CN113185692B - Hydrophobic polypyrrole porous material, preparation method and application thereof - Google Patents
Hydrophobic polypyrrole porous material, preparation method and application thereof Download PDFInfo
- Publication number
- CN113185692B CN113185692B CN202110519022.9A CN202110519022A CN113185692B CN 113185692 B CN113185692 B CN 113185692B CN 202110519022 A CN202110519022 A CN 202110519022A CN 113185692 B CN113185692 B CN 113185692B
- Authority
- CN
- China
- Prior art keywords
- polypyrrole
- porous material
- cholesterol
- hydrophobic
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a hydrophobic polypyrrole porous material, a preparation method and application thereof.
Background
In recent decades, with the acceleration of industrialization, the treatment of organic pollutants, especially petroleum leakage, has attracted more and more attention. However, the disposal of these contaminants in an effective and practical manner is an urgent challenge for scientists working in this field. Currently, the most effective method for removing contaminants from water is selective adsorption separation.
Porous materials are of great interest because of their low density, high specific surface area, good permeability and excellent adsorption. The preparation of porous materials is mainly aimed at controlling the pore size, shape, distribution, and how to introduce functional groups into the material to impart specific functionality, etc. The method for preparing the porous material mainly comprises a hard template method and a soft template method, wherein the gel emulsion template method in the soft template method is favored by researchers by virtue of the advantages of simple process and precisely controllable pore size. In the process of preparing gel emulsion, the type of stabilizer has an important influence on the properties of the gel emulsion, and at present, the stabilizer mainly comprises a surfactant, solid micro-nano particles and small molecule gelling agents (LMMGs).
Polypyrrole is used in the fields of environmental remediation and the like because of its characteristics of high thermal stability, low price, easy availability, no toxicity and the like. However, the conventional polypyrrole material has a small specific surface area, and has limitations on the removal range and capacity of organic pollutants. Therefore, there is a need to improve the adsorption capacity of polypyrrole for organic contaminants by means of other forms.
Disclosure of Invention
The invention aims to overcome the defects that the traditional polypyrrole material has a small specific surface area, cannot be prepared massively, has high energy consumption in the preparation process and the like, and provides a hydrophobic polypyrrole porous material, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of a hydrophobic polypyrrole porous material comprises 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 stabilizer;
3) And polymerizing the polypyrrole gel emulsion serving as a raw material to prepare the hydrophobic polypyrrole porous material.
Further, the specific process of step 1) is as follows:
under an inert gas atmosphere, mixing a mixture of 1:1 Boc-amino acid and cholesterol are reacted for 1-4 h under ice bath condition, and then reacted for 6-24 h at room temperature, wherein the molar ratio is 20: (1-2) dehydrating and condensing DCC and DMAP, purifying by column chromatography, forming hydrochloride under the action of HCl, and refluxing the obtained product in a benzene solvent at 80-120 ℃ for 3-6 h to obtain cholesterol amino acid ester primary amine;
mixing the components in a molar ratio of (1-3): 1, reacting the cholesterol amino acid ester primary amine with a compound containing an aldehyde group in a chloroform solvent at room temperature for 2-8 h to obtain the cholesterol derivative containing an imine bond after the reaction is finished.
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-glycine, boc-D-glycine, boc-L-glutamic acid, boc-D-glutamic acid, BOC-L-valine, BOC-D-valine, BOC-L-isoleucine or BOC-D-isoleucine.
Further, the compound containing aldehyde group is:
acetaldehyde, hexanal, butanedial, benzaldehyde, furaldehyde, malonaldehyde, n-propionaldehyde, 1-octanal, hexanal, cinnamaldehyde, decanal, glutaraldehyde, n-butyraldehyde, or trialdehyde phloroglucinol.
Further, the specific process of step 2) is as follows:
0.01-1.00 g of cholesterol derivative containing imine bond, 0.01-1.00mL of pyrrole and 0.01-5.00 mL of organic solvent are shaken and mixed evenly at room temperature, then 0.01-5.00 mL of FeCl3 aqueous solution with the concentration of 0.5-3 mol/L is added, and the mixture is fully mixed and kept stand for more than 3 min, thus obtaining the 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 as follows:
and (3) 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 then washing and drying to obtain the hydrophobic polypyrrole porous material.
The hydrophobic polypyrrole porous material is characterized by being prepared according to the preparation method of the invention.
The hydrophobic polypyrrole porous material is applied as an adsorbent for separating a homolog mixed solvent.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method, high-energy-consumption equipment such as supercritical drying, freeze drying and the like is not needed in the preparation process, and the preparation method can be used for drying under conventional conditions, is simple to operate and is green and environment-friendly; the pore structure and the microscopic morphology of the polypyrrole block can be regulated and controlled by regulating and controlling the difference between the oil-water ratio and the pyrrole content.
The hydrophobic polypyrrole porous material disclosed by the invention has an adjustable pore structure, and the contact angle of the hydrophobic polypyrrole porous material can reach 128.53 degrees, so that the hydrophobic polypyrrole porous material has a hydrophobic characteristic.
The hydrophobic polypyrrole porous material is used for adsorbing an organic solvent, and can realize separation of a homolog mixed solvent.
Drawings
FIG. 1 is a macroscopic picture of a bulk hydrophobic polypyrrole porous material of example 1;
FIG. 2 is SEM images of the bulk of the hydrophobic polypyrrole porous material of example 1, wherein FIG. 2 (a) and FIG. 2 (b) correspond to different times;
FIG. 3 is a photograph of the contact angle of the hydrophobic polypyrrole porous materials of examples 1 to 5 with water;
FIG. 4 is an adsorption curve of the hydrophobic polypyrrole porous material of example 1 to an organic solvent, wherein FIG. 4 (a) is an adsorption curve to an aromatic homologue; FIG. 4 (b) is an adsorption curve for alcohol homologues.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in other sequences than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The hydrophobic polypyrrole porous material prepared by the gel emulsion method has the characteristics of capability of being prepared in an enlarged mode, adjustable pore structure, low energy consumption in the preparation process, simple and green post-treatment and the like, and can adsorb a mixed solvent of homologous compounds.
According to the invention, a supramolecular compound assembled by dynamic covalent bonds is used as a stabilizer to prepare gel emulsion, the gel emulsion is used as a template to prepare the polypyrrole porous material, and the obtained polypyrrole porous material has an adjustable pore structure, controllable particle size of polypyrrole and no need of high-energy-consumption equipment such as supercritical drying, freeze drying and the like and is dried under conventional conditions. The preparation method is simple and green to operate, and the obtained polypyrrole porous material is successfully applied to the field of separation of homolog mixed solvents.
The invention is described in further detail below with reference to the accompanying drawings:
example 1
(1) 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 the hydrochloride is refluxed in benzene at the temperature of 80 ℃ for 4 hours 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 1 containing imine bonds.
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-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;
the aldehyde group-containing compound may be selected from: acetaldehyde, hexanal, butanedialdehyde, benzaldehyde, furfural, malonaldehyde, n-propionaldehyde, 1-octanal, hexanal, cinnamaldehyde, decanal, glutaraldehyde, n-butyraldehyde, and trialdehyde phloroglucinol;
(2) Adding 0.03g of cholesterol derivative 1 containing imine bonds as a stabilizer into a 4 mL sample bottle, adding 0.043mL of pyrrole and 500 mL of benzene, shaking and mixing uniformly, adding 500 mL of FeCl3 aqueous solution, fully mixing by using a mixer, and standing for a period of time to obtain polypyrrole gel emulsion 1.
The organic solvent can be selected from: benzene, toluene, p-xylene, o-xylene, m-xylene, chloroform, n-heptane, n-decane, n-hexane, phenol, biphenyl, ethylbenzene, and xylene.
(3) And polymerizing the obtained polypyrrole gel emulsion 1 at 0-8 ℃ for 12 h, taking out, heating to room temperature, drying in a 60 ℃ oven for 24 h, taking out the material, washing the material with water and acetone until the solution is colorless, and then fully drying in the 60 ℃ oven for 24 h to obtain the polypyrrole porous material 1.
Referring to fig. 1, fig. 1 is a macroscopic picture of the hydrophobic polypyrrole porous material block of example 1, and it can be seen from fig. 1 that the prepared polypyrrole porous material is a regular cylinder as a whole, the surface is smooth, the material does not shrink obviously before and after drying, and the shape is good.
Referring to fig. 2, fig. 2 (a) and fig. 2 (b) are SEM images of different multiples of the bulk material of the hydrophobic polypyrrole porous material of example 1, and it can be seen that the polypyrrole porous material is internally composed of a large number of well-interconnected polypyrrole particles, and the existence of gaps among clusters of the polypyrrole particles enables the polypyrrole porous material to have a hierarchical pore structure; the distribution of the pores is uniform, and the good three-dimensional space structure of the porous polypyrrole material also ensures the good shape retention of the porous polypyrrole material.
Referring to fig. 4, fig. 4 (a) is a graph of adsorption of aromatic homologues; FIG. 4 (b) is a graph of adsorption curves for alcohol homologs; as can be seen from FIG. 4 (a), the adsorption reached equilibrium at about 250 min, and the adsorption amounts of the aromatic homologues were 2330 mg/g, 2570 mg/g and 1600 mg/g, respectively; as can be seen from FIG. 4 (b), the adsorption reached equilibrium at about 200 min, and the adsorption amounts of the alcohol homologues were 1600 mg/g and 1000 mg/g, respectively. From this figure it is evident that there is a clear difference in adsorption for both the polar and non-polar homologues, and the material can be used for separation of the homologues in organic solvents.
Example 2
Adding the cholesterol derivative 1 containing an imine bond obtained in example 1 as a stabilizer into a 4 mL sample bottle, adding 0.015 mL pyrrole and 500 mL benzene, shaking and mixing uniformly, adding 500 mL FeCl3 aqueous solution, mixing fully by using a mixer, and standing for a period of time to obtain polypyrrole gel emulsion 2.
And polymerizing, washing and drying the obtained polypyrrole gel emulsion 2 to obtain the polypyrrole porous material 2. The other steps are the same as in example 1.
Example 3
Adding the cholesterol derivative 1 containing an imine bond obtained in example 1 as a stabilizer into a 4 mL sample bottle, adding 0.043mL pyrrole and 300 mL benzene, shaking and mixing uniformly, adding 700 mL FeCl3 aqueous solution, mixing fully by using a mixer, and standing for a period of time to obtain polypyrrole gel emulsion 3.
And polymerizing, washing and drying the obtained polypyrrole gel emulsion 3 to obtain the polypyrrole porous material 3. The other steps are the same as in example 1.
Example 4
Dissolving Boc-D-tyrosine and cholesterol in trichloromethane, then dissolving DCC and DMAP in dichloromethane, dropwise adding into a reaction system, reacting for 4 hours under an ice bath condition, reacting for 20 hours at room temperature, treating the reaction liquid to obtain a crude product cholesterol amino acid ester derivative 2, and treating to obtain cholesterol amino acid ester primary amine 2; dissolving the obtained cholesterol amino acid ester primary amine 2 in chloroform, dropwise adding a chloroform solution of n-propionaldehyde, reacting for 4 hours at room temperature, and treating to obtain the cholesterol derivative 2 containing imine bonds.
Adding the cholesterol derivative 2 containing imine bonds into a 4 mL sample bottle as a stabilizer, adding 0.029 mL pyrrole and 500 mL benzene, shaking and mixing uniformly, adding 500 mL FeCl3 aqueous solution, fully mixing by using a mixing instrument, and standing for a period of time to obtain polypyrrole gel emulsion 4.
And polymerizing, washing and drying the obtained polypyrrole gel emulsion 4 to obtain the polypyrrole porous material 4. The other steps are the same as in example 1.
Example 5
Adding the cholesterol derivative 2 containing imine bonds obtained in the example 4 into a 4 mL sample bottle as a stabilizer, adding 0.043mL pyrrole and 600 mL benzene, shaking and mixing uniformly, adding 400 mL FeCl3 aqueous solution, mixing fully by using a mixer, and standing for a period of time to obtain polypyrrole gel emulsion 5.
And polymerizing, washing and drying the obtained polypyrrole gel emulsion 5 to obtain the polypyrrole porous material 5. The other steps are the same as in example 1.
Referring to fig. 3, fig. 3 is a contact angle image of the hydrophobic polypyrrole porous materials prepared in examples 1 to 5 with respect to water, and it can be seen from fig. 3 that the hydrophilicity and hydrophobicity of the polypyrrole porous materials can be adjusted by changing the preparation conditions.
Example 6
The cholesterol amino acid ester primary amine 2 obtained in the example 4 is dissolved in chloroform, and then the chloroform solution of the trialdehyde phloroglucinol is added dropwise to react for 4 hours at room temperature, and the cholesterol derivative 6 containing imine bonds is obtained after treatment.
Adding the cholesterol derivative 6 containing imine bonds into a 4 mL sample bottle as a stabilizer, adding 0.057 mL pyrrole and 500 mL toluene, shaking and mixing uniformly, adding 500 mL FeCl3 aqueous solution, fully mixing by using a mixer, and standing for a period of time to obtain polypyrrole gel emulsion 6.
And polymerizing, washing and drying the obtained polypyrrole gel emulsion 6 to obtain the polypyrrole porous material 6. The other steps are the same as in example 4.
Example 7
The cholesterol amino acid ester primary amine 1 obtained in the example 1 is dissolved in chloroform, and then a chloroform solution of hexanedial is added dropwise to react for 4 hours at room temperature, and the cholesterol derivative 7 containing imine bonds is obtained after treatment.
Adding the cholesterol derivative 7 containing imine bonds into a 4 mL sample bottle as a stabilizer, adding 0.043mL pyrrole and 500 mL toluene, shaking and mixing uniformly, adding 500 mL FeCl3 aqueous solution, fully mixing by using a mixer, and standing for a period of time to obtain the polypyrrole gel emulsion 7.
And polymerizing, washing and drying the obtained polypyrrole gel emulsion 7 to obtain the polypyrrole porous material. The other steps are the same as in example 1.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110519022.9A CN113185692B (en) | 2021-05-12 | 2021-05-12 | Hydrophobic polypyrrole porous material, preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110519022.9A CN113185692B (en) | 2021-05-12 | 2021-05-12 | Hydrophobic polypyrrole porous material, preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113185692A CN113185692A (en) | 2021-07-30 |
CN113185692B true CN113185692B (en) | 2022-11-22 |
Family
ID=76981646
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110519022.9A Active CN113185692B (en) | 2021-05-12 | 2021-05-12 | Hydrophobic polypyrrole porous material, preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113185692B (en) |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4847115A (en) * | 1987-08-10 | 1989-07-11 | Rockwell International Corporation | Chemical synthesis of conducting polypyrrole using uniform oxidant/dopant reagents |
CN105368045B (en) * | 2014-08-27 | 2017-12-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene polypyrrole composite aerogel and preparation method and application |
CN105085787B (en) * | 2015-08-31 | 2018-01-05 | 陕西师范大学 | A kind of compressible low density porous polymeric material and preparation method thereof |
-
2021
- 2021-05-12 CN CN202110519022.9A patent/CN113185692B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN113185692A (en) | 2021-07-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20080249339A1 (en) | Charged Polymers for Ethanol Dehydration | |
Paik et al. | Chiral separation abilities: Aspartic acid block copolymer-imprinted mesoporous silica | |
CA2168240A1 (en) | Zirconia particles | |
Yuan et al. | Schiff base–Chitosan grafted l-monoguluronic acid as a novel solid-phase adsorbent for removal of congo red | |
CN105566383A (en) | Acyl chloride monomer and preparation method thereof and reverse osmosis composite membrane and preparation method thereof | |
CN113185692B (en) | Hydrophobic polypyrrole porous material, preparation method and application thereof | |
CN113698579A (en) | Porphyrin type conjugated microporous polymer and synthesis method and application thereof | |
Xi et al. | Novel nylon-supported organic–inorganic hybrid membrane with hierarchical pores as a potential immobilized metal affinity adsorbent | |
CN113058554A (en) | Activated carbon prepared from natural rubber seed shells and preparation method and application thereof | |
CN111921505B (en) | O-diol functionalized macroporous through hole material, preparation method thereof and boric acid adsorption application | |
CN112940269A (en) | Copper-based metal organic framework material Cu-IPA for separating ethane and methane, and preparation method and application thereof | |
CN112844338A (en) | Black talc-polyvinyl formal gel composite adsorption material | |
CN109821484B (en) | Dipeptide aerogel and preparation method and application thereof | |
CN116832781A (en) | Preparation method and application of solid amine adsorbent | |
KR930010463B1 (en) | Spherical grains of polyamino acid and production method thereof | |
Garipcan et al. | Synthesis of Poly [(hydroxyethyl methacrylate)‐co‐(methacrylamidoalanine)] Membranes and Their Utilization as an Affinity Sorbent for Lysozyme Adsorption | |
US5736259A (en) | Packing material for high-performance liquid chromatography and process for producing the same | |
KR100356043B1 (en) | A seperating membrane for treatment of volatile organic compounds, and a method of manufacturing them | |
Gao et al. | Tetrasulfonate calix [4] arene modified large pore mesoporous silica microspheres: Synthesis, characterization, and application in protein separation | |
CN115318254B (en) | Sodium lignin sulfonate/chitosan @ ZIF-8 composite material and preparation method and application thereof | |
CN106179265B (en) | It is a kind of for go water removal in trivalent chromic ion hybrid film adsorbent preparation method | |
CN114588793B (en) | Mixed matrix membrane for methane/nitrogen separation and preparation method thereof | |
CN117797777A (en) | Method for improving dye adsorption effect by green modification of alkaline lignin by using acid eutectic solvent | |
CN115386136B (en) | Preparation method and application of aminated polyacrylamide foam adsorbent | |
CN115212856B (en) | Preparation and application of surface polymer functionalized spherical metal organic framework material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |