阅读说明：本技术 极性聚合物微颗粒、制备方法及其用途 (Polar polymer microparticles, preparation method and application thereof ) 是由 刘恒瑜 于 2019-08-23 设计创作，主要内容包括：本发明提供一种极性聚合物微颗粒、制备方法及其用途,属于聚合物合成技术领域,制备方法包括如下步骤：将马来酸酐、N-乙烯吡咯烷酮、乙烯基醚和引发剂在有机溶剂中混合均匀得聚合反应体系,在搅拌下发生聚合反应,反应结束后过滤、洗涤、干燥,得到所述的极性聚合物微颗粒,即P(MA-DE-NVP)微颗粒。本发明制备方法简单易行,产率高,能够增加微颗粒表面的柔软度,使得微颗粒更易溶胀和改性。本发明微颗粒具有亲水性、较高的比表面积和吸附容量,微颗粒的粒径小、粒径分布较窄,对亲水性物质的吸附容量较大,可用于水体中有机污染物的吸附与分离。(The invention provides polar polymer microparticles, a preparation method and application thereof, belonging to the technical field of polymer synthesis, wherein the preparation method comprises the following steps: uniformly mixing maleic anhydride, N-vinyl pyrrolidone, vinyl ether and an initiator in an organic solvent to obtain a polymerization reaction system, carrying out polymerization reaction under stirring, filtering, washing and drying after the reaction is finished, thus obtaining the polar polymer microparticles, namely P (MA-DE-NVP) microparticles. The preparation method is simple and easy to implement, has high yield, and can increase the softness of the surfaces of the microparticles so that the microparticles are easier to swell and modify. The microparticles of the invention have hydrophilicity, higher specific surface area and adsorption capacity, small particle size, narrower particle size distribution and larger adsorption capacity to hydrophilic substances, and can be used for adsorbing and separating organic pollutants in water.)

1. A method for producing polar polymer microparticles, characterized in that: the method comprises the following steps:

uniformly mixing maleic anhydride, N-vinyl pyrrolidone, vinyl ether and an initiator in an organic solvent to obtain a polymerization reaction system, carrying out polymerization reaction under stirring, filtering, washing and drying after the reaction is finished, thus obtaining the polar polymer microparticles, namely P (MA-DE-NVP) microparticles.

2. A method for preparing polar polymer microparticles according to claim 2, characterized in that: the initiator is azodiisoheptane or lauroyl peroxide.

3. A method for preparing polar polymer microparticles according to claim 2, characterized in that: the reaction solvent is acetone, acetonitrile, a mixture of acetone and acetonitrile, tetrahydrofuran or dimethyl sulfoxide.

4. A method for preparing polar polymer microparticles according to claim 2, characterized in that: the polymerization reaction temperature is 60-80 ℃, and the reaction time is 3-5 h.

5. A method for preparing polar polymer microparticles according to claim 2, characterized in that: hydroxyapatite and poly-a-amino acid are also added into the polymerization reaction system.

6. A polar polymeric microparticle, characterized by: the production method according to any one of claims 1 to 5.

7. A polar polymer microparticle according to claim 6, wherein: the particle size of the microparticles is 300-800 nm.

8. A polar polymer microparticle according to claim 6 or 7, wherein: the specific surface area of the microparticles is more than 600m²/g。

9. Use of the polar polymer microparticles of any one of claims 6 to 8 for adsorption and separation of organic contaminants in a water body.

10. Use according to claim 9, characterized in that: the organic pollutants are phenolic pollutants and/or amine pollutants.

Technical Field

The invention belongs to the technical field of polymer synthesis, and particularly relates to polar polymer microparticles, a preparation method and application thereof.

Background

With the development of industries in recent years, particularly the rapid development of production industries such as organic chemical industry, petrochemical industry, medicines, pesticides, insecticides and herbicides, the variety and the yield of organic compounds are increased day by day, the environment for human survival is influenced while the industries are developed, and various industrial wastewater and domestic sewage directly enter water bodies without meeting national discharge standards. Organic compounds in industrial wastewater and domestic sewage are slowly degraded, and after the organic compounds enter an aeration zone and an aquifer, residues of the organic compounds can be maintained for tens of years or even hundreds of years, and influence on the environment and harm to human health are mostly irreversible. Among them, organic phenols and amines are used as important chemical raw materials in pharmaceutical, dye and textile industries, and are also important pollutants in the environment. The substances have high toxicity, obvious carcinogenic effect and toxicity heredity, and are listed in the blacklist of fourteen environmental typical pollutants in China. The organic chemical wastewater has high concentration and high salinity, and pollutants are difficult to biodegrade, which is a difficult point for controlling water pollution. At present, the treatment method of organic chemical wastewater comprises the following steps: wet oxidation, catalytic oxidation, ozonation, incineration, concentration, electrodialysis and reverse osmosis, adsorption, coagulation sedimentation, dilution biochemical methods, and the like. Among them, the adsorption method is a low energy consumption solid phase extraction separation method, and thus, has been widely regarded and industrially widely used.

The resin polymer is used as a novel organic adsorption material and is widely applied to separation, purification and detection of bioengineering, drug synthesis and food processing. In recent years, various gels, macroporous styrene resins, and acrylic resins have played an important role in wastewater treatment and recycling. Most of the resins are polymerized by hydrophobic monomers, and have good adsorption performance on most of hydrophobic substances in environmental water. In order to improve the adsorption removal effect on hydrophilic substances in water, the development of a novel hydrophilic polymer is one of important researches in the field of resin synthesis in the future. At present, researches on hydrophilic resin polymers mainly focus on structural modification of the polymers, and polar groups (acetyl, hydroxymethyl, benzoyl, o-carboxybenzoyl, quaternary ammonium groups and the like) are introduced to enhance the hydrophilicity of the resin polymers so as to improve the adsorption capacity of hydrophilic substances.

Disclosure of Invention

The invention aims to provide a preparation method of polar polymer microparticles, which uses maleic anhydride, N-vinyl pyrrolidone and vinyl ether (DE) as monomers and synthesizes P (MA-DE-NVP) microparticles with controllable particle size by one-step polymerization, and the preparation method is simple and easy to implement and has high yield; the obtained P (MA-DE-NVP) microparticles have high hydrophilicity, specific surface area and adsorption capacity.

The technical scheme adopted by the invention for realizing the purpose is as follows:

a method for preparing polar polymer microparticles, comprising the steps of:

uniformly mixing maleic anhydride, N-vinyl pyrrolidone, vinyl ether and an initiator in an organic solvent to obtain a polymerization reaction system, carrying out polymerization reaction under stirring, filtering, washing and drying after the reaction is finished, thus obtaining the polar polymer microparticles, namely P (MA-DE-NVP) microparticles.

Anhydride groups in the Maleic Anhydride (MA) have high reactivity and polarity, and can form charge transfer complexes with various monomers with electric conductivity so as to generate alternating copolymerization reaction; n-vinyl pyrrolidone (NVP) contains a hydrophilic N atom and a carbonyl group, has a strong polarity, and is very susceptible to polymerization reaction when an unsaturated reactive vinyl group (CH2 ═ CH-) is bonded to the N atom. The preparation method takes maleic anhydride, N-vinyl pyrrolidone and vinyl ether (DE) as monomers, synthesizes P (MA-DE-NVP) microparticles with controllable particle size by one-step polymerization, and has the advantages of simplicity, easy operation and high yield; the obtained P (MA-DE-NVP) microparticles not only have hydrophilicity and hydrophobicity (the water contact angle is less than 35 degrees), have a balanced adsorption effect on various polar and nonpolar compounds, but also have higher specific surface area and mesopores (the mesopores have narrower pore size distribution and are intensively distributed at 5-10nm), and have higher adsorption capacity on hydrophilic substances. The preparation method of the invention can also increase the softness of the surface of the microparticles, so that the microparticles are easier to swell and modify.

Preferably, the initiator is azobisisoheptyl or lauroyl peroxide.

Preferably, the reaction solvent is acetone, acetonitrile, a mixture of acetone and acetonitrile, tetrahydrofuran or dimethyl sulfoxide.

Preferably, the stirring speed is 400-500 rpm.

Preferably, the polymerization reaction temperature is 60-80, and the reaction time at DEG C is 3-5 h.

Preferably, hydroxyapatite and poly-a-amino acid are also added into the polymerization reaction system. The hydroxyapatite and the poly-a-amino acid are added into a polymerization reaction system, so that the dispersibility of maleic anhydride, N-vinyl pyrrolidone, vinyl ether and an initiator in a reaction solvent can be improved, monomer small droplets containing the maleic anhydride, the N-vinyl pyrrolidone, the vinyl ether and the initiator are formed, the reaction rate and the yield can be improved, the molecular weight distribution of a copolymer can be reduced, the particle size and the particle size distribution width of P (MA-DE-NVP) microparticles are reduced, and the specific surface area of the microparticles is improved; on the other hand, the viscosity of the polymerization reaction system can be reduced, the generated P (MA-DE-NVP) microparticles are prevented from being bonded, and the particle size and the distribution stability of the P (MA-DE-NVP) microparticles can be improved.

Another object of the present invention is to provide polar polymer microparticles having high hydrophilicity, specific surface area and adsorption capacity, small particle size and narrow particle size distribution.

The technical scheme adopted by the invention for realizing the purpose is as follows:

polar polymer microparticles, prepared according to the above-described preparation method.

The P (MA-DE-NVP) microparticles not only have hydrophilicity and hydrophobicity, have a balanced adsorption effect on various polar and nonpolar compounds, but also have a high specific surface area and mesopores (the mesopores have narrow pore size distribution and are intensively distributed at 5-10nm), have a large adsorption capacity on hydrophilic substances, and have high surface softness, are easy to swell and modify and have a wide application range.

Preferably, the particle size of the microparticles is 300-800 nm. More preferably 400-500 nm.

Preferably, the microparticles have a specific surface area > 600m²/g。

The invention also discloses the application of the polar polymer microparticles in adsorption and separation of organic pollutants in water. The polar polymer microparticles have hydrophilicity, can be stably dispersed in an aqueous solution system, and are favorable for adsorbing organic matters which can be slightly soluble and soluble in water; the polar polymer microparticles have high porosity and large surface area, can accelerate the rate of organic substances diffusing to adsorption sites through a liquid medium, improve the mass transfer efficiency, provide more adsorption sites for the organic substances and improve the adsorption capacity. Therefore, the polar polymer microparticles are extremely suitable for adsorbing and separating organic pollutants in an environmental aqueous solution system.

Preferably, the organic contaminants are phenolic and/or amine contaminants.

Compared with the prior art, the invention has the beneficial effects that: the preparation method takes maleic anhydride, N-vinyl pyrrolidone and vinyl ether (DE) as monomers, synthesizes P (MA-DE-NVP) microparticles with controllable particle size by one-step polymerization, and has the advantages of simplicity, easy operation and high yield; the preparation method of the invention can also increase the softness of the surface of the microparticles, so that the microparticles are easier to swell and modify. The P (MA-DE-NVP) microparticles not only have hydrophilicity and hydrophobicity, have a balanced adsorption effect on various polar and nonpolar compounds, but also have higher specific surface area and mesopores (the mesopores have narrower pore size distribution and are intensively distributed at 5-10nm), have higher adsorption capacity on hydrophilic substances, and can be used for adsorbing and separating organic pollutants in a water body.

The invention adopts the technical scheme to provide the polar polymer microparticles, the preparation method and the application thereof, makes up for the defects of the prior art, and has reasonable design and convenient operation.

Drawings

FIG. 1 is an infrared spectrum of P (MA-DE-NVP) fine particles obtained in example 2 of test example 1 of the present invention;

FIG. 2 is an SEM photograph of P (MA-DE-NVP) fine particles obtained in example 2 of test example 2 of the present invention;

FIG. 3 is an SEM photograph of P (MA-DE-NVP) fine particles obtained in example 3 of test example 2 of the present invention.

Detailed Description

The invention is further illustrated by the following examples. It is to be understood that the examples are for illustrative purposes only and are not intended to limit the scope and spirit of the present invention.