CN105969165A - Impact-resistant water-based polyester coating and preparation method thereof - Google Patents
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- 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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- C08G18/06—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
- C08G18/40—High-molecular-weight compounds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses an impact-resistant water-based polyester coating which is composed of the following raw materials in parts by weight: 1-2 parts of potassium titanate, 2-3 parts of cellulose propionate, 1-2 parts of polyethylene imine, 0.8-1 part of trichloroisocyanuric acid, 1.6-2 parts of Y-chloropropyl trimethoxy silane, 0.3-1 part of tri-nonylphenyl phosphite, 35-40 parts of rosin, 8-10 parts of fumaric acid, 6-7 parts of 20-30% sodium hydroxide solution, 20-34 parts of glycol, 0.1-0.2 part of antimonous oxide, 2-3 parts of sodium polyacrylate, 13-20 parts of zinc chloride, 80-90 parts of polyether glycol, 100-130 parts of toluene diisocyanate, 2-3 parts of 2,2-dimethylol propionic acid, 4-5 parts of diethylene glycol, 1-2 parts of triethylamine, 0.2-0.4 part of 2-mercapto benzimidazole, 1-2 parts of cetyl trimethyl ammonium chloride and 0.1-0.2 part of stannous sulfate. According to the coating disclosed by the invention, a stable coated film can be formed on the surface of a substrate, and the coated film has high surface strength and strong impact resistance.
Description
Technical field
The present invention relates to polyester coating technical field, particularly relate to a kind of shock resistance waterborne polyester coating and preparation method thereof.
Background technology
At present, although conventional water-base polyurethane material is widely used in the industry such as coating, adhesive due to its environmental friendliness, but the water-base polyurethane material of routine yet suffers from thermostability and the deficiency such as weatherability is the best, antistatic behaviour is poor, have impact on its wider application to preferably improve the combination property of aqueous polyurethane coating, the shortcoming such as overcome the poor water resistance that himself exists, solid content low, expand its range of application, study on the modification to aqueous polyurethane has become a big focus in recent years, and the degree of depth and the range of discussion the most more expand.The modification of aqueous polyurethane is broadly divided into two large divisions, and one is that aqueous polyurethane is composite modified with other materials, different according to modifying agent, the modification of aqueous polyurethane emulsion mainly have epoxy resin modification, acrylate modified, add nano-material modified etc..Two is that the raw material to aqueous polyurethane is modified, and introduces the biomass resources such as starch, cellulose, oils and fats, utilizes its characteristic to improve a certain performance of aqueous polyurethane；
Aqueous polyurethane and the compound two ways that is broadly divided into of inorganic nano-particle, the fillers such as montmorillonite, Muscovitum, Pulvis Talci are added in aqueous polyurethane by one, are prepared as phyllosilicate nano modified aqueous polyurethane composite；Another kind is to add in water-base polyurethane material by nanoparticles such as silicon dioxide, zinc oxide, magnesium hydroxide, nano-celluloses, is prepared as inorganic rigid Nanocomposites water-base polyurethane material.Nano zine oxide is compared with common ZnO, there is the excellent properties such as high chemical stability, relatively low dielectric constant, stronger ultraviolet and INFRARED ABSORPTION and catalysis activity, nano-ZnO is added in polyurethane, excellent in mechanical performance, uvioresistant, antistatic and the new function composite such as antibacterial can be prepared；
At present, remaining high of oil price, the production cost causing polyester and polyether polyol is also day by day to increase.People start to pay attention to the intermediate that research and development are raw material production polyurethane with Renewable resource.Colophonium is as one of important forestry biomass resource of China, existing scholar's research adds it in the synthesis of polyurethane, to improve the performances such as the gloss of polyurethane products, cohesiveness, but they are all directly to add in polyurethane by Colophonium, and Colophonium is that the mixture degree of functionality simultaneously that various kinds of resin is sour is the highest, can not join on the main chain of polyurethane, fail to significantly improve the performance so that product, it is impossible to give full play to the characteristic of Colophonium；Colophonium has that hardness is high, heat-resist and the good characteristic such as insulation, anticorrosion, if introducing it in polyurethane, can overcome the shortcomings such as standard aqueous low, the heat-resisting poor water resistance of polyurethane hardness.But forefathers the most directly apply this mixture of Colophonium, the structure of Colophonium is connected to the end of strand only as end-capping reagent, makes the performance of Colophonium sufficiently not embodied；.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of shock resistance waterborne polyester coating and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of shock resistance waterborne polyester coating, it is made up of the raw material of following weight parts:
Potassium titanate 1-2, cellulose propionate 2-3, polymine 1-2, sym-closene 0.8-1, Y-r-chloropropyl trimethoxyl silane 1.6-2, trisnonyl phenyl phosphite 0.3-1, Colophonium 35-40, fumaric acid 8-10, 20-30% sodium hydroxide solution 6-7, ethylene glycol 20-34, antimony oxide 0.1-0.2, sodium polyacrylate 2-3, zinc chloride 13-20, polyether Glycols 80-90, toluene di-isocyanate(TDI) 100-130, 2, 2-dihydromethyl propionic acid 2-3, diethylene glycol 4-5, triethylamine 1-2, 2-mercaptobenzimidazole 0.2-0.4, hexadecyltrimethylammonium chloride 1-2, stannous sulfate 0.1-0.2.
The preparation method of a kind of described shock resistance waterborne polyester coating, comprises the following steps；
(1) above-mentioned hexadecyltrimethylammonium chloride is joined in the deionized water of its weight 10-14 times, stir, add cellulose propionate, insulated and stirred 5-8 minute at 60-70 DEG C, obtain fiber dispersion；
(2) above-mentioned sym-closene is taken, join in the dehydrated alcohol of its weight 12-17 times, stir, rise high-temperature and be 70-75 DEG C, the sulfuric acid solution of dropping 96-98%, regulation pH is 3-4, insulated and stirred 20-30 minute, adding the 10-15% of above-mentioned Colophonium weight, stannous sulfate, stirring, to room temperature, obtains modified rosin alcohol liquid；
(3) by remaining Colophonium, fumaric acid mixing, 200-230 DEG C of insulation reaction 2.7-3 hour under nitrogen protection, it is cooled to 157-160 DEG C of discharging; join in the dehydrated alcohol of its weight 10-15 times; dripping above-mentioned 20-30% sodium hydroxide solution, stirring is to room temperature, sucking filtration; vacuum drying; being then added in the dehydrated alcohol of its weight 6-8 times, dropping concentration is the hydrochloric acid solution of 5-7%, and regulation pH is 3-4; stir, obtain modified fumaropimaric acid；
(4) above-mentioned 2-mercaptobenzimidazole is joined in above-mentioned abienol liquid, stir, add modified fumaropimaric acid, at 46-50 DEG C ultrasonic 2-3 minute, sucking filtration, is vacuum dried precipitation, mixes with ethylene glycol, antimony oxide, it is passed through nitrogen, stirring reaction 3-4 hour at 150-160 DEG C, rises high-temperature and is 210-220 DEG C, continue insulation 1.7-2 hour, cooling discharge, obtains modified poly ester polyhydric alcohol；
(5) above-mentioned sodium polyacrylate is joined in the deionized water of its weight 80-100 times, dropping acetic acid, regulation pH is 2-3, adds zinc chloride, stir, the sodium hydroxide of dropping 3-5mol/l, regulation pH is 10-11, insulation reaction 3-5 hour at 87-90 DEG C, centrifugation, precipitation is washed 2-3 time, is vacuum dried 10-11 hour at 60-65 DEG C, obtains water-dispersion type zinc oxide；
(6) by above-mentioned polyether Glycols, the mixing of modified poly ester polyhydric alcohol, at 118-130 DEG C, vacuum dehydration 2-3 hour, is cooled to room temperature, mix with toluene di-isocyanate(TDI), insulation reaction 100-120 minute at 76-80 DEG C, add 2,2-dihydromethyl propionic acid, continue insulation reaction 50-60 minute, add above-mentioned diethylene glycol, insulation reaction 4-5 hour at 57-60 DEG C, it is cooled to room temperature, add above-mentioned triethylamine, stir, obtain rosin acid modified poly ester；
(7) above-mentioned polymine is joined in the dehydrated alcohol of its weight 5-8 times, rise high-temperature and be 70-80 DEG C, add above-mentioned rosin acid modified poly ester, Y-r-chloropropyl trimethoxyl silane, insulated and stirred 10-20 minute, ethanol is distilled off, obtain silane-modified polyester；
(8) above-mentioned silane-modified polyester is joined in the deionized water of its weight 4-6 times, add above-mentioned water-dispersion type zinc oxide and remain each raw material, ultrasonic 20-30 minute, to obtain final product.
The invention have the advantage that the present invention prepares fumaropimaric acid by Colophonium, it is the rosin derivative having and condensing many alicyclic rings rigid structure and polyfunctionality, fumaropimaric acid PEPA is prepared as raw material, it is incorporated in aqueous polyurethane high polymer main chain, polyurethane can be made to produce crosslinking, molecular chain movement be obstructed formed hydrophilic region diminish and be crosslinked region close, reduce infiltration and the diffusion of hydrone so that paint film has relatively low water absorption rate.The introducing condensing many alicyclic structures of fumaropimaric acid simultaneously, add hot strength and the hardness of paint film, synthesis fumaropimaric acid modified aqueous polyurethane, the shortcomings such as standard aqueous low, the heat-resisting poor water resistance of polyurethane hardness can be overcome, the modified aqueous polyurethane material of the function admirables such as the hardness obtained is high, glossiness is good, thermostability and resistance to water；The present invention is also added into water-dispersion type zinc oxide, on the one hand improve the degree of crystallinity of polyurethane coating film, interaction force between polyurethane molecular is strengthened, heat resistance raises: on the other hand, the nano zine oxide being dispersed in polyurethane coating film serves the effect of similar cross-linking agent so that the free volume of polyurethane reduces, the bound degree of activity of strand increases, average chain length between adjacent " crosslinking points " diminishes, so the weightless temperature of polyurethane improves, heat resistance improves；Nano zine oxide is at sunlight simultaneously, particularly under ultraviolet light irradiates, in water and air, the electronegative electronics moved freely can be decomposited voluntarily, leave the hole of positively charged simultaneously, hole can be with excited oxygen and hydroxyl, the water and air adsorbed thereon is made to become oxygen and the hydroxyl of activity, they have the strongest redox, making cell membrane damage cause dying of antibacterial, thus improve the anti-microbial property of polyester coating, the coating of the present invention can form stable film at substrate surface, this film coated surface intensity is high, and impact resistance is strong.
Detailed description of the invention
A kind of shock resistance waterborne polyester coating, it is made up of the raw material of following weight parts:
Potassium titanate 1, cellulose propionate 2, polymine 1, sym-closene 0.8, Y r-chloropropyl trimethoxyl silane 1.6, trisnonyl phenyl phosphite 0.3, Colophonium 35, fumaric acid 8,20% sodium hydroxide solution 6, ethylene glycol 20, antimony oxide 0.1, sodium polyacrylate 2, zinc chloride 13, polyether Glycols 80, toluene di-isocyanate(TDI) 100,2,2 dihydromethyl propionic acid 2, diethylene glycol 4, triethylamine 1,2 mercaptobenzimidazole 0.2, hexadecyltrimethylammonium chloride 1, stannous sulfate 0.1.
The preparation method of a kind of described shock resistance waterborne polyester coating, comprises the following steps；
(1) being joined by above-mentioned hexadecyltrimethylammonium chloride in the deionized water of its weight 10 times, stir, add cellulose propionate, at 60 DEG C, insulated and stirred 5 minutes, obtain fiber dispersion；
(2) taking above-mentioned sym-closene, join in the dehydrated alcohol of its weight 12 times, stir, rising high-temperature is 70 DEG C, the sulfuric acid solution of dropping 96%, regulation pH is 3, insulated and stirred 20 minutes, add the 10% of above-mentioned Colophonium weight, stannous sulfate, stirring, to room temperature, obtains modified rosin alcohol liquid；
(3) by remaining Colophonium, fumaric acid mixing, 200 DEG C of insulation reaction 2.7 hours, are cooled to 157 DEG C of dischargings under nitrogen protection; join in the dehydrated alcohol of its weight 10 times; dripping above-mentioned 20% sodium hydroxide solution, stirring is to room temperature, sucking filtration; vacuum drying; being then added in the dehydrated alcohol of its weight 6 times, dropping concentration is the hydrochloric acid solution of 5%, and regulation pH is 3; stir, obtain modified fumaropimaric acid；
(4) above-mentioned 2 mercaptobenzimidazoles are joined in above-mentioned abienol liquid, stir, add modified fumaropimaric acid, at 46 DEG C ultrasonic 2 minutes, sucking filtration, is vacuum dried precipitation, mixes with ethylene glycol, antimony oxide, it is passed through nitrogen, stirring reaction 3 hours at 150 DEG C, rising high-temperature is 210 DEG C, continues insulation 1.7 hours, cooling discharge, obtains modified poly ester polyhydric alcohol；
(5) above-mentioned sodium polyacrylate is joined in the deionized water of its weight 80 times, dropping acetic acid, regulation pH is 2, adds zinc chloride, stir, the sodium hydroxide of dropping 3mol/l, regulation pH is 10, insulation reaction 3 hours at 87 DEG C, centrifugation, precipitation is washed 2 times, is vacuum dried 10 hours at 60 DEG C, obtains water-dispersion type zinc oxide；
(6) by above-mentioned polyether Glycols, the mixing of modified poly ester polyhydric alcohol, at 118 DEG C, vacuum dehydration 2 hours, are cooled to room temperature, mix with toluene di-isocyanate(TDI), insulation reaction 100 minutes at 76 DEG C, add 2,2 dihydromethyl propionic acids, continue insulation reaction 50 minutes, add above-mentioned diethylene glycol, insulation reaction 4 hours at 57 DEG C, it is cooled to room temperature, add above-mentioned triethylamine, stir, obtain rosin acid modified poly ester；
(7) above-mentioned polymine being joined in the dehydrated alcohol of its weight 5 times, rising high-temperature is 70 DEG C, adds above-mentioned rosin acid modified poly ester, Y r-chloropropyl trimethoxyl silane, insulated and stirred 10 minutes, ethanol is distilled off, obtains silane-modified polyester；
(8) above-mentioned silane-modified polyester is joined in the deionized water of its weight 4 times, add above-mentioned water-dispersion type zinc oxide and remain each raw material, ultrasonic 20 minutes, to obtain final product.
Performance test with the coating gained paint film of the present invention:
Impact strength: 120kg cm;
Adhesive force: 1；
Hot strength: 25.7MPa；
Elongation at break: 560.4%；
Water absorption rate: 12.5%；
Viscosity: 43.5 mPa s.
Claims (2)
1. a shock resistance waterborne polyester coating, it is characterised in that it is made up of the raw material of following weight parts:
Potassium titanate 1-2, cellulose propionate 2-3, polymine 1-2, sym-closene 0.8-1, Y-r-chloropropyl trimethoxyl silane 1.6-2, trisnonyl phenyl phosphite 0.3-1, Colophonium 35-40, fumaric acid 8-10, 20-30% sodium hydroxide solution 6-7, ethylene glycol 20-34, antimony oxide 0.1-0.2, sodium polyacrylate 2-3, zinc chloride 13-20, polyether Glycols 80-90, toluene di-isocyanate(TDI) 100-130, 2, 2-dihydromethyl propionic acid 2-3, diethylene glycol 4-5, triethylamine 1-2, 2-mercaptobenzimidazole 0.2-0.4, hexadecyltrimethylammonium chloride 1-2, stannous sulfate 0.1-0.2.
2. the preparation method of a shock resistance waterborne polyester coating as claimed in claim 1, it is characterised in that comprise the following steps；
(1) above-mentioned hexadecyltrimethylammonium chloride is joined in the deionized water of its weight 10-14 times, stir, add cellulose propionate, insulated and stirred 5-8 minute at 60-70 DEG C, obtain fiber dispersion；
(2) above-mentioned sym-closene is taken, join in the dehydrated alcohol of its weight 12-17 times, stir, rise high-temperature and be 70-75 DEG C, the sulfuric acid solution of dropping 96-98%, regulation pH is 3-4, insulated and stirred 20-30 minute, adding the 10-15% of above-mentioned Colophonium weight, stannous sulfate, stirring, to room temperature, obtains modified rosin alcohol liquid；
(3) by remaining Colophonium, fumaric acid mixing, 200-230 DEG C of insulation reaction 2.7-3 hour under nitrogen protection, it is cooled to 157-160 DEG C of discharging; join in the dehydrated alcohol of its weight 10-15 times; dripping above-mentioned 20-30% sodium hydroxide solution, stirring is to room temperature, sucking filtration; vacuum drying; being then added in the dehydrated alcohol of its weight 6-8 times, dropping concentration is the hydrochloric acid solution of 5-7%, and regulation pH is 3-4; stir, obtain modified fumaropimaric acid；
(4) above-mentioned 2-mercaptobenzimidazole is joined in above-mentioned abienol liquid, stir, add modified fumaropimaric acid, at 46-50 DEG C ultrasonic 2-3 minute, sucking filtration, is vacuum dried precipitation, mixes with ethylene glycol, antimony oxide, it is passed through nitrogen, stirring reaction 3-4 hour at 150-160 DEG C, rises high-temperature and is 210-220 DEG C, continue insulation 1.7-2 hour, cooling discharge, obtains modified poly ester polyhydric alcohol；
(5) above-mentioned sodium polyacrylate is joined in the deionized water of its weight 80-100 times, dropping acetic acid, regulation pH is 2-3, adds zinc chloride, stir, the sodium hydroxide of dropping 3-5mol/l, regulation pH is 10-11, insulation reaction 3-5 hour at 87-90 DEG C, centrifugation, precipitation is washed 2-3 time, is vacuum dried 10-11 hour at 60-65 DEG C, obtains water-dispersion type zinc oxide；
(6) by above-mentioned polyether Glycols, the mixing of modified poly ester polyhydric alcohol, at 118-130 DEG C, vacuum dehydration 2-3 hour, is cooled to room temperature, mix with toluene di-isocyanate(TDI), insulation reaction 100-120 minute at 76-80 DEG C, add 2,2-dihydromethyl propionic acid, continue insulation reaction 50-60 minute, add above-mentioned diethylene glycol, insulation reaction 4-5 hour at 57-60 DEG C, it is cooled to room temperature, add above-mentioned triethylamine, stir, obtain rosin acid modified poly ester；
(7) above-mentioned polymine is joined in the dehydrated alcohol of its weight 5-8 times, rise high-temperature and be 70-80 DEG C, add above-mentioned rosin acid modified poly ester, Y-r-chloropropyl trimethoxyl silane, insulated and stirred 10-20 minute, ethanol is distilled off, obtain silane-modified polyester；
(8) above-mentioned silane-modified polyester is joined in the deionized water of its weight 4-6 times, add above-mentioned water-dispersion type zinc oxide and remain each raw material, ultrasonic 20-30 minute, to obtain final product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078893A (en) * | 2019-05-27 | 2019-08-02 | 南京工业大学 | A kind of ultraviolet light solidifies the preparation method of hyperbranched abienol polyurethane acrylate resin |
| CN114015272A (en) * | 2021-11-22 | 2022-02-08 | 湖南志洲新型干混建材有限公司 | High-strength waterproof anti-cracking putty powder and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN102086337A (en) * | 2010-12-28 | 2011-06-08 | 上海海隆赛能新材料有限公司 | High-performance impact-resistance steel structure paint |
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| CN110078893A (en) * | 2019-05-27 | 2019-08-02 | 南京工业大学 | A kind of ultraviolet light solidifies the preparation method of hyperbranched abienol polyurethane acrylate resin |
| CN114015272A (en) * | 2021-11-22 | 2022-02-08 | 湖南志洲新型干混建材有限公司 | High-strength waterproof anti-cracking putty powder and preparation method thereof |
| CN114015272B (en) * | 2021-11-22 | 2022-10-11 | 湖南志洲新型干混建材有限公司 | High-strength waterproof anti-cracking putty powder and preparation method thereof |
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