CN104193969A - Preparation method, material and application of porous polymer - Google Patents
Preparation method, material and application of porous polymer Download PDFInfo
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- CN104193969A CN104193969A CN201410421283.7A CN201410421283A CN104193969A CN 104193969 A CN104193969 A CN 104193969A CN 201410421283 A CN201410421283 A CN 201410421283A CN 104193969 A CN104193969 A CN 104193969A
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Abstract
The invention discloses a preparation method, a material and an application of a porous polymer. The preparation method comprises the following steps: (1) evenly dispersing the raw material (aromatic compounds, mixtures of the aromatic compounds, polymers of the aromatic compounds and/or mixtures of the polymers) into a crosslinking agent and solvent, so as to obtain a raw material mixed solution, wherein the crosslinking agent solvent is one or more of alkane dihalides; (2) adding a catalyst, carrying out Friedel-Craft reaction, and carrying out super-crosslinking, so as to obtain a crude product; and (3) washing and extracting a filter cake which is obtained after the coarse product is filtered, removing a catalyst, and drying, so as to obtain a porous polymer. The preparation method disclosed by the invention is simple in process, uses easily available raw materials, the prepared porous polymer is adjustable in pore size and specific surface area, has low cost and good adaptability, and can be used as a catalyst carrier, a separation membrane, a gas storage material or an ion adsorbing material, especially, can be used as materials for storing hydrogen and capturing carbon dioxide or methane storage materials.
Description
Technical field
The invention belongs to polymer materials field, more specifically, relate to a kind of porous polymer preparation method, material and application.
Background technology
In recent years, organic porous polymer material (microporous organic polymers, MOPs) is adsorbing and is separating with it, heterogeneous catalyst, gas storage, photoelectricity, drug release, the widespread use in the fields such as biological response, has received domestic and international researchist's very big concern.Than traditional gac class and zeolites porous material, MOPs demonstrates high specific surface area, high chemistry and physical stability, the advantages such as low skeletal density and synthetic variation.MOPs mainly can be divided into synthetic method: from tool microporous polymer (Polymers of Intrinsic Microporosity, PIMs), covalency organic backbone polymkeric substance (Covalent-Organic Frameworks, COFs), conjugation microporous polymer (Conjugated Microporous Polymers, and super cross-linked polymer (Hypercross-linked Polymers, HCPs) CMPs).The use of transition metal and precious metal in most MOPs building-up processes, and the multistep of construction unit is synthetic, makes the cost value of porous material perhaps relatively costly.HCPs is class organic porous material cheaply in MOPs.Davankov resin is the HCPs shaped material that a class has realized suitability for industrialized production, and specific surface area is up to 2090m
2/ g, but the method complex process, energy consumption is large, and it is very limited to can be used for the styrene monomer of suitability for industrialized production.The people such as Cooper utilize dihalo methylene radical aromatics to build HCPs material from polycondensation, and material demonstrates higher specific surface area and gas storge quality, but monomer price is relatively costly; The people such as Tan Bien propose to utilize Methylal(dimethoxymethane) as outside cross-linking agent, and braiding aromatics builds HCPs shaped material, but specific surface area and gas storage capacity are moderate.Therefore, the problem that the high-specific surface area of Porous-Organic polymkeric substance and gas storage capacity and economy are laid equal stress on, limits industrialization and the development of organic poromerics.
Summary of the invention
For above defect or the Improvement requirement of prior art, the invention provides a kind of porous polymer preparation method, material and application, its object is, by optimizing synthesis material and production technique, to solve thus current porous material production cost high, the technical problem of synthesis technique complexity.
For achieving the above object, according to one aspect of the present invention, provide a kind of porous polymer preparation method, comprised the following steps:
(1) raw materials mixed solution: taking the mixture of aromatics, its mixture, its polymkeric substance and/or its polymkeric substance as raw material, raw material is dispersed in to linking agent and holds concurrently in solvent and obtain raw material mixed solution, the described linking agent solvent of holding concurrently is one or more the mixture in two halogen alkane substitutes;
(2) poromeric preparation: Friedel-Crafts reaction occurs, super crosslinked acquisition crude product after adding catalyzer in the raw material mixed solution obtaining in step (1);
(3) poromeric purifying, by filter cake washing extracting after the filtration of crude product obtaining in step (2), removes catalyzer, after being dried, makes described porous polymer.
Preferably, described porous polymer preparation method, its Friedel-Crafts reaction catalyzer is Lewis acid, in catalyzer and raw material, the ratio of phenyl ring mole number is between 0.1:1 to 50:1.
Preferably, described porous polymer preparation method, its Lewis acid is anhydrous SnCl
4, anhydrous FeCl
3, anhydrous BF
3or anhydrous AlCl
3.
Preferably, described porous polymer preparation method, its raw material mixed solution Raw concentration is between 0.01g/ml to 10g/ml.
Preferably, described porous polymer preparation method, in its Friedel-Crafts reaction process keep continue stir, add catalyzer after temperature control detailed process be:
First, be warming up to 20-40 DEG C, isothermal reaction 2-12 hour; Then, be warming up to 50-70 DEG C, isothermal reaction 2-18 hour; Finally, be warming up to 80-120 DEG C, isothermal reaction 10-72 hour.
Preferably, described porous polymer preparation method, washs concrete steps in washing extracting after filtering described in it and is:
First wash crude product 2-3 time with dilute hydrochloric acid, then use distilled water wash 2-3 time, finally use washing with alcohol crude product 2-4 time;
After described filtration, washing extracting concrete steps in also extracting is:
With apparatus,Soxhlet's ethanol extracting 24 to 72 hours.
According to another aspect of the present invention, a kind of porous polymer material is provided, it is characterized in that the porous polymer preparation method preparation of application as described in claim 1 to 6 any one.
Preferably, described how empty polymer materials, its aperture is between 0.5nm to 100nm, and its specific surface area is at 1m
2/ g to 4000m
2between/g.
According to another aspect of the present invention, the application of described porous polymer material is provided, described porous polymer material is as support of the catalyst, separatory membrane, gas storage material or ion adsorbent.
Preferably, described application, described in it, porous polymer material is used as hydrogen storage material, catches carbon dioxide material or storage methane material.
In general, the above technical scheme of conceiving by the present invention compared with prior art, can obtain following beneficial effect:
Task of the present invention is to provide a kind of organic porous polymer material, and the present invention also provides preparation method and the application of this organic porous polymer material.
Realizing technical scheme of the present invention is: this organic porous polymer material provided by the invention is that mixture taking aromatics, its mixture, its polymkeric substance and/or its polymkeric substance is as raw material, raw material is dispersed in to linking agent holds concurrently in solvent and obtains raw material mixed solution, add Louis acid catalysis Friedel-Crafts reaction, super crosslinked acquisition specific surface area is 1-5000m
2the porous polymer material of/g.The described linking agent solvent of holding concurrently is one or more the mixture in two halogen alkane substitutes.The described Lewis acid as catalyzer can be anhydrous SnCl
4, anhydrous FeCl
3, anhydrous BF
3or anhydrous AlCl
3.
The preparation method of this class organic porous polymer material provided by the invention, comprise the following steps: (1) raw materials mixed solution: taking the mixture of aromatics, its mixture, its polymkeric substance and/or its polymkeric substance as raw material, raw material is dispersed in to linking agent and holds concurrently in solvent and obtain raw material mixed solution, raw material mixed solution Raw concentration is between 0.01g/ml to 10g/ml.The described linking agent solvent of holding concurrently is one or more the mixture in two halogen alkane substitutes.
(2) poromeric preparation: Friedel-Crafts reaction occurs, super crosslinked acquisition crude product after adding catalyzer in the raw material mixed solution obtaining in step (1).Described catalyzer is preferably Lewis acid, and in catalyzer and raw material, the ratio of phenyl ring mole number is between 0.1:1 to 50:1.Described Lewis acid is preferably anhydrous SnCl
4, anhydrous FeCl
3, anhydrous BF
3or anhydrous AlCl
3.
In Friedel-Crafts reaction process keep continue stir, add catalyzer after temperature control detailed process be:
First, be warming up to 20-40 DEG C, isothermal reaction 2-12 hour; Then, be warming up to 50-70 DEG C, isothermal reaction 2-18 hour; Finally, be warming up to 80-120 DEG C, isothermal reaction 10-72 hour.
(3) poromeric purifying, by filter cake washing extracting after the filtration of crude product obtaining in step (2), removes catalyzer, after being dried, makes described porous polymer.
The concrete steps of filter cake washing are: first wash crude product 2-3 time with dilute hydrochloric acid, thereby remove most of catalyzer, then use distilled water wash 2-3 time, finally use washing with alcohol crude product 2-4 time, thereby remove residual catalyzer.
Extraction procedure detailed process was: with apparatus,Soxhlet's extracting 24 to 72 hours.
In preparation method of the present invention, change aromatics, its mixture, its polymkeric substance and/or the mixture of its polymkeric substance and the ratio of catalyzer can regulate the pore size of organic porous polymer material; The kind that changes linking agent (solvent) can regulate the pore size of porous polymer material; The kind that changes catalyzer can regulate the pore size of porous polymer material; The regulation range of pore size is 0.3-100nm.Adopt different aromatics or its polymkeric substance can obtain the porous polymer material that contains different functional groups.The content of porous polymer functional group can also be regulated and controled by changing ratio between multiple aromatics used,, by adopting one or more of different aromatics, the porous polymer material that contains different functional groups can be obtained.
Organic porous polymer material provided by the invention can be used as the application of support of the catalyst, separatory membrane, gas storage material or ion adsorbent.As gas storage material, can be used as hydrogen storage material, catch the application of carbonic acid gas and storage methane material.
In the embodiment of the present invention, confirm that by measuring Fourier's infrared spectra of organic porous polymer material of the present invention material is to have aromatics or its polymkeric substance to react acquisition with linking agent [referring to (1) C.D.Wood really, B.Tan, A.Trewin, H.J.Niu, D.Bradshaw, M.J.Rosseinsky, Y.Z.Khimyak, N.L.Campbell, R.Kirk, E.Stockel and A.I.Cooper, Chemistry of Materials, 2007, 19, 2034. (2) B.Li, R.Gong, W.Wang, X.huang, W.Zhang, H.Li, C.Hu, B.tan, Macromolecules, 2011, 44, 2410.], specific surface area, the aperture size of calculating organic porous polymer material of the present invention by measuring nitrogen adsorption-desorption curve distribute, calculate the hydrogen-storage amount of organic porous polymer material of the present invention by measuring hydrogen adsorption-desorption curve, by measuring the storage amount of carbon dioxide of the attached curve calculation of carbonic acid gas absorption-desorption organic porous polymer material of the present invention.
The present invention adopts the method for pioneering crosslinked aromatic compound, its mixture, its polymkeric substance and/or its polymeric blends both at home and abroad, solvent self is as outside cross-linking agent, " single stage method " synthesizes organic porous polymer material, and the raw material adopting is cheap aromatics, its mixture, its polymkeric substance and/or its polymeric blends, can select flexibly according to different application demands the kind of aromatics.Therefore, the present invention has prospects for commercial application widely.
The invention has the advantages that:
(1) poromeric preparation method provided by the invention, adopts reaction solvent to double as linking agent, has reduced process complexity, has significantly cut down the production cost of porous material; In addition, synthetic method is very simple, reaction conditions gentleness, and can be used as in a reaction vessels step, to complete material synthetic; The raw material adopting is aromatics or its polymkeric substance cheap and easy to get.
(2) synthetic method that the present invention adopts has suitability widely.The aromatics that the present invention adopts or its polymkeric substance can be one or more in all aromatics or its polymkeric substance that can carry out Fridel-Craft reaction.The linking agent that adopts is one or more in all saturated dihalides that can carry out Fridel-Craft reaction.
(3) synthetic method that the present invention adopts has Modulatory character to product.Can regulate and control the aperture size of product, can regulate and control the specific surface area of product, can regulate and control functional group's kind and the content of product.
(4) porous polymer material provided by the invention, aperture is adjustable, with low cost, specific surface area is high, there is good gas storage performance, be applied to the directions such as support of the catalyst, separatory membrane, gas storage material or ion adsorbent, have a good application prospect.
Brief description of the drawings
Fig. 1 is the poromeric infared spectrum (IR) in embodiment 1;
Fig. 2 is poromeric in embodiment 1
13c solid state nmr collection of illustrative plates (
13c CP-MAS NMR);
Fig. 3 is the poromeric infared spectrum (IR) in embodiment 2;
Fig. 4 is poromeric in embodiment 2
13c solid state nmr collection of illustrative plates (
13c CP-MAS NMR);
Fig. 5 is the poromeric infared spectrum (IR) in embodiment 3;
Fig. 6 is poromeric in embodiment 3
13c solid state nmr collection of illustrative plates (
13c CP-MAS NMR);
Fig. 7 is the poromeric infared spectrum (IR) in embodiment 4;
Fig. 8 is poromeric in embodiment 4
13c solid state nmr collection of illustrative plates (
13c CP-MAS NMR);
Fig. 9 is the poromeric infared spectrum (IR) in embodiment 5;
Figure 10 is poromeric in embodiment 5
13c solid state nmr collection of illustrative plates (
13c CP-MAS NMR);
Figure 11 is the poromeric infared spectrum (IR) in embodiment 6;
Figure 12 is poromeric in embodiment 6
13c solid state nmr collection of illustrative plates (
13c CP-MAS NMR);
Figure 13 is the poromeric infared spectrum (IR) in embodiment 7;
Figure 14 is poromeric in embodiment 7
13c solid state nmr collection of illustrative plates (
13c CP-MAS NMR);
Figure 15 is the poromeric infared spectrum (IR) in embodiment 8;
Figure 16 is poromeric in embodiment 8
13c solid state nmr collection of illustrative plates (
13c CP-MAS NMR);
Figure 17 is the porous polymer nitrogen adsorption-desorption thermoisopleth (77K) in embodiment 3;
Figure 18 is the poromeric pore size distribution curve in embodiment 3;
Figure 19 is the poromeric hydrogen adsorption-desorption thermoisopleth (77K) in embodiment 3;
Figure 20 is the attached thermoisopleth of poromeric carbonic acid gas absorption-desorption in embodiment 3.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.In addition,, in each embodiment of described the present invention, involved technical characterictic just can combine mutually as long as do not form each other conflict.
Porous polymer preparation method provided by the invention, comprises the following steps:
(1) raw materials mixed solution: taking the mixture of aromatics, its mixture, its polymkeric substance and/or its polymkeric substance as raw material, raw material is dispersed in to linking agent and holds concurrently in solvent and obtain raw material mixed solution, raw material mixed solution Raw concentration is between 0.01g/ml to 10g/ml.The described linking agent solvent of holding concurrently is one or more the mixture in two halogen alkane substitutes.
Adopt different aromatics or its polymkeric substance to obtain the organic porous polymer material that contains different functional groups, by changing ratio between multiple aromatics or its polymkeric substance used content with regulation and control functional group.
(2) poromeric preparation: Friedel-Crafts reaction occurs, super crosslinked acquisition crude product after adding catalyzer in the raw material mixed solution obtaining in step (1).Described catalyzer is preferably Lewis acid, and in catalyzer and raw material, the ratio of phenyl ring mole number is between 0.1:1 to 50:1.Described Lewis acid is preferably anhydrous SnCl
4, anhydrous FeCl
3, anhydrous BF
3or anhydrous AlCl
3.
In Friedel-Crafts reaction process keep continue stir, add catalyzer after temperature control detailed process be:
First, be warming up to 20-40 DEG C, isothermal reaction 2-12 hour; Then, be warming up to 50-70 DEG C, isothermal reaction 2-18 hour; Finally, be warming up to 80-120 DEG C, isothermal reaction 10-72 hour.
(3) poromeric purifying, by filter cake washing extracting after the filtration of crude product obtaining in step (2), removes catalyzer, after being dried, makes described porous polymer.
The concrete steps of filter cake washing are: first wash crude product 2-3 time with dilute hydrochloric acid, thereby remove most of catalyzer, then use distilled water wash 2-3 time, finally use washing with alcohol crude product 2-4 time, thereby remove residual catalyzer.
Extraction procedure detailed process was: with apparatus,Soxhlet's extracting 24 to 72 hours.
Porous polymer preparation method provided by the invention, changes the ratio of aromatics or its polymkeric substance and catalyzer, or changes the kind of saturated dihalide, changes the kind of catalyzer, all can regulate the pore size of organic porous polymer material.
Porous polymer material provided by the invention, applies porous polymer material preparation method preparation provided by the invention, and its aperture is between 0.3nm to 100nm, and its specific surface area is at 1m
2/ g to 5000m
2between/g.
Porous polymer material provided by the invention, owing to having applicable aperture and larger specific surface area, can be used as support of the catalyst, separatory membrane, gas storage material or ion adsorbent.Preferably, described porous polymer material is used as hydrogen storage material, catches carbon dioxide material or storage methane material.
Be below embodiment:
Embodiment 1
A kind of porous polymer preparation method, comprises the following steps:
(1) raw materials mixed solution: taking benzene as raw material; methylene dichloride is as the linking agent solvent of holding concurrently; under nitrogen protection; in the there-necked flask that reflux condensing tube, thermometer are housed, add raw material and the linking agent solvent of holding concurrently; magnetic agitation 0.2 hour; obtain raw material mixed solution, material concentration is 0.095g/ml.
(2) poromeric preparation: taking aluminum trichloride (anhydrous) as catalyzer, add catalyzer to middle the acquisition in raw material mixed solution of step (1), the ratio that makes phenyl ring mole number in catalyzer and raw material is 2:1, Friedel-Crafts reaction occurs, super crosslinked acquisition crude product.
In Friedel-Crafts reaction process keep continue stir, add catalyzer after temperature control detailed process be: be warming up to 30 DEG C, isothermal reaction 4 hours; Then, be warming up to 60 DEG C, isothermal reaction 16 hours, last, be warming up to 100 DEG C, isothermal reaction 24 hours.
(3) poromeric purifying: by filter cake washing extracting after the filtration of crude product obtaining in step (2), remove catalyzer, drying under reduced pressure makes described porous polymer after 24 hours.
The concrete steps of filter cake washing are: first wash crude product 3 times with 30ml dilute hydrochloric acid, thereby remove most of catalyzer, then use distilled water wash 3 times, finally use washing with alcohol crude product 3 times, thereby remove residual catalyzer.
Extraction procedure detailed process is: in apparatus,Soxhlet's, use extraction using alcohol crude product 48 hours.
The porous polymer material of preparing according to described porous polymer preparation method, its mean pore size is at 2.2nm, and its specific surface area is 643m
2/ g.Its infared spectrum is shown in Fig. 1,2920cm
-1for the stretching vibration absorption peak of methylene radical in Porous-Organic polymkeric substance, at 1600cm
-1, 1500cm
-1, 1450cm
-1for the skeletal vibration absorption peak of Porous-Organic polymkeric substance aromatic ring structure; Its
13accompanying drawing 2 is shown in by C solid state nmr collection of illustrative plates, and 37ppm is the C nuclear-magnetism peak of methylene radical in Porous-Organic polymkeric substance, the C nuclear-magnetism peak that 138ppm is aromatic ring structure.
Embodiment 2
A kind of porous polymer preparation method, comprises the following steps:
(1) raw materials mixed solution: taking biphenyl as raw material; methylene dichloride is the linking agent solvent of holding concurrently; under nitrogen protection; in the there-necked flask that reflux condensing tube, thermometer are housed, add raw material and the linking agent solvent of holding concurrently; magnetic agitation 0.2 hour; obtain raw material mixed solution, material concentration is 0.095g/ml.
(2) poromeric preparation: taking aluminum trichloride (anhydrous) as catalyzer, add again catalyzer to middle the acquisition in raw material mixed solution of step (1), the ratio that makes phenyl ring mole number in catalyzer and raw material is 2:1, Friedel-Crafts reaction occurs, super crosslinked acquisition crude product.
In Friedel-Crafts reaction process keep continue stir, add catalyzer after temperature control detailed process be: be warming up to 40 DEG C, isothermal reaction 8 hours; Then, be warming up to 60 DEG C, isothermal reaction 12 hours, last, be warming up to 80 DEG C, isothermal reaction 24 hours.
(3) poromeric purifying: by filter cake washing extracting after the filtration of crude product obtaining in step (2), remove catalyzer, drying under reduced pressure makes described porous polymer after 24 hours.
The concrete steps of filter cake washing are: first wash crude product 3 times with 30ml dilute hydrochloric acid, thereby remove most of catalyzer, then use distilled water wash 3 times, finally use washing with alcohol crude product 3 times, thereby remove residual catalyzer.
Extraction procedure detailed process is: in apparatus,Soxhlet's, use extraction using alcohol crude product 48 hours.
The porous polymer material of preparing according to described porous polymer preparation method, its mean pore size is at 2.1nm, and its specific surface area is 1475m
2/ g.Its infared spectrum is shown in accompanying drawing 3,2910cm
-1for the stretching vibration absorption peak of methylene radical in Porous-Organic polymkeric substance, at 1600cm
-1, 1500cm
-1, 1450cm
-1for the skeletal vibration absorption peak of Porous-Organic polymkeric substance aromatic ring structure; Its
13accompanying drawing 4 is shown in by C solid state nmr collection of illustrative plates, and 37ppm is the C nuclear-magnetism peak of methylene radical in Porous-Organic polymkeric substance, 138 and the 140ppm C nuclear-magnetism peak that is aromatic ring structure.
Embodiment 3
A kind of porous polymer preparation method, comprises the following steps:
(1) raw materials mixed solution: with 1; 3; 5-triphenylbenzene is raw material; methylene dichloride is as the linking agent solvent of holding concurrently; under nitrogen protection, in the there-necked flask that reflux condensing tube, thermometer are housed, add raw material and the linking agent solvent of holding concurrently, magnetic agitation 0.2 hour; obtain raw material mixed solution, material concentration is 0.125g/ml.
(2) poromeric preparation: taking aluminum trichloride (anhydrous) as catalyzer, add again catalyzer to middle the acquisition in raw material mixed solution of step (1), the ratio that makes phenyl ring mole number in catalyzer and raw material is 2:1, Friedel-Crafts reaction occurs, super crosslinked acquisition crude product.
In Friedel-Crafts reaction process keep continue stir, add catalyzer after temperature control detailed process be: be warming up to 40 DEG C, isothermal reaction 8 hours; Then, be warming up to 60 DEG C, isothermal reaction 12 hours, last, be warming up to 80 DEG C, isothermal reaction 24 hours.
(3) poromeric purifying: by filter cake washing extracting after the filtration of crude product obtaining in step (2), remove catalyzer, drying under reduced pressure makes described porous polymer after 24 hours.
The concrete steps of filter cake washing are: first wash crude product 3 times with 30ml dilute hydrochloric acid, thereby remove most of catalyzer, then use distilled water wash 3 times, finally use washing with alcohol crude product 3 times, thereby remove residual catalyzer.
Extraction procedure detailed process is: in apparatus,Soxhlet's, use extraction using alcohol crude product 48 hours.
The porous polymer material of preparing according to described porous polymer preparation method, its aperture is between 2.3nm, and its specific surface area is 1808m
2/ g.Its infared spectrum is shown in accompanying drawing 5,2920cm
-1for the stretching vibration absorption peak of methylene radical in Porous-Organic polymkeric substance, at 1600cm
-1, 1500cm
-1, 1450cm
-1for the skeletal vibration absorption peak of Porous-Organic polymkeric substance aromatic ring structure; Its
13accompanying drawing 6 is shown in by C solid state nmr collection of illustrative plates, and 37ppm is the C nuclear-magnetism peak of methylene radical in Porous-Organic polymkeric substance, 138 and the 140ppm C nuclear-magnetism peak that is aromatic ring structure.
Embodiment 4
A kind of porous polymer preparation method, comprises the following steps:
(1) raw materials mixed solution: taking benzene as raw material; 1; 2-ethylene dichloride is as the linking agent solvent of holding concurrently; under nitrogen protection; in the there-necked flask that reflux condensing tube, thermometer are housed, add raw material and the linking agent solvent of holding concurrently; magnetic agitation 0.2 hour, obtains raw material mixed solution, and material concentration is 0.095g/ml.
(2) poromeric preparation: taking aluminum trichloride (anhydrous) as catalyzer, add again catalyzer to middle the acquisition in raw material mixed solution of step (1), the ratio that makes phenyl ring mole number in catalyzer and raw material is 2:1, Friedel-Crafts reaction occurs, super crosslinked acquisition crude product.
In Friedel-Crafts reaction process keep continue stir, add catalyzer after temperature control detailed process be: be warming up to 30 DEG C, isothermal reaction 8 hours; Then, be warming up to 60 DEG C, isothermal reaction 16 hours, last, be warming up to 100 DEG C, isothermal reaction 24 hours.
(3) poromeric purifying: by filter cake washing extracting after the filtration of crude product obtaining in step (2), remove catalyzer, drying under reduced pressure makes described porous polymer after 24 hours.
The concrete steps of filter cake washing are: first wash crude product 3 times with 30ml dilute hydrochloric acid, thereby remove most of catalyzer, then use distilled water wash 3 times, finally use washing with alcohol crude product 3 times, thereby remove residual catalyzer.
Extraction procedure detailed process is: in apparatus,Soxhlet's, use extraction using alcohol crude product 48 hours.
The porous polymer material of preparing according to described porous polymer preparation method, its mean pore size is at 3.8nm, and its specific surface area is 659m
2/ g.Its infared spectrum is shown in accompanying drawing 7,2960cm
-1for the stretching vibration absorption peak of methylene radical in Porous-Organic polymkeric substance, at 1600cm
-1, 1500cm
-1, 1450cm
-1for the skeletal vibration absorption peak of Porous-Organic polymkeric substance aromatic ring structure; Its
13accompanying drawing 8 is shown in by C solid state nmr collection of illustrative plates, and 37ppm is the C nuclear-magnetism peak of methylene radical in Porous-Organic polymkeric substance, the C nuclear-magnetism peak that 140ppm is aromatic ring structure.
Embodiment 5
A kind of porous polymer preparation method, comprises the following steps:
(1) raw materials mixed solution: taking biphenyl as raw material; 1; 2-ethylene dichloride is as the linking agent solvent of holding concurrently; under nitrogen protection; in the there-necked flask that reflux condensing tube, thermometer are housed, add raw material and the linking agent solvent of holding concurrently; magnetic agitation 0.2 hour, obtains raw material mixed solution, and material concentration is 0.095g/ml.
(2) poromeric preparation: taking aluminum trichloride (anhydrous) as catalyzer, add again catalyzer to middle the acquisition in raw material mixed solution of step (1), the ratio that makes phenyl ring mole number in catalyzer and raw material is 2:1, Friedel-Crafts reaction occurs, super crosslinked acquisition crude product.
In Friedel-Crafts reaction process keep continue stir, add catalyzer after temperature control detailed process be: be warming up to 40 DEG C, isothermal reaction 8 hours; Then, be warming up to 60 DEG C, isothermal reaction 12 hours, last, be warming up to 80 DEG C, isothermal reaction 24 hours.
(3) poromeric purifying: by filter cake washing extracting after the filtration of crude product obtaining in step (2), remove catalyzer, drying under reduced pressure makes described porous polymer after 24 hours.
The concrete steps of filter cake washing are: first wash crude product 3 times with 30ml dilute hydrochloric acid, thereby remove most of catalyzer, then use distilled water wash 3 times, finally use washing with alcohol crude product 3 times, thereby remove residual catalyzer.
Extraction procedure detailed process is: in apparatus,Soxhlet's, use extraction using alcohol crude product 48 hours.
The porous polymer material of preparing according to described porous polymer preparation method, its mean pore size is at 2.6nm, and its specific surface area is 536m
2between/g.Its infared spectrum is shown in accompanying drawing 9,2960cm
-1for the stretching vibration absorption peak of methylene radical in Porous-Organic polymkeric substance, at 1600cm
-1, 1500cm
-1, 1450cm
-1for the skeletal vibration absorption peak of Porous-Organic polymkeric substance aromatic ring structure; Its
13accompanying drawing 10 is shown in by C solid state nmr collection of illustrative plates, and 37ppm is the C nuclear-magnetism peak of methylene radical in Porous-Organic polymkeric substance, 138 and the 140ppm C nuclear-magnetism peak that is aromatic ring structure.
Embodiment 6
A kind of porous polymer preparation method, comprises the following steps:
(1) raw materials mixed solution: with 1; 3; 5-triphenylbenzene is raw material; 1,2-ethylene dichloride is as the linking agent solvent of holding concurrently, under nitrogen protection; in the there-necked flask that reflux condensing tube, thermometer are housed, add raw material and the linking agent solvent of holding concurrently; magnetic agitation 0.2 hour, obtains raw material mixed solution, and material concentration is 0.125g/ml.
(2) poromeric preparation: taking aluminum trichloride (anhydrous) as catalyzer, add again catalyzer to middle the acquisition in raw material mixed solution of step (1), the ratio that makes phenyl ring mole number in catalyzer and raw material is 2:1, Friedel-Crafts reaction occurs, super crosslinked acquisition crude product.
In Friedel-Crafts reaction process keep continue stir, add catalyzer after temperature control detailed process be: be warming up to 40 DEG C, isothermal reaction 8 hours; Then, be warming up to 60 DEG C, isothermal reaction 12 hours, last, be warming up to 80 DEG C, isothermal reaction 24 hours.
(3) poromeric purifying: by filter cake washing extracting after the filtration of crude product obtaining in step (2), remove catalyzer, drying under reduced pressure makes described porous polymer after 24 hours.
The concrete steps of filter cake washing are: first wash crude product 3 times with 30ml dilute hydrochloric acid, thereby remove most of catalyzer, then use distilled water wash 3 times, finally use washing with alcohol crude product 3 times, thereby remove residual catalyzer.
Extraction procedure detailed process is: in apparatus,Soxhlet's, use extraction using alcohol crude product 24 hours.
The porous polymer material of preparing according to described porous polymer preparation method, its mean pore size is between 3.7nm, and its specific surface area is 934m
2/ g.Its infared spectrum is shown in accompanying drawing 11,2960cm
-1for the stretching vibration absorption peak of methylene radical in Porous-Organic polymkeric substance, at 1600cm
-1, 1500cm
-1, 1450cm
-1for the skeletal vibration absorption peak of Porous-Organic polymkeric substance aromatic ring structure; Its
13accompanying drawing 12 is shown in by C solid state nmr collection of illustrative plates, and 37ppm is the C nuclear-magnetism peak of methylene radical in Porous-Organic polymkeric substance, 138 and the 140ppm C nuclear-magnetism peak that is aromatic ring structure.
Embodiment 7
A kind of porous polymer preparation method, comprises the following steps:
(1) raw materials mixed solution: taking benzene as raw material; methylene dichloride is as the linking agent solvent of holding concurrently; under nitrogen protection; in the there-necked flask that reflux condensing tube, thermometer are housed, add raw material and the linking agent solvent of holding concurrently; magnetic agitation 0.2 hour; obtain raw material mixed solution, material concentration is 0.01g/ml.
(2) poromeric preparation: taking aluminum trichloride (anhydrous) as catalyzer, add again catalyzer to middle the acquisition in raw material mixed solution of step (1), the ratio that makes phenyl ring mole number in catalyzer and raw material is 0.1:1, Friedel-Crafts reaction occurs, super crosslinked acquisition crude product.
In Friedel-Crafts reaction process keep continue stir, add catalyzer after temperature control detailed process be: be warming up to 20 DEG C, isothermal reaction 2 hours; Then, be warming up to 50 DEG C, isothermal reaction 2 hours, last, be warming up to 80 DEG C, isothermal reaction 10 hours.
(3) poromeric purifying: by filter cake washing extracting after the filtration of crude product obtaining in step (2), remove catalyzer, drying under reduced pressure makes described porous polymer after 24 hours.
The concrete steps of filter cake washing are: first wash crude product 2 times with 30ml dilute hydrochloric acid, thereby remove most of catalyzer, then use distilled water wash 2 times, finally use washing with alcohol crude product 2 times, thereby remove residual catalyzer.
Extraction procedure detailed process is: in apparatus,Soxhlet's, use extraction using alcohol crude product 24 hours.
The porous polymer material of preparing according to described porous polymer preparation method, its mean pore size is at 4.5nm, and its specific surface area is 231m
2/ g.Its infared spectrum is shown in accompanying drawing 13,2920cm
-1for the stretching vibration absorption peak of methylene radical in Porous-Organic polymkeric substance, at 1600cm
-1, 1500cm
-1, 1450cm
-1for the skeletal vibration absorption peak of Porous-Organic polymkeric substance aromatic ring structure; Its
13accompanying drawing 14 is shown in by C solid state nmr collection of illustrative plates, and 37ppm is the C nuclear-magnetism peak of methylene radical in Porous-Organic polymkeric substance, the C nuclear-magnetism peak that 138ppm is aromatic ring structure.
Embodiment 8
A kind of porous polymer preparation method, comprises the following steps:
(1) raw materials mixed solution: taking benzene as raw material; methylene dichloride is as the linking agent solvent of holding concurrently; under nitrogen protection; in the there-necked flask that reflux condensing tube, thermometer are housed, add raw material and the linking agent solvent of holding concurrently; magnetic agitation 0.2 hour; obtain raw material mixed solution, material concentration is 10g/ml.
(2) poromeric preparation: taking aluminum trichloride (anhydrous) as catalyzer, add again catalyzer to middle the acquisition in raw material mixed solution of step (1), the ratio that makes phenyl ring mole number in catalyzer and raw material is 50:1, Friedel-Crafts reaction occurs, super crosslinked acquisition crude product.
In Friedel-Crafts reaction process keep continue stir, add catalyzer after temperature control detailed process be: be warming up to 40 DEG C, isothermal reaction 12 hours; Then, be warming up to 70 DEG C, isothermal reaction 18 hours, last, be warming up to 120 DEG C, isothermal reaction 72 hours.
(3) poromeric purifying: by filter cake washing extracting after the filtration of crude product obtaining in step (2), remove catalyzer, drying under reduced pressure makes described porous polymer after 24 hours.
The concrete steps of filter cake washing are: first wash crude product 3 times with 30ml dilute hydrochloric acid, thereby remove most of catalyzer, then use distilled water wash 3 times, finally use washing with alcohol crude product 4 times, thereby remove residual catalyzer.
Extraction procedure detailed process is: in apparatus,Soxhlet's, use extraction using alcohol crude product 72 hours.
The porous polymer material of preparing according to described porous polymer preparation method, its mean pore size is at 2.6nm, and its specific surface area is 836m
2/ g.Its infared spectrum is shown in accompanying drawing 15,2920cm
-1for the stretching vibration absorption peak of methylene radical in Porous-Organic polymkeric substance, at 1600cm
-1, 1500cm
-1, 1450cm
-1for the skeletal vibration absorption peak of Porous-Organic polymkeric substance aromatic ring structure; Its
13accompanying drawing 16 is shown in by C solid state nmr collection of illustrative plates, and 37ppm is the C nuclear-magnetism peak of methylene radical in Porous-Organic polymkeric substance, the C nuclear-magnetism peak that 138ppm is aromatic ring structure.
Embodiment 9: if industrial production is used mechanical stirring instead to ensure mass transfer, to conduct heat evenly for magnetic agitation all in embodiment 1-8.
Embodiment 10: in above embodiment, using aluminum chloride as catalyst Friedel-Crafts reaction, also can adopt other Lewis acids to carry out catalysis.Can regulate the specific surface area of organic porous polymer material by benzene and lewis acidic ratio in change embodiment 4.Along with the increase of the ratio of Lewis acid and benzene, the specific surface area first increases and then decreases of Porous-Organic polymkeric substance, aperture first increases and then decreases.
In change embodiment 1, the regulation and control of benzene and Lewis acid ratio contrast table area for example
Embodiment 11: change the kind of solvent (linking agent) in embodiment 1 and embodiment 4, can regulate the aperture size of porous polymer material.Along with the growth of linking agent segment, poromeric aperture increases, and productive rate also increases.
Embodiment 12: utilize porous polymer material that embodiment 3 prepares for storing up the application of hydrogen and storage carbonic acid gas, and press IUPAC standard, if detection is as follows: specific surface is: 1801m
2/ g is shown in specification sheets Figure 17, and its mesopore volume, micro pore volume and specific surface area are also to be measured by nitrogen adsorption method; Pore volume: 1.07cm
3/ g; Micro pore volume: 0.51cm
3/ g (P/P
0 =0.05); Figure of description 18 is shown in by pore size distribution, it is to adopt density number (DFT) modeling that Micromeritics ASAP 2020M specific surface area and pore analysis instrument carry to obtain, this curve shows that the micropore size of the porous polymer material in embodiment 3 mainly concentrates on 0.5nm, mesoporous aperture mainly concentrates on 2-5nm, and calculating the mean pore size obtaining is 2.3nm; Specific surface area and pore analysis instrument are measured porous polymer nano-grain nitrogen adsorption-desorption data, re-use pressure and the adsorptive capacity acquisition aperture data of Density functional number (DFT) the modeling matching equilibrium adsorption point that instrument carries.Hydrogen-storage amount: 2.14% (77K/1.01bar) is shown in that Figure 19, hydrogen adsorption-desorption curve show that the porous polymer in embodiment 3 is reversible to the absorption-desorption additive process of hydrogen, can be used as hydrogen storage material; Storage amount of carbon dioxide: 21.3% (273K/1.01bar) is shown in Figure 20, and the absorption-desorption additive process of its carbonic acid gas is reversible, can be as storage carbon dioxide material.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a porous polymer preparation method, is characterized in that, comprises the following steps:
(1) raw materials mixed solution: taking the mixture of aromatics, its mixture, its polymkeric substance and/or its polymkeric substance as raw material, raw material is dispersed in to linking agent and holds concurrently in solvent and obtain raw material mixed solution, the described linking agent solvent of holding concurrently is one or more the mixture in two halogen alkane substitutes;
(2) poromeric preparation: Friedel-Crafts reaction occurs, super crosslinked acquisition crude product after adding catalyzer in the raw material mixed solution obtaining in step (1);
(3) poromeric purifying: by filter cake washing extracting after the filtration of crude product obtaining in step (2), remove catalyzer, make described porous polymer after being dried.
2. porous polymer preparation method as claimed in claim 1, is characterized in that, Friedel-Crafts reaction catalyzer is Lewis acid, and in catalyzer and raw material, the ratio of phenyl ring mole number is between 0.1:1 to 50:1.
3. porous polymer preparation method as claimed in claim 2, is characterized in that, described Lewis acid is anhydrous SnCl
4, anhydrous FeCl
3, anhydrous BF
3or anhydrous AlCl
3.
4. porous polymer preparation method as claimed in claim 1, is characterized in that, described raw material mixed solution Raw concentration is between 0.01g/ml to 10g/ml.
5. porous polymer preparation method as claimed in claim 1, is characterized in that, in described Friedel-Crafts reaction process keep continue stir, add catalyzer after temperature control detailed process be:
First, be warming up to 20-40 DEG C, isothermal reaction 2-12 hour; Then, be warming up to 50-70 DEG C, isothermal reaction 2-18 hour; Finally, be warming up to 80-120 DEG C, isothermal reaction 10-72 hour.
6. the porous polymer preparation method as described in claim 1 to 5 any one, is characterized in that, after described filtration, wash and extracting in wash concrete steps and be:
First wash crude product 2-3 time with dilute hydrochloric acid, then use distilled water wash 2-3 time, finally use washing with alcohol crude product 2-4 time;
After described filtration, washing extracting concrete steps in also extracting is:
With apparatus,Soxhlet's ethanol extracting 24 to 72 hours.
7. a porous polymer material, is characterized in that, the porous polymer preparation method preparation of application as described in claim 1 to 6 any one.
8. porous polymer material as claimed in claim 7, is characterized in that, its aperture is between 0.5nm to 100nm.
9. an application for porous polymer material as claimed in claim 7 or 8, is characterized in that, described porous polymer material is as support of the catalyst, separatory membrane, gas storage material or ion adsorbent.
10. application as claimed in claim 8, is characterized in that, described porous polymer material is used as hydrogen storage material, catches carbon dioxide material or storage methane material.
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