CN104177576A - Imino organic porous polymer framework material and preparation method thereof - Google Patents
Imino organic porous polymer framework material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an imino organic porous polymer framework material and a preparation method thereof and belongs to the technical field of porous materials. The imino organic porous polymer framework material provided by the invention has highly ordered one-dimensional ducts and a lot of nitrogen atoms are distributed on the walls of the ducts. The preparation method of the imino organic porous polymer framework material provided by the invention comprises the following step of carrying out a polycondensation reaction on hydrazine hydrate and aromatic polyaldehyde molecules in a certain proportion under a solvothermal condition under the effect of acid catalysis. The imino organic porous polymer framework material provided by the invention has the characteristics of high specific surface area, uniform bore diameter, strong crystallinity, high nitrogen content and the like. Use of noble metal catalysts is avoided for preparing the organic porous polymer by means of imine condensation reaction, and by applying cheap hydrazine hydrate, the production cost of the framework material can be lowered.
Description
Technical field
The invention belongs to the technical field of porous material, particularly a kind of imido grpup Porous-Organic polymer backbone material and preparation method thereof.
Background technology
In recent years, Porous-Organic polymer backbone material synthetic obtained swift and violent development, covalency organic framework material, conjugation capillary copolymer material, element organic framework material, from the synthetic focus that becomes gradually research of tool capillary copolymer material and super crosslinked polymeric materials etc.Compare with inorganic-organic hybridization metallic organic framework as inorganic molecule sieve with traditional porous material, Porous-Organic polymer backbone material is generally by forming compared with the carbon of lightweight, hydrogen, oxygen, nitrogen and boron, there is lighter skeletal density, and there is higher specific surface area, better physical and chemical stability.And structure, character and the function of organic porous material can be by rational chemical design, select suitable structural unit, select number of chemical route of synthesis to regulate.At present, Porous-Organic polymer backbone material, owing to having high specific surface area and pore volume, shows good application prospect at aspects such as catalysis, gas storage, molecular separation, environment, the energy.
2009, Yaghi etc. [J.Am.Chem.Soc., 2009,131,4570-4571] first reported imido grpup three-dimensional order covalency 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 utilized hydrazine and 1; 3; 6,8-tetra-(formyl radical phenyl) pyrene is prepared luminous Two dimensional Crystallization covalency organic framework material by condensation reaction, and has studied it to explosive substance 1; the selective response of 3,5-trinitrophenol.By selecting different monomers, the Porous-Organic polymer backbone material that some imines connect be 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 with separate, catalysis, optoelectronic areas shown potential application.Utilize imines condensation reaction to construct imido grpup Porous-Organic polymer backbone material and have reaction conditions gentleness relatively, reaction conversion ratio is high; By product is water, is easy to remove; Do not need expensive catalyzer, removed loaded down with trivial details remainder catalyst from and removed process; Reversible reaction process may be repaired the defect in skeleton structure, obtains the crystalline polymer framework material of high-sequential.The current monomer for the synthesis of imido grpup Porous-Organic polymer backbone is synthetic more loaded down with trivial details, synthesis step is many, has increased polymkeric substance preparation cost, therefore, need to develop cheap imido grpup Porous-Organic polymer backbone material.
Summary of the invention
The technical problem to be solved in the present invention is, what a kind of cheapness was provided has porous organo polysilica laminate material of high-specific surface area and preparation method thereof.In order to address this problem, the invention provides imido grpup Porous-Organic polymer backbone material and preparation method thereof.
Concrete technical scheme of the present invention is, a kind of imido grpup Porous-Organic polymer backbone material, and structural formula is:
Wherein n=2～500.
The preparation method of imido grpup porous organo polysilica compound 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 fragrant many aldehyde cpds 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 having the imido grpup porous organo polysilica compound framework material of high-specific surface area and pore volume; Wherein said organic solvent is dioxane, tetrahydrofuran (THF), 1，3，5-trimethyl-benzene or ethanol; Described many aldehyde of fragrance molecule is 1,3,5-, tri-formyl radical benzene or 1,3,5-trihydroxy--2,4,6-, tri-formyl radical 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 framework material of one of raw material monomer, can obtain having high crystalline porous organo polysilica compound 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 organo polysilica compound framework material preparing 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 organo polysilica compound framework material provided by the invention has higher specific surface area, and contain a large amount of nitrogen-atoms, porous polymer material of the present invention can, 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.
Brief description of the drawings
Fig. 1 embodiment 1 imido grpup Porous-Organic polymer backbone material P-1 and monomer 1,3, the infrared spectrum of 5-tri-formyl radical benzene.
The carbon-13 nmr spectra figure of Fig. 2 embodiment 1 imido grpup Porous-Organic polymer backbone material P-1.
The thermogravimetric spectrogram of Fig. 3 embodiment 1 imido grpup Porous-Organic polymer backbone material P-1.
Powder χ-x ray diffration pattern x of Fig. 4 embodiment 1 imido grpup Porous-Organic polymer backbone material P-1.
The N of Fig. 5 embodiment 1 imido grpup Porous-Organic polymer backbone material P-1
2adsorption-desorption thermoisopleth.
Fig. 6 embodiment 1 imido grpup Porous-Organic polymer backbone material P-1 is according to the graph of pore diameter distribution of SF method.
Hydrogen adsorption curve at 196 DEG C of Fig. 7 imido grpup Porous-Organic polymer backbone material P-1 –.
Hydrogen adsorption curve at 186 DEG C of Fig. 8 imido grpup Porous-Organic polymer backbone material P-1 –.
Fig. 9 imido grpup Porous-Organic polymer backbone material P-1 is at 0 DEG C of carbon dioxide adsorption curve.
Figure 10 imido grpup Porous-Organic polymer backbone material P-1 is at 25 DEG C of carbon dioxide adsorption curves.
Figure 11 imido grpup Porous-Organic polymer backbone material P-1 methane adsorption curve at 0 DEG C.
Figure 12 imido grpup Porous-Organic polymer backbone material P-1 methane adsorption curve at 25 DEG C.
Figure 13 embodiment 9 imido grpup Porous-Organic polymer backbone material P-2 and monomers 1,3,5-trihydroxy--2, the infrared spectrum of 4,6-, tri-formyl radical benzene.
The carbon-13 nmr spectra figure of Figure 14 embodiment 9 imido grpup Porous-Organic polymer backbone material P-2.
The thermogravimetric spectrogram of Figure 15 embodiment 9 imido grpup Porous-Organic polymer backbone material P-2.
Powder χ-x ray diffration pattern x of Figure 16 embodiment 9 imido grpup Porous-Organic polymer backbone material P-2.
The N2 adsorption-desorption thermoisopleth of Figure 17 embodiment 9 imido grpup Porous-Organic polymer backbone material P-2.
Figure 18 embodiment 9 imido grpup Porous-Organic polymer backbone material P-2 are according to the graph of pore diameter distribution of SF method.
Hydrogen adsorption curve at 196 DEG C of Figure 19 imido grpup Porous-Organic polymer backbone material P-2 –.
Hydrogen adsorption curve at 186 DEG C of Figure 20 imido grpup Porous-Organic polymer backbone material P-2 –.
Figure 21 imido grpup Porous-Organic polymer backbone material P-2 is at 0 DEG C of carbon dioxide adsorption curve.
Figure 22 imido grpup Porous-Organic polymer backbone material P-2 is at 25 DEG C of carbon dioxide adsorption curves.
Figure 23 imido grpup Porous-Organic polymer backbone material P-2 methane adsorption curve at 0 DEG C.
Figure 24 imido grpup Porous-Organic polymer backbone material P-2 methane adsorption curve at 25 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-, tri-formyl radical benzene are dispersed in described mixing solutions, under nitrogen protection, in 120 DEG C of reactions 72 hours, filter, and wash respectively each 3 times 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 having the imido grpup Porous-Organic polymer backbone material P-1 of high-specific surface area and pore volume, productive rate 86%.
Reaction process is as follows:
Framework material P-1 is carried out to infrared spectra detection with infrared spectrometer (Avatar FT-IR 360).Fig. 1 is imido grpup Porous-Organic polymer backbone material P-1 and the reaction monomers 1,3 that adopts the inventive method to prepare, the infrared contrast spectrogram of 5-tri-formyl radical benzene; the infrared spectrum that in figure, solid line is 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.
Solid P-1 is carried out to solid-state nuclear magnetic resonance detection with nuclear magnetic resonance spectrometer (Bruker AVANCE III 400 WB), seen Fig. 2.Prove that at the nuclear-magnetism peak of 135ppm framework material P-1 has aromatic ring structure.
Solid P-1 is carried out to heat stability test with thermal gravimetric analyzer (TA Q500), seen Fig. 3.By heat weight research, polymer P-15% quality weightlessness, at 360 DEG C, shows that synthetic porous polymer framework material has good stability.
The crystallinity of solid P-1 is detected with powder x-ray diffraction, see Fig. 4.Locate sharp-pointed peak at 6.97 ° and derive from (100) face, show that polymer P-1 has the crystallinity of height.
With full-automatic specific surface area and lacunarity analysis instrument (JW-BK 132F) at 77K, 0～0.1MPa, carries out specific surface area and porosity detection to solid P-1, and the nitrogen adsorption recording is I-type thermoisopleth, as shown in Figure 5, for adopting the N of the porous polymer material that obtains of the inventive method
2xi Fu – desorption isotherm, real point is adsorption curve, ignore is desorption curve, passes through N
2xi Fu – desorption isotherm, the BET specific surface area that obtains porous polymer material reaches 1170m
2/ g.
As shown in Figure 6, the graph of pore diameter distribution that the porous polymer material obtaining for employing the inventive method calculates according to SF method, porous polymer material pore size distribution is in 0.7nm left and right.
By the porous polymer product obtaining at 87K and 77K, 0～0.1MPa, under record hydrogen adsorption thermoisopleth, as shown in Fig. 7 and Fig. 8, for adopting the adsorption isothermal line of low pressure gas storage hydrogen of the porous polymer framework material that obtains of the inventive method, Fig. 7 and Fig. 8 have provided the hydrogen adsorption thermoisopleth under differing temps, and hydrogen adsorption ability significantly increases with the reduction of temperature.
By the porous polymer product obtaining at 298K and 273K, 0～0.1MPa, under record carbonic acid gas adsorption isothermal line, as shown in Figures 9 and 10, for adopting the adsorption isothermal line that records carbonic acid gas under the low pressure of the porous polymer framework material that obtains of the inventive method, in Fig. 9 and Figure 10, provide the adsorption isothermal line of the carbonic acid gas under differing temps, in the time of 0.1MPa, 273K, reaching 17.7% according to weight percent absorbing carbon dioxide amount, is one of more excellent material of current carbon dioxide storage performance.
By the porous polymer product obtaining at 298K and 273K, 0～0.1MPa, under record methane adsorption isotherm, as shown in Figure 11 and Figure 12, for adopting the adsorption isothermal line that records methane under the low pressure of the porous polymer framework material that obtains of the inventive method, in Figure 11 and Figure 12, provide the adsorption isothermal line of the methane under differing temps, in the time of 0.1MPa, 273K, reached 1.15% according to weight percent adsorbed methane amount.
Embodiment 2
Replace dioxane with 0.0234mol trimethylbenzene, repeat embodiment 1, obtain having the imido grpup Porous-Organic polymer backbone material P-1 of high-specific surface area and pore volume, its performance characterization result is identical with embodiment 1.
Embodiment 3
Replace dioxane with 0.0234mol ethanol, repeat embodiment 1, obtain having the imido grpup Porous-Organic polymer backbone material P-1 of high-specific surface area and pore volume, its performance characterization result is identical with embodiment 1.
Embodiment 4
Replace dioxane with 0.0234mol tetrahydrofuran (THF), repeat embodiment 1, obtain having the imido grpup Porous-Organic polymer backbone material P-1 of high-specific surface area and pore volume, its performance characterization result is identical with embodiment 1.
Embodiment 5
The consumption of dioxane is become to 0.0168mol, repeat embodiment 1, the same imido grpup Porous-Organic polymer backbone material P-1 with high-specific surface area and pore volume that obtains, its performance characterization result is identical with embodiment 1.
Embodiment 6
The consumption of dioxane becomes 0.028mol, repeats embodiment 1, the same imido grpup Porous-Organic polymer backbone material P-1 with high-specific surface area and pore volume that obtains, 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, the same imido grpup Porous-Organic polymer backbone material P-1 with high-specific surface area and pore volume that obtains, 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, the same imido grpup Porous-Organic polymer backbone material P-1 with high-specific surface area and pore volume that obtains, 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-tri-formyl radical benzene are dispersed in described mixing solutions, under nitrogen protection, in 120 DEG C of reactions 72 hours, filter, wash respectively 3 times with methyl alcohol, tetrahydrofuran (THF), acetone, obtain pressed powder; By described pressed powder, 100 DEG C of vacuum-dryings 10 hours, vacuum tightness was less than 0.133Pa, obtained having the imido grpup Porous-Organic polymer backbone material P-2 of high-specific surface area and pore volume, productive rate 60%.Reaction process is as follows:
Framework material P-2 is carried out to infrared spectra detection with infrared spectrometer (Avatar FT-IR 360).If Figure 13 is imido grpup Porous-Organic polymer backbone material P-2 and the reaction monomers 1 that adopts the inventive method to prepare; 3; 5-trihydroxy--2; 4; the infrared contrast spectrogram of 6-tri-formyl radical benzene; the infrared spectrum that in figure, solid line is reaction monomers, 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, proves that polyreaction is complete, and polymkeric substance exists with keto-acid conformation.
Solid P-2 is carried out to solid-state nuclear magnetic resonance detection with nuclear magnetic resonance spectrometer (Bruker AVANCE III 400 WB), seen Figure 14.Prove that at the nuclear-magnetism peak of 181ppm framework material P-2 has ketone form structure.
Solid P-2 is carried out to heat stability test with thermal gravimetric analyzer (TA Q500), seen Figure 15.By heat weight research, polymer P-25% quality weightlessness, at 305 DEG C, shows that synthetic porous polymer framework material has good stability.
The crystallinity of solid P-2 is detected with powder x-ray diffraction, see Figure 16.Locate sharp-pointed peak at 6.97 ° and derive from (100) face, show that polymer P-2 have the crystallinity of height.
With full-automatic specific surface area and lacunarity analysis instrument (JW-BK 132F) at 77K, 0～0.1MPa, solid P-2 is carried out to specific surface area and porosity detection, the nitrogen adsorption recording is II-type thermoisopleth, as shown in figure 17, for adopting the N of the porous polymer material that obtains of the inventive method
2xi Fu – desorption isotherm, real point is adsorption curve, ignore is desorption curve, passes through N
2xi Fu – desorption isotherm, the BET specific surface area that obtains porous polymer material reaches 820m
2/ g.
As shown in figure 18, the graph of pore diameter distribution that the porous polymer material obtaining for employing the inventive method calculates according to SF method, porous polymer material pore size distribution is in 0.619nm left and right.
By the porous polymer product obtaining at 87K and 77K, 0～0.1MPa, under record hydrogen adsorption thermoisopleth, as shown in Figure 19 and Figure 20, for adopting the adsorption isothermal line of low pressure gas storage hydrogen of the porous polymer framework material that obtains of the inventive method, in Figure 19 and Figure 20, provided the hydrogen adsorption thermoisopleth under differing temps, hydrogen adsorption ability significantly increases with the reduction of temperature.
By the porous polymer product obtaining at 298K and 273K, 0～0.1MPa, under record carbonic acid gas adsorption isothermal line, as shown in Figure 21 and Figure 22, for adopting the adsorption isothermal line that records carbonic acid gas under the low pressure of the porous polymer framework material that obtains of the inventive method, in Figure 21 and Figure 22, provide the adsorption isothermal line of the carbonic acid gas under differing temps, in the time of 0.1MPa, 273K, reaching 21.2% according to weight percent absorbing carbon dioxide amount, is one of more excellent material of current carbon dioxide storage performance.
By the porous polymer product obtaining at 298K and 273K, 0～0.1MPa, under record methane adsorption isotherm, as shown in Figure 23 and Figure 24, for adopting the adsorption isothermal line that records methane under the low pressure of the porous polymer framework material that obtains of the inventive method, in Figure 23 and Figure 24, provide the adsorption isothermal line of the methane under differing temps, in the time of 0.1MPa, 273K, reached 3.97% 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 be 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 Porous-Organic polymer backbone material, its structural formula is:
Wherein n=2～500.
2. a preparation method for the imido grpup Porous-Organic polymer backbone material of claim 1, is characterized in that,
Organic solvent and Glacial acetic acid are dispersed in distilled water, form mixing solutions; Hydrazine hydrate and fragrant many aldehyde cpds 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 having the imido grpup porous organo polysilica compound framework material of high-specific surface area and pore volume; Wherein said organic solvent is dioxane, tetrahydrofuran (THF), 1，3，5-trimethyl-benzene or ethanol; Described many aldehyde of fragrance molecule is 1,3,5-, tri-formyl radical benzene or 1,3,5-trihydroxy--2,4,6-, tri-formyl radical 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 Porous-Organic polymer backbone material claimed in claim 2, is characterized in that, described organic solvent is dioxane.
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| CN105754588A (en) * | 2016-04-05 | 2016-07-13 | 吉林大学 | Light-emitting porous organic polymer material connected with imine and preparation method thereof |
| CN106693601A (en) * | 2015-11-12 | 2017-05-24 | 中国科学院大连化学物理研究所 | Method used for adsorbing iodine with covalent organic framework material |
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| US20140220477A1 (en) * | 2013-02-06 | 2014-08-07 | Avertica, Inc. | Polymers, substrates, methods for making such, and devices comprising the same |
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| US20140220477A1 (en) * | 2013-02-06 | 2014-08-07 | Avertica, Inc. | Polymers, substrates, methods for making such, and devices comprising the same |
| US20140220457A1 (en) * | 2013-02-06 | 2014-08-07 | Avertica, Inc. | Polymers, substrates, methods for making such, and devices comprising the same |
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| CN105754588A (en) * | 2016-04-05 | 2016-07-13 | 吉林大学 | Light-emitting porous organic polymer material connected with imine and preparation method thereof |
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| CN110364370A (en) * | 2019-06-19 | 2019-10-22 | 东华大学 | A kind of pyridyl group porous carbon material and its preparation method and application |
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| CN111689918A (en) * | 2020-04-30 | 2020-09-22 | 华南师范大学 | Functional diaphragm coating material for protecting lithium metal negative electrode and preparation method and application thereof |
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| CN114716630A (en) * | 2022-05-07 | 2022-07-08 | 陕西师范大学 | Forming covalent organic framework material and preparation method thereof |
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