CN103396531B - A kind of preparation method of porous aromatic skeleton compound - Google Patents
A kind of preparation method of porous aromatic skeleton compound Download PDFInfo
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- CN103396531B CN103396531B CN201310303879.2A CN201310303879A CN103396531B CN 103396531 B CN103396531 B CN 103396531B CN 201310303879 A CN201310303879 A CN 201310303879A CN 103396531 B CN103396531 B CN 103396531B
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Abstract
The invention discloses a kind of preparation method of porous aromatic skeleton compound, comprising step is: by 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 rigid unitary of unsubstituted group; Reaction terminates rear first with ethanol and dilute hydrochloric acid washing, then aftertreatment obtains porous aromatic skeleton compound.By the way, the preparation method of porous aromatic skeleton compound of the present invention, the catalyzer used in this preparation method is cheap and easy to get, with low cost, reaction yield is high, and reaction method is simple, and reaction conditions substantially easily obtains, there is very high using value and marketable value, facilitate the application prospect of such aromatic skeleton compound greatly.
Description
Technical field
The present invention relates to the synthesis field of porous material, particularly relate to a kind of preparation method of porous aromatic skeleton compound.
Background technology
In two more than ten years in the past, porous material develops as a kind of the extensive concern that type material rapidly obtains increasing chemist and scientist, especially in gas adsorption, and gas storage, gas delivery, there has been good performance the aspects such as chemical reaction catalysis.
Comparatively a series of morning is metallic organic framework series in the porous material, is the coordination utilizing inorganic metal ion and organic group, obtains a series of porous materials that aperture is adjustable.In 2005, Yaghi and its co-worker think and utilize topological framework, can design and synthesis some utilize covalent linkage and the porous organic material coupled together, and obtain satisfactory stability and regular skeleton structure, covalent organic framework expands again the vigorous growth of a new round after this.In 2009, Jilin University is after the synthesis proposing porous aromatic skeleton compound and preparation thereof, and the specific surface area of the product that this field can be obtained reaches new height, after this, more porous aromatic skeleton compound is developed out, and obtains many scientific researches and using value.
Porous aromatic skeleton compound refers to and utilizes corresponding organic reaction, make the organic molecule generation copolyreaction of aromaticity, formed a kind of have a certain size and have the organic compound of neat pore passage structure, these compounds all also exist very important value in the absorption and gas storage of gas.
At present, the synthesis of porous aromatic skeleton compound mainly make use of the polyreaction between the monomer with rigidity that can carry out connecting thus obtains microporous polymer.In usual reaction, conventional polymerization process has with amino formation reaction, the synthesis of the phthalocyanine compound of metal ion mediation, the alkynyl coupling of copper palladium chtalyst, the aromatic yl polysulfide yl coupling of palladium chtalyst, coupling between the alkynyl of palladium chtalyst and alkynyl, two (1, 5-cyclooctadiene) nickel mediation alkynyl and alkynyl between coupling, oxidative coupling between the sulphur benzene of iron trichloride mediation, what cobalt mediated contains copolyreaction between alkynes triatomic ring, the polyreaction of the nitrile triatomic ring of zinc chloride mediation, imines formation reaction, four phenylsilanes of lithium mediation are formed, the building-up reactions of boron trioxide and boron ester condensation reaction.
But these synthetic methods have 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, these all become and suppress the industrialization of porous aromatic skeleton compound and the cheap major obstacles obtained.
Summary of the invention
The technical problem that the present invention mainly solves is to provide a kind of preparation method facilitating feasible and cheap porous aromatic skeleton compound.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: the preparation method providing a kind of porous aromatic skeleton compound, and comprising step is:
(1) by 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 rigid unitary of unsubstituted group;
(2) reaction terminates rear first with ethanol and dilute hydrochloric acid washing, then aftertreatment obtains porous aromatic skeleton 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 substance withdrawl syndrome 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 react 60 minutes to 10 days at 25 ~ 120 DEG C.
In a preferred embodiment of the present invention, the temperature first with 10 ~ 100mL in step (2) is the washing with alcohol 3 ~ 5 times of 20 ~ 70 DEG C and filters.
In a preferred embodiment of the present invention, last handling process described in step (2) is be that the acetone of 20 ~ 60 DEG C and temperature are the chloroform 3 ~ 5 times of 20 ~ 60 DEG C and filter by ethanol, temperature that water, temperature that the temperature of 10 ~ 100mL is 20 ~ 70 DEG C are 20 ~ 60 DEG C successively, vacuum filtration 4 ~ 40 hours at 80 ~ 200 DEG C again, vacuum tightness is less than 10
-3mmHg.
The invention has the beneficial effects as follows: the preparation method of porous aromatic skeleton compound of the present invention, the catalyzer used in this preparation method is cheap and easy to get, with low cost, reaction yield is high, reaction method is simple, reaction conditions substantially easily obtains, and has very high using value and marketable value, facilitates the application prospect of such aromatic skeleton compound greatly.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings, wherein:
Fig. 1 is the reaction equation that the present invention first preferred embodiment generates poly-Tetrabenzene methane;
Fig. 2 is the reaction equation that the present invention first preferred embodiment generates poly-triphenylamine;
Fig. 3 is the reaction equation that the present invention first preferred embodiment generates poly-four phenylsilanes;
Fig. 4 is the reaction equation that the present invention first preferred embodiment generates poly-four benzene germanium;
Fig. 5 is 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, the described infrared spectrum gathering 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
Be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only a part of embodiment of the present invention, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments all obtained under creative work prerequisite, belong to the scope of protection of the invention.
Lewis acid (LewisAcid, LA) refers to electron acceptor, has the unoccupied orbital that can be used for receiving electron pair, also can regard the centrosome forming coordinate bond as.In organic reaction, a lot of electrophilic reagent or electron acceptor(EA) are all Lewis acids.Lewis acid, usually containing low-yield lowest unoccupied molecular orbital, can react with highest occupied molecular orbital.Concerning Lewis acid is theoretical, all electrophilic reagents, comprise hydrogen ion and can be called Lewis acid.Lewis acid of the present invention directly can buy from market, and shape and specification are solid state powder, can be dissolved in reaction solvent, thus react under liquid-phase condition.
Embodiment one:
There is provided a kind of preparation method of poly-Tetrabenzene methane, comprising step is:
(1) weigh:
The ratio being 1:1 in mass ratio by Tetrabenzene methane and aluminum chloride feeds intake, namely analytical balance accurately takes the aluminum chloride of 200mg, 1.450mmol and the Tetrabenzene methane of 200mg, 0.6242mmol, insert in 100mL round-bottomed flask, described round-bottomed flask has very strong stopping property, can carry out anhydrous and oxygen-free operation.
(2) dissolving of reactant and reaction:
Use syringe to accurate injection 30mL anhydrous chloroform in round-bottomed flask again, put into the magnetic stir bar of 1cm size, carry out gas displacement in Glass Containers, reaction is carried out under nitrogen protection.Above-mentioned round-bottomed flask is placed on magnetic stirring apparatus, stirs 3 days.Reaction equation refers to Fig. 1.
(3) aftertreatment:
After question response terminates, carry out suction filtration, leave solid insoluble to reactant, and use dilute hydrochloric acid (2mol/L), ethanol, acetone, methylene dichloride equal solvent to wash respectively to it, often kind of solvent wash 3 times, each washing time was more than 3 hours.Then, be poly-Tetrabenzene methane of the present invention to the brown ceramic powder that the sample drying obtained obtains, productive rate is 80%.
Embodiment two:
There is provided a kind of preparation method of poly-triphenylamine, temperature of reaction is carried out at 50 DEG C, and all the other steps are identical with embodiment one, and productive rate is 85%.Reaction equation refers to Fig. 2.
Embodiment three:
There is provided a kind of preparation method of four phenylsilanes, 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 refers to Fig. 3.
Embodiment four:
There is provided a kind of preparation method of four benzene germanes, step is identical with embodiment one.Reaction equation refers to Fig. 4.
Refer to 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 aromatic skeleton vibration absorption peak, at 2800-3000cm
-1the broad peak at place is 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 obtained, poly-Tetrabenzene methane, poly-four phenylsilanes and poly-four benzene germanes are at 400-4000cm
-1between mainly to go out between peak position and three kinds of monomers basic quite corresponding.At 2700-2800cm
-1between four kinds of polymkeric substance all containing a new vibration peak, according to the feature of infrared spectra, namely along with the increase of conjugated system, 2800-3000cm
-1the C-H at place can offset, and to wave number smaller part, can illustrate according to these data, four kinds of polymkeric substance there occurs polymerization.
Refer to Fig. 6, according to thermogravimetric curve, the poly-triphenylamine obtained, poly-Tetrabenzene methane, poly-four phenylsilanes and poly-four benzene germanes are under air atmosphere test condition, weightless gradually from room temperature heating, divide weightlessness at being clipped to 420 DEG C, 450 DEG C, 465 DEG C and 470 DEG C to reach 20%, decompose completely at 600 DEG C, 600 DEG C, 590 DEG C and 560 DEG C.Namely relatively stable before 300 DEG C, can maintain not caving in of skeleton, along with the rising of temperature between 300 DEG C ~ 600 DEG C, polymer quality reduces gradually, and after 600 DEG C, curve reaches stable, and organic backbone all decomposes loss.
Refer to Fig. 7, as seen from the figure, the poly-triphenylamine obtained, poly-Tetrabenzene methane, poly-four phenylsilanes and poly-four benzene germanes all have certain adsorption for nitrogen, wherein poly-Tetrabenzene methane, poly-four phenylsilanes, the nitrogen adsorption matter of poly-four benzene germanes can reach 230cc/g, 195cc/g and 201cc/g.Can calculate thus, the specific surface area (BET) of four kinds of polymkeric substance is respectively 827m
2/ g, 687m
2/ g, 539m
2/ g and 567m
2/ g.Also pore size and the pore volume of this polymkeric substance can be calculated.
Refer to Fig. 8, the poly-triphenylamine obtained, poly-Tetrabenzene methane, poly-four phenylsilanes and poly-four benzene germanes calculate according to H-K method, pore size distribution is respectively at 1.232nm, 1.232nm, 2.313nm and 1.475nm, and relative pore volume is 0.263cc/g, 0.263cc/g, 0.264cc/g and 0.273cc/g respectively.
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, has very high using value and marketable value, facilitate the application prospect of such aromatic skeleton compound greatly within the reaction times of 3 days (not comprising last handling process).
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize description of the present invention to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical field, be all in like manner included in scope of patent protection of the present invention.
Claims (4)
1. a preparation method for porous aromatic skeleton compound, is characterized in that, step is:
(1) by 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 rigid unitary of unsubstituted group, described reactant is Tetrabenzene methane, four phenylsilanes or four benzene germanes, and the condition of described linked reaction is react 60 minutes to 10 days at 25 ~ 120 DEG C;
(2) reaction terminates rear first with ethanol and dilute hydrochloric acid washing, then aftertreatment obtains porous aromatic skeleton compound.
2. preparation method according to claim 1, is characterized in that, described in step (1), organic solvent is chloroform, and the substance withdrawl syndrome that described organic solvent adds to described reactant is 0.001 ~ 10mol/L.
3. preparation method according to claim 1, is characterized in that, the temperature first with 10 ~ 100mL in step (2) is the washing with alcohol 3 ~ 5 times of 20 ~ 70 DEG C and filters.
4. preparation method according to claim 1, it is characterized in that, last handling process described in step (2) is be that the acetone of 20 ~ 60 DEG C and temperature are the chloroform 3 ~ 5 times of 20 ~ 60 DEG C and filter by ethanol, temperature that water, temperature that the temperature of 10 ~ 100mL is 20 ~ 70 DEG C are 20 ~ 60 DEG C successively, vacuum filtration 4 ~ 40 hours at 80 ~ 200 DEG C again, vacuum tightness is less than 10
-3mmHg.
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| 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 |
| CN106750190B (en) * | 2016-11-24 | 2019-07-19 | 珠海市吉林大学无机合成与制备化学重点实验室 | The porous aromatic skeleton compound preparation method of the high conductivity of thermostable and its application in Proton Exchange Membrane Fuel Cells |
| CN113117656B (en) * | 2019-12-31 | 2022-08-05 | 东北师范大学 | Multifunctional-base porous adsorbent and preparation method 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 |
| 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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| CN1403491A (en) * | 2002-10-09 | 2003-03-19 | 武汉大学 | Prepn of triphenylamine polymer as hole material |
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| WO2012103622A1 (en) * | 2011-02-02 | 2012-08-09 | Epic Ventures Inc. | Method for making poly(hydridocarbyne) |
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|---|---|---|---|---|
| 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) |
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