CN104312411A - Waterproof high-hardness waterborne polyurethane coating - Google Patents
Waterproof high-hardness waterborne polyurethane coating Download PDFInfo
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Abstract
The invention discloses a waterproof high-hardness waterborne polyurethane coating which is characterized by comprising the following components in parts by weight: 65-80 parts of modified waterborne polyurethane, 20-35 parts of waterborne polyaniline, 3-6 parts of polyisocyanate, 5-20 parts of nano-silica, 3-9 parts of isopropanol, 5-10 parts of ethylene glycol propyl ether, 0.5-1.6 parts of dipentaerythritol, 15-20 parts of polydimethylsiloxane, 3-8 parts of gamma-isocyanate propyl triethoxy silane, 3-8 parts of polytetrafluoroethylene, 0.5-3 parts of modified carbon nanotubes, 5-20 parts of precipitated barium sulphate, 2-6 parts of amino resin, 3-8 parts of zinc powder and 30-60 parts of water. The waterproof high-hardness waterborne polyurethane coating is good in water resistance, high in harness and long in service life.
Description
Technical field
The present invention relates to technical field of coatings, particularly relate to a kind of water-fast high hardness polyurethane coating.
Background technology
Urethane refers to the general designation of a base polymer of amido-containing acid ester key in molecular backbone chain, is generated under normal circumstances by isocyanic ester and polyvalent alcohol generation polyaddition reaction.Aqueous polyurethane, using water as dispersion medium, has the advantage such as environment-protecting asepsis, difficult to burn, and can be regulated the over-all properties of resin material by change soft or hard section kind and ratio.After the end of the sixties in last century, aqueous polyurethane was introduced into market, aqueous polyurethane with the viscosifying power of excellence, outstanding temp. variation resistant performance, excellent resistance to low temperature, good biocompatibility and the characteristic of environment-protecting asepsis and be widely used in multiple field.Although aqueous polyurethane molecular chain chemical structure is identical with solvent borne polyurethane, compared with solvent borne polyurethane, still there are some defects at aspect of performance, such as, molecular weight be little, poor water resistance and hardness little etc., because which limit its application.At present, aqueous polyurethane coating, in water tolerance and the requirement that can not meet society in work-ing life, needs to carry out modification.
Summary of the invention
The present invention proposes a kind of water-fast high hardness polyurethane coating, its water-tolerant, hardness are high, long service life.
The present invention proposes a kind of water-fast high hardness polyurethane coating, its raw material comprises following component by weight: modified aqueous polyurethane 65-80 part, aqueous polyanion 20-35 part, polyisocyanates 3-6 part, nano silicon 5-20 part, Virahol 3-9 part, glycol propyl ether 5-10 part, dipentaerythritol 0.5-1.6 part, polydimethylsiloxane 15-20 part, γ-isocyanic ester propyl-triethoxysilicane 3-8 part, tetrafluoroethylene 3-8 part, modified carbon nano-tube 0.5-3 part, process white 5-20 part, aminoresin 2-6 part, zinc powder 3-8 part, water 30-60 part;
Wherein, described modified aqueous polyurethane is prepared according to following technique: under nitrogen protection, by weight by 40-50 part polyoxyethylene glycol, 15-25 part glucose and 50-60 part isoflurane chalcone diisocyanate add in flask, stir under infrared lamp and be warming up to 84-87 DEG C, reaction 2.5-3h, be cooled to 41-45 DEG C, then 3-6 part 1 is added successively, 4-butyleneglycol, 5-10 part dimethylol propionic acid, 0.5-1.5 part dibutyl tin laurate and 0.5-1.5 part stannous octoate, be warming up to 72-76 DEG C, 20-35 part acetone is added after reaction 150-250min, be cooled to 25-33 DEG C, add 2-6 part triethylamine and 25-60 part deionized water, with the rotating speed dispersed with stirring 200-350min of 500-800r/min, described modified aqueous polyurethane is obtained after volatilization.
Preferably, its raw material comprises following component by weight: modified aqueous polyurethane 70-75 part, aqueous polyanion 25-30 part, polyisocyanates 3.8-5.6 part, nano silicon 10-16 part, Virahol 3.9-7 part, glycol propyl ether 7-9 part, dipentaerythritol 0.9-1.3 part, polydimethylsiloxane 17-19 part, γ-isocyanic ester propyl-triethoxysilicane 3.8-6.8 part, tetrafluoroethylene 5-6.8 part, modified carbon nano-tube 1.5-2.3 part, process white 12-17 part, aminoresin 2.8-5 part, zinc powder 4-6 part, water 40-55 part.
Preferably, its raw material comprises following component by weight: modified aqueous polyurethane 73 parts, aqueous polyanion 27 parts, polyisocyanates 5 parts, nano silicon 13 parts, Virahol 6 parts, glycol propyl ether 7.8 parts, dipentaerythritol 1.16 parts, polydimethylsiloxane 17.6 parts, γ-isocyanic ester propyl-triethoxysilicane 5.3 parts, tetrafluoroethylene 6.3 parts, modified carbon nano-tube 2.1 parts, process white 15.3 parts, 4.2 parts, aminoresin, zinc powder 4.9 parts, 47 parts, water.
Preferably, described nano silicon is coupling agent modified nano silicon, and described coupling agent is amino silicane coupling agent.
Preferably, described amino silicane coupling agent is one or more the combination in KH550, KH540, KH602.
Preferably, described modified aqueous polyurethane is prepared according to following technique: under nitrogen protection, by weight by 42-48 part polyoxyethylene glycol, 19-23 part glucose and 52-58 part isoflurane chalcone diisocyanate add in flask, stir under infrared lamp and be warming up to 85-86 DEG C, reaction 2.7-2.9h, be cooled to 42-44 DEG C, then 3.6-5.6 part 1 is added successively, 4-butyleneglycol, 6-8.9 part dimethylol propionic acid, 0.9-1.3 part dibutyl tin laurate and 0.8-1.2 part stannous octoate, be warming up to 73-75 DEG C, 26-32 part acetone is added after reaction 180-220min, be cooled to 28-31 DEG C, add 3-5.6 part triethylamine and 40-55 part deionized water, with the rotating speed dispersed with stirring 250-300min of 600-700r/min, described modified aqueous polyurethane is obtained after volatilization.
Preferably, described modified aqueous polyurethane is prepared according to following technique: under nitrogen protection, by weight by 46 parts of polyoxyethylene glycol, 21 parts of glucose and 55 parts of isoflurane chalcone diisocyanates add in flask, stir under infrared lamp and be warming up to 85 DEG C, reaction 2.75h, be cooled to 43 DEG C, then 4.9 part 1 is added successively, 4-butyleneglycol, 8.5 parts of dimethylol propionic acids, 1.1 parts of dibutyl tin laurates and 0.96 part of stannous octoate, be warming up to 74 DEG C, 29 parts of acetone are added after reaction 215min, be cooled to 30 DEG C, add 5.2 parts of triethylamines and 46 parts of deionized waters, with the rotating speed dispersed with stirring 268min of 690r/min, described modified aqueous polyurethane is obtained after volatilization.
Water-fast high hardness polyurethane coating of the present invention, in its raw material, the weight part of modified aqueous polyurethane can be 65.6, 67, 68, 68.3, 69, 72.6, 75.6, 76, 76.8, 77, 77.9, 78, 78.6, 79, 79.5 parts, the weight part of aqueous polyanion can be 20.3, 21, 21.5, 22, 22.6, 23, 23.5, 24, 24.6, 25.6, 26, 26.3, 27.4, 28, 28.5, 29, 29.6, 30.2, 31, 31.3, 32, 32.6, 33, 33.5, 34, 34.6 parts, the weight part of polyisocyanates can be 3.2, 3.5, 3.9, 4.1, 4.5, 4.7, 5.3, 5.9 parts, the weight part of nano silicon can be 5.9, 6, 6.3, 7, 7.4, 8, 8.5, 9, 9.6, 10.5, 11, 11.4, 12, 12.3, 13.4, 14, 14.6, 15, 15.9, 16.7, 17, 17.4, 18, 18.5, 19, 19.6 parts, the weight part of Virahol can be 3.6, 4, 4.5, 5, 5.2, 5.6, 6.4, 7.8, 8, 8.4 part, the weight part of glycol propyl ether can be 5.6, 6, 6.3, 7.4, 8, 8.4, 9.6 parts, the weight part of dipentaerythritol can be 0.6, 0.68, 0.7, 0.75, 0.8, 0.86, 1.0, 1.06, 1.1, 1.15, 1.2, 1.24, 1.37, 1.4, 1.48, 1.5, 1.53 parts, the weight part of polydimethylsiloxane can be 15.6, 16, 16.3, 17.8, 18, 18.4, 19.4 parts, the weight part of γ-isocyanic ester propyl-triethoxysilicane can be 3.3, 4, 4.5, 4.9, 5, 5.2, 5.8, 6, 6.3, 7, 7.4 parts, the weight part of tetrafluoroethylene can be 3.2, 3.7, 4, 4.2, 4.8, 5.3, 5.7, 6, 7, 7.8 parts, the weight part of modified carbon nano-tube can be 0.6, 0.78, 0.9, 1.05, 1.3, 1.87, 2.26, 2.45, 2.5, 2.6, 2.78, 2.9, 2.94 parts, the weight part of process white can be 5.6, 6, 6.4, 7, 7.8, 8, 8.9, 9, 9.5, 10, 11, 12.6, 13, 13.5, 14, 15, 15.6, 16, 16.7, 17.4, 18, 18.4, 19, 19.5 parts, the weight part of aminoresin can be 2.6, 3, 3.4, 4, 4.5, 5.3 parts, the weight part of zinc powder can be 3.3, 3.7, 4.2, 4.8, 5, 5.6, 6.3, 6.9, 7, 7.2 parts, the weight part of water can be 33, 36, 38.4, 39, 41.2, 42, 42.5, 43, 43.6, 44, 44.9, 49, 51, 51.3, 52, 53, 53.6, 54, 58, 59.4 parts.
In the present invention, aqueous polyurethane, using water as dispersion medium, has the advantage such as environment-protecting asepsis, difficult to burn, but compare solvent borne polyurethane, water tolerance, non-corrosibility are poor; Glucose is the most extensive most important a kind of monose of occurring in nature distribution, a kind of poly-hydroxy aldehyde, containing five hydroxyls in molecule, can react with-NCO, generate the urethane with cross-linked structure, molecular chain movement is restricted, and large-scale being cross-linked makes intermolecular space diminish, water molecules is difficult to enter polyurethane molecular inside, show as glued membrane water-intake rate constantly to decline, water tolerance improves, and the introducing of glucose makes this system polyurethane crosslinking degree increase, internal cohesive energy becomes large, improves thermostability and the hardness of coating glued membrane; Six-membered ring structure simultaneously in glucose molecule makes cross-link intensity be greatly improved, and rigidity increases, and internal cohesive energy strengthens, and further increases hardness and the thermotolerance of coating; Meanwhile, the unreacted hydroxyl contained in the glucose in molecule can form a large amount of hydrogen bonds, further increases cross-link intensity, improves its hardness and water tolerance; Group in aqueous polyurethane molecular chain and nano silicon, modified carbon nano-tube surface group can form chemical bond, improve the thermotolerance of coating, mechanical property, water tolerance and hardness, in optimal way, nano silicon is with after coupling agent modified, improve the consistency with urethane, containing the amino in amino silicane coupling agent can with polyurethane prepolymer precursor reactant, formed chemical bond, the interfacial effect of both improvement, strengthens the performance improving aqueous polyurethane; The γ added-isocyanic ester propyl-triethoxysilicane coordinates with modified carbon nano-tube, nano-calcium carbonate, improves the water tolerance of aqueous polyurethane coating, thermotolerance and hardness and shock resistance while maintaining its performance; Modified carbon nano-tube has self lubricity in addition, adds in coating, coordinates with tetrafluoroethylene, can reduce the frictional coefficient of matrix material; In addition, the electropotential of zinc will lower than iron, in electrolytic reaction, when occurring to corrode, first zinc powder is corroded as negative electrode, prevent the corrosion of iron and steel, the redox potential of aqueous polyanion is higher than the redox potential of iron, if the surface of iron and steel is oxidized, one deck compact metal oxide film can be formed between steel surface and polyaniline, the electropotential of iron is made to be in passivation region, prevent the further corrosion of iron and steel, the synergy of zinc powder and aqueous polyanion, improve the Corrosion Protection of coating.In the present invention, many kinds of substance combines with modified aqueous polyurethane, while respectively getting the chief, play coordinative role, makes that the water-resistant coating that obtains is good, hardness is high, long service life.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail; should understand; embodiment is only for illustration of the present invention, instead of for limiting the present invention, any amendment, equivalent replacement etc. made on basis of the present invention is all in protection scope of the present invention.
Embodiment 1
Water-fast high hardness polyurethane coating of the present invention, its raw material comprises following component by weight: modified aqueous polyurethane 65 parts, aqueous polyanion 35 parts, polyisocyanates 3 parts, nano silicon 20 parts, Virahol 3 parts, glycol propyl ether 10 parts, dipentaerythritol 0.5 part, polydimethylsiloxane 20 parts, γ-isocyanic ester propyl-triethoxysilicane 3 parts, tetrafluoroethylene 8 parts, modified carbon nano-tube 0.5 part, process white 20 parts, 2 parts, aminoresin, zinc powder 8 parts, 30 parts, water;
Wherein, described modified aqueous polyurethane is prepared according to following technique: under nitrogen protection, by weight by 40 parts of polyoxyethylene glycol, 25 parts of glucose and 50 parts of isoflurane chalcone diisocyanates add in flask, stir under infrared lamp and be warming up to 87 DEG C, reaction 2.5h, be cooled to 45 DEG C, then 3 part 1 is added successively, 4-butyleneglycol, 10 parts of dimethylol propionic acids, 0.5 part of dibutyl tin laurate and 1.5 parts of stannous octoates, be warming up to 72 DEG C, 20 parts of acetone are added after reaction 250min, be cooled to 33 DEG C, add 2 parts of triethylamines and 60 parts of deionized waters, with the rotating speed dispersed with stirring 350min of 500r/min, described modified aqueous polyurethane is obtained after volatilization.
Embodiment 2
Water-fast high hardness polyurethane coating of the present invention, its raw material comprises following component by weight: modified aqueous polyurethane 80 parts, aqueous polyanion 20 parts, polyisocyanates 6 parts, nano silicon 5 parts, Virahol 9 parts, glycol propyl ether 5 parts, dipentaerythritol 1.6 parts, polydimethylsiloxane 15 parts, γ-isocyanic ester propyl-triethoxysilicane 8 parts, tetrafluoroethylene 3 parts, modified carbon nano-tube 3 parts, process white 5 parts, 6 parts, aminoresin, zinc powder 3 parts, 60 parts, water; Described nano silicon is aminosilane coupling agent modifying nano silicon;
Wherein, described modified aqueous polyurethane is prepared according to following technique: under nitrogen protection, by weight by 50 parts of polyoxyethylene glycol, 15 parts of glucose and 60 parts of isoflurane chalcone diisocyanates add in flask, stir under infrared lamp and be warming up to 84 DEG C, reaction 3h, be cooled to 41 DEG C, then 6 part 1 is added successively, 4-butyleneglycol, 5 parts of dimethylol propionic acids, 1.5 parts of dibutyl tin laurates and 0.5 part of stannous octoate, be warming up to 76 DEG C, 35 parts of acetone are added after reaction 150min, be cooled to 25 DEG C, add 6 parts of triethylamines and 25 parts of deionized waters, with the rotating speed dispersed with stirring 200min of 800r/min, described modified aqueous polyurethane is obtained after volatilization.
Embodiment 3
Water-fast high hardness polyurethane coating of the present invention, its raw material comprises following component by weight: modified aqueous polyurethane 77 parts, aqueous polyanion 23 parts, polyisocyanates 3.9 parts, nano silicon 13.4 parts, Virahol 5.6 parts, glycol propyl ether 8.4 parts, dipentaerythritol 1.37 parts, polydimethylsiloxane 18 parts, γ-isocyanic ester propyl-triethoxysilicane 5 parts, tetrafluoroethylene 6 parts, modified carbon nano-tube 2.26 parts, process white 18 parts, 4.5 parts, aminoresin, zinc powder 6.3 parts, 52 parts, water; Described nano silicon is amino silicane coupling agent KH550 modified manometer silicon dioxide;
Wherein, described modified aqueous polyurethane is prepared according to following technique: under nitrogen protection, by weight by 46 parts of polyoxyethylene glycol, 19 parts of glucose and 52 parts of isoflurane chalcone diisocyanates add in flask, stir under infrared lamp and be warming up to 86 DEG C, reaction 2.55h, be cooled to 42 DEG C, then 3.7 part 1 is added successively, 4-butyleneglycol, 7.6 parts of dimethylol propionic acids, 1.16 parts of dibutyl tin laurates and 1.23 parts of stannous octoates, be warming up to 73 DEG C, 32 parts of acetone are added after reaction 198min, be cooled to 29 DEG C, add 3.6 parts of triethylamines and 49 parts of deionized waters, with the rotating speed dispersed with stirring 325min of 545r/min, described modified aqueous polyurethane is obtained after volatilization.
Embodiment 4
Water-fast high hardness polyurethane coating of the present invention, its raw material comprises following component by weight: modified aqueous polyurethane 73 parts, aqueous polyanion 27 parts, polyisocyanates 5 parts, nano silicon 13 parts, Virahol 6 parts, glycol propyl ether 7.8 parts, dipentaerythritol 1.16 parts, polydimethylsiloxane 17.6 parts, γ-isocyanic ester propyl-triethoxysilicane 5.3 parts, tetrafluoroethylene 6.3 parts, modified carbon nano-tube 2.1 parts, process white 15.3 parts, 4.2 parts, aminoresin, zinc powder 4.9 parts, 47 parts, water; Described nano silicon is modified manometer silicon dioxide, and properties-correcting agent is KH550, KH540, KH602 combination by any weight ratio;
Wherein, described modified aqueous polyurethane is prepared according to following technique: under nitrogen protection, by weight by 46 parts of polyoxyethylene glycol, 21 parts of glucose and 55 parts of isoflurane chalcone diisocyanates add in flask, stir under infrared lamp and be warming up to 85 DEG C, reaction 2.75h, be cooled to 43 DEG C, then 4.9 part 1 is added successively, 4-butyleneglycol, 8.5 parts of dimethylol propionic acids, 1.1 parts of dibutyl tin laurates and 0.96 part of stannous octoate, be warming up to 74 DEG C, 29 parts of acetone are added after reaction 215min, be cooled to 30 DEG C, add 5.2 parts of triethylamines and 46 parts of deionized waters, with the rotating speed dispersed with stirring 268min of 690r/min, described modified aqueous polyurethane is obtained after volatilization.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (7)
1. a water-fast high hardness polyurethane coating, it is characterized in that, its raw material comprises following component by weight: modified aqueous polyurethane 65-80 part, aqueous polyanion 20-35 part, polyisocyanates 3-6 part, nano silicon 5-20 part, Virahol 3-9 part, glycol propyl ether 5-10 part, dipentaerythritol 0.5-1.6 part, polydimethylsiloxane 15-20 part, γ-isocyanic ester propyl-triethoxysilicane 3-8 part, tetrafluoroethylene 3-8 part, modified carbon nano-tube 0.5-3 part, process white 5-20 part, aminoresin 2-6 part, zinc powder 3-8 part, water 30-60 part,
Wherein, described modified aqueous polyurethane is prepared according to following technique: under nitrogen protection, by weight by 40-50 part polyoxyethylene glycol, 15-25 part glucose and 50-60 part isoflurane chalcone diisocyanate add in flask, stir under infrared lamp and be warming up to 84-87 DEG C, reaction 2.5-3h, be cooled to 41-45 DEG C, then 3-6 part 1 is added successively, 4-butyleneglycol, 5-10 part dimethylol propionic acid, 0.5-1.5 part dibutyl tin laurate and 0.5-1.5 part stannous octoate, be warming up to 72-76 DEG C, 20-35 part acetone is added after reaction 150-250min, be cooled to 25-33 DEG C, add 2-6 part triethylamine and 25-60 part deionized water, with the rotating speed dispersed with stirring 200-350min of 500-800r/min, described modified aqueous polyurethane is obtained after volatilization.
2. water-fast high hardness polyurethane coating according to claim 1, it is characterized in that, its raw material comprises following component by weight: modified aqueous polyurethane 70-75 part, aqueous polyanion 25-30 part, polyisocyanates 3.8-5.6 part, nano silicon 10-16 part, Virahol 3.9-7 part, glycol propyl ether 7-9 part, dipentaerythritol 0.9-1.3 part, polydimethylsiloxane 17-19 part, γ-isocyanic ester propyl-triethoxysilicane 3.8-6.8 part, tetrafluoroethylene 5-6.8 part, modified carbon nano-tube 1.5-2.3 part, process white 12-17 part, aminoresin 2.8-5 part, zinc powder 4-6 part, water 40-55 part.
3. water-fast high hardness polyurethane coating according to claim 1 or 2, it is characterized in that, its raw material comprises following component by weight: modified aqueous polyurethane 73 parts, aqueous polyanion 27 parts, polyisocyanates 5 parts, nano silicon 13 parts, Virahol 6 parts, glycol propyl ether 7.8 parts, dipentaerythritol 1.16 parts, polydimethylsiloxane 17.6 parts, γ-isocyanic ester propyl-triethoxysilicane 5.3 parts, tetrafluoroethylene 6.3 parts, modified carbon nano-tube 2.1 parts, process white 15.3 parts, 4.2 parts, aminoresin, zinc powder 4.9 parts, 47 parts, water.
4. water-fast high hardness polyurethane coating according to any one of claim 1-3, is characterized in that, described nano silicon is coupling agent modified nano silicon, and described coupling agent is amino silicane coupling agent.
5. water-fast high hardness polyurethane coating according to claim 4, it is characterized in that, described amino silicane coupling agent is one or more the combination in KH550, KH540, KH602.
6. water-fast high hardness polyurethane coating according to any one of claim 1-5, it is characterized in that, described modified aqueous polyurethane is prepared according to following technique: under nitrogen protection, by weight by 42-48 part polyoxyethylene glycol, 19-23 part glucose and 52-58 part isoflurane chalcone diisocyanate add in flask, stir under infrared lamp and be warming up to 85-86 DEG C, reaction 2.7-2.9h, be cooled to 42-44 DEG C, then 3.6-5.6 part 1 is added successively, 4-butyleneglycol, 6-8.9 part dimethylol propionic acid, 0.9-1.3 part dibutyl tin laurate and 0.8-1.2 part stannous octoate, be warming up to 73-75 DEG C, 26-32 part acetone is added after reaction 180-220min, be cooled to 28-31 DEG C, add 3-5.6 part triethylamine and 40-55 part deionized water, with the rotating speed dispersed with stirring 250-300min of 600-700r/min, described modified aqueous polyurethane is obtained after volatilization.
7. water-fast high hardness polyurethane coating according to claim 6, it is characterized in that, described modified aqueous polyurethane is prepared according to following technique: under nitrogen protection, by weight by 46 parts of polyoxyethylene glycol, 21 parts of glucose and 55 parts of isoflurane chalcone diisocyanates add in flask, stir under infrared lamp and be warming up to 85 DEG C, reaction 2.75h, be cooled to 43 DEG C, then 4.9 part 1 is added successively, 4-butyleneglycol, 8.5 parts of dimethylol propionic acids, 1.1 parts of dibutyl tin laurates and 0.96 part of stannous octoate, be warming up to 74 DEG C, 29 parts of acetone are added after reaction 215min, be cooled to 30 DEG C, add 5.2 parts of triethylamines and 46 parts of deionized waters, with the rotating speed dispersed with stirring 268min of 690r/min, described modified aqueous polyurethane is obtained after volatilization.
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