CN110016135A - A kind of organic porous polymer material and preparation method thereof of ketone-hydrazone skeleton structure - Google Patents
A kind of organic porous polymer material and preparation method thereof of ketone-hydrazone skeleton structure Download PDFInfo
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Abstract
The present invention provides a kind of ketone-hydrazone skeleton structure organic porous polymer materials and preparation method thereof, which comprises step 1, carries out the first reaction to aryl diamine shown in structural formula IV, obtains Bisdiazonium salts shown in formula II I；Step 2, under alkaline condition, made 1 shown in formula II by the second reaction, 3,5- hexamethylene triketone occurs coupling polymerization with the Bisdiazonium salts and reacts, post-processed to obtain ketone shown in structural formula I-hydrazone skeleton structure organic porous polymer, the ketone-hydrazone skeleton structure organic porous polymer material structure novel being related in the present invention, preparation method is high-efficient, environmental-friendly.The ketone-hydrazone skeleton structure organic porous polymer material can play a significant role in the field closely bound up with the energy and environment
Description
Technical field
The present invention relates to chemical material fields, more particularly to a kind of ketone-hydrazone skeleton structure organic porous polymer material
Material and preparation method thereof.
Background technique
Organic porous polymer material (POPs, Porous Organic Polymers) due to have its large specific surface area,
The advantages that chemical stability is good and the modification of easy functional modification, thus gas absorption, heterocatalysis and in terms of
Show brilliant application prospect.The final application performance of organic porous polymer material is by its pore properties (such as specific surface
Product, aperture and hole appearance etc.) and the co-determination of functional group's property.Accurately functional organic porous polymer material is simultaneously for structure
Have porosity and characteristics of functional groups abundant, there are potential excellent properties, but its preparation condition is usually harsher.Cause
This, the novel functional organic porous polymer material of development structure simultaneously provides corresponding simple, efficient, environmental protection preparation side
Method is the hot spot of current research.
Summary of the invention
The embodiment of the present invention provides a kind of organic porous polymer of ketone-hydrazone skeleton structure, can be poly- using Porous-Organic
The advantages of object material is provided simultaneously with porosity and characteristics of functional groups abundant is closed, there are potential excellent properties, while providing one
The preparation method of kind of ketone-hydrazone skeleton structure organic porous polymer, 1,3,5- hexamethylene triketones based on active methylene group and easily
Coupling polymerization occurs for the Bisdiazonium salts obtained, prepares high-specific surface area and rich heteroatomic ketone-hydrazone skeleton structure Porous-Organic polymerization
Object, to solve the problems, such as its preparation condition harshness.
According to the first aspect of the invention, the present invention provides a kind of system of the organic porous polymer of ketone-hydrazone skeleton structure
Preparation Method, which comprises
Step 1, the first reaction is carried out to aryl diamine shown in structural formula IV, obtains dual nitrogen shown in formula II I
Salt；
Step 2, under alkaline condition, 1,3,5- hexamethylene triketones shown in formula II and described pair are made by the second reaction
Coupling polymerization reaction occurs for diazonium salt, and it is poly- to be post-processed to obtain ketone shown in structural formula I-hydrazone skeleton structure Porous-Organic
Close object
Optionally, the X in the Bisdiazonium salts includes Cl, BF4、PF6With any one in OAc.
Optionally, the aryl diamine includes 4,4'- benzidine, 4,4'- diaminodiphenylmethane, 4,4'- diamino
Bis- (4- aminophenyl) fluorenes of base hexichol dimethylmethane, 9,9'-, Isosorbide-5-Nitrae-diaminobenzene and 1,3- diaminobenzene, 4,4'- diamino
Terphenyl, 1,5- diaminonaphthalene, 2,6- diaminoanthraquinone-, 3,3', 5,5'- tetramethyl benzidine, 4,4'- diaminodiphenyl ether, 4,
4'- diamino diphenyl sulfone, 4,4'- diamino bipyridyl, any one in 4,4'- chrysoidine；
The aryl of the aryl diamine includes:
Optionally, it is described first reaction include:
Under the conditions of ice-water bath, the aryl diamine is dissolved in the mixed solution of acid medium and the first solvent, is stirred
Uniformly；
The nitrosification agent being pre-chilled in ice-water bath is added drop-wise in the mixed solution of the aryl diamine with pre-set velocity,
The Bisdiazonium salts are obtained after reacting the first preset time；The pre-set velocity is 1 second/drop~5 seconds/drop；Described first is default
Time is 25-120 minutes.
Optionally, the nitrosification agent includes sodium nitrite, potassium nitrite, isobutyl nitrite and isoamyl nitrite
In any one.
Optionally, the acid medium includes any one in hydrochloric acid, fluoboric acid, hexafluorophosphoric acid and acetic acid.
Optionally, the molar ratio of the aryl diamine and the acid medium is 1:4~1:10.
Optionally, first solvent includes deionized water, methanol, ethyl alcohol, acetonitrile, acetone, any in methylene chloride
It is a kind of.
Optionally, it is described second reaction include:
Under the conditions of ice-water bath, the solution of the Bisdiazonium salts is adjusted as neutrality using alkaline solution；
Described 1,3,5- hexamethylene triketone is mixed with alkaline matter and is dissolved in the second solvent, aqueous slkali is prepared；The alkali soluble
Liquid is placed in ice-water bath and is pre-chilled；
The aqueous slkali is added dropwise into the solution of the Bisdiazonium salts with pre-set velocity, reacts the second preset time；It is described
Second preset time is 6h~for 24 hours；
It is post-processed to obtain the ketone-hydrazone skeleton structure organic porous polymer.
Optionally, the alkaline solution include sodium carbonate liquor, sodium hydroxide solution, sodium acetate solution, solution of potassium carbonate,
Any one in potassium hydroxide solution and triethylamine solution；
The alkaline matter includes appointing in sodium carbonate, sodium hydroxide, sodium acetate, potassium carbonate, potassium hydroxide and triethylamine
It anticipates one kind.
Optionally, the molar ratio of 1,3,5- hexamethylene triketones described in second reaction and the Bisdiazonium salts is 1:1.5
~1:9.
Optionally, second solvent includes deionized water, methanol, ethyl alcohol, acetone, acetonitrile and N, N- dimethyl methyl
Any one in amide.
Optionally, including vacuum drying oven, dry, supercritical carbon dioxide is dried and frozen appointing in dry for the post-processing
It anticipates one kind.
According to the second aspect of the invention, the present invention provides a kind of organic porous polymer material of ketone-hydrazone skeleton structure,
The ketone-hydrazone skeleton structure organic porous polymer material is prepared by the method for above-mentioned any one.
The present invention provides a kind of organic porous polymer material (TKH-POP, the Tris (β-Keto- of ketone-hydrazone skeleton structure
Hydrazo)-Porous Organic Polymer), ketone-hydrazone skeleton structure organic porous polymer can be miscellaneous by N and O etc.
Atom is accurately embedded into stephanoporate framework, therefore can deposit in adsorption of metal ions, volatile organic matter absorption and gas
Storage etc. plays a significant role, while also can be as the good carrier of high-performance different-phase catalyst.The present invention also provides ketone-
The preparation method of the organic porous polymer material of hydrazone skeleton structure by the hexamethylene triketone with active methylene group and is easy big
The Bisdiazonium salts of amount preparation carry out efficient coupling polymerization reaction, can in the case where environmental-friendly, mild condition preparation tool
There is ketone-hydrazone bond structure Porous-Organic polymeric material, which can carry out in water phase, environmentally protective and easy a large amount of systems
It is standby.
Detailed description of the invention
Fig. 1 is one of embodiment of the present invention ketone-hydrazone skeleton structure organic porous polymer preparation method；
Fig. 2 is the Fourier Transform Infrared Spectroscopy figure of TKH-POP-1 in the embodiment of the present invention；
The cross polarization that Fig. 3 is TKH-POP-1 in the embodiment of the present invention/evil spirit angle spin13C nmr spectrum；
Fig. 4 is the Elemental analysis data of TKH-POP-1 in the embodiment of the present invention；
Fig. 5 is the thermogravimetric analysis spectrogram of TKH-POP-1 in the embodiment of the present invention；
Fig. 6 is TKH-POP-2 Fourier Transform Infrared Spectroscopy figure in the embodiment of the present invention；
Fig. 7 is TKH-POP-2 cross polarization in the embodiment of the present invention/evil spirit angle spin13C nmr spectrum；
Fig. 8 is TKH-POP-2 Elemental analysis data in the embodiment of the present invention；
Fig. 9 is TKH-POP-2 thermogravimetric analysis spectrogram in the embodiment of the present invention；
Figure 10 is TKH-POP-3 Fourier Transform Infrared Spectroscopy figure in the embodiment of the present invention；
Figure 11 is TKH-POP-3 cross polarization in the embodiment of the present invention/evil spirit angle spin13C nmr spectrum；
Figure 12 is TKH-POP-3 Elemental analysis data in the embodiment of the present invention；
Figure 13 is TKH-POP-3 thermogravimetric analysis spectrogram in the embodiment of the present invention；
Figure 14 is TKH-POP-4 Fourier Transform Infrared Spectroscopy figure in the embodiment of the present invention；
Figure 15 is TKH-POP-4 cross polarization in the embodiment of the present invention/evil spirit angle spin13C nmr spectrum；
Figure 16 is TKH-POP-4 Elemental analysis data in the embodiment of the present invention；
Figure 17 is the pore size distribution curve figure that the TKH-POP-1 prepared in the embodiment of the present invention is calculated through NLDFT；
Figure 18 is the thermogravimetric analysis spectrogram of the TKH-POP-1 prepared in the embodiment of the present invention；
Figure 19 be in the embodiment of the present invention TKH-POP-1 for preparing at 25 DEG C to the adsorption isotherm of benzene vapour.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are some of the embodiments of the present invention, instead of all the embodiments.Based on this hair
Embodiment in bright, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, shall fall within the protection scope of the present invention.
Referring to Fig.1, a kind of step flow chart of the organic porous polymer preparation method of ketone-hydrazone skeleton structure is shown,
The described method includes:
Step 101, the first reaction is carried out to aryl diamine shown in structural formula IV, obtained dual shown in formula II I
Nitrogen salt.
Preferably, the X in the Bisdiazonium salts includes any one in Cl, BF4, PF6 and OAc.
Preferably, the aryl diamine includes 4,4'- benzidine, 4,4'- diaminodiphenylmethane, 4,4'- diamino
Bis- (4- aminophenyl) fluorenes of base hexichol dimethylmethane, 9,9'-, Isosorbide-5-Nitrae-diaminobenzene and 1,3- diaminobenzene, 4,4'- diamino
Terphenyl, 1,5- diaminonaphthalene, 2,6- diaminoanthraquinone-, 3,3', 5,5'- tetramethyl benzidine, 4,4'- diaminodiphenyl ether, 4,
4'- diamino diphenyl sulfone, 4,4'- diamino bipyridyl, any one in 4,4'- chrysoidine.
The aryl of the aryl diamine includes:
Term used in the embodiment of the present invention " aryl " means the virtue with a monocycle or two or more phenyl ring
Race's carbocylic radical.The aryl preferably has 5-24,5-18,5-14,5-10,5-8,5-6 or 6
Carbon atom.The representative instance of " aryl " includes but is not limited to phenyl, xenyl etc.." aryl " is preferably following institute
The aryl shown:
When aryl is aryl as shown above, it is preferable that the aryl diamine can be 4,4'- benzidine, 4,4'-
Bis- (4- aminophenyl) fluorenes of diaminodiphenylmethane, 4,4'- diamino hexichol dimethylmethane, 9,9'-, Isosorbide-5-Nitrae-diaminobenzene
With 1,3- diaminobenzene, 4,4'- diamino terphenyl, 1,5- diaminonaphthalene, 2,6- diaminoanthraquinone-, 3,3', 5,5'- tetramethyl
Benzidine, 4,4'- diaminodiphenyl ether, 4,4'- diamino diphenyl sulfone, 4,4'- diamino bipyridyl, 4,4'- diamino are even
Any one in pyridine.The type of above-mentioned aryl is only used for illustrating, as long as including the structure within the scope of above-mentioned aryl species
It all can be used for the embodiment of the present invention, the embodiment of the present invention is not specifically limited in this embodiment.
Optionally, the step 101 includes:
Under the conditions of ice-water bath, the aryl diamine is dissolved in the mixed solution of acid medium and the first solvent, is stirred
Uniformly.
Preferably, the acid medium includes any one in hydrochloric acid, fluoboric acid, hexafluorophosphoric acid and acetic acid.
Preferably, the molar ratio of the aryl diamine and the acid medium is 1:4~1:10.
In the embodiment of the present invention, the ratio of aryl diamine and acid medium is molar ratio, the i.e. ratio of the amount of substance, wherein
Molar ratio should be 1:4~1:10, i.e. 1 groups diamines of every addition, it is necessary to 4~10 moles of acid medium is added, it is acid
The additional amount of medium can be 4 moles, 5 moles, 6 moles, 7 moles, 8 moles, 9 moles or 10 moles, as long as acid medium pair
Answer the additional amount of 1 groups diamines at 4~10 moles, the present invention is not specifically limited in this embodiment.
Preferably, first solvent includes deionized water, methanol, ethyl alcohol, acetonitrile, acetone, any in methylene chloride
It is a kind of.
The nitrosification agent being pre-chilled in ice-water bath is added drop-wise in the mixed solution of the aryl diamine with pre-set velocity,
The Bisdiazonium salts are obtained after reacting the first preset time；The pre-set velocity is 1 second/drop~5 seconds/drop；Described first is default
Time is 25-120 minutes.
In the embodiment of the present invention, nitrosification agent is using preceding needing to be pre-chilled in ice-water bath, because nitrosification agent is low
It is relatively stable under temperature, the speed of nitrosification agent~5 seconds/drop of 1 second/drop is added dropwise to the mixed solution of aryl diamine again later
In, carry out diazo-reaction Bisdiazonium salts are made during, need to remain the addition speed of nitrosification agent to prevent
Only from the generation of coupling reaction, it is therefore desirable to control the addition speed of nitrosification agent, charging rate is excessively slow, not diazotizing virtue
Base diamines can occur with diazonium salt action from coupling reaction, and excessive velocities, which are added, can occur nitrous acid decomposition or other side reactions.
It reacts Shi Keyong starch-kalium iodide test paper to examine, be judged according to the difference of color.In the embodiment of the present invention, nitrosification agent
Addition speed should be at 1 second/drop~5 seconds/drop, it can be 1 second/drop, 2 seconds/drop, 3 seconds/drop, 4 seconds/drop and 5 seconds/drop, only
Will be in the velocity interval section of~5 seconds/drop of 1 second/drop, the present invention is without limitation.
In the embodiment of the present invention, the initial time of the first preset time is counted since nitrosification agent is dripped in addition first,
Stop reaction after reaction 25-120 minutes, reaction process can be used thin-layer chromatography and be monitored, is reacted to centainly in raw material
Stop reaction after degree or fully reacting, the reaction time can be 25 minutes, 50 minutes, 75 minutes, 100 minutes or 120 points
Clock, as long as the present invention is not specifically limited in this embodiment in 25-120 minutes.
Preferably, the nitrosification agent includes sodium nitrite, potassium nitrite, isobutyl nitrite and isoamyl nitrite
In any one.
Step 102, under alkaline condition, by second reaction make 1,3,5- hexamethylene triketones shown in formula II with it is described
Coupling polymerization reaction occurs for Bisdiazonium salts, is post-processed to obtain ketone shown in structural formula I-hydrazone skeleton structure Porous-Organic
Polymer.
Optionally, the step 102 includes:
Under the conditions of ice-water bath, the solution of the Bisdiazonium salts is adjusted as neutrality using alkaline solution.
Preferably, the alkaline solution include sodium carbonate liquor, sodium hydroxide solution, sodium acetate solution, solution of potassium carbonate,
Any one in potassium hydroxide solution and triethylamine solution.
Described 1,3,5- hexamethylene triketone is mixed with alkaline matter and is dissolved in the second solvent, aqueous slkali is prepared；The alkali soluble
Liquid is placed in ice-water bath and is pre-chilled.
Preferably, the alkaline matter includes sodium carbonate, sodium hydroxide, sodium acetate, potassium carbonate, potassium hydroxide and triethylamine
In any one.
Preferably, described 1, the molar ratio of 3,5- hexamethylene triketones and the Bisdiazonium salts is 1:1.5~1:9.
In the embodiment of the present invention, the molar ratio of 1,3,5- hexamethylene triketone and Bisdiazonium salts is 1:1.5~1:9, i.e., every to be added 1
Mole 1,3,5- hexamethylene triketones, it is necessary to 1.5~9 moles of Bisdiazonium salts be added, the additional amount of Bisdiazonium salts can be 1.5 and rub
You, 3 moles, 4.5 moles, 6 moles, 7.5 moles or 9 moles, as long as Bisdiazonium salts are 1 mole 1 corresponding, 3,5- hexamethylene triketones add
Enter amount at 1.5~9 moles, the present invention is not specifically limited in this embodiment.
Preferably, second solvent includes deionized water, methanol, ethyl alcohol, acetone, acetonitrile and N, N- dimethyl
Any one in formamide.
The aqueous slkali is added dropwise into the solution of the Bisdiazonium salts with pre-set velocity, reacts the second preset time；It is described
Second preset time is 6h~for 24 hours.
In the embodiment of the present invention, the initial time of the second preset time is counted since aqueous slkali is dripped in addition first, anti-
Stop reaction after answering 6~24 hours, reaction process can be used thin-layer chromatography and is monitored, raw material reaction to a certain extent or
Stop reaction after fully reacting, the reaction time can be 6 hours, 12 hours, 18 hours or 24 hours, as long as at 6~24 hours
Interior, the present invention is not specifically limited in this embodiment.
It is post-processed to obtain the ketone-hydrazone skeleton structure organic porous polymer.
Preferably, including vacuum drying oven, dry, supercritical carbon dioxide is dried and frozen appointing in dry for the post-processing
It anticipates one kind.
The embodiment of the invention also provides a kind of ketone-hydrazone skeleton structure organic porous polymer material, the ketone-hydrazone bone
The organic porous polymer material of frame structure is prepared by the above method.
The embodiment of the invention provides a kind of preparation methods of ketone-hydrazone skeleton structure organic porous polymer material, lead to
The hexamethylene triketone with active methylene group is crossed to react with the efficient coupling polymerization of Bisdiazonium salts progress for being easy largely to prepare, it can
Preparation has ketone-hydrazone bond structure Porous-Organic polymeric material in the case where environmental-friendly, mild condition, which can
It is carried out in water phase, environmentally protective and easy a large amount of preparations.A kind of Porous-Organic of ketone-hydrazone skeleton structure prepared by the present invention is poly-
Object material is closed, the hetero atoms such as N and O can be accurately embedded into porous bone by ketone-hydrazone skeleton structure organic porous polymer
It in frame, therefore can play a significant role in terms of adsorption of metal ions, volatile organic matter absorption and gas, together
When also can be as the good carrier of high-performance different-phase catalyst.
The preparation of one TKH-POP-1 of embodiment
The embodiment of the present invention provides a kind of preparation method of the organic porous polymer material of ketone-hydrazone skeleton structure, to make
Those skilled in the art more fully understand the present invention, illustrate in the present invention below by way of the specific example for preparing TKH-POP-1
The preparation method of ketone-hydrazone skeleton structure organic porous polymer material:
As follows, it is the preparation of ketone-hydrazone skeleton structure organic porous polymer material TKH-POP-1:
Step 1: the preparation of the dual nitrogen tetrafluoroborate of xenyl.In ice-water bath, by 4,4 '-benzidines
(276mg, 1.5mmol, 1eq) is dissolved in HBF4In (2.30mL, 15mmol, 10eq) and the deionized water of 25mL, stirring 5min makes
After mixing.Then by the 10mL sodium nitrite in aqueous solution (217mg, 3.15mmol, 2.1eq) being pre-chilled in ice water with 1 second/
The speed of drop is added drop-wise in reaction system, after reacting 25min, obtains the dual nitrogen tetrafluoro boric acid salting liquid of xenyl.
Step 2: the preparation of ketone-hydrazone skeleton structure organic porous polymer material TKH-POP-1.Under ice-water bath, use
Na2CO3The dual nitrogen tetrafluoroborate solution ph of xenyl in solution regulating step 1 is to neutrality.By 1,3,5- hexamethylene triketone
(162mg, 1mmol, 1eq) and sodium carbonate (318 mg, 3mmol, 3eq) is dissolved in 30mL aqueous solution, is then pre-chilled and with 3 seconds/drop
Speed be added dropwise in the dual nitrogen tetrafluoro boric acid salting liquid of xenyl.It is filtered after reaction 12h, obtains solid product, and use is gone
Ionized water, methanol, tetrahydrofuran, n,N-Dimethylformamide, methanol, deionized water are successively washed, and are then freeze-dried, and are obtained
Ketone-hydrazone skeleton structure organic porous polymer material TKH-POP-1 426mg (yield 98%).
Referring to Fig. 2, the TKH-POP-1 Fourier Transform Infrared Spectroscopy figure prepared in the embodiment of the present invention, TKH- are shown
POP-1 Fourier Transform Infrared Spectroscopy data are as follows:
FT-IR(cm-1):2988(w),2908(w),1601(m),1471(vs),1432(m),1400 (vs),1316
(m),1213(vs),1167(s),1088(m),1049(s),1031(m),1001(m), 818(s),732(w),629(vw)。
Referring to Fig. 3, it is total to show the TKH-POP-1 cross polarization/evil spirit angle spin 13C nuclear-magnetism prepared in the embodiment of the present invention
Shake spectrogram, TKH-POP-1 cross polarization/evil spirit angle spin13C nuclear magnetic resonance modal data is as follows:
13C-CP/MAS NMR(15kHz)δ(ppm):177.73,140.95,127.92,117.67；
Referring to Fig. 4, the TKH-POP-1 Elemental analysis data TKH-POP-1 element prepared in the embodiment of the present invention is shown
It is as follows to analyze data:
Carbon element content 65.90%, protium content 4.62%, nitrogen 12.33%.
Referring to Fig. 5, the thermogravimetric analysis spectrogram of the TKH-POP-1 prepared in the embodiment of the present invention is shown.
The embodiment of the invention provides a kind of preparation methods of ketone-hydrazone skeleton structure organic porous polymer material, lead to
The hexamethylene triketone with active methylene group is crossed to react with the efficient coupling polymerization of Bisdiazonium salts progress for being easy largely to prepare, it can
Preparation has ketone-hydrazone bond structure Porous-Organic polymeric material in the case where environmental-friendly, mild condition, which can
It is carried out in water phase, environmentally protective and easy a large amount of preparations.A kind of Porous-Organic of ketone-hydrazone skeleton structure prepared by the present invention is poly-
Object material is closed, the hetero atoms such as N and O can be accurately embedded into porous bone by ketone-hydrazone skeleton structure organic porous polymer
It in frame, therefore can play a significant role in terms of adsorption of metal ions, volatile organic matter absorption and gas, together
When also can be as the good carrier of high-performance different-phase catalyst.
The preparation of two TKH-POP-2 of embodiment
The embodiment of the present invention provides a kind of preparation method of the organic porous polymer material of ketone-hydrazone skeleton structure, to make
Those skilled in the art more fully understand the present invention, illustrate in the present invention below by way of the specific example for preparing TKH-POP-2
The preparation method of ketone-hydrazone skeleton structure organic porous polymer material:
As follows, it is the preparation of ketone-hydrazone skeleton structure organic porous polymer material TKH-POP-2:
Step 1: the preparation of diphenylmethane group Bisdiazonium salts hydrochlorate.In ice-water bath, by 4,4'- diaminodiphenylmethane
(595mg, 3mmol, 1eq) is dissolved in HCl (12N, 1.245mL, 15mmol, 5eq) and the ethyl alcohol of 25mL, and stirring 5min makes to mix
After closing uniformly.Then the 10mL being pre-chilled in ice water is dissolved in the potassium nitrite solution (535mg, 6.3mmol, 2.1eq) of ethyl alcohol with 5
The speed of second/drop is added drop-wise in reaction system, after reacting 90min, obtains diphenylmethane group Bisdiazonium salts acid salt solution.
Step 2: ketone-hydrazone skeletal porous polymer TKH-POP-2 preparation.Under ice-water bath, with NaOH solution regulating step
Diphenylmethane group Bisdiazonium salts acid salt solution pH value in 1 is to neutrality.By 1,3,5- hexamethylene triketone (162mg, 1mmol, 1eq) with
Sodium hydroxide (120mg, 3mmol, 3eq) is dissolved in 30mL methanol solution, is then pre-chilled and is added dropwise to two with the speed of 1 second/drop
In phenylmethane base Bisdiazonium salts acid salt solution.It is filtered after reaction 18h, obtains solid product, and use deionized water, methanol, four
Hydrogen furans, n,N-Dimethylformamide, methanol, deionized water are successively washed, and then vacuum drying oven is dry, obtain ketone-hydrazone skeleton
Porous polymer TKH-POP-2 438mg (yield 96%).
Referring to Fig. 6, the TKH-POP-2 Fourier Transform Infrared Spectroscopy figure prepared in the embodiment of the present invention, TKH- are shown
POP-2 Fourier Transform Infrared Spectroscopy data are as follows:
FT-IR(cm-1):3047(w),2918(w),1602(m),1478(vs),1423(m),1400 (vs),1305
(m),1220(vs),1167(s),1091(m),1049(s),1031(m),1001(m), 912(w),816(s),772(w),
629(vw),520(w)。
Referring to Fig. 7, the TKH-POP-2 cross polarization/evil spirit angle spin prepared in the embodiment of the present invention is shown13C nuclear-magnetism is total
Shake spectrogram, TKH-POP-2 cross polarization/evil spirit angle spin13C nuclear magnetic resonance modal data is as follows:
CP/MAS13C-NMR(15kHz)δ(ppm):177.23,140.60,129.14,117.32, 40.95。
Referring to Fig. 8, the TKH-POP-2 Elemental analysis data prepared in the embodiment of the present invention, TKH-POP-2 member are shown
Element analysis data are as follows:
Carbon element content 65.02%, protium content 4.32%, nitrogen 15.36%.
Referring to Fig. 9, the TKH-POP-2 thermogravimetric analysis spectrogram prepared in the embodiment of the present invention is shown.
The embodiment of the invention provides a kind of preparation methods of ketone-hydrazone skeleton structure organic porous polymer material, lead to
The hexamethylene triketone with active methylene group is crossed to react with the efficient coupling polymerization of Bisdiazonium salts progress for being easy largely to prepare, it can
Preparation has ketone-hydrazone bond structure Porous-Organic polymeric material in the case where environmental-friendly, mild condition, which can
It is carried out in water phase, environmentally protective and easy a large amount of preparations.A kind of Porous-Organic of ketone-hydrazone skeleton structure prepared by the present invention is poly-
Object material is closed, the hetero atoms such as N and O can be accurately embedded into porous bone by ketone-hydrazone skeleton structure organic porous polymer
It in frame, therefore can play a significant role in terms of adsorption of metal ions, volatile organic matter absorption and gas, together
When also can be as the good carrier of high-performance different-phase catalyst.
The preparation of three TKH-POP-3 of embodiment
The embodiment of the present invention provides a kind of preparation method of the organic porous polymer material of ketone-hydrazone skeleton structure, to make
Those skilled in the art more fully understand the present invention, illustrate in the present invention below by way of the specific example for preparing TKH-POP-3
The preparation method of ketone-hydrazone skeleton structure organic porous polymer material:
As follows, it is the preparation of ketone-hydrazone skeleton structure organic porous polymer material TKH-POP-3:
Step 1: the preparation of the dual nitrogen hexafluorophosphate of diphenyl ether base.In ice-water bath, by 4,4'- diaminodiphenyl ether
(1.202g, 6mmol, 1eq) is dissolved in HPF6In (7.359mL, 48mmol, 8eq) and the methanol of 25mL, stirring 5min makes to mix
After uniformly.Then by the 10mL being pre-chilled in ice water be dissolved in methanol isoamyl nitrite solution (1.476g, 12.6mmol,
It 2.1eq) is added drop-wise in reaction system with the speed of 2 seconds/drop, after reacting 60min, obtains the dual nitrogen hexafluorophosphoric acid of diphenyl ether base
Salting liquid.
Step 2: ketone-hydrazone skeletal porous polymer TKH-POP-3 preparation.Under ice-water bath, with KOH solution regulating step 1
In the dual nitrogen hexafluorophosphate solution ph of diphenyl ether base to neutrality.By 1,3,5- hexamethylene triketone (162mg, 1mmol, 1eq)
It is dissolved in 30mL acetone soln with potassium hydroxide (168mg, 3mmol, 3eq), is then pre-chilled and is added dropwise to the speed of 5 seconds/drop
In the dual nitrogen hexafluorophosphoric acid salting liquid of diphenyl ether base.Reaction filters afterwards for 24 hours, obtains solid product, and use deionized water, first
Alcohol, tetrahydrofuran, n,N-Dimethylformamide, methanol, deionized water are successively washed, and then supercritical carbon dioxide is dry, are obtained
Obtain ketone-hydrazone skeletal porous polymer TKH-POP-3 418mg (yield 91%).
Referring to Fig.1 0, show the TKH-POP-3 Fourier Transform Infrared Spectroscopy figure prepared in the embodiment of the present invention, TKH-
POP-3 Fourier Transform Infrared Spectroscopy data are as follows:
FT-IR(cm-1):3071(vw),2938(vw),1593(m),1478(vs),1430(m), 1400(vs),1311
(m),1181(vs),1087(m),1049(s),1031(m),1008(m),834 (m),763(w),703(w),607(w),524
(w)。
Referring to Fig.1 1, show the TKH-POP-3 cross polarization/evil spirit angle spin prepared in the embodiment of the present invention13C nuclear-magnetism is total
Shake spectrogram, TKH-POP-3 cross polarization/evil spirit angle spin13C nuclear magnetic resonance modal data is as follows:
CP/MAS13C-NMR(15kHz)δ(ppm):177.96,156.57,138.29,129.74, 119.15。
Referring to Fig.1 2, show the TKH-POP-3 Elemental analysis data prepared in the embodiment of the present invention, TKH-POP-3 member
Element analysis data are as follows:
Carbon element content 65.13%, protium content 4.35%, nitrogen 15.32%.
Referring to Fig.1 3, show the TKH-POP-3 thermogravimetric analysis spectrogram prepared in the embodiment of the present invention.
The embodiment of the invention provides a kind of preparation methods of ketone-hydrazone skeleton structure organic porous polymer material, lead to
The hexamethylene triketone with active methylene group is crossed to react with the efficient coupling polymerization of Bisdiazonium salts progress for being easy largely to prepare, it can
Preparation has ketone-hydrazone bond structure Porous-Organic polymeric material in the case where environmental-friendly, mild condition, which can
It is carried out in water phase, environmentally protective and easy a large amount of preparations.A kind of Porous-Organic of ketone-hydrazone skeleton structure prepared by the present invention is poly-
Object material is closed, the hetero atoms such as N and O can be accurately embedded into porous bone by ketone-hydrazone skeleton structure organic porous polymer
It in frame, therefore can play a significant role in terms of adsorption of metal ions, volatile organic matter absorption and gas, together
When also can be as the good carrier of high-performance different-phase catalyst.
The preparation of example IV TKH-POP-4
The embodiment of the present invention provides a kind of preparation method of the organic porous polymer material of ketone-hydrazone skeleton structure, to make
Those skilled in the art more fully understand the present invention, illustrate in the present invention below by way of the specific example for preparing TKH-POP-4
The preparation method of ketone-hydrazone skeleton structure organic porous polymer material:
As follows, it is the preparation of ketone-hydrazone skeleton structure organic porous polymer material TKH-POP-4:
The preparation of bis- (the 4- phenyldiazonium acetate) fluorenes of step 1:9,9'-.In ice-water bath, by bis- (the 4- amino of 9,9'-
Phenyl) fluorenes (3.132g, 9mmol, 1eq) is dissolved in HOAc (6.404mL, 36mmol, 4eq) and the acetonitrile of 25mL, stir 5min
Make after mixing.Then by the 10mL being pre-chilled in ice water be dissolved in acetonitrile Isobutyl ester solution (1.949g,
18.9mmol, 2.1eq) it is added drop-wise in reaction system with the speed of 4 seconds/drop, after reacting 120min, obtain bis- (the 4- benzene of 9,9'-
Base weight nitrogen acetate) fluorenes solution.
Step 2: ketone-hydrazone skeletal porous polymer TKH-POP-4 preparation.Under ice-water bath, K is used2CO3Solution regulating step
Bis- (4- phenyldiazonium acetate) fluorenes solution ph of 9,9'- in 1 are to neutrality.By 1,3,5- hexamethylene triketone (162mg, 1mmol,
It 1eq) is dissolved in 30mL n,N-Dimethylformamide solution, is then pre-chilled and with 2 with potassium carbonate (415mg, 3mmol, 3eq)
The speed of second/drop is added dropwise in bis- (4- phenyldiazonium acetate) the fluorenes solution of 9,9'-.It is filtered after reaction 6h, obtains solid product,
And successively washed using deionized water, methanol, tetrahydrofuran, n,N-Dimethylformamide, methanol, deionized water, then freeze
It is dry, obtain ketone-hydrazone skeletal porous polymer TKH-POP-4 848mg (yield 98%).
Referring to Fig.1 4, show the TKH-POP-4 Fourier Transform Infrared Spectroscopy figure prepared in the embodiment of the present invention, TKH-
POP-4 Fourier Transform Infrared Spectroscopy data are as follows:
FT-IR(cm-1):3439(w),3060(w),1608(m),1475(vs),1448(m),1419(vs), 1402
(vs),1317(s),1276(m),1220(s),1171(s),1115(w),1090(m),1050(s), 1029(s),998(m),
914(m),823(s),747(s),732(s),629(m)；
Referring to Fig.1 5, show the TKH-POP-4 cross polarization/evil spirit angle spin prepared in the embodiment of the present invention13C nuclear-magnetism is total
Shake spectrogram, TKH-POP-4 cross polarization/evil spirit angle spin13C nuclear magnetic resonance modal data is as follows:
13C-CP/MAS NMR(15kHz)δ(ppm):177.89,149.60,140.17,127.48, 119.47,64.95；
Referring to Fig.1 6, show the TKH-POP-4 Elemental analysis data prepared in the embodiment of the present invention 4, TKH-POP-4 member
Element analysis data are as follows:
Carbon element content 69.47%, protium content 4.91%, nitrogen 11.79%.
The embodiment of the invention provides a kind of preparation methods of ketone-hydrazone skeleton structure organic porous polymer material, lead to
The hexamethylene triketone with active methylene group is crossed to react with the efficient coupling polymerization of Bisdiazonium salts progress for being easy largely to prepare, it can
Preparation has ketone-hydrazone bond structure Porous-Organic polymeric material in the case where environmental-friendly, mild condition, which can
It is carried out in water phase, environmentally protective and easy a large amount of preparations.A kind of Porous-Organic of ketone-hydrazone skeleton structure prepared by the present invention is poly-
Object material is closed, the hetero atoms such as N and O can be accurately embedded into porous bone by ketone-hydrazone skeleton structure organic porous polymer
It in frame, therefore can play a significant role in terms of adsorption of metal ions, volatile organic matter absorption and gas, together
When also can be as the good carrier of high-performance different-phase catalyst.
The pore analysis of five TKH-POP-1 of embodiment
In the embodiment of the present invention, 1,3, the 5- hexamethylene triketones based on active methylene group are coupled with the Bisdiazonium salts being easy to get
Polymerization reaction, the ketone prepared-hydrazone skeleton structure organic porous polymer have high-specific surface area and pore structure abundant etc. excellent
Anisotropic energy, has potential application prospect.The embodiment of the present invention polymerize ketone-hydrazone skeletal porous using TKH-POP-1 as representative
The porous performance of object is characterized, and describes ketone-hydrazone skeletal porous polymer application direction.
The specific surface area of porous material is usually measured by gas absorption-desorption isotherm method, i.e., with gas molecule (such as nitrogen
Gas) it is probe, under constant temperature conditions, adsorbance corresponding to different pressures obtains adsorption isotherm to record porous material.Later
It is calculated by BET model inference and compares BET surface area.BET is three scientists (Brunauer, Emmett and Teller)
Acronym, on the basis of the multi-molecular absorption formula that three scientists derive from classical statistical theory, i.e., famous BET
Equation, becomes the theoretical basis of particle surface adsorption science, and is widely used in particle surface Study on adsorption properties and phase
Close the Data processing of detecting instrument.
Referring to Fig.1 7, show the pore-size distribution that the TKH-POP-1 prepared in the embodiment of the present invention one is calculated through NLDFT
Curve graph.
It is as shown in the table that the specific surface area of the TKH-POP-1 prepared in the embodiment of the present invention two and hole hold numerical value:
The present invention is by being simple and efficient, a kind of ketone-hydrazone skeleton structure Porous-Organic of environmental-friendly method preparation is poly-
Close object material, ketone-hydrazone skeleton structure organic porous polymer has functional group abundant, biggish specific surface area, larger
Total pore volume and lesser average pore size, will adsorption of metal ions, volatile organic matter absorption and gas storage etc. with
Environment and energy related field play a significant role.The thermal stability of six TKH-POP-1 of embodiment
In the embodiment of the present invention, 1,3, the 5- hexamethylene triketones based on active methylene group are coupled with the Bisdiazonium salts being easy to get
Polymerization reaction, the ketone prepared-hydrazone skeleton structure organic porous polymer have good thermal stability, are conducive to the material
It promotes and applies.The embodiment of the present invention carries out ketone-hydrazone skeletal porous polymer thermal stability using TKH-POP-1 as representative
Characterization.
Thermogravimetric analysis (Thermogravimetric Analysis, TGA) refer to measured under programed temperature it is to be measured
The quality of sample and a kind of thermoanalysis technology of temperature change relationship can obtain for the thermal stability and component of research material
Information in terms of hot physical property caused by thermal change to sample.The thermal stability of porous material reflects porous material high temperature resistant
Property, that is, refer to porous material in case of heating and can keep that attribute is stablized.
Referring to Fig.1 8, show the thermogravimetric analysis spectrogram of the TKH-POP-1 prepared in the embodiment of the present invention one.
TKH-POP-1 starts to degrade after being higher than 220 DEG C, and shows multistage signs of degradation.First rank first
220 DEG C -300 DEG C of section degradation is more apparent and mass loss about 15%, be that the N atom loss in structure causes, and at 274 DEG C
When N bleed rate reach highest.The degradation rate that 300 DEG C -500 DEG C of second stage is relatively slow, and mass loss about 15%, is structure
In O atom loss cause, at 415 DEG C, the bleed rate of O is higher.500 DEG C of later degradations of phase III are that C atom is lost
Cause, and degradation rate is slow.TKH-POP-1 degradation temperature with higher, good thermal stability are conducive to the material in height
Popularization and application under the harsh environments such as temperature.
The present invention is by being simple and efficient, a kind of ketone-hydrazone skeleton structure Porous-Organic of environmental-friendly method preparation is poly-
Close object material, ketone-hydrazone skeleton structure organic porous polymer has functional group abundant, biggish specific surface area, larger
Total pore volume and lesser average pore size, will adsorption of metal ions, volatile organic matter absorption and gas storage etc. with
Environment and energy related field play a significant role.
Absorption of seven TKH-POP-1 of embodiment to VOCs
Volatile organic matter (volatile organic compounds, VOCs) refers to that vapour pressure is greater than at room temperature
70.91Pa, for aerial boiling point in 260 DEG C of organic gas and liquid below, relatively common has benzene, toluene, alcohols, aldehyde
Class, ketone etc..Most of VOCs are toxic, foul odour, and there are also carcinogenic, teratogenesis and mutagenesis by part VOCs, furthermore
VOCs easily causes the environmental problems such as photochemical fog, the increase of haze number, can influence human health indirectly.Porous material is as one
Kind space three-dimensional porous type network material is a kind of novel adsorption most with broad prospect of application administering VOCs pollution field
Material.In the embodiment of the present invention, ketone-hydrazone skeleton structure organic porous polymer for preparing has high-specific surface area, perforation
Aperture structure, good thermal stability and absorption property, in adsorption treatment VOCs pollution, not only removal efficiency is high, low energy consumption,
And it is recoverable, easy to spread, there are good environment and economic benefit, is conducive to the material in VOCs and pollutes process field
Popularization and application.The embodiment of the present invention carries out ketone-hydrazone skeletal porous Polymer adsorption benzene vapour using TKH-POP-1 as representative
Characterization.
At 25 DEG C, TKH-POP-1 carries out being adsorbed on Full-automatic physical Sorption Analyzer for benzene vapour, in constant temperature
Under, it is respectively pressed when calculating adsorption equilibrium using perfect gas law by the difference between adsorption equilibrium pressure and initial vapour pressure
Under power on porous material VOCs adsorbance, obtain porous material under constant temperature conditions to the adsorption isotherm of benzene vapour.
Referring to Fig.1 9, show absorption of the TKH-POP-1 prepared in the embodiment of the present invention one at 25 DEG C to benzene vapour
Thermoisopleth.
TKH-POP-1 is at 25 DEG C to the adsorbance of benzene vapour up to 2.07mmol/g.TKH-POP-1 not only has height
Specific surface area, the aperture structure of perforation and higher pore volume, and aryl group rich in can pass through π-π phase interaction
It is combined with benzene molecular, to promote the absorption to benzene vapor.
The present invention is by being simple and efficient, a kind of ketone-hydrazone skeleton structure Porous-Organic of environmental-friendly method preparation is poly-
Close object material, ketone-hydrazone skeleton structure organic porous polymer has functional group abundant, biggish specific surface area, larger
Total pore volume and lesser average pore size, will adsorption of metal ions, volatile organic matter absorption and gas storage etc. with
Environment and energy related field play a significant role.
It should be noted that, in this document, the terms "include", "comprise" or its any other variant are intended to non-row
His property includes, so that the process, method, article or the device that include a series of elements not only include those elements, and
And further include other elements that are not explicitly listed, or further include for this process, method, article or device institute it is intrinsic
Element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that including being somebody's turn to do
There is also other identical elements in the process, method of element, article or device.
The embodiment of the present invention is described with above attached drawing, but the invention is not limited to above-mentioned specific
Embodiment, the above mentioned embodiment is only schematical, rather than restrictive, those skilled in the art
Under the inspiration of the present invention, without breaking away from the scope protected by the purposes and claims of the present invention, it can also make very much
Form, all of these belong to the protection of the present invention.
Claims (14)
1. a kind of preparation method of ketone-hydrazone skeleton structure organic porous polymer, which is characterized in that the described method includes:
Step 1, the first reaction is carried out to aryl diamine shown in structural formula IV, obtains Bisdiazonium salts shown in formula II I；
Step 2, under alkaline condition, 1,3,5- hexamethylene triketones shown in formula II and the dual nitrogen are made by the second reaction
Coupling polymerization reaction occurs for salt, is post-processed to obtain ketone shown in structural formula I-hydrazone skeleton structure organic porous polymer
。
2. the method according to claim 1, wherein the X in the Bisdiazonium salts includes Cl, BF4、PF6And OAc
In any one.
3. the method according to claim 1, wherein the aryl diamine include 4,4'- benzidine, 4,
Bis- (4- aminophenyl) fluorenes of 4'- diaminodiphenylmethane, 4,4'- diamino hexichol dimethylmethane, 9,9'-, Isosorbide-5-Nitrae-diamino
Benzene and 1,3- diaminobenzene, 4,4'- diamino terphenyl, 1,5- diaminonaphthalene, 2,6- diaminoanthraquinone-, 3,3', 5,5'- tetramethyl
Benzidine, 4,4'- diaminodiphenyl ether, 4,4'- diamino diphenyl sulfone, 4,4'- diamino bipyridyl, 4,4'- diamino are even
Any one in pyridine；
The aryl of the aryl diamine includes:
。
4. the method according to claim 1, wherein first reaction includes:
Under the conditions of ice-water bath, the aryl diamine is dissolved in the mixed solution of acid medium and the first solvent, is stirred evenly；
The nitrosification agent being pre-chilled in ice-water bath is added drop-wise in the mixed solution of the aryl diamine with pre-set velocity, is reacted
The Bisdiazonium salts are obtained after first preset time；The pre-set velocity is 1 second/drop~5 seconds/drop；First preset time
It is 25-120 minutes.
5. according to the method described in claim 4, it is characterized in that, the nitrosification agent include sodium nitrite, potassium nitrite,
Any one in isobutyl nitrite and isoamyl nitrite.
6. according to the method described in claim 4, it is characterized in that, the acid medium includes hydrochloric acid, fluoboric acid, hexafluorophosphoric acid
With any one in acetic acid.
7. according to the method described in claim 4, it is characterized in that, the molar ratio of the aryl diamine and the acid medium is
1:4~1:10.
8. according to the method described in claim 4, it is characterized in that, first solvent includes deionized water, methanol, ethyl alcohol,
Acetonitrile, acetone, any one in methylene chloride.
9. the method according to claim 1, wherein second reaction includes:
Under the conditions of ice-water bath, the solution of the Bisdiazonium salts is adjusted as neutrality using alkaline solution；
Described 1,3,5- hexamethylene triketone is mixed with alkaline matter and is dissolved in the second solvent, aqueous slkali is prepared；The aqueous slkali is set
It is pre-chilled in ice-water bath；
The aqueous slkali is added dropwise into the solution of the Bisdiazonium salts with pre-set velocity, reacts the second preset time；Described second
Preset time is 6h~for 24 hours；
It is post-processed to obtain the ketone-hydrazone skeleton structure organic porous polymer.
10. according to the method described in claim 9, it is characterized in that, the alkaline solution includes sodium carbonate liquor, sodium hydroxide
Any one in solution, sodium acetate solution, solution of potassium carbonate, potassium hydroxide solution and triethylamine solution；
The alkaline matter includes any one in sodium carbonate, sodium hydroxide, sodium acetate, potassium carbonate, potassium hydroxide and triethylamine
Kind.
11. according to the method described in claim 9, it is characterized in that, it is described second reaction described in 1,3,5- hexamethylene triketones with
The molar ratio of the Bisdiazonium salts is 1:1.5~1:9.
12. according to the method described in claim 9, it is characterized in that, second solvent include deionized water, methanol, ethyl alcohol,
Any one in acetone, acetonitrile and N,N-dimethylformamide.
13. the method according to claim 1, wherein the post-processing includes vacuum drying oven drying, overcritical two
Carbonoxide is dried and frozen any one in dry.
14. a kind of ketone-hydrazone skeleton structure organic porous polymer material, which is characterized in that the ketone-hydrazone skeleton structure has
Machine porous polymer material is prepared by the method for the claims 1-13 any one.
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| GUIPENG JI等: ""Hierarchically Mesoporous o-Hydroxyazobenzene Polymers: Synthesis and Their Applications in CO2 Capture and Conversion and Their Applications in CO2 Capture and Conversion"", 《ANGEW. CHEM. INT. ED》 * |
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| CN115947938B (en) * | 2023-02-05 | 2024-05-17 | 赣南师范大学 | Ellagic acid-based organic porous polymer and preparation method and application thereof |
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