CN103396531A - Preparation method of porous aromatic skeleton compound - Google Patents
Preparation method of porous aromatic skeleton compound Download PDFInfo
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- CN103396531A CN103396531A CN2013103038792A CN201310303879A CN103396531A CN 103396531 A CN103396531 A CN 103396531A CN 2013103038792 A CN2013103038792 A CN 2013103038792A CN 201310303879 A CN201310303879 A CN 201310303879A CN 103396531 A CN103396531 A CN 103396531A
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Abstract
The invention discloses a preparation method of a porous aromatic skeleton compound. The preparation method of the porous aromatic skeleton compound comprises the following steps of: adding a reactant and lewis acid at a mass ratio of (0.1-10):1 into an organic solvent, and carrying out a coupling reaction, wherein the reactant is a substituent-group-free aromatic rigid monomer; after the coupling reaction is finished, firstly washing by adopting ethyl alcohol and diluted hydrochloric acid, and then carrying out post processing, thus obtaining the porous aromatic skeleton compound. By adopting the manner, the preparation method of the porous aromatic skeleton compound has the advantages that a catalyst used in the preparation method of the porous aromatic skeleton compound is cheap and easily available, the cost is low, the reaction yield is extremely high, the reaction method is simple and practicable, reaction conditions can be easily realized, the preparation method of the porous aromatic skeleton compound has extremely high application value and market value, and application prospect of the aromatic skeleton compound is greatly expanded.
Description
Technical field
The present invention relates to the synthetic field of porous material, particularly relate to a kind of preparation method of porous fragrance framework compound.
Background technology
In two more than ten years in the past, porous material as a kind of development rapidly type material obtained increasing chemist and scientist's extensive concern, especially in gas adsorption, gas storage, gas delivery, there has been good performance the aspects such as chemical reaction catalysis.
The series of morning is metallic organic framework series in porous material, is the coordination that utilizes inorganic metal ion and organic group, has obtained the adjustable a series of porous materials in aperture.In 2005, Yaghi thinks and utilizes topological framework with its co-worker, can design more synthetic utilize covalent linkage and the porous organic material that couples together, and obtain satisfactory stability and regular skeleton structure, the covalency organic backbone has launched again the vigorous growth of a new round after this.In 2009, Jilin University is after the synthetic and preparation that has proposed porous fragrance framework compound, and the specific surface area of the product that can obtain this field has arrived new height, after this, more porous fragrance framework compound is developed out, and has obtained many scientific researches and using value.
Porous fragrance framework compound refers to and utilizes corresponding organic reaction, make the organic molecule generation copolyreaction of aromaticity, form a kind of organic compound certain size and that neat pore passage structure is arranged that has, these compounds all exist very important value on the absorption of gas and gas storage.
At present, thus the synthetic of porous fragrance framework compound is mainly to have utilized the polyreaction between the monomer with rigidity that can connect to obtain microporous polymer.usually in reaction, polymerization process commonly used has with amino formation reaction, synthesizing of the phthalocyanine compound of metal ion mediation, the alkynyl coupling of copper palladium catalysis, the aromatic yl polysulfide yl coupling of palladium catalysis, the alkynyl of palladium catalysis and the coupling between alkynyl, two (1, the 5-cyclooctadiene) alkynyl of nickel mediation and the coupling between alkynyl, oxidative coupling between the sulphur benzene of iron trichloride mediation, cobalt mediation contain copolyreaction between the alkynes triatomic ring, the polyreaction of the nitrile triatomic ring of zinc chloride mediation, the imines formation reaction, four phenylsilanes of lithium mediation form, the building-up reactions of boron trioxide and boron ester condensation reaction.
But these synthetic methods exist in reaction process that reaction yield is on the low side, reaction conditions is complicated and harsh, reactant has the shortcomings such as danger, catalysts selling at exorbitant prices, and these all become and suppress the framework compound industrialization of porous fragrance and the cheap major obstacles that obtains.
Summary of the invention
The technical problem that the present invention mainly solves is to provide the preparation method of the feasible and cheap porous fragrance framework compound of a kind of convenience.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of preparation method of porous fragrance framework compound is provided, comprises that step is:
(1) with amount of substance than being that the reactant of 0.1～10:1 and Lewis acid join in organic solvent and carry out linked reaction, described reactant is the aromatic series rigidity monomer of unsubstituted group;
(2) first with ethanol and dilute hydrochloric acid, wash after reaction finishes, then aftertreatment obtains porous fragrance framework compound.
In a preferred embodiment of the present invention, reactant described in step (1) is triphenylamine, Tetrabenzene methane, four phenylsilanes or four benzene germanes.
In a preferred embodiment of the present invention, described in step (1), organic solvent is chloroform, and the amount of substance concentration that described organic solvent adds to described reactant is 0.001～10mol/L.
In a preferred embodiment of the present invention, the condition of linked reaction described in step (1) is to react 60 minutes to 10 days under 25～120 ℃.
In a preferred embodiment of the present invention, with the temperature of 10～100mL, be first the washing with alcohol 3～5 times of 20～70 ℃ in step (2) and filter.
In a preferred embodiment of the present invention, chloroform washing 3～5 time and the filtration of last handling process described in step (2) for being 20～60 ℃ with the temperature of 10～100mL is the water of 20～70 ℃, ethanol that temperature is 20～60 ℃, temperature is 20～60 ℃ acetone and temperature successively, 80～200 ℃ of lower vacuum filtrations 4～40 hours, vacuum tightness was less than 10 again
-3MmHg.
The invention has the beneficial effects as follows: the preparation method of porous fragrance framework compound of the present invention, the catalyzer that uses in this preparation method is cheap and easy to get, with low cost, reaction yield is high, reaction method is simple, reaction conditions is basic easily to be obtained, and has very high using value and marketable value, has promoted greatly the application prospect of such fragrant framework compound.
Description of drawings
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, in below describing embodiment, the accompanying drawing of required use is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings, wherein:
Fig. 1 is the reaction equation that the present invention's the first preferred embodiment generates poly-Tetrabenzene methane;
Fig. 2 is the reaction equation that the present invention's the first preferred embodiment generates poly-triphenylamine;
Fig. 3 is the reaction equation that the present invention's the first preferred embodiment generates poly-four phenylsilanes;
Fig. 4 is the reaction equation that the present invention's the first preferred embodiment generates poly-four benzene germanium;
Fig. 5 is the infrared spectrum of poly-triphenylamine of the present invention and described triphenylamine, described poly-Tetrabenzene methane and described Tetrabenzene methane, described poly-four phenylsilanes and described four phenylsilanes, described poly-four benzene germanium and described four benzene germanes;
Fig. 6 is the thermogravimetric curve figure of poly-triphenylamine of the present invention, described poly-Tetrabenzene methane, described poly-four phenylsilanes, described poly-four benzene germanium;
Fig. 7 is the nitrogen adsorption-desorption isotherm figure of poly-triphenylamine of the present invention, described poly-Tetrabenzene methane, described poly-four phenylsilanes, described poly-four benzene germanium;
Fig. 8 is the graph of pore diameter distribution of poly-triphenylamine of the present invention, described poly-Tetrabenzene methane, described poly-four phenylsilanes, described poly-four benzene germanium;
In each figure of accompanying drawing, a represents poly-triphenylamine, the poly-Tetrabenzene methane of b representative, poly-four phenylsilanes of c representative, the poly-four benzene germanium of d representative.
Embodiment
Below will the technical scheme in the embodiment of the present invention be clearly and completely described, obviously, described embodiment is only a part of embodiment of the present invention, rather than whole embodiment.Based on the embodiment in the present invention, those of ordinary skills, not making all other embodiment that obtain under the creative work prerequisite, belong to the scope of protection of the invention.
Lewis acid (Lewis Acid, LA) refers to electron acceptor, and the unoccupied orbital that can be used for receiving electron pair is arranged, and also can regard the centrosome that forms coordinate bond as.In organic reaction, a lot of electrophilic reagents or electron acceptor(EA) are all Lewis acids.Lewis acid contains low-yield lowest unoccupied molecular orbital usually, can react with highest occupied molecular orbital.Concerning the Lewis acid theory, all electrophilic reagents, comprise that hydrogen ion can be called Lewis acid.Lewis acid of the present invention is directly to have bought from market, and shape and specification are the solid state powder, can be dissolved in reaction solvent, thereby react under liquid-phase condition.
Embodiment one:
A kind of preparation method of poly-Tetrabenzene methane is provided, comprises that step is:
(1) weighing:
Tetrabenzene methane and aluminum chloride are fed intake for the ratio of 1:1 in mass ratio, be that analytical balance accurately takes the aluminum chloride of 200mg, 1.450mmol and the Tetrabenzene methane of 200mg, 0.6242mmol, insert in the 100mL round-bottomed flask, described round-bottomed flask has very strong stopping property, can carry out the anhydrous and oxygen-free operation.
(2) dissolving of reactant and reaction:
Accurately inject the 30mL anhydrous chloroform with syringe in round-bottomed flask again, put into the magnetic stir bar of 1cm size, to carrying out gas displacement in Glass Containers, reaction is carried out under nitrogen protection.Above-mentioned round-bottomed flask is placed on magnetic stirring apparatus, stirred 3 days.Reaction equation sees also Fig. 1.
(3) aftertreatment:
After question response finishes, reactant is carried out suction filtration, stay solid insoluble, and to it, use respectively dilute hydrochloric acid (2 mol/L), ethanol, acetone, methylene dichloride equal solvent to wash, every kind of solvent wash 3 times, each washing time was over 3 hours.Then, the brown ceramic powder that the sample drying that obtains is obtained is poly-Tetrabenzene methane of the present invention, and productive rate is 80%.
Embodiment two:
A kind of preparation method of poly-triphenylamine is provided, and temperature of reaction is to carry out under 50 ℃, and all the other steps are identical with embodiment one, and productive rate is 85%.Reaction equation sees also Fig. 2.
Embodiment three:
A kind of preparation method of four phenylsilanes is provided, and the lewis acidic quality of catalyzer is 1g, and all the other steps are identical with embodiment one, and productive rate is 90%.Reaction equation sees also Fig. 3.
Embodiment four:
A kind of preparation method of four benzene germanes is provided, and step is identical with embodiment one.Reaction equation sees also Fig. 4.
See also Fig. 5, in figure, the curve of top is the infrared spectrum of polymkeric substance, and the curve of below belongs to reactant, 1500cm
-1, 1600cm
-1And 1700cm
-1The vibration peak of left and right is fragrant skeletal vibration absorption peak, at 2800-3000cm
-1The broad peak at place is the ν=C-H vibration absorption peak of phenyl ring and the out-of-plane vibration absorption peak of phenyl ring δ=C-H.The poly-triphenylamine that obtains, poly-Tetrabenzene methane, poly-four phenylsilanes and poly-four benzene germanes are at 400-4000 cm
-1Between mainly go out between peak position and three kinds of monomers basic quite corresponding.At 2700-2800cm
-1Between four kinds of polymkeric substance all contain a new vibration peak, according to the characteristics of infrared spectra, namely along with the increase of conjugated system, 2800-3000cm
-1The C-H at place can be offset, and, to the wave number smaller part, according to these data, can illustrate, polymerization has occurred four kinds of polymkeric substance.
See also Fig. 6, according to thermogravimetric curve as can be known, the poly-triphenylamine that obtains, poly-Tetrabenzene methane, poly-four phenylsilanes and poly-four benzene germanes are under the air atmosphere test condition, start weightless gradually from the room temperature heating, minute being clipped to weightlessness under 420 ℃, 450 ℃, 465 ℃ and 470 ℃ reaches 20%, decomposes fully under 600 ℃, 600 ℃, 590 ℃ and 560 ℃.Namely relatively stable before 300 ℃, can keep not caving in of skeleton, along with the rising of temperature, polymer quality reduces gradually between 300 ℃～600 ℃, and after 600 ℃, it is stable that curve reaches, and organic backbone all decomposes loss.
See also Fig. 7, as seen from the figure, the poly-triphenylamine that obtains, poly-Tetrabenzene methane, poly-four phenylsilanes and poly-four benzene germanes all have certain adsorption for nitrogen, wherein gather Tetrabenzene methane, poly-four phenylsilanes, the nitrogen adsorption matter of poly-four benzene germanes can reach 230 cc/g, 195 cc/g and 201 cc/g.Can calculate thus, the specific surface area of four kinds of polymkeric substance (BET) is respectively 827 m
2/ g, 687 m
2/ g, 539 m
2/ g and 567 m
2/ g.Also can calculate pore size and the pore volume of this polymkeric substance.
See also Fig. 8, the poly-triphenylamine that obtains, poly-Tetrabenzene methane, poly-four phenylsilanes and poly-four benzene germanes calculate according to the H-K method, pore size distribution is respectively at 1.232 nm, 1.232nm, 2.313 nm and 1.475 nm, and relative pore volume is respectively 0.263 cc/g, 0.263 cc/g, 0.264 cc/g and 0.273 cc/g.
The present invention use aluminum chloride as catalyzer replace in traditional method first by carrying out the method for the graceful polymerization of ell after the halo of bromine, greatly reduce the production cost in polymerization.Reaction conditions after optimization can shorten reaction time greatly, obtains product within the reaction times of 3 days (not comprising last handling process), has very high using value and marketable value, has promoted greatly the application prospect of such fragrant framework compound.
The foregoing is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or equivalent flow process conversion that utilizes description of the present invention to do; or directly or indirectly be used in other relevant technical field, all in like manner be included in scope of patent protection of the present invention.
Claims (6)
1. the preparation method of a porous fragrance framework compound, is characterized in that, comprises that step is:
(1) with amount of substance than being that the reactant of 0.1～10:1 and Lewis acid join in organic solvent and carry out linked reaction, described reactant is the aromatic series rigidity monomer of unsubstituted group;
(2) first with ethanol and dilute hydrochloric acid, wash after reaction finishes, then aftertreatment obtains porous fragrance framework compound.
2. preparation method according to claim 1, is characterized in that, reactant described in step (1) is triphenylamine, Tetrabenzene methane, four phenylsilanes or four benzene germanes.
3. preparation method according to claim 1, is characterized in that, described in step (1), organic solvent is chloroform, and the amount of substance concentration that described organic solvent adds to described reactant is 0.001～10mol/L.
4. preparation method according to claim 1, is characterized in that, the condition of linked reaction described in step (1) is to react 60 minutes to 10 days under 25～120 ℃.
5. preparation method according to claim 1, is characterized in that, with the temperature of 10～100mL, is first the washing with alcohol 3～5 times of 20～70 ℃ in step (2) and filters.
6. preparation method according to claim 1, it is characterized in that, chloroform washing 3～5 time and the filtration of last handling process described in step (2) for being 20～60 ℃ with the temperature of 10～100mL is the water of 20～70 ℃, ethanol that temperature is 20～60 ℃, temperature is 20～60 ℃ acetone and temperature successively, 80～200 ℃ of lower vacuum filtrations 4～40 hours, vacuum tightness was less than 10 again
-3MmHg.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106390931A (en) * | 2015-07-29 | 2017-02-15 | 中国科学院大连化学物理研究所 | Applications of covalent organic compound having azo functional group as gas adsorption material |
| WO2018095074A1 (en) * | 2016-11-24 | 2018-05-31 | 珠海市吉林大学无机合成与制备化学重点实验室 | Ultra-high-temperature resistant, high-conductivity porous aromatic framework compound and method for preparation thereof, and application thereof in proton-exchange membrane fuel cell |
| CN111154074A (en) * | 2020-01-13 | 2020-05-15 | 东北师范大学 | Sulfonate porous aromatic skeleton material and application thereof |
| CN113117656A (en) * | 2019-12-31 | 2021-07-16 | 东北师范大学 | Multifunctional-base porous adsorbent and preparation method and application thereof |
| CN114566703A (en) * | 2022-02-25 | 2022-05-31 | 东北师范大学 | Quasi-solid polymer electrolyte based on PAF material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403491A (en) * | 2002-10-09 | 2003-03-19 | 武汉大学 | Prepn of triphenylamine polymer as hole material |
| CN1760235A (en) * | 2005-10-18 | 2006-04-19 | 武汉大学 | Method for synthesizing polymer of poly-triphenylamine |
| WO2012103622A1 (en) * | 2011-02-02 | 2012-08-09 | Epic Ventures Inc. | Method for making poly(hydridocarbyne) |
-
2013
- 2013-07-19 CN CN201310303879.2A patent/CN103396531B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403491A (en) * | 2002-10-09 | 2003-03-19 | 武汉大学 | Prepn of triphenylamine polymer as hole material |
| CN1760235A (en) * | 2005-10-18 | 2006-04-19 | 武汉大学 | Method for synthesizing polymer of poly-triphenylamine |
| WO2012103622A1 (en) * | 2011-02-02 | 2012-08-09 | Epic Ventures Inc. | Method for making poly(hydridocarbyne) |
Non-Patent Citations (2)
| Title |
|---|
| 元野等: ""新型锗中心多孔芳香材料的设计合成和表征"", 《化学学报》, 14 July 2012 (2012-07-14) * |
| 裴翠颖: ""多孔芳香骨化合物的合成及储气性能研究"", 《中国优秀硕士学位论文全文数据库工程科技I辑》, no. 7, 15 July 2012 (2012-07-15) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106390931A (en) * | 2015-07-29 | 2017-02-15 | 中国科学院大连化学物理研究所 | Applications of covalent organic compound having azo functional group as gas adsorption material |
| WO2018095074A1 (en) * | 2016-11-24 | 2018-05-31 | 珠海市吉林大学无机合成与制备化学重点实验室 | Ultra-high-temperature resistant, high-conductivity porous aromatic framework compound and method for preparation thereof, and application thereof in proton-exchange membrane fuel cell |
| CN113117656A (en) * | 2019-12-31 | 2021-07-16 | 东北师范大学 | Multifunctional-base porous adsorbent and preparation method and application thereof |
| CN111154074A (en) * | 2020-01-13 | 2020-05-15 | 东北师范大学 | Sulfonate porous aromatic skeleton material and application thereof |
| CN111154074B (en) * | 2020-01-13 | 2022-08-02 | 东北师范大学 | Sulfonate porous aromatic skeleton material and application thereof |
| CN114566703A (en) * | 2022-02-25 | 2022-05-31 | 东北师范大学 | Quasi-solid polymer electrolyte based on PAF material and preparation method thereof |
| CN114566703B (en) * | 2022-02-25 | 2022-09-30 | 东北师范大学 | Quasi-solid polymer electrolyte based on PAF material and preparation method thereof |
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