阅读说明：本技术 一种磁性超疏水聚苯乙烯基多孔材料及其制备方法 (Magnetic super-hydrophobic polystyrene porous material and preparation method thereof ) 是由 赵春霞 黄浩然 郭长远 李云涛 邓诗琴 向东 郭翠翠 于 2019-10-25 设计创作，主要内容包括：本发明公开了一种磁性超疏水聚苯乙烯基多孔材料的制备方法,由原料苯乙烯单体、含环氧基烯类单体、氨基改性四氧化三铁和交联剂,在引发剂、水和乳化剂作用下,于40-80℃聚合反应4-24h,得到磁性超疏水聚苯乙烯基多孔材料。所述交联剂为二甲基丙烯酸乙二醇酯、二乙烯基苯、三烯丙基异氰脲酸酯、季戊四醇三丙烯酸酯、三羟甲基丙烷三丙烯酸酯中的一种。所述含环氧基烯类单体是甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯、硬脂酸缩水甘油基酯中的一种。本发明制备的磁性超疏水聚苯乙烯基多孔材料同时具备超疏水、磁性响应,可用于食品行业,化学化工行业以及石油行业的油水分离,并且能够在磁性驱动下进行自动油水分离。(The invention discloses a preparation method of a magnetic super-hydrophobic polystyrene-based porous material, which comprises the step of carrying out polymerization reaction on a styrene monomer, an epoxy group-containing alkene monomer, amino modified ferroferric oxide and a cross-linking agent at 40-80 ℃ for 4-24 hours under the action of an initiator, water and an emulsifier to obtain the magnetic super-hydrophobic polystyrene-based porous material. The cross-linking agent is one of ethylene glycol dimethacrylate, divinyl benzene, triallyl isocyanurate, pentaerythritol triacrylate and trimethylolpropane triacrylate. The epoxy group-containing alkene monomer is one of glycidyl methacrylate, glycidyl acrylate and glycidyl stearate. The magnetic super-hydrophobic polystyrene-based porous material prepared by the invention has super-hydrophobic and magnetic responses, can be used for oil-water separation in the food industry, the chemical industry and the petroleum industry, and can perform automatic oil-water separation under the magnetic drive.)

1. The preparation method of the magnetic super-hydrophobic polystyrene-based porous material is characterized in that the magnetic super-hydrophobic polystyrene-based porous material is prepared by carrying out in-situ polymerization reaction on a styrene monomer, an alkene monomer containing epoxy groups, amino modified ferroferric oxide and a cross-linking agent.

2. The preparation method of the magnetic super-hydrophobic polystyrene-based porous material as claimed in claim 1, wherein the magnetic super-hydrophobic polystyrene-based porous material is obtained by carrying out polymerization reaction on raw materials of a styrene monomer, an epoxy group-containing alkene monomer, amino modified ferroferric oxide and a cross-linking agent at 40-80 ℃ for 4-24h under the action of an initiator, water and an emulsifier.

3. The method for preparing a magnetic superhydrophobic polystyrene-based porous material according to claim 2, comprising the steps of:

s1, preparation of amino modified ferroferric oxide, which comprises the following steps:

s11, dispersing ferric chloride hexahydrate in an organic solvent to form a transparent solution A; then dispersing anhydrous sodium acetate and the amino-containing polymer in the solution A to form a uniformly mixed solution B;

s12, heating the mixed solution B to 100 ℃ and 300 ℃, reacting for 4-24h to form a black product, and then cleaning the black product by absolute ethyl alcohol and deionized water under the action of a magnetic field to prepare amino modified ferroferric oxide;

s2, adding deionized water into a mixed system of styrene, an epoxy group-containing alkene monomer, a cross-linking agent, amino modified ferroferric oxide, an initiator and an emulsifier, and stirring and emulsifying to obtain a prepolymerization system;

s3, heating the prepolymerization system to 40-80 ℃ for polymerization reaction for 4-24h, cleaning the polymerization product with deionized water and absolute ethyl alcohol, and drying by blowing at 40-100 ℃ for 8-24h to obtain the magnetic super-hydrophobic polystyrene-based porous material.

4. The method for preparing a magnetic super-hydrophobic polystyrene-based porous material as claimed in claim 3, wherein the amino-containing polymer is one of polyetheramine, polyethyleneimine, amino-terminated polydimethylsiloxane, polyacrylamide and polydopamine.

5. The method for preparing a magnetic superhydrophobic polystyrene-based porous material according to claim 3, wherein the organic solvent is one of ethanol, ethylene glycol and glycerol.

6. The method for preparing a magnetic superhydrophobic polystyrene-based porous material according to claim 3, wherein the epoxy group-containing olefinic monomer is one of glycidyl methacrylate, glycidyl acrylate and glycidyl stearate.

7. The method for preparing a magnetic superhydrophobic polystyrene-based porous material according to claim 3, wherein the crosslinking agent is one of ethylene glycol dimethacrylate, divinylbenzene, triallyl isocyanurate, pentaerythritol triacrylate, and trimethylolpropane triacrylate.

8. The method for preparing the magnetic super-hydrophobic polystyrene-based porous material as claimed in claim 3, wherein the emulsifier is one of span60, span80, Tween20, Tween60 and Tween 80.

9. The method for preparing a magnetic superhydrophobic polystyrene-based porous material according to claim 3, wherein the initiator is one of azobisisobutyronitrile, ammonium persulfate, potassium persulfate and benzoyl peroxide.

10. A magnetic super-hydrophobic polystyrene-based porous material, characterized by being prepared by the preparation method of any one of claims 1 to 9.

Technical Field

The invention relates to the technical field of composite materials, in particular to a magnetic super-hydrophobic polystyrene-based porous material and a preparation method thereof.

Background

In the world, a large amount of oily wastewater is generated in the industries of mining, textile, food, petrochemical industry, metal/steel and the like, becomes a main pollutant in the world, and has serious influence on the daily life and the ecological environment of people. However, the removal of oil from oily wastewater remains a challenge. Methods such as gravity separation, centrifugation, ultrasonic separation, air flotation, electric field, adsorption, biological treatment and the like are widely applied to the treatment of oily wastewater. Among these methods, the application of adsorption is considered as one of the most promising technologies in terms of its convenience, low cost, high efficiency, no secondary pollution, and the like.

Therefore, researchers have developed various functional materials for treating oily wastewater. Functional materials with special wettability, such as super-hydrophilic/super-oleophobic or super-hydrophobic/super-oleophilic porous materials, can selectively filter or absorb oil in oil-water mixtures. The functional materials are successfully designed and prepared and are widely applied to oil-water separation. However, research on such functional materials with special wettability has yet to be further advanced.

Disclosure of Invention

The invention aims to provide a magnetic super-hydrophobic polystyrene-based porous material for oil-water separation

The invention also aims to provide a preparation method of the magnetic super-hydrophobic polystyrene-based porous material.

The magnetic super-hydrophobic polystyrene-based porous material provided by the invention is prepared by in-situ polymerization of styrene, an epoxy group-containing vinyl monomer, a cross-linking agent and amino modified ferroferric oxide under the action of an initiator, water and an emulsifier.

The preparation method comprises the following steps:

s1, preparation of amino modified ferroferric oxide, which comprises the following steps:

s11, dispersing 5-20 parts by weight of ferric chloride hexahydrate in 50-90 parts by weight of organic solvent to form a transparent solution A; then dispersing 4-20 parts by weight of anhydrous sodium acetate and 1-10 parts by weight of amino-containing polymer in the solution A, and mechanically stirring at 200-1000rpm for 5-60min to form a uniformly mixed solution B; the organic solvent is one of ethanol, glycol and glycerol. The amino-containing polymer is one of polyetheramine, polyethyleneimine, amino-terminated polydimethylsiloxane, polyacrylamide and polydopamine.

S12, adding the mixed solution B into a polytetrafluoroethylene reaction kettle, heating to 100-300 ℃, reacting for 4-24h to form a black product, and then washing for several times through absolute ethyl alcohol and deionized water under the action of a magnetic field to prepare the amino modified ferroferric oxide.

S2, adding 100-3000 parts by weight of deionized water into a mixed system of 10-50 parts by weight of styrene, 10-50 parts by weight of epoxy group-containing vinyl monomer, 10-50 parts by weight of cross-linking agent, 5-20 parts by weight of amino modified ferroferric oxide, 1-10 parts by weight of initiator and 5-50 parts by weight of emulsifier, and stirring and emulsifying for 5-60min to obtain a prepolymerization system;

s3, heating the prepolymerization system to 40-80 ℃ for reaction for 4-24h, washing the product with deionized water and absolute ethyl alcohol, and drying by blowing at 40-100 ℃ for 8-24h to obtain the magnetic super-hydrophobic polystyrene-based porous material.

Preferably, the epoxy group-containing olefinic monomer is one of glycidyl methacrylate, glycidyl acrylate and glycidyl stearate.

Preferably, the crosslinking agent is one of ethylene glycol dimethacrylate, divinylbenzene, triallyl isocyanurate, pentaerythritol triacrylate, and trimethylolpropane triacrylate.

Preferably, the emulsifier is one of span60, span80, Tween20, Tween60 and Tween 80.

Preferably, the initiator is one of azobisisobutyronitrile, ammonium persulfate, potassium persulfate and benzoyl peroxide.

Compared with the prior art, the invention has the advantages that:

firstly, the added ferroferric oxide can not only increase the rough structure of the porous material, but also endow the material with magnetic response, so that the material is controlled by an external magnetic field; the porous material is driven to carry out automatic oil-water separation under the action of an external magnetic field. And the amino-modified ferroferric oxide and the epoxy group in the epoxy group-containing alkene monomer are subjected to ring-opening reaction, so that the ferroferric oxide has stronger binding capacity with the porous material skeleton and is not easy to separate and fall off, and the polystyrene-based porous material has stable and lasting superhydrophobic performance.

Secondly, the porous material has higher contact angle and durable oil-water separation capability, has a stable micro-nano layered structure, and can be used for high-flux continuous operation. The magnetic separator has the characteristics of super-hydrophobicity and magnetic response, can be used for oil-water separation in the food industry, the chemical industry and the petroleum industry, and can perform automatic oil-water separation under the magnetic drive.

Thirdly, the magnetic super-hydrophobic polystyrene porous material is prepared by polymerization by taking water as a dispersion medium, and the experimental process is simple and is easy to prepare in batches; and toxic and harmful solvents are not used, so that the method conforms to the sustainable development trend of environment-friendly materials.

Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.

Drawings

FIG. 1 is a scanning electron microscope photograph of an amino-modified ferroferric oxide according to example 1.

Fig. 2 is a scanning electron microscope image of the magnetic porous material prepared in example 1.

FIG. 3 is an infrared absorption spectrum of amino-modified ferroferric oxide and a magnetic porous material in example 1.

Fig. 4 is a static contact angle of the magnetic superhydrophobic polystyrene-based porous material of example 1.

FIG. 5 is a simulated oil-water separation oil absorption performance test of the magnetic super-hydrophobic polystyrene-based porous material of example 1.

Detailed Description

The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.

The performance test related in the embodiment of the invention is carried out according to the following method:

1. scanning Electron microscope Picture (SEM)

And adopting a JSM-7500F scanning electron microscope to analyze the shapes of the amino modified ferroferric oxide and the magnetic porous material, wherein the accelerating voltage is 20.0KV, and the surface gold spraying treatment is required before the sample is tested.

2. Infrared absorption Spectrum (FTIR)

A KBr tabletting method is adopted for sample preparation, and a Nicolet FTIR 6700 type Fourier transform infrared spectrometer is used for testing the amino modified ferroferric oxide and the magnetic porous material.

3. Static contact Angle (WCA)

The contact angle test is to drop a liquid drop on the surface of a material, the liquid drop stays on the surface of the material, and the static hydrophobic angle of the liquid drop is obtained through the Laplace algorithm. The contact angle of the surface of the magnetic porous material with water was measured and analyzed by using a tester model OCA25 from Dataphysics, germany.