CN102408768B - Solvent-free two-component polyurethane putty for rotor wing - Google Patents
Solvent-free two-component polyurethane putty for rotor wing Download PDFInfo
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- CN102408768B CN102408768B CN 201110377622 CN201110377622A CN102408768B CN 102408768 B CN102408768 B CN 102408768B CN 201110377622 CN201110377622 CN 201110377622 CN 201110377622 A CN201110377622 A CN 201110377622A CN 102408768 B CN102408768 B CN 102408768B
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Abstract
The invention relates to solvent-free two-component polyurethane putty for a rotor wing. The component A of the putty comprises the following components in parts by weight: 20-30 parts of hydroxy resin, 2-6 parts of titanium dioxide powder, 0.5-2 parts of carbon black, 15-25 parts of precipitated barium sulfate, 40-60 parts of talcum powder, 2-6 parts of dolomite, 0.1-1 part of dispersant, 0.1-1 part of defoaming agent and 0.1-1 part of flatting agent, wherein the hydroxy resin is a mixture of long-chain vegetable oleic acid modified polyester resin and self-prepared reactive diluent at a weight ratio of 1:(3-7). The component B is prepared by mixing crude polyaryl-polymethylene isocyanate (PAPI) and modified methylene diphenyl diisocyanate (MDI) according to a weight ratio of (1-4):1. When the solvent-free two-component polyurethane putty is used, the component A and the component B are mixed evenly according to a weight ratio of (4-6):1. The putty has extremely high adhesion to the epoxy glass fiber reinforced plastic type composite, good filling property, convenience in construction and easiness in polishing and meets the requirements of environmental protection. The comprehensive performance of the putty can completely meet the operational requirement of the rotor wing.
Description
Technical field
The present invention relates to a kind of rotor with solvent-free dual-component polyurethane putty.
Background technology
Rotor is made of propeller hub and several pieces blades.Most of matrix material such as the fiber glass epoxy of adopting of the blade of rotor done base material, and the characteristics of this class matrix material are that relative density is little, specific tenacity is big, chemical resistance is good.But the effect of factors such as can being subjected to Exposure to Sunlight at occurring in nature, drenching with rain, dust storm impacts produces catabiosis, and the outward appearance of matrix material, mechanical property are changed.In order to improve the weather resistance of matrix material, need the matrix material sprayed coating is protected.And before spraying priming paint, finish paint, need the defective that substrate surface exists is handled, so need fill up defective with putty.This putty need have stronger sticking power and intensity, snappiness is in order to resist the deformation of blade and the external force effects such as impact that are subjected to preferably.The quality of putty performance directly has influence on the construction of follow-up blade coating simultaneously.The putty of comparative maturity has atom ash, epoxy putty and solvent borne polyurethane putty etc. at present.The atom ash has advantages such as fast drying, easily polishing, strong adhesion, but its snappiness variation and shrinkability is big, force of cohesion is not enough at low temperatures is not suitable for the rotor use; Though epoxy putty has fast drying, strong adhesion, easy advantage such as polishing, reactive behavior of (below 5 ℃) is lower and often need toughness reinforcing processing at low temperatures for it; Solvent borne polyurethane putty causes shrinkage strain big and limited its application on rotor to environment is friendly inadequately because containing solvent.
Summary of the invention
The objective of the invention is: provide that a kind of normal temperature quick-drying, fillibility are good, easy construction, easily polishing, the blade of rotor had than strong adhesive force and intensity and snappiness hold concurrently excellent rotor with solvent-free dual-component polyurethane putty.
The technical scheme that realizes the object of the invention is: a kind of rotor is with solvent-free dual-component polyurethane putty, constituted by component A and B component, it is characterized in that each component and the weight part consumption thereof of component A are: hydroxy resin 20～30, titanium dioxide 2～6, carbon black 0.5～2, process white 15～25, talcum powder 40～60, rhombspar 2～6, dispersion agent 0.1～1, defoamer 0.1～1, flow agent 0.1～1;
Described hydroxy resin is the long-chain vegetable oil acid modified polyester resin of weight ratio 1: 3～7 and the mixture of self-control reactive thinner, wherein, the hydroxyl value of long-chain vegetable oil acid modified polyester resin is 50～250mgKOH/g, relative molecular mass is that 2000～3000,25 ℃ of viscosity of making reactive thinner down by oneself are 200～400mPas;
Ring-opening polymerization forms described self-control reactive thinner under the initiation of polyvalent alcohol, catalyzer by caprolactone or butyrolactone monomer, wherein, caprolactone or butyrolactone monomer: polyvalent alcohol: the weight part ratio of catalyzer is 190～860: 100: 0.3～1, described polyvalent alcohol is ethylene glycol, Diethylene Glycol, 1,2-propylene glycol, 1,4-butyleneglycol, 1, one or more in 6-hexylene glycol, neopentyl glycol, TriMethylolPropane(TMP), the trimethylolethane; Described catalyzer is one or more in tetrabutyl titanate, titanium isopropylate or the stannous octoate;
Described long-chain vegetable oil acid modified polyester resin is by after polyprotonic acid and/or acid anhydrides, the polyvalent alcohol heating esterification, adds long-chain vegetable oil acid, catalyzer and carries out that modification makes;
B component is homemade isocyanates solidifying agent, it be by rough poly methylene poly phenyl poly isocyanate and modified diphenylmethane diisocyanate by 1～4: 1 weight ratio mixes;
During use, component A and B component mix by weight 4～6: 1 and are solvent-free dual-component polyurethane putty.
In the above-mentioned solvent-free dual-component polyurethane putty, the titanium dioxide among the described component A is homemade anatase thpe white powder; Carbon black is last marine products 3
#Carbon black; Talcum powder is 400～800 purpose talcum powder; Dispersion agent is BYK-161 or BYK-163; Defoamer is AFCONA-2722 or AFCONA-3280; Flow agent is EFKA-3777 or EFKA-3772.
In the above-mentioned solvent-free dual-component polyurethane putty, the concrete preparation technology of described long-chain vegetable oil acid modified polyester resin: by polyprotonic acid and/or acid anhydrides, polyvalent alcohol esterification 8～12h under 160～220 ℃ of temperature to acid value less than 5mgKOH/g after, add long-chain vegetable oil acid, catalyzer and carry out that modification makes, wherein polyprotonic acid and/or acid anhydrides: polyvalent alcohol: long-chain vegetable oil acid: the weight part ratio of catalyzer is 100: 90～232: 6.7～67: 0.2～0.4; Described polyprotonic acid is one or more in hexanodioic acid, m-phthalic acid, terephthalic acid, the 1,4 cyclohexanedicarboxylic acid; Described acid anhydrides is trimellitic acid 1,2-anhydride or phthalic anhydride; Described polyvalent alcohol is ethylene glycol, Diethylene Glycol, 1,2-propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, 2,2, one or more in 4-neopentyl glycol, 1,4 cyclohexane dimethanol, TriMethylolPropane(TMP), the trimethylolethane; Described long-chain vegetable oil acid is one or more in ricinolic acid, cocinic acid, soybean oleic acid or the Zoomeric acid; Described catalyzer is one or more in tetrabutyl titanate, titanium isopropylate or the stannous octoate.
Technique effect of the present invention is: the solvent-free dual-component polyurethane putty of technical solution of the present invention, the hydroxy resin of its component A is to select the long-chain vegetable oil acid modified polyester resin of suitable proportion and the mixture of self-control reactive thinner for use, its long-chain vegetable oil acid modified polyester resin has not only improved sticking power and the snappiness of putty, improve the wettability of resin to pigment, filler simultaneously, helped the construction of putty; Its self-control reactive thinner has further reduced the viscosity of long-chain vegetable oil acid modified polyester resin and has regulated long-chain vegetable oil acid modified polyester resin reactive behavior, reduces the discharging of VOC, more compliance with environmental protection requirements; B component selects for use rough poly methylene poly phenyl poly isocyanate and modified diphenylmethane diisocyanate as solidifying agent, except the normal temperature quick-drying performance that has guaranteed putty, has also solved the excessive contradiction with grinability of putty elasticity simultaneously.Evidence putty of the present invention has to fiber glass epoxy class matrix material that extremely strong sticking power, normal temperature quick-drying, fillibility are good, the easy blade coating of construction party is easily polished, intensity and snappiness hold concurrently excellent (seeing Table 1) after the putty drying.
Embodiment
Be further described in detail below in conjunction with the present invention of embodiment, but not limited.
Raw materials used among the embodiment, unless otherwise indicated be the coatings industry industrial goods, can buy by the commercial channel.
" part " among each embodiment is " weight part ";
Embodiment 1 preparation long-chain vegetable oil acid modified polyester resin
Take by weighing 90 parts of hexanodioic acids; 10 parts of phthalic anhydrides; 84 parts of Diethylene Glycols; TriMethylolPropane(TMP) joins for 11 parts thermometer is housed; in the four-hole boiling flask of water-and-oil separator and agitator; the about 15min of inflated with nitrogen protection; after slowly being heated to about 60 ℃ of material fusions; begin reflux dewatering when starting agitator and continuing to be heated to 150 ℃; control the rate of output water and water-and-oil separator capital temperature are in 100 ± 2 ℃ of scopes; 10 ℃/h of control temperature rise rate; between 160 ℃～220 ℃, react 8～12h; after the survey acid value is less than 5mgKOH/g; after adding 31 parts of reactions of ricinolic acid 3h; adding the inferior tin of octoate catalyst promotes reaction further to carry out for 0.2 part; when water-and-oil separator capital temperature drops to below 70 ℃; sampling detecting acid number is when acid number finishes reaction during less than 2.0mg KOH/g.Vacuumize and remove a small amount of solvent and residual monomer namely obtains long-chain vegetable oil acid modified polyester resin, its hydroxyl value is 179mg KOH/g, relative molecular mass is 2750, preserve standbyly, wherein polyprotonic acid and/or acid anhydrides: polyvalent alcohol: long-chain vegetable oil acid: the weight part ratio of catalyzer is 100: 95: 31: 0.2.
Embodiment 2 preparation self-control reactive thinners
Take by weighing 254 parts of caprolactone monomers, 1,58 parts of 4-butyleneglycols, 42 parts of TriMethylolPropane(TMP)s and 0.4 part of input of catalyzer metatitanic acid four butyl esters are equipped with in the four-hole boiling flask of thermometer, prolong and agitator, the about 15min of inflated with nitrogen protection, start agitator after slowly being heated to the material fusion, continue the about 1h of heating and be warming up to 175 ℃～180 ℃, cooling discharge behind the insulation 3h namely gets the self-control reactive thinner, its viscosity is 280mPas under 25 ℃, preserves standby; Wherein, caprolactone monomer: polyvalent alcohol: the weight part ratio of catalyzer is 254: 100: 0.4,
The solvent-free dual-component polyurethane putty 1# of embodiment 3 preparations
The self-control reactive thinner that the long-chain vegetable oil acid modified polyester resin that embodiment 1 is made and embodiment 2 make mixed by weight 1: 4 and namely gets hydroxy resin.Take by weighing 25 parts of hydroxy resins, 3.75 parts of homemade anatase thpe white powders, last marine products 3
#0.75 part of carbon black, 22.5 parts of process whites, 45 parts of talcum powder, 3.75 parts of rhombspars, dispersant B YK-1610.1 part, defoamer AFCONA-27220.1 part and flow agent EFKA-37770.1 part add in the kneader, after mediating 10～15min, being ground to fineness with three-roller is 60 μ m, and discharging is component A;
Commercially available rough poly methylene poly phenyl poly isocyanate and modified diphenylmethane diisocyanate mixed with 4: 1 weight ratio be B component;
Get component A and B component and mixed by weight 6: 1, be solvent-free dual-component polyurethane putty 1#.
The solvent-free dual-component polyurethane putty 2# of embodiment 4 preparations
The self-control reactive thinner that the long-chain vegetable oil acid modified polyester resin that embodiment 1 is made and embodiment 2 make mixed by weight 1: 5 and namely gets hydroxy resin.Take by weighing 25 parts of hydroxy resins, 3.75 parts of homemade anatase thpe white powders, last marine products 3
#0.75 part of carbon black, 20 parts of process whites, 47.5 parts of talcum powder, 3.75 parts of rhombspars, dispersant B YK-1610.1 part, defoamer AFCONA-32800.5 part and flow agent EFKA-37770.1 part add in the kneader, after mediating 10～15min, being ground to fineness with three-roller is 60 μ m, and discharging is component A;
Commercially available rough poly methylene poly phenyl poly isocyanate and modified diphenylmethane diisocyanate mixed with 3: 1 weight ratio be B component;
Get component A and B component and mixed by weight 6: 1, be solvent-free dual-component polyurethane putty 2#.
The solvent-free dual-component polyurethane putty 3# of embodiment 5 preparations
The self-control reactive thinner that the long-chain vegetable oil acid modified polyester resin that embodiment 1 is made and embodiment 2 make mixed by weight 1: 7 and namely gets hydroxy resin.Take by weighing 25 parts of hydroxy resins, 3.75 parts of homemade anatase thpe white powders, last marine products 3
#0.75 part of carbon black, 21 parts of process whites, 47.5 parts of talcum powder, 2.75 parts of rhombspars, dispersant B YK-1630.5 part, defoamer AFCONA-32800.5 part and flow agent EFKA-37720.5 part add in the kneader, after mediating 10～15min, being ground to fineness with three-roller is 60 μ m, and discharging is component A;
Commercially available rough poly methylene poly phenyl poly isocyanate and modified diphenylmethane diisocyanate mixed with 4: 1 weight ratio be B component;
Get component A and B component and mixed by weight 4: 1, be solvent-free dual-component polyurethane putty 3#.
The Performance Detection of embodiment 6 solvent-free dual-component polyurethane putty
Solvent-free dual-component polyurethane putty 1#～3# that embodiment 3, embodiment 4 and embodiment 5 are made carries out Performance Detection, and detection method is all undertaken by relevant national standard, the results are shown in table 1.
Table 1
As can be seen from Table 1, putty of the present invention have that extremely strong sticking power, fillibility are good, the easy polishing of construction party, compliance with environmental protection requirements.Its dried over-all properties can satisfy the service requirements of rotor fully.
Claims (3)
1. a rotor is with solvent-free dual-component polyurethane putty, constituted by component A and B component, it is characterized in that each component and the weight part consumption thereof of component A are: hydroxy resin 20～30, titanium dioxide 2～6, carbon black 0.5～2, process white 15～25, talcum powder 40～60, rhombspar 2～6, dispersion agent 0.1～1, defoamer 0.1～1, flow agent 0.1～1;
Described hydroxy resin is the long-chain vegetable oil acid modified polyester resin of weight ratio 1: 3～7 and the mixture of self-control reactive thinner, wherein, the hydroxyl value of long-chain vegetable oil acid modified polyester resin is 50～250mgKOH/g, relative molecular mass is that 2000～3000,25 ℃ of viscosity of making reactive thinner down by oneself are 200～400mPas;
Ring-opening polymerization forms described self-control reactive thinner under the initiation of polyvalent alcohol, catalyzer by caprolactone monomer or butyrolactone monomer, wherein, caprolactone monomer or butyrolactone monomer: polyvalent alcohol: the weight part ratio of catalyzer is 190～860: 100: 0.3～1, described polyvalent alcohol is ethylene glycol, Diethylene Glycol, 1,2-propylene glycol, 1,4-butyleneglycol, 1, one or more in 6-hexylene glycol, neopentyl glycol, TriMethylolPropane(TMP), the trimethylolethane; Described catalyzer is one or more in tetrabutyl titanate, titanium isopropylate or the stannous octoate;
Described long-chain vegetable oil acid modified polyester resin is by after polyprotonic acid and/or acid anhydrides, the polyvalent alcohol heating esterification, adds long-chain vegetable oil acid, catalyzer and carries out that modification makes;
B component is homemade isocyanates solidifying agent, it be by rough poly methylene poly phenyl poly isocyanate and modified diphenylmethane diisocyanate by 1～4: 1 weight ratio mixes;
During use, component A and B component mix by weight 4～6: 1 and are solvent-free dual-component polyurethane putty.
2. solvent-free dual-component polyurethane putty according to claim 1 is characterized in that, the titanium dioxide among the described component A is homemade anatase thpe white powder; Carbon black is last marine products 3
#Carbon black; Talcum powder is 400～800 purpose talcum powder; Dispersion agent is BYK-161 or BYK-163; Defoamer is AFCONA-2722 or AFCONA-3280; Flow agent is EFKA-3777 or EFKA-3772.
3. solvent-free dual-component polyurethane putty according to claim 1, it is characterized in that, the concrete preparation technology of described long-chain vegetable oil acid modified polyester resin: by polyprotonic acid and/or acid anhydrides, polyvalent alcohol esterification 8～12h under 160～220 ℃ of temperature to acid value less than 5mgKOH/g after, add long-chain vegetable oil acid, catalyzer and carry out that modification makes, wherein polyprotonic acid and/or acid anhydrides: polyvalent alcohol: long-chain vegetable oil acid: the weight part ratio of catalyzer is 100: 90～232: 6.7～67: 0.2～0.4; Described polyprotonic acid is one or more in hexanodioic acid, m-phthalic acid, terephthalic acid, the 1,4 cyclohexanedicarboxylic acid; Described acid anhydrides is trimellitic acid 1,2-anhydride or phthalic anhydride; Described polyvalent alcohol is ethylene glycol, Diethylene Glycol, 1,2-propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, 2,2, one or more in 4-neopentyl glycol, 1,4 cyclohexane dimethanol, TriMethylolPropane(TMP), the trimethylolethane; Described long-chain vegetable oil acid is one or more in ricinolic acid, cocinic acid, soybean oleic acid or the Zoomeric acid; Described catalyzer is one or more in tetrabutyl titanate, titanium isopropylate or the stannous octoate.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102775834A (en) * | 2012-08-24 | 2012-11-14 | 西北永新化工股份有限公司 | Polyurethane specular putty coating and preparation method thereof |
| CN104387829B (en) * | 2014-11-03 | 2016-08-24 | 中山大桥化工企业集团中山智亨实业发展有限公司 | A kind of locomotive elastic polyurethane putty repairing type and preparation method thereof |
| CN108659710B (en) * | 2017-11-07 | 2021-02-09 | 株洲飞鹿高新材料技术股份有限公司 | Solvent-free finish paint composition for wind power blade and preparation method and application thereof |
| CN108586698B (en) * | 2018-05-14 | 2020-12-29 | 美瑞新材料股份有限公司 | Preparation method of self-lubricating thermoplastic polyurethane elastomer |
| CN113549362A (en) * | 2020-04-26 | 2021-10-26 | 榕珍新材料科技发展(上海)有限公司 | Two-component polyurethane putty for repairing vehicle body coating and application method thereof |
| CN111621185A (en) * | 2020-07-24 | 2020-09-04 | 榕珍新材料科技发展(上海)有限公司 | Sprayable solvent-free two-component polyurethane putty and preparation method and use method thereof |
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| CN101665617A (en) * | 2009-09-28 | 2010-03-10 | 石家庄市油漆厂 | Hydroxyl resin composition and solvent-free polyurethane putty containing same |
| CN102241908A (en) * | 2011-05-24 | 2011-11-16 | 江苏普兰纳涂料有限公司 | Polyurethane grizzly for megawatt wind-power blade with high performance and preparation method thereof |
| CN102250505A (en) * | 2011-07-27 | 2011-11-23 | 株洲时代电气绝缘有限责任公司 | Putty for repairing aerogenerator blade and preparation method therefore |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101665617A (en) * | 2009-09-28 | 2010-03-10 | 石家庄市油漆厂 | Hydroxyl resin composition and solvent-free polyurethane putty containing same |
| CN102241908A (en) * | 2011-05-24 | 2011-11-16 | 江苏普兰纳涂料有限公司 | Polyurethane grizzly for megawatt wind-power blade with high performance and preparation method thereof |
| CN102250505A (en) * | 2011-07-27 | 2011-11-23 | 株洲时代电气绝缘有限责任公司 | Putty for repairing aerogenerator blade and preparation method therefore |
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Address after: 100010 Dongcheng District, Chaoyangmen, North Street, No. 4705, No. 25, box office, Beijing Patentee after: China National Offshore Oil Corporation Patentee after: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE CO., LTD. Patentee after: CNOOC Energy Development Co., Ltd. Address before: 100010 Dongcheng District, Chaoyangmen, North Street, No. 4705, No. 25, box office, Beijing Patentee before: China National Offshore Oil Corporation Patentee before: CNOOC Changzhou Paint & Coatings Industry Research Institute Patentee before: CNOOC Energy Development Co., Ltd. |
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Address after: 100010 Box 25, 4705 North Street, Beijing, Dongcheng District, Chaoyangmen Co-patentee after: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Co-patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Box 25, 4705 North Street, Beijing, Dongcheng District, Chaoyangmen Co-patentee before: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Co-patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |