CN113185692B - Hydrophobic polypyrrole porous material, preparation method and application thereof - Google Patents

Abstract

The invention discloses a hydrophobic polypyrrole porous material, a preparation method and application thereof, and belongs to the field of material preparation. According to the preparation method of the hydrophobic polypyrrole porous material, the synthesized micromolecule gelling agent containing imine bonds is used as a stabilizer, the gel emulsion is used as a template to prepare the hydrophobic polypyrrole porous material, the difference of oil-water ratio and pyrrole content can regulate and control the pore structure of a polypyrrole block material and the size under the micro-morphology, and the polypyrrole porous material has the characteristics of pore characteristics and hydrophobicity, so that the polypyrrole porous material can be used for adsorbing an organic solvent; the method has the advantages of mild reaction conditions, simple synthesis process, low energy consumption, simple post-treatment and greenness. The invention solves the problems that the porous material has large energy consumption in the preparation process and the polypyrrole material can not be prepared in a large scale.

Description

A kind of hydrophobic polypyrrole porous material, preparation method and application thereof

technical field

The invention belongs to the field of material preparation, in particular to a hydrophobic polypyrrole porous material, a preparation method and an application thereof.

Background technique

In recent decades, with the acceleration of industrialization, the control of organic pollutants, especially oil spills, has attracted more and more attention. However, dealing with these pollutants in an efficient and practical manner is an imminent challenge for scientists working in this field. Currently, the most effective method for removing pollutants in water is selective adsorption separation.

Porous materials have attracted extensive attention due to their low density, high specific surface area, good permeability, and excellent adsorption. The preparation of porous materials is mainly focused on controlling the pore size, shape, distribution, and how to introduce functional groups into the material to endow specific functionality. The methods for preparing porous materials mainly include hard template method and soft template method, among which the gel emulsion template method in the soft template method is favored by researchers for its advantages of simple process and precise control of pore size. In the process of preparing gel emulsion, the type of stabilizer has an important influence on its properties. Currently, it is mainly divided into surfactants, solid micro-nano particles and small molecule gelling agents (LMMGs).

Polypyrrole is used in environmental remediation and other fields because of its high thermal stability, low cost, easy availability and non-toxicity. However, the specific surface area of traditional polypyrrole materials is small, and there are limitations in the removal range and ability of organic pollutants. Therefore, other forms are needed to improve the adsorption capacity of polypyrrole for organic pollutants.

Contents of the invention

The purpose of the present invention is to overcome the disadvantages of traditional polypyrrole materials such as small specific surface area, incapable of mass production and high energy consumption in the preparation process, and provide a hydrophobic polypyrrole porous material, a preparation method and its application.

In order to achieve the above object, the present invention adopts the following technical solutions to achieve:

A method for preparing a hydrophobic polypyrrole porous material, comprising the following steps:

1) Preparation of cholesterol derivatives containing imine bonds;

2) preparing a polypyrrole gel emulsion by using the cholesterol derivative containing imine bonds as a stabilizer;

3) Polymerizing the polypyrrole gel emulsion as a raw material to prepare a hydrophobic polypyrrole porous material.

Further, the specific process of step 1) is:

Under an inert gas atmosphere, react Boc-amino acid with a molar ratio of 1:1 and cholesterol in an ice bath for 1-4 hours, and then react at room temperature for 6-24 hours, and then react with DCC with a molar ratio of 20:(1-2) After dehydration and condensation with DMAP, it is purified by column chromatography, and then hydrochloride is formed under the action of HCl, and the obtained product is refluxed in a benzene solvent at 80-120 ° C for 3-6 h to obtain cholesterol amino acid ester primary amine;

The cholesteryl amino acid ester primary amine with a molar ratio of (1-3):1 and the compound containing an aldehyde group are reacted in a chloroform solvent at room temperature for 2-8 h, and a cholesterol derivative containing an imine bond is obtained after the reaction is completed.

Further, the Boc-amino acid is:

Boc-D-Phenylalanine, Boc-L-Phenylalanine, Boc-D-Tryptophan, Boc-L-Tryptophan, Boc-D-Tyrosine, Boc-L-Tyrosine, Boc-D-lysine, Boc-L-lysine, Boc-D-serine, Boc-L-serine, Boc-L-glycine, Boc-D-glycine, Boc-L-glutamic acid, Boc- D-glutamate, BOC-L-valine, BOC-D-valine, BOC-L-isoleucine, or BOC-D-isoleucine.

Further, the compound containing aldehyde group is:

Acetaldehyde, caproaldehyde, succinaldehyde, benzaldehyde, furfuraldehyde, malondialdehyde, n-propionaldehyde, 1-octylaldehyde, adipaldehyde, cinnamaldehyde, decanal, glutaraldehyde, n-butyraldehyde or trialdehyde Phloroglucinol.

Further, the specific process of step 2) is:

Shake and mix 0.01-1.00 g of cholesterol derivatives containing imine bonds, 0.01-1.00 mL of pyrrole and 0.01-5.00 mL of organic solvent at room temperature, and then add 0.01-5.00 mL of 0.5-3 mol/L FeCl3 aqueous solution, Mix well and let stand for more than 3 minutes to get polypyrrole gel emulsion.

Further, the organic solvent is:

Benzene, toluene, p-xylene, o-xylene, m-xylene, chloroform, n-heptane, n-decane, n-hexane, phenol, biphenyl, ethylbenzene or xylene.

Further, the specific process of step 3) is:

The polypyrrole gel emulsion is polymerized at 0-8°C for 12-24 hours, and then placed in an oven at 40-100°C to dry for 12-36 hours after returning to room temperature, and then washed and dried to obtain a hydrophobic polypyrrole porous material.

A hydrophobic polypyrrole porous material is characterized in that it is prepared according to the preparation method of the present invention.

The application of the hydrophobic polypyrrole porous material of the invention is used as an adsorbent for the separation of homologue mixed solvents.

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

The preparation method of the present invention does not need high-energy-consuming equipment such as supercritical drying and freeze-drying in the preparation process, and can be dried under normal conditions, and the operation is simple and environmentally friendly; the polypyrrole block can be regulated by regulating the oil-water ratio and the difference in pyrrole content The pore structure and microscopic appearance of the material, the hydrophobic polypyrrole porous material prepared by the present invention has a controllable volume, and solves the problem of the small specific surface area of the traditional polypyrrole material.

The hydrophobic polypyrrole porous material of the invention has an adjustable pore structure, the contact angle of the hydrophobic polypyrrole porous material can reach 128.53°, and has the characteristic of hydrophobicity.

The hydrophobic polypyrrole porous material of the invention is used for the adsorption of organic solvents, and can realize the separation of homologue mixed solvents.

Description of drawings

Fig. 1 is the macroscopic picture of the hydrophobic polypyrrole porous material block material of embodiment 1;

Figure 2 is the SEM image of the hydrophobic polypyrrole porous material block in Example 1, where Figure 2(a) and Figure 2(b) correspond to different multiples;

Fig. 3 is the contact angle picture of the hydrophobic polypyrrole porous material of embodiment 1-5 for water;

Figure 4 is the adsorption curve of the hydrophobic polypyrrole porous material of Example 1 to organic solvents, wherein Figure 4(a) is the adsorption curve for aromatic homologues; Figure 4(b) is the adsorption curve for alcohol homologues .

Detailed ways

In order to enable those skilled in the art to better understand the solutions of the present invention, the following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only It is an embodiment of a part of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

It should be noted that the terms "first" and "second" in the description and claims of the present invention and the above drawings are used to distinguish similar objects, but not necessarily used to describe a specific sequence or sequence. It is to be understood that the data so used are interchangeable under appropriate circumstances such that the embodiments of the invention described herein can be practiced in sequences other than those illustrated or described herein. Furthermore, the terms "comprising" and "having", as well as any variations thereof, are intended to cover a non-exclusive inclusion, for example, a process, method, system, product or device comprising a sequence of steps or elements is not necessarily limited to the expressly listed instead, may include other steps or elements not explicitly listed or inherent to the process, method, product or apparatus.

The hydrophobic polypyrrole porous material prepared based on the gel emulsion method has the characteristics of scalable preparation, adjustable pore structure, low energy consumption in the preparation process, simple and green post-processing, and can adsorb mixed solvents of homologues.

In the present invention, the supramolecular compound assembled by dynamic covalent bonds is used as a stabilizer to prepare gel emulsion, and the polypyrrole porous material is prepared by using the gel emulsion as a template, and the obtained polypyrrole porous material has adjustable pore structure and polypyrrole particle size. It is controlled and does not require high energy-consuming equipment such as supercritical drying and freeze drying, and is dried under normal conditions. The preparation method of the invention has simple operation and is green, and the obtained polypyrrole porous material is successfully applied to the field of separation of homologue mixed solvents.

The present invention is described in further detail below in conjunction with accompanying drawing:

Example 1

(1) Under an inert gas atmosphere, dissolve 0.04 mol Boc-D-phenylalanine and 0.04 mol cholesterol in chloroform, then dissolve 0.04 mol DCC and 0.004 mol DMAP in 10 mL of dichloromethane, dropwise Add the reaction system, react for 4 hours under ice bath conditions, and then react for 20 hours at room temperature. After the reaction solution is processed, the crude product cholesterol amino acid ester derivative 1 is obtained. Phase, the crude product was purified by column chromatography to obtain pure cholesterol amino acid ester derivative 1; the above cholesterol amino acid ester derivative 1 formed hydrochloride under the action of HCl, and then refluxed in benzene at 80 °C for 4 h to obtain cholesterol Amino acid ester primary amine 1; the obtained cholesterol amino acid ester primary amine 1 was dissolved in chloroform, then added dropwise to a chloroform solution of furanformaldehyde, reacted at room temperature for 4 h, and after treatment, cholesterol derivative 1 containing an imine bond was obtained.

Boc-amino acids can also be selected: Boc-D-phenylalanine, Boc-L-phenylalanine, Boc-D-tryptophan, Boc-L-tryptophan, Boc-D-tyrosine, Boc -L-Tyrosine, Boc-D-Lysine, Boc-L-Lysine, Boc-D-Serine, Boc-L-Serine, Boc-L-Glycine, Boc-D-Glycine, Boc-L - Glutamic acid, Boc-D-glutamic acid, BOC-L-valine, BOC-D-valine, BOC-L-isoleucine and BOC-D-isoleucine;

Compounds containing aldehyde groups can be selected: acetaldehyde, hexanal, succinaldehyde, benzaldehyde, furan formaldehyde, malondialdehyde, n-propanal, 1-octylaldehyde, adipaldehyde, cinnamaldehyde, decanal, amylaldehyde Dialdehyde, n-butyraldehyde and trialdehyde phloroglucinol;

(2) Add 0.03g of imine bond-containing cholesterol derivative 1 as a stabilizer to a 4 mL sample bottle, add 0.043 mL of pyrrole and 500 mL of benzene, shake and mix evenly, then add 500 mL of FeCl3 aqueous solution, and use a mixer to make It was thoroughly mixed, and after standing for a period of time, polypyrrole gel emulsion 1 was obtained.

Organic solvents can be selected: benzene, toluene, p-xylene, o-xylene, m-xylene, chloroform, n-heptane, n-decane, n-hexane, phenol, biphenyl, ethylbenzene and xylene.

(3) Place the obtained polypyrrole gel emulsion 1 at 0-8°C for 12 hours, take it out and let the temperature rise to room temperature, place it in an oven at 60°C to dry for 24 hours, take out the material and wash it with water and acetone The solution was colorless, and then placed in an oven at 60 °C for 24 h to fully dry to obtain polypyrrole porous material 1.

Referring to Fig. 1, Fig. 1 is the macroscopic picture of the hydrophobic polypyrrole porous material block material of embodiment 1, it can be seen from Fig. 1 that the prepared polypyrrole porous material is a regular cylinder as a whole, the surface is smooth, and the material has no obvious shrinkage before and after drying, Good shape.

Referring to Figure 2, Figure 2(a) and Figure 2(b) are SEM images of different multiples of the hydrophobic polypyrrole porous material block in Example 1. It can be seen from the figure that the polypyrrole porous material is composed of a large number of well-connected The composition of polypyrrole particles and the existence of gaps between polypyrrole particle clusters make polypyrrole porous materials have a multi-level pore structure; the distribution of pores is relatively uniform, and its good three-dimensional space structure also ensures that polypyrrole porous materials have better retention. Type.

See Figure 4, Figure 4(a) is the adsorption curve for aromatic homologues; Figure 4(b) is the adsorption curve for alcohol homologues; it can be seen from Figure 4(a) that the adsorption at about 250 min When reaching equilibrium, the adsorption amounts of aromatic homologues were 2330 mg/g, 2570 mg/g, and 1600 mg/g respectively; from Figure 4(b), it can be seen that the adsorption reached equilibrium at about 200 min, and the adsorption amounts of alcohol homologues They are 1600 mg/g and 1000 mg/g respectively. From this figure, it can be clearly seen that there are obvious adsorption differences for polar homologues and non-polar homologues, and this material can be used for the separation of organic solvents for homologues.

Example 2

Add the cholesterol derivative 1 containing imine bonds obtained in Example 1 into a 4 mL sample bottle as a stabilizer, add 0.015 mL of pyrrole and 500 mL of benzene, shake and mix evenly, then add 500 mL of FeCl3 aqueous solution, and use the Apparatus made it fully mixed, after standing for a period of time, polypyrrole gel emulsion 2 was obtained.

The obtained polypyrrole gel emulsion 2 is polymerized, washed and dried to obtain a polypyrrole porous material 2 . Other steps are with embodiment 1.

Example 3

Add the cholesterol derivative 1 containing an imine bond obtained in Example 1 into a 4 mL sample bottle as a stabilizer, add 0.043 mL of pyrrole and 300 mL of benzene, shake and mix evenly, then add 700 mL of FeCl3 aqueous solution, and use the Apparatus made it fully mixed, after standing for a period of time, polypyrrole gel emulsion 3 was obtained.

The obtained polypyrrole gel emulsion 3 is polymerized, washed and dried to obtain a polypyrrole porous material 3 . Other steps are with embodiment 1.

Example 4

Dissolve Boc-D-tyrosine and cholesterol in chloroform, then dissolve DCC and DMAP in dichloromethane, add dropwise to the reaction system, react in ice bath for 4 h, and then react at room temperature for 20 h. After the treatment, the crude product cholesterol amino acid ester derivative 2 is obtained, and the cholesterol amino acid ester primary amine 2 is obtained after the treatment; the obtained cholesterol amino acid ester primary amine 2 is dissolved in chloroform, and then the chloroform solution of n-propionaldehyde is added dropwise, After reacting at room temperature for 4 h, the cholesterol derivative 2 containing an imine bond was obtained after treatment.

Add the cholesterol derivative 2 containing imine bonds as a stabilizer into a 4 mL sample bottle, add 0.029 mL of pyrrole and 500 mL of benzene, shake and mix evenly, then add 500 mL of FeCl3 aqueous solution, use a mixer to make it fully mixed, and statically After standing for a period of time, polypyrrole gel emulsion 4 was obtained.

The obtained polypyrrole gel emulsion 4 is polymerized, washed and dried to obtain a polypyrrole porous material 4 . Other steps are with embodiment 1.

Example 5

Add the imine bond-containing cholesterol derivative 2 obtained in Example 4 as a stabilizer into a 4 mL sample bottle, add 0.043 mL of pyrrole and 600 mL of benzene, shake and mix evenly, then add 400 mL of FeCl3 aqueous solution, and use the Apparatus made it fully mixed, after standing for a period of time, polypyrrole gel emulsion 5 was obtained.

The obtained polypyrrole gel emulsion 5 is polymerized, washed and dried to obtain a polypyrrole porous material 5 . Other steps are with embodiment 1.

Referring to Fig. 3, Fig. 3 is a picture of the contact angle of the hydrophobic polypyrrole porous material prepared in Example 1 to Example 5 for water. It can be seen from Fig. 3 that the hydrophilicity and hydrophobicity of the polypyrrole porous material can be adjusted by changing the preparation conditions.

Example 6

The cholesterol amino acid ester primary amine 2 obtained in Example 4 was dissolved in chloroform, and then a chloroform solution of trialdehyde phloroglucinol was added dropwise, reacted at room temperature for 4 h, and after treatment, cholesterol derivative 6 containing imine bonds was obtained. .

Add the cholesterol derivative 6 containing imine bonds as a stabilizer into a 4 mL sample bottle, add 0.057 mL of pyrrole and 500 mL of toluene, shake and mix evenly, then add 500 mL of FeCl3 aqueous solution, use a mixer to make it fully mixed, and statically After standing for a period of time, polypyrrole gel emulsion 6 was obtained.

The obtained polypyrrole gel emulsion 6 is polymerized, washed and dried to obtain a polypyrrole porous material 6 . Other steps are the same as in Example 4.

Example 7

Dissolve the cholesterol amino acid ester primary amine 1 obtained in Example 1 in chloroform, then add adipaldehyde in chloroform dropwise, react at room temperature for 4 h, and obtain cholesterol derivative 7 containing imine bonds after treatment.

Add the cholesterol derivative 7 containing imine bonds as a stabilizer into a 4 mL sample bottle, add 0.043 mL of pyrrole and 500 mL of toluene, shake and mix evenly, then add 500 mL of FeCl3 aqueous solution, use a mixer to make it fully mixed, and statically After standing for a period of time, polypyrrole gel emulsion 7 was obtained.

The obtained polypyrrole gel emulsion 7 is polymerized, washed and dried to obtain a polypyrrole porous material. Other steps are with embodiment 1.

The above content is only to illustrate the technical ideas of the present invention, and cannot limit the protection scope of the present invention. Any changes made on the basis of the technical solutions according to the technical ideas proposed in the present invention shall fall within the scope of the claims of the present invention. within the scope of protection.

Claims (5)

1. The preparation method of the hydrophobic polypyrrole porous material is characterized by comprising the following steps:

1) Preparing an imine bond-containing cholesterol derivative;

2) Preparing polypyrrole gel emulsion by taking the cholesterol derivative containing the imine bond as a stabilizing agent;

0.01 to 1.00 g of cholesterol derivative containing imine bond, 0.01 to 1.00mL of pyrrole and 0.01 to 5.00 mL of organic solvent are shaken and mixed evenly at room temperature, and then 0.01 to 5.00 mL of FeCl with the concentration of 0.5 to 3 mol/L is added ₃ Fully mixing the aqueous solution, and standing for more than 3 min to obtain polypyrrole gel emulsion;

3) Polymerizing by taking the polypyrrole gel emulsion as a template to prepare a hydrophobic polypyrrole porous material;

and polymerizing the polypyrrole gel emulsion for 12-24 h at 0-8 ℃, recovering the room temperature, drying in an oven at 40-100 ℃ for 12-36 h, and washing and drying to obtain the hydrophobic polypyrrole porous material.

2. The preparation method of the hydrophobic polypyrrole porous material according to claim 1, wherein the specific process of step 1) is:

under the inert gas atmosphere, dissolving 0.04 mol of Boc-D-phenylalanine and 0.04 mol of cholesterol in trichloromethane, then dissolving 0.04 mol of DCC and 0.004 mol of DMAP in 10 mL of dichloromethane, dropwise adding the solution into a reaction system, reacting for 4 h under the ice bath condition, reacting for 20 h at room temperature, treating the reaction solution to obtain a crude product cholesterol amino acid ester derivative 1, and further purifying the crude product by using a column chromatography method to obtain a pure cholesterol amino acid ester derivative 1 by using tetrahydrofuran: n-hexane = 16 (v/v); the cholesterol amino acid ester derivative 1 forms hydrochloride under the action of HCl, and then is refluxed in benzene at the temperature of 80 ℃ for 4 h to obtain cholesterol amino acid ester primary amine 1; dissolving the obtained cholesterol amino acid ester primary amine 1 in chloroform, dropwise adding a chloroform solution of furan formaldehyde, reacting at room temperature for 4 h, and treating to obtain the cholesterol derivative containing imine bonds.

3. The preparation method of the hydrophobic polypyrrole porous material according to claim 1, wherein the organic solvent is:

benzene, toluene, p-xylene, o-xylene, m-xylene, chloroform, n-heptane, n-decane, n-hexane or xylene.

4. A hydrophobic polypyrrole porous material, characterized by being prepared according to the preparation method of any one of claims 1 to 3.

5. Use of the hydrophobic polypyrrole porous material according to claim 4 as an adsorbent for the separation of homolog mixed solvents.

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