阅读说明：本技术 一种磁性超疏水聚氨酯海绵油水分离材料及其制法 (Magnetic super-hydrophobic polyurethane sponge oil-water separation material and preparation method thereof ) 是由 林多炉 于 2020-06-02 设计创作，主要内容包括：本发明涉及聚氨酯材料技术领域,且公开了一种磁性超疏水聚氨酯海绵油水分离材料,包括以下配方原料及组分：SiO<Sub>2</Sub>-Fe<Sub>3</Sub>O<Sub>4</Sub>接枝氟化聚丙烯酸、聚酯多元醇、六亚甲基二异氰酸酯、催化剂、稳泡剂、扩链剂。该一种磁性超疏水聚氨酯海绵油水分离材料,在纳米Fe<Sub>3</Sub>O<Sub>4</Sub>中空球的表面形成一层比表面积巨大纳米SiO<Sub>2</Sub>的包覆层,高接枝率的乙烯基三甲氧基硅烷接枝改性SiO<Sub>2</Sub>包覆Fe<Sub>3</Sub>O<Sub>4</Sub>,与1H,1H,2H,2H-全氟癸基丙烯酸酯、巯基乙醇和4,4’-偶氮双(4-氰基戊醇)交联聚合,再与聚酯多元醇和六亚甲基二异氰酸酯,进行反应和发泡过程,并且通过化学共价键的修饰,改善了纳米SiO<Sub>2</Sub>和纳米Fe<Sub>3</Sub>O<Sub>4</Sub>与聚氨酯海绵的相容性,赋予了聚氨酯海绵优异的超疏水性能和磁性,对油水混合物具有良好的吸油特性。(The invention relates to the technical field of polyurethane materials, and discloses a magnetic super-hydrophobic polyurethane sponge oil-water separation material which comprises the following formula raw materials and components: SiO 2 2 ‑Fe 3 O 4 Grafted fluorinated polyacrylic acid, polyester polyol, hexamethylene diisocyanate, a catalyst, a foam stabilizer and a chain extender. The magnetic super-hydrophobic polyurethane sponge oil-water separation material is prepared by mixing nano Fe 3 O 4 A layer of nano SiO with huge specific surface area is formed on the surface of the hollow sphere 2 Coating layer of (1), vinyl trimethoxy silane graft modified SiO with high graft rate 2 Coated with Fe 3 O 4 With 1H,1H,2H, 2H-perfluorodecyl acrylate or mercaptoThe base ethanol and the 4,4' -azo-bis (4-cyanopentanol) are subjected to cross-linking polymerization, then are reacted with polyester polyol and hexamethylene diisocyanate, the foaming process is carried out, and the modification of chemical covalent bonds is carried out, so that the nano SiO is improved 2 And nano Fe 3 O 4 The polyurethane sponge has compatibility with polyurethane sponge, excellent super-hydrophobic property and magnetism, and good oil absorption property for oil-water mixture.)

1. The magnetic super-hydrophobic polyurethane sponge oil-water separation material comprises the following formula raw materials and components, and is characterized in that: 8-28 parts of SiO₂-Fe₃O₄Grafted fluorinated polyacrylic acid, 45-52 parts of polyester polyol, 22-28 parts of hexamethylene diisocyanate, 0.5-1 part of catalyst, 0.5-3 parts of foam stabilizer and 4-8 parts of chain extender.

2. The magnetic super-hydrophobic polyurethane sponge oil-water separation material as claimed in claim 1, wherein: the catalyst is stannous octoate, the foam stabilizer is silicone oil foam stabilizer, and the chain extender is 1, 4-butanediol.

3. The magnetic super-hydrophobic polyurethane sponge oil-water separation material as claimed in claim 1, wherein: the SiO₂-Fe₃O₄The preparation method of the grafted fluorinated polyacrylic acid comprises the following steps:

(1) adding FeCl to ethylene glycol solvent₃And NaHCO₃Transferring the solution into a reaction kettle after uniform stirring, placing the solution into a heating box, heating the solution to the temperature of 180-240 ℃, reacting for 10-18h, filtering, washing and drying to prepare the nano Fe₃O₄A hollow ball;

(2) adding nano Fe into a mixed solvent of distilled water and ethanol with the volume ratio of 1:4-5₃O₄Ultrasonically dispersing the hollow spheres uniformly, adding ammonia water to adjust the pH value of the solution to 8-9, adding ethyl orthosilicate, reacting for 12-18h, filtering, washing and drying to obtain the nano SiO₂Coated with Fe₃O₄；

(3) Adding nano SiO into a mixed solvent of distilled water and ethanol with the volume ratio of 1:20-30₂Coated with Fe₃O₄Adding vinyltrimethoxysilane after ultrasonic dispersion is uniform, reacting for 2-5h at 40-60 ℃, filtering, washing and drying to prepare the vinyltrimethoxysilane grafted modified SiO₂Coated with Fe₃O₄；

(4) Adding modified SiO into tetrahydrofuran solvent₂Coated with Fe₃O₄Adding 1H,1H,2H, 2H-perfluorodecyl acrylate, mercaptoethanol and 4,4' -azobis (4-cyanopentanol) after ultrasonic dispersion is uniform, heating to 65-85 ℃, reacting for 25-35H, removing the solvent, washing and drying to prepare the SiO₂-Fe₃O₄Grafted fluorinated polyacrylic acid.

4. The magnetic super-hydrophobic polymer as claimed in claim 3The oil-water separation material for the polyurethane sponge is characterized in that: the FeCl₃And NaHCO₃The mass ratio of (A) to (B) is 1: 4-6.

5. The magnetic super-hydrophobic polyurethane sponge oil-water separation material as claimed in claim 3, wherein: the nano Fe₃O₄The mass ratio of the hollow ball to the ethyl orthosilicate is 1: 18-25.

6. The magnetic super-hydrophobic polyurethane sponge oil-water separation material as claimed in claim 3, wherein: the nano SiO₂Coated with Fe₃O₄And the mass ratio of the vinyltrimethoxysilane to the vinyltrimethoxysilane is 6-10: 1.

7. The magnetic super-hydrophobic polyurethane sponge oil-water separation material as claimed in claim 3, wherein: the modified SiO₂Coated with Fe₃O₄The mass ratio of the 1H,1H,2H, 2H-perfluorodecyl acrylate to the mercaptoethanol to the 4,4' -azobis (4-cyanopentanol) is 1:8-12:3-5: 10-15.

8. The magnetic super-hydrophobic polyurethane sponge oil-water separation material as claimed in claim 3, wherein: the heating cabinet includes that the inside fixedly connected with of box, box adds the heat ring, the bottom of box is provided with the base, the inside fixedly connected with rotary device of base, the inside swing joint of rotary device has the bearing, bearing and rotary rod swing joint, the upper end fixedly connected with objective table of rotary rod, being provided with reation kettle of objective table, objective table top fixedly connected with slide rail, slide rail and pulley swing joint, pulley swing joint has the stopper, the top of stopper is provided with the fixture block, the fixture block is with the draw-in groove swing joint of apron.

9. The magnetic super-hydrophobic polyurethane sponge oil-water separation material as claimed in claim 1, wherein: the preparation method of the magnetic super-hydrophobic polyurethane sponge oil-water separation material comprises the following steps:

(1) adding 8-28 parts of SiO into acetone solvent₂-Fe₃O₄Grafting polyacrylic acid fluoride, 22-28 parts of hexamethylene diisocyanate and 0.5-1 part of catalyst stannous octoate, heating to 70-90 ℃, reacting for 4-6h, cooling to 60-70 ℃, adding 45-52 parts of polyester polyol, 4-8 parts of chain extender 1, 4-butanediol and 0.5-3 parts of foam stabilizer, and carrying out reaction, foaming and expansion processes on the materials in a polyurethane foaming machine to prepare the magnetic super-hydrophobic polyurethane sponge oil-water separation material.

Technical Field

The invention relates to the technical field of polyurethane materials, in particular to a magnetic super-hydrophobic polyurethane sponge oil-water separation material and a preparation method thereof.

Background

Along with the development of industrialization, the discharge amount of industrial oily wastewater is continuously increased, meanwhile, in recent years, offshore oil leakage events frequently occur, serious pollution and damage are caused to the ecological environment, the traditional adsorptive oil-water separation material is low in superhydrophobic performance, low in separation efficiency and difficult to recycle, the stable contact angle of the surface of the superhydrophobic material is larger than 150 degrees, the rolling contact angle is smaller than 10 degrees, and the superhydrophobic material has excellent hydrophobic performance, antifouling capability and self-cleaning property, and has wide application prospects in the aspects of outdoor building rain and snow prevention, ocean ship antifouling and anticorrosion, petroleum pipeline transportation and the like.

The polyurethane has good stability, rebound resilience, chemical resistance and mechanical property, can be prepared into materials such as polyurethane plastics, polyurethane fibers, polyurethane elastomers, polyurethane coatings, polyurethane sponge and the like, wherein the polyurethane sponge has the advantages of three-dimensional porous structure, good flexibility, high oil absorption capacity, low cost and the like, has great application potential in the field of oil-water separation, but the traditional polyurethane sponge does not have super-hydrophobic property and is difficult to recycle, and magnetic nano Fe can be added into the polyurethane sponge₃O₄The polyurethane sponge material is recycled by an external magnetic field, and the nano Fe₃O₄The compatibility with polyurethane sponge is poor, and the nano Fe can be generated by a physical blending method₃O₄Not tightly combined with polyurethane sponge, nano Fe₃O₄Is easy to fall off, and greatly reduces the magnetism and the recyclability of the polyurethane sponge.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a magnetic super-hydrophobic polyurethane sponge oil-water separation material and a preparation method thereof, solves the problem that the traditional polyurethane sponge does not have super-hydrophobic property, and simultaneously solves the problem that nano Fe₃O₄Poor compatibility with polyurethane sponge and untight combination.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: a magnetic super-hydrophobic polyurethane sponge oil-water separation material comprises the following formula raw materials and components: 8-28 parts of SiO₂-Fe₃O₄Grafted fluorinated polyacrylic acid, 45-52 parts of polyester polyol, 22-28 parts of hexamethylene diisocyanate, 0.5-1 part of catalyst and 0.5-3 parts of4-8 parts of a chain extender.

Preferably, the catalyst is stannous octoate, the foam stabilizer is a silicone oil foam stabilizer, and the chain extender is 1, 4-butanediol.

Preferably, the SiO₂-Fe₃O₄The preparation method of the grafted fluorinated polyacrylic acid comprises the following steps:

(1) adding glycol solvent, FeCl into a reaction bottle₃And NaHCO₃After the solution is uniformly stirred, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle in a heating box, heating the solution to 180-240 ℃, reacting for 10-18h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the nano Fe₃O₄A hollow ball.

(2) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1:4-5, and adding nano Fe₃O₄Ultrasonically dispersing the hollow spheres uniformly, adding ammonia water to adjust the pH value of the solution to 8-9, adding ethyl orthosilicate, stirring at a constant speed to react for 12-18h, filtering the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to obtain the nano SiO₂Coated with Fe₃O₄。

(3) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1:20-30, and then adding nano SiO₂Coated with Fe₃O₄Adding vinyltrimethoxysilane after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 2-5h at 40-60 ℃, filtering the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the vinyltrimethoxysilane grafted modified SiO₂Coated with Fe₃O₄。

(4) Adding tetrahydrofuran solvent and modified SiO into a reaction bottle₂Coated with Fe₃O₄Adding 1H,1H,2H, 2H-perfluorodecyl acrylate, mercaptoethanol and 4,4' -azobis (4-cyanopentanol) after uniform ultrasonic dispersion, placing in a constant temperature water bath, heating to 65-85 ℃, stirring at constant speed for reaction for 25-35H, drying the solution in vacuum to remove the solvent, washing the solid product with diethyl ether, and fully dryingTo prepare SiO₂-Fe₃O₄Grafted fluorinated polyacrylic acid.

Preferably, the FeCl₃And NaHCO₃The mass ratio of (A) to (B) is 1: 4-6.

Preferably, the nano Fe₃O₄The mass ratio of the hollow ball to the ethyl orthosilicate is 1: 18-25.

Preferably, the nano SiO₂Coated with Fe₃O₄And the mass ratio of the vinyltrimethoxysilane to the vinyltrimethoxysilane is 6-10: 1.

Preferably, the modified SiO₂Coated with Fe₃O₄The mass ratio of the 1H,1H,2H, 2H-perfluorodecyl acrylate to the mercaptoethanol to the 4,4' -azobis (4-cyanopentanol) is 1:8-12:3-5: 10-15.

Preferably, the bottom that the heating cabinet includes the inside fixedly connected with heating collar of box, box is provided with the base, the inside fixedly connected with rotary device of base, the inside swing joint of rotary device has the bearing, bearing and rotary rod swing joint, the upper end fixedly connected with objective table of rotary rod, being provided with reation kettle of objective table, objective table top fixedly connected with slide rail, slide rail and pulley swing joint, pulley swing joint has the stopper, the top of stopper is provided with the fixture block, the fixture block is with the draw-in groove swing joint of apron.

Preferably, the preparation method of the magnetic super-hydrophobic polyurethane sponge oil-water separation material comprises the following steps:

(1) adding acetone solvent and 8-28 parts of SiO into a reaction bottle₂-Fe₃O₄Grafting polyacrylic acid fluoride, 22-28 parts of hexamethylene diisocyanate and 0.5-1 part of catalyst stannous octoate, placing the materials in a constant-temperature water bath kettle, heating the materials to 70-90 ℃, uniformly stirring the materials for reaction for 4-6 hours, cooling the temperature to 60-70 ℃, adding 45-52 parts of polyester polyol, 4-8 parts of chain extender 1, 4-butanediol and 0.5-3 parts of foam stabilizer, and carrying out reaction, foaming and expansion processes on the materials in a polyurethane foaming machine to prepare the magnetic super-hydrophobic polyurethane sponge oil-water separation material.

(III) advantageous technical effects

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

the magnetic super-hydrophobic polyurethane sponge oil-water separation material is prepared by taking sodium bicarbonate as a sacrificial template and a pore-foaming agent through a hot solvent method to obtain nano Fe with smaller particle size and larger specific surface area₃O₄Hollow ball, and then in-situ polymerization is carried out on the nano Fe₃O₄A layer of nano SiO with huge specific surface area is formed on the surface of the hollow sphere₂Coating layer of (2), SiO₂The high specific surface has more hydroxyl groups, and the reaction with the vinyltrimethoxysilane is easy to obtain the vinyltrimethoxysilane grafted modified SiO with high grafting rate₂Coated with Fe₃O₄。

The magnetic super-hydrophobic polyurethane sponge oil-water separation material is modified SiO₂Coated with Fe₃O₄The vinyl trimethoxy silane is cross-linked and polymerized with 1H,1H,2H, 2H-perfluorodecyl acrylate with strong hydrophobicity, mercaptoethanol and 4,4' -azobis (4-cyanopentanol) to obtain hydroxyl-terminated SiO by a chemical bond bonding method₂-Fe₃O₄Grafting fluorinated polyacrylic acid, then reacting with polyester polyol and hexamethylene diisocyanate, and foaming to obtain polyurethane sponge with excellent hydrophobic performance, and greatly improving the nano SiO through modification of chemical covalent bond instead of physical blending₂And nano Fe₃O₄Compatibility with polyurethane sponge, so that nano SiO₂And nano Fe₃O₄The oil-water mixture oil-water composite material is uniformly dispersed in a matrix of the polyurethane sponge, is very tight in combination and difficult to fall off, has excellent super-hydrophobic property and magnetism, has a good oil absorption characteristic on the oil-water mixture, can magnetically recover the polyurethane sponge through an external magnetic field, and avoids causing secondary pollution.

Drawings

FIG. 1 is a schematic front view of a reaction tank;

fig. 2 is an enlarged schematic view of the stage.

1. A box body; 2. heating a ring; 3. a base; 4. a rotating device; 5. a bearing; 6. rotating the rod; 7. an object stage; 8. a reaction kettle; 9. a slide rail; 10. a pulley; 11. a limiting block; 12. a clamping block; 13. a cover plate; 14. a clamping groove.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: a magnetic super-hydrophobic polyurethane sponge oil-water separation material comprises the following formula raw materials and components: 8-28 parts of SiO₂-Fe₃O₄The modified polyacrylic acid polyester polyol is prepared from the following raw materials, by weight, 45-52 parts of grafted fluorinated polyacrylic acid, 22-28 parts of hexamethylene diisocyanate, 0.5-1 part of a catalyst, 0.5-3 parts of a foam stabilizer and 4-8 parts of a chain extender, wherein the catalyst is stannous octoate, the foam stabilizer is a silicone oil foam stabilizer and the chain extender is 1, 4-butanediol.

SiO₂-Fe₃O₄The preparation method of the grafted fluorinated polyacrylic acid comprises the following steps:

(1) adding glycol solvent, FeCl into a reaction bottle₃And NaHCO₃The mass ratio of the two is 1:4-6, the solution is transferred into a polytetrafluoroethylene reaction kettle after being stirred evenly, and the heating box comprises a box body, a heating ring is fixedly connected inside the box body, a base is arranged at the bottom of the box body, a rotating device is fixedly connected inside the base, a bearing is movably connected inside the rotating device, the bearing is movably connected with a rotating rod, an objective table is fixedly connected to the upper end of the rotating rod, a reaction kettle is arranged on the objective table, a sliding rail is fixedly connected above the objective table, the sliding rail is movably connected with a pulley, a limiting block is movably connected with the pulley, a clamping block is arranged above the limiting block, the clamping block is movably connected with a clamping groove of a cover plate, the heating is carried out to 180 degrees centigrade, the reaction is carried out for 10-18 hours, the solution is cooled to room temperature, a solvent is filtered and removed.₃O₄A hollow ball.

(2) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1:4-5, and adding nano Fe₃O₄Ultrasonically dispersing the hollow spheres uniformly, adding ammonia water to adjust the pH of the solution to 8-9, adding ethyl orthosilicate according to the mass ratio of 1:18-25, stirring at a constant speed for reaction for 12-18h, filtering the solution to remove the solvent, washing with distilled water and ethanolWashing the solid product and fully drying to prepare the nano SiO₂Coated with Fe₃O₄。

(3) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 1:20-30, and then adding nano SiO₂Coated with Fe₃O₄Uniformly dispersing by ultrasonic, adding vinyl trimethoxy silane with the mass ratio of 6-10:1, uniformly stirring at 40-60 ℃ for reaction for 2-5h, filtering the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the modified SiO grafted by the vinyl trimethoxy silane₂Coated with Fe₃O₄。

(4) Adding tetrahydrofuran solvent and modified SiO into a reaction bottle₂Coated with Fe₃O₄Uniformly dispersing by ultrasonic wave, adding 1H,1H,2H, 2H-perfluorodecyl acrylate, mercaptoethanol and 4,4' -azobis (4-cyanopentanol) in a mass ratio of 1:8-12:3-5:10-15, placing in a constant-temperature water bath, heating to 65-85 ℃, uniformly stirring for reaction for 25-35H, drying the solution in vacuum to remove the solvent, washing the solid product by using ether, and fully drying to obtain SiO₂-Fe₃O₄Grafted fluorinated polyacrylic acid.

The preparation method of the magnetic super-hydrophobic polyurethane sponge oil-water separation material comprises the following steps:

(1) adding acetone solvent and 8-28 parts of SiO into a reaction bottle₂-Fe₃O₄Grafting polyacrylic acid fluoride, 22-28 parts of hexamethylene diisocyanate and 0.5-1 part of catalyst stannous octoate, placing the materials in a constant-temperature water bath kettle, heating the materials to 70-90 ℃, uniformly stirring the materials for reaction for 4-6 hours, cooling the temperature to 60-70 ℃, adding 45-52 parts of polyester polyol, 4-8 parts of chain extender 1, 4-butanediol and 0.5-3 parts of foam stabilizer, and carrying out reaction, foaming and expansion processes on the materials in a polyurethane foaming machine to prepare the magnetic super-hydrophobic polyurethane sponge oil-water separation material.