阅读说明：本技术 一种有机-无机硅改性聚氨酯超疏水涂料及其制法 (Organic-inorganic silicon modified polyurethane super-hydrophobic coating and preparation method thereof ) 是由 姚国江 于 2019-10-28 设计创作，主要内容包括：本发明涉及聚氨酯超疏水涂料技术领域,且公开了一种有机-无机硅改性聚氨酯超疏水涂料及其制法,包括以下配方原料：十八烷基三乙氧基硅烷、纳米二氧化硅、碳纳米管、固化剂、异佛尔酮二异氰酸酯、1,5-戊二醇、二羟甲基丙酸、羟基封端聚硅氧烷硅油、中和剂、水合肼。该一种有机-无机硅改性聚氨酯超疏水涂料及其制法,有机硅双羟基封端聚硅氧烷硅油作为扩链剂制备得到改性聚氨酯,其含有大量的疏水性基团甲基和烷烃链,大幅增强了聚氨酯疏水性能,SiO<Sub>2</Sub>和碳纳米管具有较高的化学惰性、良好的力学性能和机械性能,提高了聚氨酯涂料的化学稳定性和韧性,避免涂料在长时间使用过程中容易损耗和脱落的现象。(The invention relates to the technical field of polyurethane super-hydrophobic coatings, and discloses an organic-inorganic silicon modified polyurethane super-hydrophobic coating and a preparation method thereof, wherein the organic-inorganic silicon modified polyurethane super-hydrophobic coating comprises the following formula raw materials: octadecyl triethoxy silane, nano silicon dioxide, a carbon nano tube, a curing agent, isophorone diisocyanate, 1, 5-pentanediol, dimethylolpropionic acid, hydroxyl-terminated polysiloxane silicone oil, a neutralizer and hydrazine hydrate. The organic-inorganic silicon modified polyurethane super-hydrophobic coating and the coating thereofThe preparation method comprises the step of preparing modified polyurethane by using the organosilicon dihydroxy-terminated polysiloxane silicone oil as a chain extender, wherein the modified polyurethane contains a large amount of hydrophobic groups, namely methyl and alkane chains, so that the hydrophobic property of the polyurethane is greatly enhanced, and SiO 2 And the carbon nano tube has higher chemical inertia, good mechanical property and mechanical property, improves the chemical stability and toughness of the polyurethane coating, and avoids the phenomena that the coating is easy to lose and fall off in the long-time use process.)

1. An organic-inorganic silicon modified polyurethane super-hydrophobic coating and a preparation method thereof, which comprises the following formula raw materials in parts by weight, and is characterized in that: 5-7 parts of octadecyl triethoxy silane, 4-6 parts of nano silicon dioxide, 4-24 parts of carbon nano tube, 4-6 parts of curing agent, 45-50 parts of isophorone diisocyanate, 1-2 parts of 1, 5-pentanediol, 4-6 parts of dimethylolpropionic acid, 8-10 parts of dihydroxy terminated polysiloxane silicone oil, 3-5 parts of neutralizing agent and 2-4 parts of hydrazine hydrate, and the preparation method comprises the following experimental medicines: distilled water, ethylene glycol, absolute ethyl alcohol and sodium hydroxide.

2. The organic-inorganic silicon modified polyurethane super-hydrophobic coating and the preparation method thereof as claimed in claim 1, wherein the coating is characterized in that: the average particle size of the nano silicon dioxide is 15 nm.

3. The organic-inorganic silicon modified polyurethane super-hydrophobic coating and the preparation method thereof as claimed in claim 1, wherein the coating is characterized in that: the carbon nano tube is an aminated multi-wall carbon nano tube, and the amino content is more than or equal to 0.45 percent.

4. The organic-inorganic silicon modified polyurethane super-hydrophobic coating and the preparation method thereof as claimed in claim 1, wherein the coating is characterized in that: the curing agent is curing agent N-dodecyl succinic anhydride.

5. The organic-inorganic silicon modified polyurethane super-hydrophobic coating and the preparation method thereof as claimed in claim 1, wherein the coating is characterized in that: the neutralizing agent is triethanolamine.

6. The organic-inorganic silicon modified polyurethane super-hydrophobic coating and the preparation method thereof as claimed in claim 1, wherein the coating is characterized in that: NH in the hydrazine hydrate₂-NH₂The mass fraction is more than or equal to 51 percent.

7. The organic-inorganic silicon modified polyurethane super-hydrophobic coating and the preparation method thereof as claimed in claim 1, wherein the coating is characterized in that: the preparation method of the organic-inorganic silicon modified polyurethane super-hydrophobic coating comprises the following steps:

(1) preparation of modified Nano SiO₂: adding 200-600mL of absolute ethyl alcohol into a reaction bottle, sequentially adding 5-7 parts of octadecyl triethoxysilane and 4-6 parts of nano silicon dioxide, uniformly stirring, slowly adding sodium hydroxide while uniformly stirring to adjust the pH value of the solution to 8-9, transferring the solution into a hydrothermal synthesis reaction kettle, placing the kettle in an oven, heating to 120-130 ℃, reacting for 6-8h, easily cooling to room temperature after the reaction is finished, filtering to remove the solvent, sequentially washing the solid product with a proper amount of absolute ethyl alcohol and distilled water, and fully drying to obtain octadecyl triethoxysilane modified nano SiO₂。

(2) Preparation of modified Nano SiO₂Loading aminated carbon nanotubes: adding 800mL of distilled water into the reaction kettle, and sequentially adding 4-24 parts of carbon nano tube and the modified nano SiO prepared in the step (1)₂Heating the reaction kettle in an oven to 80-90 ℃ for reaction for 3-5h, and reactingAfter the reaction is finished, cooling the solution to room temperature, filtering to remove the solvent, washing the product by using a proper amount of distilled water, and fully drying to obtain the modified nano SiO₂And loading the aminated carbon nanotube.

(3) Preparing organic silicon modified polyurethane: adding 1000mL of 200-mL of ethylene glycol into a reaction bottle, adding 45-50 parts of isophorone diisocyanate, 8-10 parts of dihydroxy-terminated polysiloxane silicone oil and 1-2 parts of 1, 5-pentanediol, placing the reaction bottle into a constant-temperature water bath kettle, heating to 85-90 ℃, uniformly stirring for reaction for 1-1.5h, adding 4-6 parts of dimethylolpropionic acid, uniformly stirring for reaction for 3-5h, cooling to 60-70 ℃ in the water bath kettle, adding 3-5 parts of triethanolamine as a neutralizing agent, uniformly stirring for reaction for 30-50min, reducing the temperature of the water bath kettle to 30-35 ℃, slowly adding 2-4 parts of hydrazine hydrate, uniformly stirring for reaction for 2-4h, placing the material into a high-speed centrifuge after the reaction is finished, centrifuging at a centrifugal speed of not less than 12000rpm, removing the upper-layer ethylene glycol solution, washing the product with a proper amount of anhydrous ether and distilled water, and fully drying to obtain the organic silicon modified polyurethane.

(4) Preparing an organic-inorganic silicon modified polyurethane super-hydrophobic coating: adding a proper amount of N-methyl pyrrolidone into a reaction bottle, and then sequentially adding 4-6 parts of curing agent N-dodecyl succinic anhydride and the modified nano SiO prepared in the step (2)₂Loading an aminated carbon nanotube and the organic silicon modified polyurethane prepared in the step (3), controlling the solid-liquid mass ratio to be 35-60%, placing a reaction bottle in an ultrasonic dispersion instrument, and heating to 50-70 ℃. And performing ultrasonic dispersion treatment for 3-6h at the ultrasonic frequency of 20-28KHz to prepare the organic-inorganic silicon modified polyurethane super-hydrophobic coating.

Technical Field

The invention relates to the technical field of polyurethane super-hydrophobic coatings, in particular to an organic-inorganic silicon modified polyurethane super-hydrophobic coating and a preparation method thereof.

Background

The self-cleaning surface is a super-hydrophobic surface, pollutants on the surface of the super-hydrophobic surface can automatically fall off under the action of external force such as gravity or rainwater, the surface hydrophobic technology is widely applied in daily life of people, through designing coatings with different chemical and physical characteristics, new functions and effects can be provided for solid materials, the super-hydrophobic coating is a novel coating with special surface properties, the contact angle between the smooth surface of a coating film and water is larger than 150 degrees, the contact angle hysteresis is smaller than 5 degrees, the super-hydrophobic coating has the effects of water prevention, snow prevention, pollution prevention, adhesion prevention, oxidation prevention, self-cleaning and the like, and the super-hydrophobic coating has a huge application prospect in a plurality of fields such as scientific research and production, life and the like.

The prior super-hydrophobic polyurethane coating has fluorine/silicon materials such as fluorinated polyethylene, fluorocarbon wax and the like, organic-inorganic hybrid materials with a nano structure such as alkoxy silane sol-gel hybrid materials and the like, high molecular melt polymers such as polyacrylonitrile, polyolefin, polycarbonate, polyamide and the like, wherein polyurethane has wide application prospects in the daily life and industrial fields due to the unique functionality of the polyurethane, the surface energy of the polyurethane material is reduced by adopting a fluorination method or the super-hydrophobic material is prepared by adopting an electrostatic spinning technology, the preparation method is difficult, the prior polyurethane super-hydrophobic material has no scale production due to immature technology, the types of the super-hydrophobic polyurethane coating in the market are few, the hydrophobic properties are uneven, meanwhile, the mechanical properties are poor, the wear resistance is poor, and the coating is easy to lose, resulting in a low durability of the superhydrophobic property.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides the organic-inorganic silicon modified polyurethane super-hydrophobic coating and the preparation method thereof, not only provides the preparation process of the super-hydrophobic polyurethane coating with simple method and simple and convenient operation, but also solves the problems of poor mechanical property and poor wear resistance of the polyurethane coating, easy loss of the coating and low durability of the super-hydrophobic property.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: the organic-inorganic silicon modified polyurethane super-hydrophobic coating comprises the following formula raw materials, by weight, 5-7 parts of octadecyl triethoxysilane, 4-6 parts of nano silicon dioxide, 4-24 parts of carbon nano tubes, 4-6 parts of a curing agent, 45-50 parts of isophorone diisocyanate, 1-2 parts of 1, 5-pentanediol, 4-6 parts of dimethylolpropionic acid, 8-10 parts of dihydroxy terminated polysiloxane silicone oil, 3-5 parts of a neutralizing agent, and 2-4 parts of hydrazine hydrate, and the preparation method comprises the following experimental medicines: distilled water, ethylene glycol, absolute ethyl alcohol and sodium hydroxide.

Preferably, the average particle size of the nano-silica is 15 nm.

Preferably, the carbon nano tube is an aminated multi-wall carbon nano tube, and the amino content is more than or equal to 0.45 percent.

Preferably, the curing agent is N-dodecyl succinic anhydride.

Preferably, the neutralizing agent is triethanolamine.

Preferably, NH in said hydrazine hydrate₂-NH₂The mass fraction is more than or equal to 51 percent.

Preferably, the preparation method of the organic-inorganic silicon modified polyurethane super-hydrophobic coating comprises the following steps:

(1) preparation of modified Nano SiO₂: adding 200-600mL of absolute ethyl alcohol into a reaction bottle, sequentially adding 5-7 parts of octadecyl triethoxysilane and 4-6 parts of nano silicon dioxide, uniformly stirring, slowly adding sodium hydroxide while uniformly stirring to adjust the pH value of the solution to 8-9, transferring the solution into a hydrothermal synthesis reaction kettle, placing the kettle in an oven, heating to 120-130 ℃, reacting for 6-8h, easily cooling to room temperature after the reaction is finished, filtering to remove the solvent, sequentially washing the solid product with a proper amount of absolute ethyl alcohol and distilled water, and fully drying to obtain octadecyl triethoxysilane modified nano SiO₂。

(2) Preparation of modified Nano SiO₂Loading aminated carbon nanotubes: adding 800mL of distilled water into the reaction kettle, and sequentially adding 4-24 parts of carbon nano tube and the modified nano SiO prepared in the step (1)₂Heating the reaction kettle in an oven to 80-90 ℃ for reaction for 3-5h, cooling the solution to room temperature after the reaction is finished, filtering to remove the solvent, washing the product with a proper amount of distilled water, and fully drying to obtain the modified nano SiO₂And loading the aminated carbon nanotube.

(3) Preparing organic silicon modified polyurethane: adding 1000mL of 200-mL of ethylene glycol into a reaction bottle, adding 45-50 parts of isophorone diisocyanate, 8-10 parts of dihydroxy-terminated polysiloxane silicone oil and 1-2 parts of 1, 5-pentanediol, placing the reaction bottle into a constant-temperature water bath kettle, heating to 85-90 ℃, uniformly stirring for reaction for 1-1.5h, adding 4-6 parts of dimethylolpropionic acid, uniformly stirring for reaction for 3-5h, cooling to 60-70 ℃ in the water bath kettle, adding 3-5 parts of triethanolamine as a neutralizing agent, uniformly stirring for reaction for 30-50min, reducing the temperature of the water bath kettle to 30-35 ℃, slowly adding 2-4 parts of hydrazine hydrate, uniformly stirring for reaction for 2-4h, placing the material into a high-speed centrifuge after the reaction is finished, centrifuging at a centrifugal speed of not less than 12000rpm, removing the upper-layer ethylene glycol solution, washing the product with a proper amount of anhydrous ether and distilled water, and fully drying to obtain the organic silicon modified polyurethane.

(4) Preparing an organic-inorganic silicon modified polyurethane super-hydrophobic coating: adding a proper amount of N-methyl pyrrolidone into a reaction bottle, and then sequentially adding 4-6 parts of curing agent N-dodecyl succinic anhydride and the modified nano SiO prepared in the step (2)₂Loading an aminated carbon nanotube and the organic silicon modified polyurethane prepared in the step (3), controlling the solid-liquid mass ratio to be 35-60%, placing a reaction bottle in an ultrasonic dispersion instrument, and heating to 50-70 ℃. And performing ultrasonic dispersion treatment for 3-6h at the ultrasonic frequency of 20-28KHz to prepare the organic-inorganic silicon modified polyurethane super-hydrophobic coating.

(III) advantageous technical effects

Compared with the prior art, the invention has the following beneficial technical effects:

according to the organic-inorganic silicon modified polyurethane super-hydrophobic coating and the preparation method thereof, the modified polyurethane is prepared by taking the organic silicon dihydroxy terminated polysiloxane silicone oil as a chain extender, the modified polyurethane contains a large amount of hydrophobic groups, namely methyl and alkane chains, so that the hydrophobic property of the polyurethane is greatly enhanced, and the octadecyl triethoxy silane modified nano SiO prepared by a hydrothermal synthesis method is used for preparing the modified polyurethane₂Octadecyl has strong hydrophobicity, and the ethoxy group forms stable hydrogen bond with amino and imino in the carbon nano tube, so that the nano SiO₂The nano SiO is uniformly loaded in the huge specific surface area and pores of the carbon nano tube, and the modified nano SiO is avoided₂Agglomeration occurs, resulting in a phenomenon of lowering hydrophobic property, and dodecyl group of N-dodecylsuccinic anhydride which is a polyurethane curing agentThe modified polyurethane coating prepared by the ultrasonic dispersion method has strong hydrophobic property.

The organic-inorganic silicon modified polyurethane super-hydrophobic coating and the preparation method thereof are characterized in that nano SiO is modified₂Load aminated carbon nanotube doped polyurethane coating, nano SiO₂The carbon nano tube has high chemical inertia and good mechanical property, improves the chemical stability and toughness of the polyurethane coating, and avoids the phenomena that the coating is easy to lose and fall off in the long-time use process.

Detailed Description

In order to achieve the purpose, the invention provides the following technical scheme: the organic-inorganic silicon modified polyurethane super-hydrophobic coating comprises the following formula raw materials, by weight, 5-7 parts of octadecyl triethoxysilane, 4-6 parts of nano silicon dioxide, 4-24 parts of carbon nano tubes, 4-6 parts of a curing agent, 45-50 parts of isophorone diisocyanate, 1-2 parts of 1, 5-pentanediol, 4-6 parts of dimethylolpropionic acid, 8-10 parts of dihydroxy terminated polysiloxane silicone oil, 3-5 parts of a neutralizing agent, and 2-4 parts of hydrazine hydrate, and the preparation method comprises the following experimental medicines: distilled water, ethylene glycol, absolute ethyl alcohol and sodium hydroxide, wherein the average particle size of nano silicon dioxide is 15nm, the carbon nano tube is an aminated multi-wall carbon nano tube, the amino content is more than or equal to 0.45 percent, the curing agent is N-dodecyl succinic anhydride, the neutralizing agent is triethanolamine, and NH in hydrazine hydrate₂-NH₂The mass fraction is more than or equal to 51 percent.

The preparation method of the organic-inorganic silicon modified polyurethane super-hydrophobic coating comprises the following steps:

(1) preparation of modified Nano SiO₂: adding 200-600mL of anhydrous ethanol into a reaction bottle, sequentially adding 5 parts of octadecyl triethoxysilane and 4 parts of nano silicon dioxide, uniformly stirring, slowly adding sodium hydroxide while stirring at a constant speed to adjust the pH value of the solution to 8-9, transferring the solution into a hydrothermal synthesis reaction kettle, placing the kettle in an oven, heating to 120-130 ℃, reacting for 6-8h, and easily cooling to room temperature after the reaction is finishedFiltering to remove the solvent, washing the solid product with a proper amount of absolute ethyl alcohol and distilled water in sequence, and fully drying to obtain the octadecyl triethoxy silane modified nano SiO₂。

(2) Preparation of modified Nano SiO₂Loading aminated carbon nanotubes: adding 800mL of distilled water into the reaction kettle, and sequentially adding 4-24 parts of carbon nano tube and the modified nano SiO prepared in the step (1)₂Heating the reaction kettle in an oven to 80-90 ℃ for reaction for 3-5h, cooling the solution to room temperature after the reaction is finished, filtering to remove the solvent, washing the product with a proper amount of distilled water, and fully drying to obtain the modified nano SiO₂And loading the aminated carbon nanotube.

(3) Preparing organic silicon modified polyurethane: adding 1000mL of 200-mL of glycol into a reaction bottle, adding 45 parts of isophorone diisocyanate, 8-dihydroxy terminated polysiloxane silicone oil and 1 part of 1, 5-pentanediol, placing the reaction bottle into a constant-temperature water bath, heating to 85-90 ℃, uniformly stirring for reaction for 1-1.5h, adding 4 parts of dimethylolpropionic acid, uniformly stirring for reaction for 3-5h, cooling the water bath to 60-70 ℃, adding 3 parts of neutralizing agent triethanolamine, uniformly stirring for reaction for 30-50min, reducing the temperature of the water bath to 30-35 ℃, slowly adding 2 parts of hydrazine hydrate, uniformly stirring for reaction for 2-4h, placing the materials into a high-speed centrifuge at the centrifugal rotation speed of more than or equal to 12000rpm, centrifugally separating to remove the upper layer of glycol solution, washing the product with a proper amount of anhydrous ether and distilled water, and fully drying to obtain the organic silicon modified polyurethane.

(4) Preparing an organic-inorganic silicon modified polyurethane super-hydrophobic coating: adding a proper amount of N-methyl pyrrolidone into a reaction bottle, and then sequentially adding 4-6 parts of curing agent N-dodecyl succinic anhydride and the modified nano SiO prepared in the step (2)₂Loading an aminated carbon nanotube and the organic silicon modified polyurethane prepared in the step (3), controlling the solid-liquid mass ratio to be 35-60%, placing a reaction bottle in an ultrasonic dispersion instrument, and heating to 50-70 ℃. And performing ultrasonic dispersion treatment for 3-6h at the ultrasonic frequency of 20-28KHz to prepare the organic-inorganic silicon modified polyurethane super-hydrophobic coating.