TiO22Grafted fluorine-long carbon chain-containing polyurethane super-hydrophobic material and preparation method thereof
阅读说明：本技术 一种TiO2接枝含氟-长碳链的聚氨酯超疏水材料及其制法 (TiO22Grafted fluorine-long carbon chain-containing polyurethane super-hydrophobic material and preparation method thereof ) 是由 李金妹 于 2020-08-12 设计创作，主要内容包括：本发明涉及聚氨酯超疏水领域,且公开了一种TiO<Sub>2</Sub>接枝含氟-长碳链的聚氨酯超疏水材料,侧链含长碳链的聚酯二元醇,与聚四氢呋喃醚二醇和异佛尔酮二异氰酸酯共聚,得到侧链含长碳链的聚氨酯预聚体,甲基丙烯酸羟乙酯作为封端剂,得到烯基封端的聚氨酯预聚体,纳米TiO<Sub>2</Sub>修饰的甲基丙烯酸、聚氨酯预聚体封端的羧基、以及含氟丙烯酸酯进行自由基共聚,得到TiO<Sub>2</Sub>接枝含氟-长碳链的聚氨酯,将长碳链和碳氟链作为侧链引入聚氨酯分子链中,降低聚氨酯的表面能,通过双齿配位键将纳米TiO<Sub>2</Sub>与聚氨酯有机结合,改善了纳米TiO<Sub>2</Sub>与聚氨酯的界面相容性,形成均匀的纳米乳突状高粗糙度结构,赋予了聚氨酯材料优异的超疏水性能和耐水性能。(The invention relates to the field of polyurethane super-hydrophobicity and discloses TiO 2 Grafting a fluorine-long carbon chain-containing polyurethane super-hydrophobic material, copolymerizing polyester diol with a side chain containing a long carbon chain with polytetrahydrofuran ether diol and isophorone diisocyanate to obtain a polyurethane prepolymer with a side chain containing a long carbon chain, taking hydroxyethyl methacrylate as a capping agent to obtain an alkenyl-terminated polyurethane prepolymer, and preparing nano TiO 2 Carrying out free radical copolymerization on modified methacrylic acid, carboxyl terminated by polyurethane prepolymer and fluorine-containing acrylate to obtain TiO 2 Grafting polyurethane containing fluorine-long carbon chain, introducing long carbon chain and fluorocarbon chain into polyurethane molecular chain as side chain, reducing surface energy of polyurethane, and coordinating nano TiO by bidentate coordination bond 2 Organically combined with polyurethane, improves the nano TiO 2 The polyurethane material has interface compatibility with polyurethane, forms a uniform nano-papillary high-roughness structure, and endows the polyurethane material with excellent super-hydrophobic property and water resistance.)
1. TiO22The grafted fluorine-long carbon chain-containing polyurethane super-hydrophobic material is characterized in that: the TiO is2The preparation method of the grafted fluorine-long carbon chain-containing polyurethane super-hydrophobic material comprises the following steps:
(1) adding nano TiO into propanol solvent2Uniformly dispersing by ultrasonic, adding methacrylic acid with the mass ratio of 10:80-120, placing in a constant temperature reactor, heating to 80-90 ℃, stirring, refluxing for 10-20h, filtering, washing and drying to obtain the methacrylic acid modified nano TiO2；
(2) Adding succinic anhydride into glycerol monooleate in a nitrogen atmosphere, heating to the temperature of 120-;
(3) adding polyester diol with a long carbon chain at a side chain and isophorone diisocyanate into polytetrahydrofuran ether glycol, heating to 70-85 ℃, stirring to react for 20-40min, adding stannous zincate serving as a catalyst, reacting for 1-2h, cooling to 50-60 ℃, adding an acetone solvent and a small molecular chain extender 1, 4-butanediol, reacting for 2-3h, heating to 75-90 ℃, adding hydroxyethyl methacrylate, reacting for 30-60min, adding distilled water, and emulsifying at a high speed to prepare an emulsion containing an alkenyl-terminated polyurethane prepolymer;
(4) adding methacrylic acid modified nano TiO into emulsion containing alkenyl-terminated polyurethane prepolymer2Methyl methacrylate, perfluoroacrylate and an emulsifier OP-10, dropwise adding a potassium persulfate solution, heating to 80-90 ℃, stirring for reaction for 5-10h, pouring the emulsion into a mold, drying and curing to form a film, and preparing the TiO2Grafting the fluorine-long carbon chain-containing polyurethane super-hydrophobic material.
2. A TiO according to claim 12The grafted fluorine-long carbon chain-containing polyurethane super-hydrophobic material is characterized in that: the nano TiO in the step (1)2Has an average particle diameter of 10 to 200 nm.
3. A TiO according to claim 12The grafted fluorine-long carbon chain-containing polyurethane super-hydrophobic material is characterized in that: the constant temperature reaction appearance in step (1) includes the oil bath groove, and oil bath groove top swing joint has the top cap, and the inside fixedly connected with heating ring of oil bath groove, the inside below of inhaling of oil bath groove is provided with the reaction bottle, and constant temperature reaction appearance below is provided with the kerve, the inside fixedly connected with screw rod of kerve, screw rod swing joint have adjusting gear, and adjusting gear swing joint has the carriage release lever, and carriage release lever swing joint has the pulley.
4. A TiO according to claim 12The grafted fluorine-long carbon chain-containing polyurethane super-hydrophobic material is characterized in that: the mass ratio of the succinic anhydride to the glycerol monooleate in the step (2) is 10: 40-45.
5. A TiO according to claim 12The grafted fluorine-long carbon chain-containing polyurethane super-hydrophobic material is characterized in that: the mass ratio of the polytetrahydrofuran ether glycol, the isophorone diisocyanate, the stannous zincate, the 1, 4-butanediol and the hydroxyethyl methacrylate in the step (3) is 100:15-35:60-80:0.5-1.5:6-8: 5-10.
6. A TiO according to claim 12The grafted fluorine-long carbon chain-containing polyurethane super-hydrophobic material is characterized in that: the perfluoroacrylate in the step (4) is any one of 2- (perfluorooctyl) ethyl methacrylate or perfluorooctyl ethyl acrylate.
7. A TiO according to claim 12The grafted fluorine-long carbon chain-containing polyurethane super-hydrophobic material is characterized in that: the alkenyl-terminated polyurethane prepolymer and the methacrylic acid modified nano TiO in the step (4)2The mass ratio of the methyl methacrylate to the perfluoroacrylate to the emulsifier OP-10 to the potassium persulfate is 100:20-40:4-8:4-10:2-3: 0.05-0.1.
Technical Field
The invention relates to the field of polyurethane super-hydrophobicity, in particular to TiO2Grafted fluorine-long carbon chain-containing polyurethane super-hydrophobic material and a preparation method thereof.
Background
The super-hydrophobic material is a novel functional material with strong hydrophobicity, the water-water contact angle of the surface of the super-hydrophobic material is larger than 150 degrees, the super-hydrophobic material has excellent hydrophobicity, water resistance and self-cleaning property, and the novel super-hydrophobic material is very wide, such as rain prevention and snow prevention of outdoor building materials, antifouling and corrosion prevention of the surface of a ship body, conveying of petroleum pipelines and the like.
The polyurethane has excellent mechanical property, rebound resilience and chemical resistance, the performance of a polyurethane elastomer is between that of plastic and rubber, and the polyurethane has the advantages of oil resistance, wear resistance, aging resistance, high hardness and the like.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides TiO2The polyurethane super-hydrophobic material grafted with fluorine-long carbon chains and the preparation method thereof solve the problem that the traditional polyurethane material does not have super-hydrophobic performance.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: TiO22Grafting a fluorine-long carbon chain-containing polyurethane super-hydrophobic material: the TiO is2Grafted fluorine-containing long carbon chain-containing polymersThe preparation method of the polyurethane super-hydrophobic material comprises the following steps:
(1) adding a propylene alcohol solvent and nano TiO into a reaction bottle2Uniformly dispersing by ultrasonic, adding methacrylic acid with the mass ratio of 10:80-120, placing in a constant temperature reactor, heating to 80-90 ℃, stirring at a constant speed for reflux reaction for 10-20h, filtering out the solvent, washing with distilled water and drying to prepare the methacrylic acid modified nano TiO2。
(2) Adding succinic anhydride and glycerol monooleate into a reaction bottle in a nitrogen atmosphere, heating to 120-130 ℃, uniformly stirring, heating to 200-220 ℃, uniformly stirring for reaction for 12-36h, adding n-hexane, uniformly stirring to remove the upper-layer liquid, drying the lower-layer oily product, and preparing the polyester diol with the side chain containing long carbon chains.
(3) Adding polytetrahydrofuran ether glycol, polyester diol with a long carbon chain at a side chain and isophorone diisocyanate into a reaction bottle, heating to 70-85 ℃, stirring at a constant speed for reaction for 20-40min, adding a catalyst stannous zincate, reacting for 1-2h, cooling to 50-60 ℃, adding an acetone solvent and a small
(4) Adding emulsion containing alkenyl-terminated polyurethane prepolymer and methacrylic acid modified nano TiO into a reaction bottle2Methyl methacrylate, perfluoroacrylate and an emulsifier OP-10, slowly dripping a potassium persulfate solution after uniformly stirring, heating to 80-90 ℃, uniformly stirring for reaction for 5-10 hours, pouring the emulsion into a mold, drying and curing to form a film, and preparing to obtain TiO2Grafting the fluorine-long carbon chain-containing polyurethane super-hydrophobic material.
Preferably, the nano TiO in the step (1)2Has an average particle diameter of 10 to 200 nm.
Preferably, the constant temperature reaction instrument in the step (1) comprises an oil bath groove, a top cover is movably connected above the oil bath groove, a heating ring is fixedly connected inside the oil bath groove, a reaction bottle is arranged below the oil bath groove, a bottom groove is arranged below the constant temperature reaction instrument, a screw rod is fixedly connected inside the bottom groove, an adjusting gear is movably connected with the screw rod, a moving rod is movably connected with the adjusting gear, and a pulley is movably connected with the moving rod.
Preferably, the mass ratio of the succinic anhydride to the glycerol monooleate in the step (2) is 10: 40-45.
Preferably, the mass ratio of the polytetrahydrofuran ether glycol, the isophorone diisocyanate, the stannous zincate, the 1, 4-butanediol and the hydroxyethyl methacrylate in the step (3) is 100:15-35:60-80:0.5-1.5:6-8: 5-10.
Preferably, the perfluoroacrylate in the step (4) is any one of 2- (perfluorooctyl) ethyl methacrylate and perfluorooctyl ethyl acrylate.
Preferably, the alkenyl-terminated polyurethane prepolymer and the methacrylic acid modified nano TiO in the step (4)2The mass ratio of the methyl methacrylate to the perfluoroacrylate to the emulsifier OP-10 to the potassium persulfate is 100:20-40:4-8:4-10:2-3: 0.05-0.1.
(III) advantageous technical effects
Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:
the TiO is2Grafting a fluorine-long carbon chain-containing polyurethane super-hydrophobic material, and forming a bidentate coordination bond by a coupling reaction between carboxyl of methacrylic acid and a Ti atom in the nano TiO2 to obtain the methacrylic acid modified nano TiO22。
The TiO is2Grafting a fluorine-long carbon chain-containing polyurethane super-hydrophobic material, carrying out ring-opening polymerization on hydroxyl of glycerol monooleate and succinic anhydride to obtain polyester diol with a side chain containing a long carbon chain, then carrying out polymerization on the polyester diol with polytetrahydrofuran ether diol and isophorone diisocyanate as monomers to obtain a polyurethane prepolymer with a side chain containing a long carbon chain, preparing an alkenyl-terminated polyurethane prepolymer by taking hydroxyethyl methacrylate as a capping agent, and enabling nano TiO to react under the initiation action of potassium persulfate to obtain the polyurethane prepolymer2Carrying out free radical copolymerization on modified methacrylic acid, carboxyl terminated by polyurethane prepolymer and fluorine-containing acrylate to obtainTiO2Polyurethane containing fluorine-long carbon chains is grafted.
The TiO is2The polyurethane super-hydrophobic material grafted with the fluorine-long carbon chain introduces the long carbon chain and the fluorocarbon chain into a polyurethane molecular chain as side chains, greatly reduces the surface energy of polyurethane, and simultaneously connects nano TiO through bidentate coordination bonds2The organic combination with polyurethane obviously improves the nanometer TiO2Interfacial compatibility with polyurethane, nano TiO2The nano-emulsion type water-based polyurethane material is dispersed in a matrix of the polyurethane material to form a uniform nano-emulsion-shaped high-roughness structure, and under the synergistic effect, the polyurethane material is endowed with excellent super-hydrophobic property and water resistance, so that the application field and the practical application of the polyurethane are widened.
Drawings
FIG. 1 is a schematic front view of an isothermal reactor;
FIG. 2 is a schematic top view of a heating collar;
FIG. 3 is an enlarged schematic view of the adjustment gear;
fig. 4 is a schematic diagram of a pulley adjustment.
1-constant temperature reaction instrument; 2-oil bath groove; 3-a top cover; 4-heating a ring; 5-reaction flask; 6-bottom groove; 7-a screw; 8-adjusting the gear; 9-moving the rod; 10-pulley.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: TiO22The preparation method of the grafted fluorine-long carbon chain-containing polyurethane super-hydrophobic material comprises the following steps:
(1) adding propanol solvent and nano TiO with average particle diameter of 10-200nm into a reaction bottle2Adding methacrylic acid after ultrasonic dispersion is uniform, wherein the mass ratio of the methacrylic acid to the methacrylic acid is 10:80-120, placing the mixture into a constant temperature reactor, wherein the constant temperature reactor comprises an oil bath groove, a top cover is movably connected above the oil bath groove, a heating ring is fixedly connected inside the oil bath groove, a reaction bottle is arranged below the oil bath groove, a bottom groove is arranged below the constant temperature reactor, a screw rod is fixedly connected inside the bottom groove, the screw rod is movably connected with an adjusting gear, the adjusting gear is movably connected with a movable rod, the movable rod is movably connected with a pulley, heating is carried out to 80-90 ℃, and the mixture isStirring at a high speed for reflux reaction for 10-20h, filtering out the solvent, washing with distilled water and drying to obtain the methacrylic acid modified nano TiO2。
(2) Adding succinic anhydride and glycerol monooleate in a mass ratio of 10:40-45 into a reaction bottle in a nitrogen atmosphere, heating to 120-130 ℃, uniformly stirring, heating to 200-220 ℃, uniformly stirring for reaction for 12-36h, adding n-hexane, uniformly stirring to remove the upper liquid, drying the lower oily product, and preparing the polyester diol with the side chain containing the long carbon chain.
(3) Adding polytetrahydrofuran ether glycol, polyester diol with a long carbon chain at a side chain and isophorone diisocyanate into a reaction bottle, heating to 70-85 ℃, stirring at a constant speed for reaction for 20-40min, adding a catalyst stannous zincate, reacting for 1-2h, cooling to 50-60 ℃, adding an acetone solvent and a small
(4) Adding emulsion containing alkenyl-terminated polyurethane prepolymer and methacrylic acid modified nano TiO into a reaction bottle2Methyl methacrylate, perfluoroacrylate and an emulsifier OP-10, evenly stirring, and slowly dripping potassium persulfate solution, wherein the alkenyl-terminated polyurethane prepolymer and the methacrylic acid modified nano TiO2The mass ratio of the methyl methacrylate to the perfluoroacrylic ester to the emulsifier OP-10 to the potassium persulfate is 100:20-40:4-8:4-10:2-3:0.05-0.1, the perfluoroacrylic ester is any one of 2- (perfluorooctyl) ethyl methacrylate or perfluorooctyl ethyl acrylate, the mixture is heated to 80-90 ℃, the mixture is stirred at a constant speed for reaction for 5-10 hours, the emulsion is poured into a mold for drying and curing to form a film, and TiO is prepared2Grafting the fluorine-long carbon chain-containing polyurethane super-hydrophobic material.