B and preparation method thereof are provided; 3, another object of the present invention provides the novel anti-ultraviolet of a kind of preparation, anti-marquis, freezing, wear-resisting, tough and resilient wind-powered electricity generation coating and preparation method thereof; To tower tube, engine room cover and high-performance wind-power coating of blade application, to reach under severe environmental conditions purpose to the protection of wind power plant top layer.
The objective of the invention is to realize through following technical scheme:
A kind of high-performance wind-power coating is made up of following raw materials according (weight percent),
Organic fluorinated silicone modified elastic polyurethane urea resin base A component: 20～70%;
Organic fluorinated silicone modified elastic polyurethane urea resin base B component: 30～80%.
The component A of above-mentioned organic fluorinated silicone modified elastic polyurethane urea resin, its composition comprises:
Polyester 10～35%;
Polytetrahydrofuran diol 8～35%;
Vulcabond 10～25%;
Terminal hydroxy group (amino) siloxanes (properties-correcting agent) 0.5～30%;
The fluorine-containing siloxanes of terminal hydroxy group (amino) (properties-correcting agent) 0.1～10%;
YLENE 20～35%;
Butylacetate 10～20%;
Pimelinketone 2～5%;
Catalyzer 0.1～0.5%.
Polyester among the component A of above-mentioned organic fluorinated silicone modified elastic polyurethane urea resin, its composition comprises:
Di-carboxylic acid 10～60%;
Divalent alcohol 10～70%;
Polyvalent alcohol 0～30%;
Catalyzer 0.1～0.5%;
Stablizer 0.1～0.5%.
The preparation method of polyester among the component A of above-mentioned organic fluorinated silicone modified elastic polyurethane urea resin, its step is with di-carboxylic acid, linking agent and binary (polynary) alcohol joins reaction kettle; And adding catalyzer-tosic acid, stablizer-triphenylphosphate is warming up to 180 ℃; Be incubated 2 hours; After vacuumized about 1.5 hours, minor amount of water and unnecessary glycol are removed in decompression, polyester.
The preparation method of the component A of above-mentioned organic fluorinated silicone modified elastic polyurethane urea resin, its step is with polyester, polytetrahydrofuran diol (PTMG1500), terminal hydroxy group (amino) siloxanes (molecular weight 1500); YLENE melts mixing and is warming up to 130 ℃ of reflux dewaterings, is cooled to 75 ℃ then, adds the anhydrous acetic acid butyl ester; Or ETHYLE ACETATE, anhydrous pimelinketone begins to drip vulcabond; 0.5 drip off in hour, drip off the back after dripping off and add catalyzer, and insulation reaction 3 hours; After begin to drip the fluorine-containing siloxanes of terminal hydroxy group (amino) (holding amino fluorinated polysiloxane (molecular weight 1500)), drip off in 40 minutes, continued insulation reaction 1.5 hours; Finish reaction, cooling discharge is canned, is the A component of organic fluorinated silicone modified elastic polyurethane urea resin.
The B component of above-mentioned organic fluorinated silicone modified elastic polyurethane urea resin, its composition comprises:
Resistance type amine 10～60%;
Flow agent 0.1～0.8%;
Siccative 0.1～0.5%;
UV light absorber 0.1～0.8%;
White titanium pigment 5～25%;
Mullite fiber 1～5%;
Surface intercalation modifying polynite 2～5%;
Silicon powder 2～10%;
4A molecular sieve powder 2～10%;
Aerosil 0.5～5%;
Hydrolysis-resisting agent 0.1～0.5%;
Anti-settling agent 0.1～0.5%;
Dispersion agent 0.1～2%.
Thinner 15～60%
Wherein: white titanium pigment is a rutile-type, median size 0.1um; Silicon powder 600 orders; Mullite fiber, 1000 orders; The intercalation modifying polynite, 600 orders; 4A molecular sieve powder, 600 orders.
The preparation method of the B component of above-mentioned organic fluorinated silicone modified elastic polyurethane urea resin; Its step is white titanium pigment, mullite fiber, surperficial intercalation modifying polynite, the silicon powder with oven dry; 4A molecular sieve powder, aerosil adds thinner and dispersion agent; High speed dispersion 40 minutes, after change conoidal mill mesh-of-grind to 0.1～0.01um over to; Ground slurry is added impeller; Add flow agent, siccative (lead naphthenate), UV light absorber, hydrolysis-resisting agent, anti-settling agent, thinner and resistance type amine one by one; Stir the canned organic fluorinated silicone modified elastic polyurethane urea resin B component that promptly gets of discharging.
Above-mentioned surperficial intercalation modifying polynite is to add in the solution of cetyl trimethylammonium bromide in polynite, and 80 ℃ were stirred 6 hours down, and repeatedly washes clean is dried, and porphyrize sieves, and filler has adopted mullite fiber and 4A molecular sieve powder.
Above-mentioned wind-powered electricity generation preparation method for coating is that organic fluorinated silicone modified elastic polyurethane urea resin A and organic fluorinated silicone modified elastic polyurethane urea resin B are joined the even application of carrying out by 1: 1～1: 10 (weight ratio).
Used vulcabond is isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI), 1 among the component A of above-mentioned organic fluorinated silicone modified elastic polyurethane urea resin; 4-cyclohexyl diisocyanate (CHDI), cyclohexanedimethyleterephthalate vulcabond (HXDI), trimethylammonium-1, one or more in 6-hexamethylene diisocyanate (TMHDI), the toluene cyclohexyl diisocyanate (HTDI).
Used polytetrahydrofuran diol is PolyTHF 250, the PolyTHF 650 of BASF AG among the component A of above-mentioned organic fluorinated silicone modified elastic polyurethane urea resin, one or more among the PTMG 850 of Mitsubishi KCC, PTMG 1000, PTMG 1300, PTMG 1500, PTMG 1800, PTMG2000, the PTMG 3000.
Used linking agent is 1 among the component A of above-mentioned organic fluorinated silicone modified elastic polyurethane urea resin; 4-butyleneglycol, glycol ether, DPG, Tri Ethyleneglycol; 1,2-Ucar 35, NSC 6366, methyl propanediol, 1,6-pinakon, 1; Ammediol, 1, one or more in 5-pentanediol, 12 carbon glycol, 12 carbon naphthene glycol, the cyclohexanediol.
Used di-carboxylic acid is one or more in pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid, the 1,4 cyclohexanedicarboxylic acid among the component A of above-mentioned organic fluorinated silicone modified elastic polyurethane urea resin.
Used binary (polynary) alcohol is 1 among the component A of above-mentioned organic fluorinated silicone modified elastic polyurethane urea resin; 4-butyleneglycol, glycol ether, DPG, Tri Ethyleneglycol; Three TEGs, 1,2-Ucar 35,1, ammediol, TriMethylolPropane(TMP), glycerine, 1; 2, one or more in 6-hexanetriol, the tetramethylolmethane.
By the wind-powered electricity generation coating that optimum formula makes, its appearance of film porcelain white; Elastic extension is 770%; Tensile strength is 37Mpa; Wear resistance 0.2mg (C17 rubber wheel; 1000g load; 1000 change; Adopt standard ISO 7784-2:1997), coating surface drying time 4 hours is done solid work 16 hours time.
Advantage of the present invention is:
The high-performance wind-power top coat has adopted two-pack organic fluorinated silicone modified elastic polyurethane urea resin; Wherein the A component adopts cohesive strength, sticking power, polyester that wear resistance is high; High-modulus and intensity, water-fast, dynamic property and electrical insulating property and the high polytetrahydrofuran diol of low temperature kindliness; Anti-marquis, anti-xanthochromia, wear-resisting, chemical resistant isophorone diisocyanate; In low molecular weight hydroxy-terminated (amino) ZGK 5 and side chain contain-the CF3 group the fluorine-containing siloxanes of terminal hydroxy group (amino) jointly as properties-correcting agent, high branching linking agent polymerization and getting, the B component adopts steric hindrance type amine.Two components spray by the proportioning mixing during use.It is tough wear-resisting to solidify the back coating, and mechanical property is outstanding, has fabulous high and low temperature resistance, excellent electric insulation property and chemicalstability, hydrophobic moistureproofness; The introducing of physiology inert siloxanes; Show good low temperature kindliness, dielectricity and gloss retention; The fluorine atom radius is little; Electronegativity is strong, the carbon-fluorine bond bond energy high, has therefore given fabulous UV resistant of coating and radioprotective property, low surface energy, high-tensile, high resistivity, high-weatherability, chemicals-resistant, hydrophobicity, oleophobic property, mildew-proof flame retarded, resistance toheat.Because ZGK 5, fluorine-containing siloxanes and urethane solubility parameters differ greatly, through molecular designing, process control; Select suitable solvent, block copolymerization obtains suitable micro phase separation structure; Form high-strength and tough cross-linked network after the film forming, and fluorine atom is enriched in and films and air surface.With this resin is base-material, preparation wind-powered electricity generation top coat, and its anti-ultraviolet, over-all properties such as wear-resistant are extremely excellent.Accelerated deterioration 5000 hours, this product appearance no change.Excellent combination property.
Carry sandstone secretly with high wind under the open-air wind of sandblast experimental simulation " three Norths " the district higher wind velocity condition wearing and tearing of wind-powered electricity generation tower machine are made an experiment, the sandblast experiment condition is seen table 1, and experimental result is seen table 2.
Table 1: sandblast experiment condition
| Project | Blasting pressure | The rifle distance | Caliber in the nozzle | The sandblast mode | Spray angle | The sandblast machine model | The sandblast pellet |
| Parameter/unit | 8kgf/cm2 | 10cm | 8mm | Point of fixity sprays | 90℃ | SY-4720 portable sandblaster (Qingdao execute brave sand-blast device ltd) | Silica sand (40 order) |
Table 2: sandblast experimental result
| Project | Novel wind power coating (compound coating) | Abroad with type coating 1 | Abroad with type coating 2 | Abroad with type coating 3 |
| Film thickness (μ m) before the sandblast | 242 | ?239 | ?251 | ?246 |
| The sandblast time (s) | 60 | ?60 | ?60 | ?60 |
| Film thickness after the sandblast (μ m) | 211 | ?0 | ?0 | ?0 |
| Ground situation after the sandblast | Intact | Damaged | Damaged | Damaged |
Can be known that by experimental result after the abrasive jet wear experiment, the wearing and tearing of this product are slight, effect obviously is better than external product.Genesis mechanism analysis to the wind erosion wearing and tearing can be known; The hardness of general sandstone is far above organic coating, and the wedge angle of abrasive material can produce micro-cutting and little ploughing effect to organic coating, and sandstone particle wedge angle causes the cut crackle to increase; Surfaceness improves, and then produces sharp wear.Sandstone is because the wind-force mechanical force of giving in addition, and kinetic energy is very high, has wedge angle and has the sandstone of kinetic energy; Destructive force 90 ℃ of angle direct projection coatings is the strongest; If the inclination certain angle, organic coating layer surface is smooth more, and grit is not easy to wear and tear above that more; So the wearing and tearing of the windward side of wind-powered electricity generation tower machine significantly, the leeward side wearing and tearing are slight.Along with the aggravation of wearing and tearing, the coatingsurface roughness increases, and the rate of wear also increases greatly.So can see that from above-mentioned the kinetic energy that sandstone had has played main effect to wearing and tearing, kinetic energy is big more, the cutting power of sandstone is strong more, and kinetic energy is more little, and the cutting power of sandstone is more little.By kinetic energy formula
(wherein E is a sandstone kinetic energy, and m is the sandstone quality, and v is a sandstone speed, is approximately wind speed here) can know that the quality of gravel is big more, and speed is fast more, and then kinetic energy is big more, and this its medium velocity accounts for essential factor.Wind power generation blade is except receiving the suffered abrasive action of stationary parts such as wind-power tower, and owing to rotated by wind-force, wind-force is bigger to the wearing and tearing that blade produces.
Theoretical now according to shellfish, the trappable mechanical rotational energy of wind wheel does
(wherein Pm is a mechanical rotational energy, and ρ is a density of air, and A is the wind wheel sectional area, and V is a wind speed, and Cp is a power coefficient) can be known by following formula, under the certain situation of wind-powered electricity generation tower machine, wishes to get electric power efficiently, and wind-powered electricity generation tower machine must be placed on the powerful area of wind-force.Can know that but go up the abrasion mechanism analysis according to this wind-force is stronger, wearing and tearing are more serious.Desire solves this double-barreled question, must start with from the principal element that produces wearing and tearing.The kinetic energy that has the sandstone of shear action is the principal element that produces wearing and tearing, and it is crucial reducing sandstone kinetic energy and momentum.
This patent has been invented the organic fluorinated silicone modified elastic polyurethane urea coating, and it not only has HS, and has snappiness and supporting capacity, effectively absorbs the striking energy of sandstone through elastic deformation, so its wear resisting property is outstanding.In the main chain-and the introducing of Si-O-group, improved coating winter hardiness and thermotolerance.The introducing of side chain fluoro-containing group has greatly improved the coating weather resisteant of anti-ultraviolet ability.
It is wear-resisting and have snappiness concurrently that the high-performance wind-power coating is tough, and mechanical property is outstanding; Anti-xanthochromia, tint retention are good; High anti-ultraviolet, high-weatherability; Fabulous high and low temperature resistance, excellent electric insulation property and chemicalstability, hydrophobic moistureproofness and anti-freeze property.Disadvantages such as it is weak to the invention solves current domestic wind-powered electricity generation coating research, and external product exists performance not enough, and cost is higher.Has promotional value.
Embodiment:
Following instance will be done further elaboration to the present invention, but not limit the scope of the invention.
Embodiment one:
The first step: polyester synthetic
With 26.5% hexanodioic acid, 36.25% sebacic acid, 32.9%1, the 4-butyleneglycol, 4% TriMethylolPropane(TMP) joins reaction kettle, and adds catalyzer---0.2% tosic acid, stablizer---0.15% triphenylphosphate.Be warming up to 180 ℃, be incubated 2 hours, after vacuumized about 1.5 hours, minor amount of water and unnecessary glycol are removed in decompression.Back discharging.
Second the step: with the first step synthetic 32.9% polyester, 9.2%PTMG1500,0.3% 1, the 4-butyleneglycol; 5.6% terminal hydroxy group siloxanes (molecular weight 1500), 18% YLENE melts mixing and is warming up to 130 ℃ of reflux dewaterings, is cooled to 75 ℃ then; Add 9% anhydrous ethyl acetate, anhydrous pimelinketone begins to drip 20% isophorone diisocyanate; 0.5 drip off in hour, drip off the back and add catalyzer---0.2% tosic acid, and insulation reaction 3 hours; After begin Dropwise 5 % and hold amino fluorinated polysiloxane (molecular weight 1500), drip off in 40 minutes, continued insulation reaction 1.5 hours; Finish reaction, cooling discharge is canned, is the A component of organic fluorinated silicone modified elastic polyurethane urea resin.
The 3rd step: with white titanium pigment 24.6%, 3% mullite fiber, 3% surperficial intercalation modifying polynite, 6.4% silicon powder of oven dry; 4%4A molecular sieve powder; 0.8% aerosil; Add 53% thinner and 0.4% dispersion agent (Paasche chemical industry ltd of Foshan City section, DS-2040), high speed dispersion 40 minutes.Thinner is the mixed solvent of YLENE and butanone, ETHYLE ACETATE, and wherein, YLENE, butanone, ETHYLE ACETATE weight ratio are 60: 20: 20.After change the conoidal mill mesh-of-grind over to 0.1um.Ground slurry is added impeller; Add 0.4% flow agent (Shanghai Ze Chuan chemical industry ltd one by one; ZC-420), (Taiwan is photochemistry limited-liability company forever for 0.2% siccative-lead naphthenate, 0.5% UV light absorber; Eversorb 73), (Tianjin is prone to into International Trading Company Ltd, HX-301) with 6% resistance type amine---diethyl toluene diamine (DETDA) for 0.3% hydrolysis-resisting agent (Glenn chemistry, ALTFONA 5151), 0.4% anti-settling agent; Stir the canned organic fluorinated silicone modified elastic polyurethane urea resin B component that promptly gets of discharging.
The preparation of high-performance wind-power coating.During use, organic fluorinated silicone modified elastic polyurethane urea resin A and organic fluorinated silicone modified elastic polyurethane urea resin B join the even application of carrying out by 1: 1 (weight ratio).This coating surface drying time 4 hours was done solid work 15 hours.Elongation at break 400,15 milligrams of wear(ing)values (1000 grams/1000 change, the C17 wheel).
Embodiment 2
The first step: polyester synthetic
With 66.3% sebacic acid, 12.5%1, ammediol and 20.85% glycol ether join reaction kettle, and add catalyzer---0.2% tosic acid, stablizer---0.15% triphenylphosphate.Be warming up to 180 ℃, be incubated 2 hours, after vacuumized 2 hours, minor amount of water and unnecessary glycol are removed in decompression.Back discharging.
Second step: with the first step synthesizing polyester 26.4% and 6.1%PTMG2000,10.1% hydroxy-terminated polysiloxane (molecular weight 2000), 1.4% TriMethylolPropane(TMP); 18% YLENE melts mixing and is warming up to 130 ℃ of reflux dewaterings, is cooled to 80 ℃ then, adds 9% anhydrous ethyl acetate; 3% anhydrous pimelinketone begins to drip 26% sym.-diisopropylideneacetone vulcabond (IPDI), drips off in 0.5 hour; Drip off the back and add catalyzer---0.2% tosic acid, and insulation reaction 2.5 hours, after begin to drip the amino fluorinated polysiloxane (molecular weight 2000) of 4% end; Drip off in 40 minutes, continued insulation reaction 1.5 hours, finish reaction; Cooling discharge is canned, is the A component of organic fluorinated silicone modified elastic polyurethane urea resin.
The 3rd step: with white titanium pigment 12.6%, mullite fiber, 5% surperficial intercalation modifying polynite, 5% silicon powder of oven dry; 9%4A molecular sieve powder; 5% aerosil; Add 53.9% thinner and 0.4% dispersion agent (Linan, Hangzhou coatings additive(s) chemical industry ltd, F-300), high speed dispersion 40 minutes.Thinner is the mixture of YLENE and butanone, ETHYLE ACETATE, and wherein YLENE, butanone, ETHYLE ACETATE weight ratio are 60: 20: 20.After change the conoidal mill mesh-of-grind over to 0.1um.Ground slurry is added impeller; Add 0.4% flow agent (the auspicious chemical TRM003 of ltd of Dalian gold ancient cooking vessel), siccative-0.2% 2 cinnamic acid dibutyl tin, 0.5% UV light absorber (Switzerland CIBA company one by one; Tinuvin 101), 0.3% hydrolysis-resisting agent (TUV P-200), (Tianjin is prone to into International Trading Company Ltd to 0.4% anti-settling agent; HX-301); With 7% resistance type amine---diformazan sulfenyl tolylene diamine (DMTDA), stir the canned organic fluorinated silicone modified elastic polyurethane urea resin B component that promptly gets of discharging.
The preparation of high-performance wind-power coating.During use, organic fluorinated silicone modified elastic polyurethane urea resin A and organic fluorinated silicone modified elastic polyurethane urea resin B join the even application of carrying out by 1: 1 (weight ratio).This coating surface drying time 1 hour was done solid work 4 hours.Elongation at break 550%, 20 milligrams of wear(ing)values (1000 grams/1000 change, the C17 wheel).
Embodiment 3
The first step: polyester synthetic
With 27.55% nonane diacid, 21.6% hexanodioic acid, 34.5% tetraethylene-glycol, 16%1, the 4-butyleneglycol joins reaction kettle, and adds 0.2% tosic acid (catalyzer), 0.15% triphenylphosphate (stablizer).Be warming up to 180 ℃, be incubated 1.5 hours, after vacuumized about 1 hour, minor amount of water and unnecessary glycol are removed in decompression.Back discharging.
Second step: with the first step synthesizing polyester 30.4% and 13.4%PTMG3000,0.8% glycerine, 13.4% end amino silicones (molecular weight 3000); YLENE melts mixing and is warming up to 130 ℃ of reflux dewaterings, is cooled to 90 ℃ then, adds 9% anhydrous ethyl acetate; 3% anhydrous pimelinketone begins to drip 12% hexamethylene diisocyanate (HDI), drips off in 0.5 hour; Drip off back insulation reaction 3 hours, after begin to drip the amino fluorinated polysiloxane (molecular weight 3000) of 18% end, drip off in 40 minutes; Drip off the back and add catalyzer--0.2% toluenesulphonic acids, and continued insulation reaction 1.5 hours, finish reaction; Cooling discharge is canned, is the A component of organic fluorinated silicone modified elastic polyurethane urea resin.
The 3rd step: 10% white titanium pigment that will dry, 4% mullite fiber, 7% surperficial intercalation modifying polynite, 10% silicon powder; 9.1%4A molecular sieve powder; 3% aerosil; Add 49.7% thinner and 0.4% dispersion agent (Paasche chemical industry ltd of Foshan City section, DS-2040), high speed dispersion 40 minutes.Thinner is the mixture of YLENE and butanone, ETHYLE ACETATE, and wherein YLENE, butanone, ETHYLE ACETATE weight ratio are 60: 20: 20.After change the conoidal mill mesh-of-grind over to 0.1um.Ground slurry is added impeller; Add 0.4% flow agent (Guangzhou hat will chemical industry ltd one by one; PU-8080), 0.2% dibutyltin diacetate (siccative), 0.5% UV light absorber (Switzerland Ciba speciality chemical company's T inuvin 622), 0.3% hydrolysis-resisting agent (Glenn chemistry; ALTFONA5151), 0.4% anti-settling agent (Tianjin is prone to into International Trading Company Ltd, HX-301), with 5% resistance type amine---diformazan sulfenyl tolylene diamine (MOCA); Stir the canned organic fluorinated silicone modified elastic polyurethane urea resin B component that promptly gets of discharging.
The preparation of high-performance wind-power coating.During use, organic fluorinated silicone modified elastic polyurethane urea resin A and organic fluorinated silicone modified elastic polyurethane urea resin B join the even application of carrying out by 1: 1 (weight ratio).This coating surface drying time 1 hour was done solid work 8 hours.Elongation at break 600%, 10 milligrams of wear(ing)values (1000 grams/1000 change, the C17 wheel).
Claims (10)
1. a high-performance wind-power coating is characterized in that forming by containing weight percent organic fluorinated silicone modified elastic polyurethane urea resin base A component 20～70% and containing weight percent organic fluorinated silicone modified elastic polyurethane urea resin base B component 30～80%, wherein:
A. organic fluorinated silicone modified elastic polyurethane urea resin base A component comprises:
Polyester 10～35%;
Polytetrahydrofuran diol 8～35%;
Vulcabond 10～25%;
Terminal hydroxy group (amino) siloxanes 0.5～30%;
The fluorine-containing siloxanes 0.1～10% of terminal hydroxy group (amino);
YLENE 20～35%;
Butylacetate; Or ETHYLE ACETATE 10～20%;
Pimelinketone 2～5%;
Catalyzer 0.1～0.5%;
B. organic fluorinated silicone modified elastic polyurethane urea resin base B component comprises:
Resistance type amine 10～60%;
Flow agent 0.1～0.8%;
Siccative 0.1～0.5%;
UV light absorber 0.1～0.8%;
White titanium pigment 5～25%;
Mullite fiber 1～5%;
Surface intercalation modifying polynite 2～5%;
Silicon powder 2～10%;
4A molecular sieve powder 2～10%;
Aerosil 0.5～5%;
Hydrolysis-resisting agent 0.1～0.5%;
Anti-settling agent 0.1～0.5%;
Dispersion agent 0.1～2%,
Thinner 15～60%
Wherein: white titanium pigment is a rutile-type, median size 0.1um; Silicon powder 600 orders; Mullite fiber, 1000 orders; The intercalation modifying polynite, 600 orders; 4A molecular sieve powder, 600 orders.
2. a kind of high-performance wind-power coating according to claim 1 is characterized in that polyester among the component A of organic fluorinated silicone modified elastic polyurethane urea resin, and its composition comprises:
Di-carboxylic acid 10～60%;
Divalent alcohol 10～70%;
Polyvalent alcohol 0～30%;
Catalyzer 0.1～0.5%;
Stablizer 0.1～0.5%.
3. a kind of high-performance wind-power coating according to claim 1 and 2 is characterized in that the preparation method of polyester among the component A of organic fluorinated silicone modified elastic polyurethane urea resin, and its step is that di-carboxylic acid, binary, polyvalent alcohol are joined reaction kettle; And adding catalyzer---tosic acid, stablizer---triphenylphosphate is warming up to 180 ℃; Be incubated 2 hours; After vacuumized 1.5 hours, minor amount of water and unnecessary glycol are removed in decompression, polyester.
4. a kind of high-performance wind-power coating according to claim 1 is characterized in that the preparation method of the component A of organic fluorinated silicone modified elastic polyurethane urea resin, and its step is with polyester, polytetrahydrofuran diol; Terminal hydroxy group (amino) siloxanes, YLENE melts mixing and is warming up to 130 ℃ of reflux dewaterings, is cooled to 75 ℃ then; Add anhydrous acetic acid butyl ester or ETHYLE ACETATE, anhydrous pimelinketone begins to drip vulcabond; 0.5 drip off in hour, drip off the back and add catalyzer, and insulation reaction 3 hours; After begin to drip the fluorine-containing siloxanes of terminal hydroxy group (amino), drip off in 40 minutes, continued insulation reaction 1.5 hours; Finish reaction, cooling discharge is canned, is the A component of organic fluorinated silicone modified elastic polyurethane urea resin.
5. a kind of high-performance wind-power coating according to claim 1; The preparation method who it is characterized in that the B component of organic fluorinated silicone modified elastic polyurethane urea resin, its step are white titanium pigment, mullite fiber, surperficial intercalation modifying polynite, the silicon powders with oven dry, 4A molecular sieve powder; Aerosil; Add thinner and dispersion agent, high speed dispersion 40 minutes, after change conoidal mill mesh-of-grind to 0.1～0.01um over to; Ground slurry is added impeller; Add flow agent, siccative one by one---lead naphthenate, UV light absorber, hydrolysis-resisting agent, anti-settling agent, thinner and resistance type amine; Stir the canned organic fluorinated silicone modified elastic polyurethane urea resin B component that promptly gets of discharging.
6. according to the said a kind of high-performance wind-power coating of claim 5; It is characterized in that above-mentioned surperficial intercalation modifying polynite is to add in the solution of cetyl trimethylammonium bromide in polynite; 80 ℃ were stirred 6 hours down, and repeatedly washes clean is dried; Porphyrize sieves, and filler adopts mullite fiber and 4A molecular sieve powder.
7. a kind of high-performance wind-power coating according to claim 1; It is characterized in that used vulcabond is isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI), 1 among the component A of organic fluorinated silicone modified elastic polyurethane urea resin; 4-cyclohexyl diisocyanate (CHDI), cyclohexanedimethyleterephthalate vulcabond (HXDI), trimethylammonium-1, one or more in 6-hexamethylene diisocyanate (TMHDI), the toluene cyclohexyl diisocyanate (HTDI).
8. a kind of high-performance wind-power coating according to claim 1; It is characterized in that used polytetrahydrofuran diol is PolyTHF 250, the PolyTHF 650 of BASF AG among the component A of organic fluorinated silicone modified elastic polyurethane urea resin, one or more among the PTMG 850 of Mitsubishi KCC, PTMG1000, PTMG 1300, PTMG 1500, PTMG 1800, PTMG 2000, the PTMG 3000.
9. a kind of high-performance wind-power coating according to claim 4; It is characterized in that used di-carboxylic acid among the component A of organic fluorinated silicone modified elastic polyurethane urea resin is one or more in pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid, the 1,4 cyclohexanedicarboxylic acid.
10. a kind of high-performance wind-power coating according to claim 2; It is characterized in that among the component A of organic fluorinated silicone modified elastic polyurethane urea resin that used divalent alcohol or polyvalent alcohol are 1,4-butyleneglycol, glycol ether, DPG, Tri Ethyleneglycol, three TEGs, 1; 2-Ucar 35,1; Ammediol, TriMethylolPropane(TMP), glycerine, 1,2, one or more in 6-hexanetriol, the tetramethylolmethane.
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| CN102031057B (en) * | 2010-11-09 | 2012-07-18 | 上海康达新能源材料有限公司 | Anti-icing and abrasion-resistant coating suitable for blades of wind driven generator |
| CN102746782B (en) * | 2011-04-18 | 2014-08-13 | 中国科学院化学研究所 | Anti-icing and anti-frosting polyurethane coating and preparation method thereof |
| CN102775890B (en) * | 2012-08-01 | 2014-05-14 | 江苏科技大学 | Automatic marking and color developing function coating and preparation method thereof |
| CN105463856B (en) * | 2016-01-06 | 2017-11-17 | 江苏工程职业技术学院 | A kind of novel ultrahigh molecular weight polyethylene braiding fire hose and its manufacture method |
| CN105646828A (en) * | 2016-03-31 | 2016-06-08 | 青岛科技大学 | Organic fluorine-silicone-polyurethane block copolymer synthesizing method |
| CN106366822A (en) * | 2016-08-27 | 2017-02-01 | 合肥普庆新材料科技有限公司 | Water-based organic-inorganic hybrid anti-freezing coating |
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| WO2009053304A1 (en) * | 2007-10-22 | 2009-04-30 | Wacker Chemie Ag | Fluoropolymer-silicon compounds and method for production |
| CN101553514A (en) * | 2006-09-29 | 2009-10-07 | 建筑研究和技术有限公司 | Functionalized polyurethane resin, method for the production thereof, and use thereof |
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| WO2009053304A1 (en) * | 2007-10-22 | 2009-04-30 | Wacker Chemie Ag | Fluoropolymer-silicon compounds and method for production |
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