CN108610504A - A kind of preparation method with hierarchical porous structure integral material - Google Patents
A kind of preparation method with hierarchical porous structure integral material Download PDFInfo
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- CN108610504A CN108610504A CN201611127503.0A CN201611127503A CN108610504A CN 108610504 A CN108610504 A CN 108610504A CN 201611127503 A CN201611127503 A CN 201611127503A CN 108610504 A CN108610504 A CN 108610504A
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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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
- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
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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
- C08J2383/00—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
- C08J2383/10—Block- or graft-copolymers containing polysiloxane sequences
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- Engineering & Computer Science (AREA)
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Abstract
The present invention relates to a kind of preparation methods of the multi-stage porous integral material containing covalent organic framework polymer (covalent organic frameworks, COF).Specifically by covalent organic framework polymer, containing epoxy-functional compounds (function monomer), containing the mixing such as amino-functional compounds (function monomer) and pore-foaming agent simultaneously vibrating dispersion, then epoxy ring-opening polymerization (ring opening polymerization reaction) occurs at a certain temperature, you can a step prepares the integral material with hierarchical porous structure (microporous mesoporous macropore).The preparation method have many advantages, such as mild condition, efficiently it is controllable.Furthermore it is also possible to select different covalent organic framework polymer according to different application requirements, or the incorporation of covalent organic framework polymer is adjusted, prepares a series of multi-stage porous integral materials with different physics and chemical property.
Description
Technical field
The present invention relates to one kind containing covalent organic framework polymer (covalent organic frameworks, COF)
Multi-stage porous integral material preparation method.Specifically by covalent organic framework the polymer, (function containing epoxy-functional compounds
Monomer), containing the mixing such as amino-functional compounds (function monomer), pore-foaming agent and vibrating dispersion, then send out at a certain temperature
Raw epoxy addition polymerisation (ring-opening polymerization reaction), you can prepared by a step have multistage
The integral material of pore structure (micropore-mesopore-macropore).
Background technology
Multi-stage porous integral material generally has two or more pore sizes, and (micropore, aperture are less than 2nm；Mesoporous, aperture is more than
2nm and be less than 50nm；Macropore, aperture are more than 50nm).This hierarchical porous structure not only increases the specific surface area of integral material,
And improve mass transport process of the substance inside integral material.Currently, multi-stage porous integral material includes polymer substrate, silica gel
Matrix, carbon matrix, metal organic framework polymer substrate etc., are widely used in catalysis, absorption, separating medium and storage carrier etc.
Field.However, according to the preparation method reported, in a kind of pore structure of scale of adjusting, often to another scale
Pore structure impacts.Therefore, the hierarchical porous structure for effectively adjusting integral material still faces huge challenge.
Covalent organic framework polymer (covalent organic frameworks, COF) is emerging in recent years one kind
Light porous material has larger specific surface area and abundant micropore or meso-hole structure.But it is limited to existing technology of preparing,
Obtained covalent organic polymer often exists in powder form, and the material does not have remoldability, seriously constrains the material
The practical application of material.To solve these problems, the present invention has developed a kind of based on epoxy addition polymerisation, effectively by powder
The COF of form is converted to integral material.Integral material prepared by this method not only remains the intrinsic pore structures of COF, but also
With continuous macroporous structure.In addition, this method also has the characteristics that：1, preparation process is easier；2, versatile, it can
Applied to covalent organic polymer；3, reaction condition is mild, easily controllable, favorable reproducibility.
Invention content
The purpose of the invention is to simple and efficient prepare a series of integral materials with hierarchical porous structure.
To achieve the above object, the technical solution adopted by the present invention is：
Using ring-opening polymerization (ring-opening polymerization reaction), by adjusting COF's
Content and the different COF of selection prepare a series of multi-stage porous integral materials with different physics and chemical property.It is this
Multi-stage porous integral material prepared by method preferably remains the intrinsic microcellular structures of COF, and produces continuous macropore
Structure is expected to improve integral material to the adsorbance of substance and improves mass-transfer performance of the substance inside integral material.
The multi-stage porous integral material containing COF is prepared in conjunction with ring-opening polymerization：Specifically by COF, containing epoxy-functional
Compound (function monomer) after mixing shaken well containing amino-functional compounds (function monomer) and porogenic solvents etc., heats
One step of epoxy ring-opening polymerization occurs and prepares the integral material with hierarchical porous structure.
Its detailed process is as follows：
1) 30-70mg is added into reaction vessel and contains epoxy-functional compounds；
2) 30-70mg is added into reaction vessel and contains amino-functional compounds；
3) polyethylene glycol (PEG, Mn=10,000) of 10-35mg, the normal propyl alcohol of 100-500 μ L are added into reaction vessel
The 1,4- butanediols (1,4-butanediol) of (1-propanol) and 80-400 μ L；
4) COF of 1-100mg is added into reaction vessel；
5) above-mentioned mixed system is vibrated 1min or more at normal temperatures makes its dispersion form uniform suspension；
6) the obtained container for filling mixed solution in step 5) is placed in heating device and reacts 1 minute or more, directly
To formation solid；
7) rinse above-mentioned integral material with methanol, with remove pore-foaming agent and unreacted or it is unbonded on substance, had
There is the integral material of hierarchical porous structure.
The present invention is based on the mistakes that epoxy addition polymerisation prepares the multi-stage porous entirety containing covalent organic framework polymer
Journey is as shown in Figure 1.
, 3) and 4) step 1), 2) reaction vessel is centrifuge tube used in；Contain ring employed in the step 1)
Epoxy-functional compound is eight glycidyl dimethylsilane POSS (octaglycidyldimethylsilyl POSS, POSS-
epoxy)；Employed in the step 2) is polyethyleneimine (poly (ethylenimine) containing amino-functional compounds
Solution, PEI, Mn=1200,50wt%in H2)) or 1,8- octamethylenediamines (1,8-diaminooctane) or the 1,10- last of the ten Heavenly stems O
One or two or more kinds in diamines (1,10-diaminodecane)；COF employed in the step 4) is by equal benzene
Material (azine-linked COF) is prepared in trioxin and hydrazine hydrate；Container used in the step 6) is plastic centrifuge
Pipe, heating device are water-bath or insulating box, and heating temperature is 0-100 DEG C, and the reaction time is 1 hour or more；The step 7)
In pore-foaming agent be polyethylene glycol (PEG, Mn=10,000), normal propyl alcohol (1-propanol) and 1,4-butanediol (Isosorbide-5-Nitrae-
butanediol)。
Integral material prepared by the present invention has hierarchical porous structure.Wherein, micropore or meso-hole structure are determined by the type of COF
Fixed, and macroporous structure is determined by ring-opening polymerization.Therefore, the multistage pore size of the integral material prepared by the present invention is easy to
It adjusts.In addition, the covalent organic framework polymer of powder type is prepared into integral material, it will promote covalent organic framework poly-
Close the application of object industrially.
Description of the drawings
Fig. 1 is to prepare the multi-stage porous integral material containing covalent organic framework polymer based on epoxy addition polymerisation
Schematic diagram.
Fig. 2 is suction of the multi-stage porous integral material (embodiment 1) of azine-linked COF doping to bisphenol-A in aqueous solution
Attached kinetic curve.
Fig. 3 is suction of the multi-stage porous integral material (embodiment 2) of azine-linked COF doping to bisphenol-A in aqueous solution
Attached kinetic curve.
Specific implementation mode
Embodiment 1
1, the POSS-epoxy reagents of 50.0mg are added into centrifuge tube.
2, the PEI aqueous solutions of 54.0mg are added into above-mentioned centrifuge tube.
3,25mg PEG, the 1,4-butanediol of the normal propyl alcohol of 280 μ L and 40 μ L are added into above-mentioned centrifuge tube.
4,20mg azine-linked COF are added into above-mentioned centrifuge tube, above-mentioned centrifuge tube oscillation 5min is made wherein
Each component be uniformly mixed.
5, the centrifuge tube in step 4 is reacted 10 hours in 50 DEG C of water-baths, the mixed liquor in centrifuge tube forms yellow
Solid.
6, it is to obtain the multi-stage porous of azine-linked COF doping with the material in methanol repeatedly washing by soaking centrifuge tube
Integral material.
Embodiment 2
1, the POSS-epoxy reagents of 50.0mg are added into centrifuge tube.
2, the PEI aqueous solutions of 54.0mg are added into above-mentioned centrifuge tube.
3,25mg PEG, the 1,4-butanediol of the normal propyl alcohol of 280 μ L and 40 μ L are added into above-mentioned centrifuge tube.
4, the pre-saturated azine-linked COF of 40mg toluene are added into above-mentioned centrifuge tube, above-mentioned centrifuge tube is vibrated
5min makes each component therein be uniformly mixed.
5, the centrifuge tube in step 4 is reacted 10 hours in 50 DEG C of water-baths, the mixed liquor in centrifuge tube forms yellow
Solid.
6, it is to obtain the multi-stage porous of azine-linked COF doping with the material in methanol repeatedly washing by soaking centrifuge tube
Integral material.
Fig. 2 is suction of the multi-stage porous integral material (embodiment 1) of azine-linked COF doping to bisphenol-A in aqueous solution
Attached kinetic curve.Experiment condition：Bisphenol-A aqueous solution (22.8mg/L)；UV-vis Detection wavelengths, 276nm.Illustrate institute of the present invention
The multi-stage porous integral material of preparation has fast and efficiently absorption behavior to bisphenol-A.
Fig. 3 is suction of the multi-stage porous integral material (embodiment 2) of Azine-linked COF doping to bisphenol-A in aqueous solution
Attached kinetic curve.Experiment condition：Bisphenol-A aqueous solution (22.8mg/L)；UV-vis Detection wavelengths, 276nm.Illustrate institute of the present invention
The multi-stage porous integral material of preparation has fast and efficiently absorption behavior to bisphenol-A.
Claims (7)
1. a kind of preparing the method with hierarchical porous structure integral material, it is characterised in that：Its process is as follows,
1) 30-70mg is added into reaction vessel and contains epoxy-functional compounds；
2) 30-70mg is added into reaction vessel and contains amino-functional compounds；
3) polyethylene glycol (PEG, Mn=10,000) of 10-35mg, the normal propyl alcohol (1- of 100-500 μ L are added into reaction vessel
) and the 1,4- butanediols of 80-400 μ L (1,4-butanediol) propanol；
4) covalent organic framework polymer (the covalent organic of 1-100mg are added into reaction vessel
frameworks,COF)；
5) above-mentioned mixed system is vibrated 1min or more at normal temperatures makes its dispersion form uniform suspension；
6) the obtained container for filling mixed solution in step 5) is placed in heating device and is reacted 1 minute or more, until shape
At solid；
7) rinse above-mentioned integral material with methanol, with remove pore-foaming agent and unreacted or it is unbonded on substance, obtain having more
The integral material of grade pore structure.
2. according to the method described in claim 1, it is characterized in that：, 3) and 4) step 1), 2) reaction vessel used in
For centrifuge tube.
3. according to the method described in claim 1, it is characterized in that：Chemical combination containing epoxy-functional employed in the step 1)
Object is eight glycidyl dimethylsilane POSS (octaglycidyldimethylsilyl POSS, POSS-epoxy).
4. according to the method described in claim 1, it is characterized in that：Chemical combination containing amido functional group employed in the step 2)
Object is polyethyleneimine (poly (ethylenimine) solution, PEI, Mn=1200,50wt%in H2O)) or 1,8- is pungent
Diamines (1,8-diaminooctane) or 1,10- decamethylene diamines, the one or two or more kinds in (1,10-diaminodecane).
5. according to the method described in claim 1, it is characterized in that：Covalent organic framework polymerization employed in the step 4)
Object is the material (azine-linked COF) being prepared by equal benzene trioxin and hydrazine hydrate.
6. according to the method described in claim 1, it is characterized in that：Container used in the step 6) is centrifuge tube；Heating
Device is water-bath or insulating box；Heating temperature is 0-100 DEG C (preferably 50)；Reaction time is 1 (preferably 10) more than hour.
7. according to the method described in claim 1, it is characterized in that：Pore-foaming agent in the step 7) be polyethylene glycol (PEG,
Mn=10,000), normal propyl alcohol (1-propanol) and 1,4-butanediol (Isosorbide-5-Nitrae-butanediol).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316284A (en) * | 2021-11-18 | 2022-04-12 | 国科广化精细化工孵化器(南雄)有限公司 | Three-dimensional covalent organic framework compound containing polyhedral oligomeric silsesquioxane, and preparation method and application thereof |
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| CN102492116A (en) * | 2011-11-27 | 2012-06-13 | 吉林大学 | Epoxy resin and polyhedral silsesquioxane nano hybrid material and its preparation method |
| US20130017390A1 (en) * | 2011-07-13 | 2013-01-17 | Xerox Corporation | Porous structured organic film compositions |
| CN103741243A (en) * | 2013-12-20 | 2014-04-23 | 北京化工大学常州先进材料研究院 | Preparation method of fiber containing porous covalent organic framework compound |
| CN103881057A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | Preparation method for organic-inorganic hybrid porous monolith material based on epoxide ring-opening reaction |
| CN104109222A (en) * | 2013-04-22 | 2014-10-22 | 中国科学院大连化学物理研究所 | Preparation of hybrid integral materials containing polyhedral oligomeric silsesquioxane reagent |
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2016
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130017390A1 (en) * | 2011-07-13 | 2013-01-17 | Xerox Corporation | Porous structured organic film compositions |
| CN102492116A (en) * | 2011-11-27 | 2012-06-13 | 吉林大学 | Epoxy resin and polyhedral silsesquioxane nano hybrid material and its preparation method |
| CN103881057A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | Preparation method for organic-inorganic hybrid porous monolith material based on epoxide ring-opening reaction |
| CN104109222A (en) * | 2013-04-22 | 2014-10-22 | 中国科学院大连化学物理研究所 | Preparation of hybrid integral materials containing polyhedral oligomeric silsesquioxane reagent |
| CN103741243A (en) * | 2013-12-20 | 2014-04-23 | 北京化工大学常州先进材料研究院 | Preparation method of fiber containing porous covalent organic framework compound |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114316284A (en) * | 2021-11-18 | 2022-04-12 | 国科广化精细化工孵化器(南雄)有限公司 | Three-dimensional covalent organic framework compound containing polyhedral oligomeric silsesquioxane, and preparation method and application thereof |
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