CN111825865A - Method for preparing metal organic framework material polymer profile by using ultraviolet light - Google Patents

Method for preparing metal organic framework material polymer profile by using ultraviolet light Download PDF

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CN111825865A
CN111825865A CN202010553040.4A CN202010553040A CN111825865A CN 111825865 A CN111825865 A CN 111825865A CN 202010553040 A CN202010553040 A CN 202010553040A CN 111825865 A CN111825865 A CN 111825865A
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organic framework
metal organic
ultraviolet light
framework material
polymer profile
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兰亚乾
高广阔
陈宜法
王艺蓉
杨汝欣
王思博
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Nanjing Normal University
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Nanjing Normal University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds

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Abstract

The invention discloses a method for preparing a metal organic framework material polymer profile by utilizing ultraviolet light, which comprises the following steps: dissolving a photoinitiator, a monomer, an additive and a surfactant in a solvent, adding a metal organic framework material into the solvent, uniformly dispersing to obtain a mixed solution, dropwise adding the mixed solution onto a carrier, then transferring the carrier to ultraviolet light to induce polymerization until the liquid does not flow, finally drying, and stripping from the carrier to obtain the material. Compared with the traditional preparation method, the invention adopts a simple photoinduction monomer polymerization method to obtain the MOF-based materials with different shapes loaded with different metal organic framework materials, and has the advantages of simple process, convenient operation, suitability for batch production and the like.

Description

Method for preparing metal organic framework material polymer profile by using ultraviolet light
Technical Field
The invention relates to a method for preparing a metal organic framework material polymer profile by utilizing ultraviolet light, belonging to the technical field of metal organic framework material polymer profiles.
Background
Metal-Organic Frameworks (MOFs) are a class of porous materials obtained by bonding metals or Metal clusters and Organic ligands through coordination bonds, and have the advantages of high specific surface area, ordered pore channel structures, excellent structural adjustability and the like. The catalyst has good application prospect in gas storage/separation, catalysis, sensing, pollutant treatment and the like in recent years. However, as a crystalline material, MOFs are easily pulverized and broken into smaller particles and powders in industrial processes such as catalysis and separation. This can be a significant problem in practical applications, for example, small particles or extremely fine dust generated by the fragmentation of MOFs crystals can easily block the reaction pipeline, even cause explosion and other problems. This greatly limits the practical applications of MOFs materials. The exploration of a novel MOFs processing and forming method is very important.
Generally, the process of granulating MOFs powder is common in industry. The common granulation method is to directly form the MOFs materials under high pressure or add an adhesive. However, the high-pressure granulation method can affect the properties of the MOFs to a certain extent, so that the use efficiency of the formed device is greatly reduced. The addition of the adhesive in the molding method by adding the adhesive can reduce the proportion of the active ingredients of the MOFs material to a certain extent, and can bring certain influence on the performance of the MOFs material which can be exerted in a final device.
In order to solve the above problems, a series of attempts have been made in reported works. The known main forming methods can be mainly divided into two main categories: MOFs grows in situ on various substrates and is compounded with macromolecules for processing and molding. These two methods are mainly through: (1) MOFs grow in situ on various substrates (such as porous titanium dioxide, silicon wafers and the like) by methods such as solvothermal, seeded growth, electrodeposition and the like; (2) MOFs are combined with various types of polymers and then subjected to special post-treatments (such as knife coating or freeze drying). However, the reported MOFs films obtained by the in-situ growth method generally have the disadvantages of poor stability, brittleness, and often requiring a production process with relatively high energy consumption.
The other novel method combines the MOFs with various types of polymers, can combine the excellent properties of the MOFs material and the polymer material at the same time, and has potential application in many aspects such as gas separation, ion conduction, pollutant filtering and the like. However, the compatibility of the MOFs with polymers, the dispersion uniformity of the MOFs particles, and the like in the material obtained by this method are all problems to be solved.
Furthermore, processing MOFs into devices is currently dominated by membrane materials, but how to process MOFs into different shapes to meet different equipment or different environments remains a challenging problem.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the technical problems, the invention discloses a method for processing MOF into devices with different structures by using a photopolymerizable monomer and using ultraviolet photopolymerization as a silk thread and using a photo-induced thermal auxiliary processing method, wherein the material has good strength and pore canal reservation by combining the advantages of a photo-polymerized polymer and the MOF.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a metal organic framework material polymer profile by using ultraviolet light comprises the following steps:
dissolving a photoinitiator, a monomer, an additive and a surfactant in a solvent, adding a metal organic framework material into the solvent, uniformly dispersing to obtain a mixed solution, dropwise adding the mixed solution onto a carrier, then transferring the carrier to ultraviolet light to induce polymerization until the liquid does not flow, finally drying, and stripping from the carrier to obtain the composite material.
Preferably, the method comprises the following steps:
the photoinitiator is selected from 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone.
The monomer is selected from one or more of methyltrimethoxysilane and hydroxyethyl acrylate.
The surfactant is selected from cetyl trimethyl ammonium bromide.
The solvent is selected from deionized water.
The additive is selected from urea.
The metal organic framework material is selected from one or a combination of several of UiO-66, HKUST-1, ZIF-8 or MOF-801.
The carrier is selected from a mold, a membrane, or a substrate. The mold is preferably polytetrafluoroethylene and the membrane is preferably a commercial polypropylene membrane.
The ratio of the mass of the metal organic framework material to the total mass of all raw materials is 0.01:1-0.5: 1.
According to the invention, MOFs and monomers are combined, photopolymerization preparation research is carried out by regulating and controlling various MOFs and siloxane monomers, and a photoinduced polymerization forming process is combined, so that the photopolymerizable monomers are used as silk threads by utilizing ultraviolet photopolymerization, and MOFs are processed into devices with different compositions by utilizing a photoinduced heat conduction auxiliary processing method. The material has the advantages of good strength, good reserved pore channels and excellent performance by combining the advantages of the photopolymer and the MOF.
The technical effects are as follows: compared with the traditional preparation method, the invention adopts a simple photoinduction monomer polymerization method to obtain the MOF-based materials with different shapes loaded with different metal organic framework materials, and has the advantages of simple process, convenient operation, suitability for batch production and the like.
Drawings
FIG. 1 is a PXRD and SEM image (scale 10 μm) of the UiO-66 material obtained by the present invention;
FIG. 2 is a PXRD and SEM image (scale 10 μm) of HKUST-1 material obtained by the present invention;
FIG. 3 is a PXRD and SEM image (scale 10 μm) of the ZIF-8 material obtained by the present invention;
FIG. 4 is a PXRD and SEM image (scale 10 μm) of MOF-801 material obtained by the present invention;
FIG. 5 is a photograph and an SEM image of a ZIF-8 hollow tube material obtained by the present invention;
FIG. 6 is a schematic and SEM image of a UiO-66 and ZIF-8 composite hollow tube material obtained by the present invention.
FIG. 7 NH obtained by the present invention2Photographs of the complex films of UIO-66, HKUST-1 and ZIF-8
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1:
photoinduced polymerization film forming
(1) At room temperature, 0.16g of hexadecyl trimethyl ammonium bromide, 0.24g of urea, 0.28g of 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, 5.68mL of methyl trimethoxy silane, 12.56mL of hydroxyethyl acrylate and 20mL of water are added into a centrifugal tube coated with tin foil paper, and ultrasonic treatment is carried out until the mixture is uniformly dispersed so as to avoid direct irradiation of strong light.
(2) And (3) adding 0.76g of synthesized UiO-66 material and 4.78mL of the solution obtained in the step (1) into a round-bottom centrifuge tube, and placing the round-bottom centrifuge tube into an ultrasonic cleaner for ultrasonic dispersion for 30min-1 h. Wherein, UiO-66 accounts for 24 percent of the total mass of the system.
(3) And (3) dripping a proper amount of the light-induced precursor solution prepared in the step (2) into a mould, and carrying out light-induced polymerization under an ultraviolet light source until the solution does not flow any more.
(4) And transferring the system to a 60 ℃ oven, taking out after 15min, and stripping the film from the die to obtain the photoinduced polymerized metal organic framework film.
The structure of the resulting HKUST-1@ PVDF film material was analyzed by X-Ray powder diffraction (PXRD) (FIG. 1); the resulting material was analyzed for size, morphology and microstructure using a Scanning Electron Microscope (SEM).
Example 2:
the preparation procedure and procedure in this example are essentially the same as in example 1 above, except that: the MOF in the mixed solution of this example was HKUST-1, and the characterization is shown in FIG. 2.
Example 3:
the preparation procedure and procedure in this example are essentially the same as in example 1 above, except that: the MOF in the mixed solution of this example was ZIF-8, and the characterization is shown in FIG. 3.
Example 4:
the preparation procedure and procedure in this example are essentially the same as in example 1 above, except that: the MOF in the mixed solution of this example was MOF-801, and the characterization is shown in FIG. 4.
Example 5:
(1) 0.76g of synthesized ZIF-8 was added to 4.78mL of the solution obtained in the step (1) in example 1, and the mixture was placed in an ultrasonic cleaner for ultrasonic dispersion for 30min to 1 hour. Wherein, ZIF-8 accounts for 24 percent of the total mass of the system.
(2) And (2) dripping a proper amount of the light-induced precursor solution prepared in the step (1) into a hollow tube mold, and carrying out light-induced polymerization under an ultraviolet light source until the solution does not flow any more.
(3) And transferring the system to a 60 ℃ oven, taking out after 15min, and stripping the film from the die to obtain the hollow tube of the photoinduced polymerization metal-organic framework.
The microstructure was characterized by scanning electron microscopy as shown in FIG. 5.
Example 6:
(1) 0.76g of synthesized ZIF-8 and UiO-66 was added to two 4.78mL of the solutions obtained in the step (1) in example 1, and the mixture was placed in an ultrasonic cleaner for ultrasonic dispersion for 30min to 1 h. Wherein ZIF-8 and UiO-66 account for 24 percent of the total mass of the system.
(2) And (2) dripping a proper amount of the ZIF-8 photoinduction precursor solution prepared in the step (1) into a hollow tube mold, and photoinduction polymerizing under an ultraviolet light source until the solution does not flow any more.
(3) And transferring the system to a 60 ℃ oven, taking out after 15min, and stripping the film from the die to obtain the hollow tube of the photoinduced polymerization metal-organic framework.
(4) The hollow tube was cut in half and then replaced in the mold and the solution of UiO-66 was added and steps (2) (3) were repeated. The hollow pipe can be obtained
The microstructure was characterized by scanning electron microscopy as shown in FIG. 6.
Example 7:
a composite membrane can be obtained by first obtaining a thin film and then repeating the assembly using a method similar to that of example 6. The photograph is shown in FIG. 7.

Claims (9)

1. A method for preparing a metal organic framework material polymer profile by using ultraviolet light is characterized by comprising the following steps:
dissolving a photoinitiator, a monomer, an additive and a surfactant in a solvent, adding a metal organic framework material into the solvent, uniformly dispersing to obtain a mixed solution, dropwise adding the mixed solution onto a carrier, then transferring the carrier to ultraviolet light to induce polymerization until the liquid does not flow, finally drying, and stripping from the carrier to obtain the composite material.
2. The method for preparing polymer profile of metal organic framework material by using ultraviolet light as claimed in claim 1, wherein the photoinitiator is selected from 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone.
3. The method for preparing metal organic framework material polymer profile using ultraviolet light as claimed in claim 1, wherein the monomer is selected from one or more of methyltrimethoxysilane and hydroxyethyl acrylate.
4. The method for preparing polymer profile of metal organic framework material using ultraviolet light as claimed in claim 1, wherein the additive is selected from urea.
5. The method for preparing polymer profile of metal organic framework material using ultraviolet light as claimed in claim 1, wherein the surfactant is selected from cetyl trimethyl ammonium bromide.
6. The method for preparing polymer profile of metal organic framework material by using ultraviolet light as claimed in claim 1, wherein the solvent is selected from deionized water.
7. The method for preparing the polymer profile of the metal organic framework material by using the ultraviolet light as claimed in claim 1, wherein the metal organic framework material is selected from one or more of UiO-66, HKUST-1, ZIF-8 or MOF-801.
8. The method for preparing polymer profile of metal organic framework material by using ultraviolet light as claimed in claim 1, wherein the carrier is selected from a mold, a diaphragm or a substrate.
9. The method for preparing polymer profile of metal organic framework material by using ultraviolet light as claimed in claim 1, wherein the ratio of the mass of the metal organic framework material to the total mass of all raw materials is 0.01:1-0.5: 1.
CN202010553040.4A 2020-06-17 2020-06-17 Method for preparing metal organic framework material polymer profile by using ultraviolet light Pending CN111825865A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140212944A1 (en) * 2013-11-29 2014-07-31 Beijing Star New Material Co., Ltd. MOF-based hierarchical porous materials, methods for preparation, methods for pore regulation and uses thereof
CN104710559A (en) * 2015-02-15 2015-06-17 北京理工大学 Method for preparing metal-organic framework material film
CN106397797A (en) * 2016-08-29 2017-02-15 山东师范大学 Gold-MOFs-polymer composite membrane, and production method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140212944A1 (en) * 2013-11-29 2014-07-31 Beijing Star New Material Co., Ltd. MOF-based hierarchical porous materials, methods for preparation, methods for pore regulation and uses thereof
CN104710559A (en) * 2015-02-15 2015-06-17 北京理工大学 Method for preparing metal-organic framework material film
CN106397797A (en) * 2016-08-29 2017-02-15 山东师范大学 Gold-MOFs-polymer composite membrane, and production method and application thereof

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