CN115350604B - Preparation method of chiral porous composite membrane material - Google Patents
Preparation method of chiral porous composite membrane material Download PDFInfo
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- CN115350604B CN115350604B CN202211006853.7A CN202211006853A CN115350604B CN 115350604 B CN115350604 B CN 115350604B CN 202211006853 A CN202211006853 A CN 202211006853A CN 115350604 B CN115350604 B CN 115350604B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/025—Aluminium oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
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- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
Abstract
The invention belongs to the technical field of high polymer materials, and in particular relates to a preparation method of a chiral porous composite membrane material, which comprises the following steps: an activated porous alumina film is obtained through activation pretreatment; under the protection of nitrogen, placing the activated porous alumina membrane and benzyl dimethyl chlorosilane into an anhydrous toluene solvent, stirring at room temperature, and drying to obtain a coupled porous alumina membrane; under the protection of nitrogen, the coupled porous alumina film, dibromo-p-xylene and R- (+) -alpha-phenethylamine are soaked in a 1, 2-dichloroethane solvent to obtain a mixed solution A; and adding aluminum chloride into the mixed solution A, and then sequentially carrying out oil bath stirring, flushing and drying to obtain the porous aluminum oxide film loaded with the ultra-high crosslinked porous organic polymer. In conclusion, the preparation method has the advantages of low energy consumption, low cost and simple flow, and the prepared chiral porous composite membrane material has the characteristics of uniform polymer distribution, high resolution efficiency, good stability and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a chiral porous composite membrane material.
Background
Currently, several chiral porous composite membrane materials have been explored including Chiral Metal Organic Frameworks (CMOF), chiral Covalent Organic Frameworks (CCOF), molecularly Imprinted Polymers (MIP), chiral Mesoporous Silica (CMS), and the like. The chiral porous composite membrane material has rich pore structure and large specific surface area, and can be split by identifying enantiomers of chiral recognition sites, but most of the existing chiral porous composite membrane materials have high preparation cost, more byproducts, complex preparation process and higher energy consumption.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method of a chiral porous composite membrane material which has the advantages of uniform polymer distribution, high resolution efficiency, good stability, simple preparation and recycling.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a preparation method of a chiral porous composite membrane material comprises the following steps:
an activated porous alumina film is obtained through activation pretreatment;
under the protection of nitrogen, placing the activated porous alumina membrane and benzyl dimethyl chlorosilane into an anhydrous toluene solvent, stirring at room temperature, and drying to obtain a coupled porous alumina membrane;
under the protection of nitrogen, the coupled porous alumina film, dibromo-p-xylene and R- (+) -alpha-phenethylamine are soaked in a 1, 2-dichloroethane solvent to obtain a mixed solution A;
and adding aluminum chloride into the mixed solution A, and then sequentially carrying out oil bath stirring, flushing and drying to obtain the porous aluminum oxide film loaded with the ultra-high crosslinked porous organic polymer.
Wherein the porous alumina film loaded with the ultra-high crosslinked porous organic polymer is the required chiral porous composite film material.
Specifically, the chiral porous composite membrane material prepared by the invention takes a porous alumina membrane as a matrix, wherein membrane cells of the porous alumina membrane are arranged in a hexagonal close-packed manner, and the porous composite membrane material has a permanent porous structure and a large specific surface area, so that polymer growth sites are increased, and the resolution performance is obviously improved. In addition, the porous alumina membrane has the characteristic of simple modification, and the pore canal of the porous alumina membrane is basically vertical to the surface of the porous alumina membrane, so that the whole preparation process of the chiral porous composite membrane material is changed from complex and toxic processes into simple and environment-friendly processes, and the resolution efficiency is greatly improved.
Preferably, for this preparation process, the activation pretreatment is carried out with a dilute hydrochloric acid solution:
and (3) activating the surface of the double-channel porous alumina membrane with a dilute hydrochloric acid solution for 2.5 hours at room temperature, and then washing and drying to obtain the activated porous alumina membrane.
Further, in the dilute hydrochloric acid solution, HCl and H 2 The mixing volume ratio of O is 2:1.
further, after surface activation, the surfaces were washed at least once with deionized water and tetrahydrofuran, respectively, and then dried in a vacuum oven for 12 hours.
Preferably for the preparation method, the mass ratio of the activated porous alumina film to the benzyl dimethyl chlorosilane is 1: 135-140.
Further, after stirring at room temperature for 12 hours, toluene and methanol are respectively used for washing at least once, and then the porous alumina membrane is dried in a vacuum oven for 24 hours, so that the coupled porous alumina membrane is obtained.
Preferably for the preparation method, the mixing mass ratio of the dibromo-p-xylene, the R- (+) -alpha-phenethylamine and the alumina is 5.4:1.2:16.
further, aluminum chloride was added to the mixed solution a in proportion, followed by oil bath stirring at a temperature of 80 ℃ for 24 hours.
Further, after stirring in an oil bath, 1, 2-dichloroethane, deionized water and methanol are adopted to wash at least once respectively, and then the porous alumina membrane loaded with the ultra-high crosslinked porous organic polymer is obtained after drying in a vacuum oven for 12-24 hours.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of a porous alumina membrane loaded with an ultra-high crosslinked porous organic polymer, which is simple and convenient to prepare, good in stability, low in cost and capable of being repeatedly used for many times, accords with the green chemistry concept, has great research significance and scientific value in the chiral resolution field, and can further improve the selectivity and the permeation quantity of enantiomers of chiral porous composite membrane materials;
specifically, in the preparation method provided by the invention, dilute hydrochloric acid is used as an oxidant to prepare an oxidized porous alumina film, so that hydroxyl is generated on the surface of the oxidized porous alumina film; benzyl dimethyl chlorosilane is used as a coupling agent, the coupling agent containing benzyl is connected to a porous alumina membrane through a coupling reaction, and then the coupling agent and phenethylamine are subjected to an ultrahigh crosslinking reaction through Friede-Crafts reaction, so that an ultrahigh crosslinking porous organic polymer grows on the porous alumina, the highest reaction temperature of the reaction system is 80 ℃, high-temperature calcination is not needed, or mixed strong acid is not needed, the organic solvent usage amount in the preparation process is less, the problems of low polymerization degree, low material stability, complex synthesis process, high energy consumption and the like commonly existing in the traditional preparation process of the chiral porous composite membrane material are effectively solved, a novel thought is provided for preparing the porous alumina membrane, and the preparation method has important significance for fundamentally improving chiral resolution performance and reducing cost.
Drawings
FIG. 1 is a flow chart of a method of making the present invention;
FIG. 2 is an infrared spectrum of a chiral porous composite membrane material prepared according to the present invention;
FIG. 3 is a scanning electron microscope image of the chiral porous composite membrane material prepared by the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, the invention provides a preparation method of a chiral porous composite membrane material, which specifically comprises the following steps:
s1, activating pretreatment: activating the surface of the double-channel porous alumina membrane by adopting a dilute hydrochloric acid solution for 2.5 hours at room temperature, then respectively washing at least once by adopting deionized water and tetrahydrofuran, and drying in vacuum for 12 hours to obtain an activated porous alumina membrane;
s2, under the protection of nitrogen, the mass ratio is 1: placing 135-140 activated porous alumina membrane and benzyl dimethyl chlorosilane in anhydrous toluene solvent, stirring at room temperature for 12h, respectively washing at least once by toluene and methanol, and vacuum drying for 24h to obtain coupled porous alumina membrane;
s3, under the protection of nitrogen, soaking a coupled porous alumina film, dibromo-p-xylene and R- (+) -alpha-phenethylamine in a 1, 2-dichloroethane solvent to obtain a mixed solution A;
s4, adding aluminum chloride into the mixed solution A according to a proportion, then carrying out oil bath stirring for 24 hours at the temperature of 80 ℃, respectively washing at least once by adopting 1, 2-dichloroethane, deionized water and methanol after the oil bath stirring, and carrying out vacuum drying for 12-24 hours to obtain the porous alumina membrane loaded with the ultra-high crosslinked porous organic polymer.
The porous alumina membrane loaded with the ultra-high crosslinked porous organic polymer is the required chiral porous composite membrane material.
In summary, for the above preparation method, based on further preferred reaction data, the following specific preparation examples are also provided in the present invention:
1. preparation of activated porous alumina film
(11) According to the following steps: 1 volume ratio of HCl to H 2 O, obtaining a dilute hydrochloric acid solution;
(11) And (3) activating the surface of the double-channel porous alumina film by adopting the dilute hydrochloric acid solution at the room temperature of 25 ℃ for 2.5 hours, then respectively washing three times by adopting deionized water and tetrahydrofuran, and drying in vacuum for 12 hours to obtain the activated porous alumina film.
2. Preparation of coupled porous alumina membranes
(21) Under the protection of nitrogen, placing 1 activated porous alumina film and 732mL of benzyl dimethyl chlorosilane into 25mL of anhydrous toluene solvent;
(22) Stirring is continued for 12 hours at room temperature of 25 ℃, then toluene and methanol are adopted to wash for three times respectively, and vacuum drying is carried out for 24 hours, thus obtaining the coupled porous alumina membrane.
3. Preparation of porous alumina film loaded with ultra-high crosslinked porous organic Polymer
(31) Under the protection of nitrogen, the coupled porous alumina membrane, 580mg of dibromo-p-xylene and 145mg of R- (+) -alpha-phenethylamine are soaked in 6mL of 1, 2-dichloroethane solvent to obtain a mixed solution A;
(32) 2184mg of aluminum chloride is added into the mixed solution A, then the mixed solution A is stirred for 24 hours in an oil bath at the temperature of 80 ℃, and after the oil bath is stirred, the mixed solution A is respectively washed three times by adopting 1, 2-dichloroethane, deionized water and methanol, and the mixed solution A is dried in vacuum for 12 to 24 hours to obtain the porous alumina membrane loaded with the ultra-high crosslinked porous organic polymer.
Based on the specific preparation example, the prepared porous alumina film loaded with the ultra-high crosslinked porous organic polymer is subjected to infrared scanning and electron microscope scanning, and the specific preparation method comprises the following steps of:
FIG. 2 shows an infrared spectrum
Clearly, this figure 2 shows:
3436cm -1 (characteristic peak of N-H in phenethylamine), 2964cm -1 (CH 3 Asymmetric stretching vibration peaks of (2); 2924cm -1 (CH 2 Asymmetric stretching vibration peak) of 2852cm -1 (CH 2 Symmetrically stretched vibration peak) of 2366cm -1 (CO 2 Absorption peak of (2), 1632cm -1 (stretching vibration peak of benzene ring skeleton), 1461cm -1 (CH 3 Bending stretching vibration peak) of 1258cm -1 (stretching vibration peak of Si-C in benzyl dimethyl chlorosilane), 1098cm -1 (Si-O stretching vibration peak), 800cm -1 (Si-O stretching vibration peak).
Scanning electron microscope image shown in FIG. 3
It is apparent from this FIG. 3 that the polymer grows in the pores of the porous alumina film, and the morphology is spherical, and has a large specific surface area.
In summary, successful preparation of porous alumina membranes loaded with ultra-high crosslinked porous organic polymers was demonstrated. In addition, the membrane cells of the porous alumina membrane are arranged in a hexagonal close-packed manner, and have a permanent porous structure and a large specific surface area, so that the growth sites of the polymer are increased, and the resolution performance is obviously improved.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The preparation method of the chiral porous composite membrane material is characterized in that the chiral porous composite membrane material is a porous alumina membrane loaded with an ultra-high crosslinked porous organic polymer, and the preparation method comprises the following steps:
an activated porous alumina film is obtained through activation pretreatment;
under the protection of nitrogen, placing the activated porous alumina membrane and benzyl dimethyl chlorosilane into an anhydrous toluene solvent, stirring at room temperature, and drying to obtain a coupled porous alumina membrane;
under the protection of nitrogen, the coupled porous alumina film, alpha' -dibromo-p-xylene and R- (+) -alpha-phenethylamine are soaked in a 1, 2-dichloroethane solvent to obtain a mixed solution A;
and adding aluminum chloride into the mixed solution A, and then sequentially carrying out oil bath stirring, flushing and drying to obtain the porous aluminum oxide film loaded with the ultra-high crosslinked porous organic polymer.
2. The method for preparing the chiral porous composite membrane material according to claim 1, wherein the activating pretreatment is performed by adopting a dilute hydrochloric acid solution:
and (3) activating the surface of the double-channel porous alumina membrane with a dilute hydrochloric acid solution for 2.5 hours at room temperature, and then washing and drying to obtain the activated porous alumina membrane.
3. The method for preparing the chiral porous composite membrane material according to claim 2, wherein the method comprises the following steps: after surface activation, the surfaces were washed at least once with deionized water and tetrahydrofuran, respectively, and then dried in a vacuum oven for 12 hours.
4. The method for preparing the chiral porous composite membrane material according to claim 1, wherein the method comprises the following steps: the mass ratio of the activated porous alumina film to the benzyl dimethyl chlorosilane is 1: 135-140.
5. The method for preparing the chiral porous composite membrane material according to claim 4, wherein the method comprises the following steps: after stirring at room temperature for 12 hours, the porous alumina membrane is obtained by washing at least once with toluene and methanol respectively and then drying the porous alumina membrane in a vacuum oven for 24 hours.
6. The method for preparing the chiral porous composite membrane material according to claim 1, wherein the method comprises the following steps: the mixing mass ratio of the alpha, alpha' -dibromo-p-xylene, R- (+) -alpha-phenethylamine and aluminum oxide is 5.4:1.2:16.
7. the method for preparing the chiral porous composite membrane material according to claim 6, wherein the method comprises the following steps: aluminum chloride was added to the mixed solution a in proportion, followed by oil bath stirring at a temperature of 80 ℃ for 24 hours.
8. The method for preparing the chiral porous composite membrane material according to claim 7, wherein the method comprises the following steps: and (3) after oil bath stirring, respectively washing at least once by adopting 1, 2-dichloroethane, deionized water and methanol, and then drying in a vacuum oven for 12-24 hours to obtain the porous alumina membrane loaded with the ultra-high crosslinked porous organic polymer.
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| GB201117950D0 (en) * | 2011-10-18 | 2011-11-30 | Imp Innovations Ltd | Membranes for separation |
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