CN104177576B - A kind of imido grpup organic porous polymer framework material and preparation method thereof - Google Patents
A kind of imido grpup organic porous polymer framework material and preparation method thereof Download PDFInfo
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Abstract
A kind of imido grpup organic porous polymer framework material of the present invention and preparation method thereof belongs to the technical field of porous material.A kind of imido grpup organic porous polymer framework material provided by the invention has the one-dimensional channels of high-sequential, and hole wall is dispersed with a large amount of nitrogen-atoms; The preparation method of imido grpup organic porous polymer framework material provided by the invention is under acid catalysis, and a certain proportion of hydrazine hydrate and fragrance many aldehyde molecule, under the condition of solvent thermal, polycondensation is occurred.Imido grpup organic porous polymer framework material provided by the invention has high specific surface area, homogeneous aperture, the strong feature such as crystallinity, high nitrogen-containing, utilizes imines condensation reaction to prepare the use of the noble metal catalyst that organic porous polymer is avoided, production cost that the application of cheap hydrazine hydrate all can reduce such framework material.
Description
Technical field
The invention belongs to the technical field of porous material, particularly a kind of imido grpup organic porous polymer framework material and preparation method thereof.
Background technology
In recent years, the synthesis of organic porous polymer framework material obtains swift and violent development, covalent organic framework material, conjugation capillary copolymer material, element organic framework material, becomes the focus of research gradually from the synthesis of tool capillary copolymer material and super crosslinked polymeric materials etc.To sieve as inorganic molecule with traditional porous material and compare with inorganic-organic hybridization metallic organic framework, organic porous polymer framework material is generally made up of the carbon of lighter weight, hydrogen, oxygen, nitrogen and boron, there is lighter skeletal density, and there is higher specific surface area, better physical and chemical stability.And, the structure of organic porous material, character and function can by rational chemical design, select suitable structural unit, select number of chemical route of synthesis to regulate.At present, organic porous polymer framework material, owing to having high specific surface area and pore volume, shows good application prospect in catalysis, gas storage, molecular separation, environment, the energy etc.
2009, Yaghi etc. [J.Am.Chem.Soc., 2009,131,4570-4571] first reported imido grpup three-dimensional order covalent organic framework material, and its specific surface area is up to arriving 1360m
2/ g.2013; [the J.Am.Chem.Soc. such as Jiang; 2013,135,17310-17313] report and utilize hydrazine and 1; 3; 6,8-tetra-(Fonnylphenyl) pyrene by the Two dimensional Crystallization covalent organic framework material of condensation reaction preparation luminescence, and have studied it to explosive substance 1; the selective response of 3,5-trinitrophenol.By selecting different monomers, the organic porous polymer framework material that some imines connect has been in the news [Angew.Chem.Int.Ed.2013,52,3770-3774; J.Am.Chem.Soc., 2013,135,546-549; J.Am.Chem.Soc., 2013,135,5328-5331; Angew.Chem.Int.Ed.2013,52,13052-13056; Chem.Eur.J.2013,19,3324-3328.], gas adsorption be separated, catalysis, optoelectronic areas show potential application.Utilizing imines condensation reaction to construct imido grpup organic porous polymer framework material, to have reaction conditions relatively gentle, and reaction conversion ratio is high; By product is water, is easy to removing; Do not need expensive catalyzer, eliminate loaded down with trivial details remainder catalyst removing process; Reversible reaction process may repair the defect in skeleton structure, obtains the crystalline polymer framework material of high-sequential.At present more loaded down with trivial details for the synthesis of the monomer synthesize of imido grpup organic porous polymer skeleton, synthesis step is many, adds polymkeric substance preparation cost, therefore, needs the imido grpup organic porous polymer framework material that exploitation is cheap.
Summary of the invention
The technical problem to be solved in the present invention is, provides porous organic polymer material with high-specific surface area of a kind of cheapness and preparation method thereof.In order to address this problem, the invention provides imido grpup organic porous polymer framework material and preparation method thereof.
Concrete technical scheme of the present invention is, a kind of imido grpup organic porous polymer framework material, and structural formula is:
Wherein n=2 ~ 500.
The preparation method of imido grpup porous organic polymer framework material provided by the invention, step is as follows:
Organic solvent and Glacial acetic acid are dispersed in distilled water, form mixing solutions; Hydrazine hydrate and the many aldehyde cpds of fragrance are dispersed in described mixing solutions, under nitrogen protection, in 80 ~ 140 DEG C of reactions 24 ~ 96 hours, filter, wash respectively with methyl alcohol, tetrahydrofuran (THF), acetone, obtain pressed powder; Described pressed powder was 100 DEG C of vacuum-dryings 10 hours, and vacuum tightness is less than 0.133Pa, obtained the imido grpup porous organic polymer framework material with high-ratio surface sum pore volume; Wherein said organic solvent is dioxane, tetrahydrofuran (THF), 1，3，5-trimethyl-benzene or ethanol; Described fragrance many aldehyde molecule is 1,3,5-trifonnyl benzene or 1,3,5-trihydroxy--2,4,6-trifonnyl benzene; The mol ratio of hydrazine hydrate, fragrant many aldehyde molecule, organic solvent, Glacial acetic acid and distilled water is 1:0.66 ~ 0.67:30 ~ 50:2.1 ~ 2.2:19.8 ~ 19.9.
The preferred dioxane of organic solvent.
According to preparation method provided by the invention, adopt hydrazine hydrate as the synthesizing porous organic polymer backbones material of one of raw material monomer, can obtain that there is high crystalline porous organic polymer framework material.
Synthetic method provided by the invention, selects cheap hydrazine hydrate as raw material, effectively reduces the preparation cost of framework material.
The pore size of the porous organic polymer framework material prepared by the present invention is all at nanoscale, and its pore structure is formed by connecting by covalent linkage, and therefore skeleton structure is relatively stable.
Porous organic polymer framework material provided by the invention has higher specific surface area, and containing a large amount of nitrogen-atoms, make porous polymer material of the present invention may be used for gas storage, gas delivery, catalysis and support of the catalyst, water phase organic matters and heavy metal ion adsorbed, be with a wide range of applications.
Accompanying drawing explanation
The infrared spectrum of Fig. 1 embodiment 1 imido grpup organic porous polymer framework material P-1 and monomer 1,3,5-trifonnyl benzene.
The carbon-13 nmr spectra figure of Fig. 2 embodiment 1 imido grpup organic porous polymer framework material P-1.
The thermogravimetric spectrogram of Fig. 3 embodiment 1 imido grpup organic porous polymer framework material P-1.
Powder χ-the x ray diffration pattern x of Fig. 4 embodiment 1 imido grpup organic porous polymer framework material P-1.
The N of Fig. 5 embodiment 1 imido grpup organic porous polymer framework material P-1
2adsorption-desorption isothermal.
Fig. 6 embodiment 1 imido grpup organic porous polymer framework material P-1 is according to the graph of pore diameter distribution of SF method.
Hydrogen adsorption curve at Fig. 7 imido grpup organic porous polymer framework material P-1 – 186 DEG C.
Hydrogen adsorption curve at Fig. 8 imido grpup organic porous polymer framework material P-1 – 196 DEG C.
Fig. 9 imido grpup organic porous polymer framework material P-1 is at 25 DEG C of carbon dioxide adsorption curves.
Figure 10 imido grpup organic porous polymer framework material P-1 is at 0 DEG C of carbon dioxide adsorption curve.
Figure 11 imido grpup organic porous polymer framework material P-1 methane adsorption curve at 25 DEG C.
Figure 12 imido grpup organic porous polymer framework material P-1 methane adsorption curve at 0 DEG C.
The infrared spectrum of Figure 13 embodiment 9 imido grpup organic porous polymer framework material P-2 and monomer 1,3,5-trihydroxy--2,4,6-trifonnyl benzene.
The carbon-13 nmr spectra figure of Figure 14 embodiment 9 imido grpup organic porous polymer framework material P-2.
The thermogravimetric spectrogram of Figure 15 embodiment 9 imido grpup organic porous polymer framework material P-2.
Powder χ-the x ray diffration pattern x of Figure 16 embodiment 9 imido grpup organic porous polymer framework material P-2.
The N2 adsorption-desorption isothermal of Figure 17 embodiment 9 imido grpup organic porous polymer framework material P-2.
Figure 18 embodiment 9 imido grpup organic porous polymer framework material P-2 is according to the graph of pore diameter distribution of SF method.
Hydrogen adsorption curve at Figure 19 imido grpup organic porous polymer framework material P-2 – 186 DEG C.
Hydrogen adsorption curve at Figure 20 imido grpup organic porous polymer framework material P-2 – 196 DEG C.
Figure 21 imido grpup organic porous polymer framework material P-2 is at 25 DEG C of carbon dioxide adsorption curves.
Figure 22 imido grpup organic porous polymer framework material P-2 is at 0 DEG C of carbon dioxide adsorption curve.
Figure 23 imido grpup organic porous polymer framework material P-2 methane adsorption curve at 25 DEG C.
Figure 24 imido grpup organic porous polymer framework material P-2 methane adsorption curve at 0 DEG C.
Embodiment
Below by embodiment, the present invention is described, but is not limited to this.
Embodiment 1
0.0234mol dioxane and 1.2mmol Glacial acetic acid are dispersed in 11.11mmol distilled water, form mixing solutions; By 0.56mmol hydrazine hydrate and 0.37mmol1,3,5-trifonnyl benzene is dispersed in described mixing solutions, under nitrogen protection, in 120 DEG C of reactions 72 hours, filters, washs each 3 times respectively, obtain pressed powder with methyl alcohol, tetrahydrofuran (THF), acetone; Described pressed powder was 100 DEG C of vacuum-dryings 10 hours, and vacuum tightness is less than 0.133Pa, obtained the imido grpup organic porous polymer framework material P-1 with high-ratio surface sum pore volume, productive rate 86%.
Reaction process is as follows:
With infrared spectrometer (AvatarFT-IR360), infrared spectra detection is carried out to framework material P-1.Fig. 1 is the infrared contrast spectrogram of imido grpup organic porous polymer framework material P-1 and reaction monomers 1,3, the 5-trifonnyl benzene adopting the inventive method to prepare; in figure, solid line is the infrared spectrum of reaction monomers;, dotted line is the infrared spectrum of the porous polymer material of preparation, 1702cm
-1for C=O charateristic avsorption band, after polyreaction, the C=O charateristic avsorption band of correspondence position obviously disappears, and at 1628cm
-1there is C=N charateristic avsorption band in place, proves that polyreaction is complete.
With nuclear magnetic resonance spectrometer (BrukerAVANCEIII400WB), solid-state nuclear magnetic resonance detection is carried out to solid P-1, seen Fig. 2.Demonstrate framework material P-1 at the nuclear-magnetism peak of 135ppm and there is aromatic ring structure.
With thermal gravimetric analyzer (TAQ500), heat stability test is carried out to solid P-1, seen Fig. 3.By heat weight research, polymer P-15% quality is weightless at 360 DEG C, shows that the porous polymer framework material synthesized has good stability.
Detect by the crystallinity of powder x-ray diffraction to solid P-1, see Fig. 4.Derive from (100) face at sharp-pointed peak, 6.97 ° of places, show that polymer P-1 has the crystallinity of height.
With full-automatic specific surface area and lacunarity analysis instrument (JW-BK132F) at 77K, 0 ~ 0.1MPa, carries out specific surface area to solid P-1 and porosity detects, and the nitrogen adsorption recorded is I-type thermoisopleth, as shown in Figure 5, the N of porous polymer material for adopting the inventive method to obtain
2xi Fu – desorption isotherm, real point is adsorption curve, and ignore is desorption curve, passes through N
2xi Fu – desorption isotherm, the BET specific surface area obtaining porous polymer material reaches 1170m
2/ g.
As shown in Figure 6, the graph of pore diameter distribution that the porous polymer material obtained for adopting the inventive method calculates according to SF method, porous polymer material pore size distribution is at about 0.7nm.
By the porous polymer product that obtains at 87K and 77K, 0 ~ 0.1MPa, under record hydrogen adsorption thermoisopleth, as illustrated in figs. 7 and 8, the adsorption isothermal line of the low pressure gas storage hydrogen of the porous polymer framework material obtained for adopting the inventive method, Fig. 7 and Fig. 8 gives the thermoisopleth of the hydrogen adsorption under differing temps, and hydrogen adsorption ability significantly increases with the reduction of temperature.
By the porous polymer product that obtains at 298K and 273K, 0 ~ 0.1MPa, under record carbon dioxide adsorption thermoisopleth, as shown in Figures 9 and 10, the adsorption isothermal line of carbonic acid gas is recorded under the low pressure of the porous polymer framework material obtained for adopting the inventive method, the adsorption isothermal line of the carbonic acid gas under differing temps is given in Fig. 9 and Figure 10, reaching 17.7% when 0.1MPa, 273K according to weight percent absorbing carbon dioxide amount, is one of material that in current carbon dioxide storage, performance is more excellent.
By the porous polymer product that obtains at 298K and 273K, 0 ~ 0.1MPa, under record methane adsorption isotherm, as shown in Figure 11 and Figure 12, the adsorption isothermal line of methane is recorded under the low pressure of the porous polymer framework material obtained for adopting the inventive method, give the adsorption isothermal line of the methane under differing temps in Figure 11 and Figure 12, reach 1.15% when 0.1MPa, 273K according to weight percent adsorbed methane amount.
Embodiment 2
Replace dioxane with 0.0234mol trimethylbenzene, repeat embodiment 1, obtain the imido grpup organic porous polymer framework material P-1 with high-ratio surface sum pore volume, its performance characterization result is identical with embodiment 1.
Embodiment 3
Replace dioxane with 0.0234mol ethanol, repeat embodiment 1, obtain the imido grpup organic porous polymer framework material P-1 with high-ratio surface sum pore volume, its performance characterization result is identical with embodiment 1.
Embodiment 4
Replace dioxane with 0.0234mol tetrahydrofuran (THF), repeat embodiment 1, obtain the imido grpup organic porous polymer framework material P-1 with high-ratio surface sum pore volume, its performance characterization result is identical with embodiment 1.
Embodiment 5
The consumption of dioxane is become 0.0168mol, repeats embodiment 1, same acquisition has the imido grpup organic porous polymer framework material P-1 of high-ratio surface sum pore volume, and its performance characterization result is identical with embodiment 1.
Embodiment 6
The consumption of dioxane becomes 0.028mol, repeats embodiment 1, and same acquisition has the imido grpup organic porous polymer framework material P-1 of high-ratio surface sum pore volume, and its performance characterization result is identical with embodiment 1.
Embodiment 7
Changing temperature of reaction is 80 DEG C, 96 hours reaction times, repeats embodiment 1, and same acquisition has the imido grpup organic porous polymer framework material P-1 of high-ratio surface sum pore volume, and its performance characterization result is identical with embodiment 1.
Embodiment 8
Changing temperature of reaction is 140 DEG C, 24 hours reaction times, repeats embodiment 1, and same acquisition has the imido grpup organic porous polymer framework material P-1 of high-ratio surface sum pore volume, and its performance characterization result is identical with embodiment 1.
Embodiment 9
0.0234mol tetrahydrofuran (THF) is dispersed in the aqueous acetic acid of 1.2mmol6mol/L, forms mixing solutions; By 0.56mmol hydrazine hydrate and 0.37mmol1,3,5-trihydroxy--2,4,6-trifonnyl benzene is dispersed in described mixing solutions, under nitrogen protection, in 120 DEG C of reactions 72 hours, filter, wash 3 times respectively with methyl alcohol, tetrahydrofuran (THF), acetone, obtain pressed powder; By described pressed powder 100 DEG C of vacuum-dryings 10 hours, vacuum tightness is less than 0.133Pa, obtains the imido grpup organic porous polymer framework material P-2 with high-ratio surface sum pore volume, productive rate 60%.Reaction process is as follows:
With infrared spectrometer (AvatarFT-IR360), infrared spectra detection is carried out to framework material P-2.If Figure 13 is the imido grpup organic porous polymer framework material P-2 and reaction monomers 1 that adopt the inventive method to prepare; 3; 5-trihydroxy--2; 4; the infrared contrast spectrogram of 6-trifonnyl benzene; in figure, solid line is the infrared spectrum of reaction monomers, and dotted line is the infrared spectrum of the porous polymer material of preparation, 1639cm
-1for C=O charateristic avsorption band, after polyreaction, the C=O charateristic avsorption band of correspondence position obviously disappears, and at 1578cm
-1there is C=C charateristic avsorption band in place, prove that polyreaction is complete, polymkeric substance exists with keto-acid conformation.
With nuclear magnetic resonance spectrometer (BrukerAVANCEIII400WB), solid-state nuclear magnetic resonance detection is carried out to solid P-2, seen Figure 14.Demonstrate framework material P-2 at the nuclear-magnetism peak of 181ppm and there is ketone form structure.
With thermal gravimetric analyzer (TAQ500), heat stability test is carried out to solid P-2, seen Figure 15.By heat weight research, polymer P-25% quality is weightless at 305 DEG C, shows that the porous polymer framework material synthesized has good stability.
Detect by the crystallinity of powder x-ray diffraction to solid P-2, see Figure 16.Derive from (100) face at sharp-pointed peak, 6.97 ° of places, show that polymer P-2 has the crystallinity of height.
With full-automatic specific surface area and lacunarity analysis instrument (JW-BK132F) at 77K, 0 ~ 0.1MPa, specific surface area and porosity detection are carried out to solid P-2, the nitrogen adsorption recorded is II-type thermoisopleth, as shown in figure 17, and the N of the porous polymer material obtained for adopting the inventive method
2xi Fu – desorption isotherm, real point is adsorption curve, and ignore is desorption curve, passes through N
2xi Fu – desorption isotherm, the BET specific surface area obtaining porous polymer material reaches 820m
2/ g.
As shown in figure 18, the graph of pore diameter distribution that the porous polymer material obtained for adopting the inventive method calculates according to SF method, porous polymer material pore size distribution is at about 0.619nm.
By the porous polymer product that obtains at 87K and 77K, 0 ~ 0.1MPa, under record hydrogen adsorption thermoisopleth, as shown in Figure 19 and Figure 20, the adsorption isothermal line of the low pressure gas storage hydrogen of the porous polymer framework material obtained for adopting the inventive method, give the thermoisopleth of the hydrogen adsorption under differing temps in Figure 19 and Figure 20, hydrogen adsorption ability significantly increases with the reduction of temperature.
By the porous polymer product that obtains at 298K and 273K, 0 ~ 0.1MPa, under record carbon dioxide adsorption thermoisopleth, as shown in Figure 21 and Figure 22, the adsorption isothermal line of carbonic acid gas is recorded under the low pressure of the porous polymer framework material obtained for adopting the inventive method, the adsorption isothermal line of the carbonic acid gas under differing temps is given in Figure 21 and Figure 22, reaching 21.2% when 0.1MPa, 273K according to weight percent absorbing carbon dioxide amount, is one of material that in current carbon dioxide storage, performance is more excellent.
By the porous polymer product that obtains at 298K and 273K, 0 ~ 0.1MPa, under record methane adsorption isotherm, as shown in Figure 23 and Figure 24, the adsorption isothermal line of methane is recorded under the low pressure of the porous polymer framework material obtained for adopting the inventive method, give the adsorption isothermal line of the methane under differing temps in Figure 23 and Figure 24, reach 3.97% when 0.1MPa, 273K according to weight percent adsorbed methane amount.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For the person of ordinary skill of the art, can according to technical scheme of the present invention and inventive concept, make corresponding change and substitute, and performance or purposes identical, all should be considered as protection scope of the present invention.
Claims (3)
1. an imido grpup organic porous polymer framework material, its structural formula is:
，
Wherein n=2 ~ 500.
2. a preparation method for the imido grpup organic porous polymer framework material of claim 1, is characterized in that, be dispersed in distilled water by organic solvent and Glacial acetic acid, forms mixing solutions; Hydrazine hydrate and the many aldehyde cpds of fragrance are dispersed in described mixing solutions, under nitrogen protection, in 80 ~ 140 DEG C of reactions 24 ~ 96 hours, filter, wash respectively with methyl alcohol, tetrahydrofuran (THF), acetone, obtain pressed powder; Described pressed powder was 100 DEG C of vacuum-dryings 10 hours, and vacuum tightness is less than 0.133Pa, obtained the imido grpup porous organic polymer framework material with high-ratio surface sum pore volume; Wherein said organic solvent is dioxane, tetrahydrofuran (THF), 1，3，5-trimethyl-benzene or ethanol; Described fragrance many aldehyde molecule is 1,3,5-trihydroxy--2,4,6-trifonnyl benzene; The mol ratio of hydrazine hydrate, fragrant many aldehyde molecule, organic solvent, Glacial acetic acid and distilled water is 1:0.66 ~ 0.67:30 ~ 50:2.1 ~ 2.2:19.8 ~ 19.9.
3. a preparation method for imido grpup organic porous polymer framework material according to claim 2, is characterized in that, described organic solvent is dioxane.
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| CN105754588B (en) * | 2016-04-05 | 2018-07-17 | 吉林大学 | A kind of luminous porous organic polymer material and preparation method of imines connection |
| CN107129583B (en) * | 2017-05-25 | 2019-11-15 | 西北师范大学 | The synthetic method of porous organic covalent frame material with triazine structure |
| CN107540801B (en) * | 2017-09-29 | 2020-07-07 | 中国科学院上海有机化学研究所 | Covalent organic framework and preparation method thereof |
| CN110364370B (en) * | 2019-06-19 | 2021-05-11 | 东华大学 | Pyridyl porous carbon material and preparation method and application thereof |
| CN111689918B (en) * | 2020-04-30 | 2022-02-18 | 华南师范大学 | Functional diaphragm coating material for protecting lithium metal negative electrode and preparation method and application thereof |
| CN113045722A (en) * | 2021-03-11 | 2021-06-29 | 兰州大学 | Imino covalent organic framework polymer, preparation method and application thereof, ammonia gas sensor and preparation method thereof, and ammonia gas sensing detection method |
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