CN103012705B - Preparation method and application of nitrogen-rich organic microporous polymer material - Google Patents

Preparation method and application of nitrogen-rich organic microporous polymer material Download PDF

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CN103012705B
CN103012705B CN201210546499.7A CN201210546499A CN103012705B CN 103012705 B CN103012705 B CN 103012705B CN 201210546499 A CN201210546499 A CN 201210546499A CN 103012705 B CN103012705 B CN 103012705B
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卜显和
宋伟朝
徐笑康
陈强
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Nankai University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention relates to a preparation method of a nitrogen-rich organic microporous polymer material, which comprises the following steps of: 1, under the protection of nitrogen, dissolving p-6,6'-bis(2,4-diamino-1,3,5-triazine)-based benzene and aromatic aldehyde into dimethyl sulfoxide, and stirring until solid is totally dissolved; and 2, under the nitrogen protection and under the stirring condition, performing reaction for 72 hours under the pressure of 433 to 458K, filtering, sequentially washing the obtained solid by dimethyl sulfoxide and dichloromethane, and sequentially and respectively carrying out extraction on the obtained gray white solid for 48 hours in a Soxhlet extractor by dichloromethane and tetrahydrofuran so as to obtain the powder organic microporous polymer material. The preparation method has the advantages that the nitrogen-rich organic microporous polymer material has strong adsorption property for hydrogen under normal pressure of 77K, has strong adsorption property for carbon dioxide under both normal pressures of 273K and 298K and can be widely applied as a hydrogen and carbon dioxide adsorption material.

Description

Preparation method and the application thereof of the organic capillary copolymer material of a kind of rich nitrogen
Technical field
The present invention relates to micropore organic polymer material, particularly preparation method and the application thereof of the organic capillary copolymer material of a kind of rich nitrogen.
Background technology
In recent years, the research that covalent linkage by between organic functions primitive is connected to the micropore organic polymer material being prepared into is very active, and has the trend developing in depth, and the system of various complex structures, function uniqueness is reported in succession, referring to: Dawson, R.; Cooper, A.I.; Adams, D.J.; Prog.Polym.Sci., 2012,37,530.Zhang, Y.; Riduan, S.N.; Chem.Soc.Rev., 2012,41,2083.With respect to traditional inorganic porous material and porous metal organic framework materials, this polyporous materials has good stability concurrently, specific surface is large, density is low, the tailorability of organic monomer and the feature such as modifiability is good, preparation feedback type is various, at present research concentrates on and environment and the closely bound up field of the energy, particularly its property is especially come into one's own as the research of fractionation by adsorption, gas storage energy storage, catalysis etc. and performance and structural relation, and provide the power of innovation and development for relevant type material research.But the bibliographical information with the capture ability of higher temperatures chamber gas and the micropore organic polymer material of hydrogen storage ability is also relative less, referring to: Katsoulidis, A.P.; Kanatzidis, M.G.Chem.Mater.2011,23,1818-1824.Rabbani, M.G.; El-Kadri, H.M.Chem.Mater.2012,24,1511-1517.Chen, Q.; Luo, M.
Figure BDA00002587308900011
p.; Zhou, D.; Han, Y.; Laursen, B.W.; Yan, C.-G.; Han, B.-H.J.Am.Chem.Soc.2012,134,6084-6087.Rabbani, M.G.; Reich, T.E.; Kassab, R.M.; Jackson, K.T.; El-Kaderi, H.M.Chem.Commun., 2012,48,1141 – 1143., the synthetic and exploration of this class material, particularly expand and the hole wall of modified polymer by the organic synthesis unit of rational design, and then provide new way for developing high performance novel material.
Summary of the invention
The object of the invention is to for above-mentioned existing problems, preparation and the application thereof of the organic capillary copolymer material of a kind of rich nitrogen are provided, this material has stronger absorption property to hydrogen under 77K condition of normal pressure, under 273K, 298K condition of normal pressure, carbonic acid gas is all had to stronger absorption property.
Technical scheme of the present invention:
A preparation for the organic capillary copolymer material of rich nitrogen, by p-6,6 '-bis-(2,4-diamino-1,3,5-triazines) base benzene and aromatic aldehyde carry out condensation reaction, and extract and remove small molecules and low-molecular(weight)polymer and obtain through Soxhlet, its preparation method comprises the steps:
1) under argon shield, p-6,6 '-bis-(2,4-diamino-1,3,5-triazines) base benzene and aromatic aldehyde are dissolved in methyl-sulphoxide, are stirred to solid and dissolve completely;
2) under argon shield agitation condition, react 72 hours in 433-458K; after filtration; wash successively after solid with methyl-sulphoxide and methylene dichloride; the pale solid obtaining is extracted 48 hours with methylene dichloride and tetrahydrofuran (THF) respectively successively in apparatus,Soxhlet's, obtain pulverous organic capillary copolymer material.
Described aromatic aldehyde is phenyl aldehyde, salicylic aldehyde, 4-hydroxy benzaldehyde, 2-fluorobenzaldehyde, 4-fluorobenzaldehyde or 9-anthracene aldehyde.
The mol ratio of described p-6,6 '-bis-(2,4-diamino-1,3,5-triazines) base benzene and aromatic aldehyde is 1:3-6.
An application for the prepared organic capillary copolymer material of rich nitrogen, with the sorbing material of doing hydrogen and carbonic acid gas.
Advantage of the present invention is: the organic capillary copolymer material of this richness nitrogen has stronger absorption property to hydrogen under 77K condition of normal pressure, under 273K, 298K condition of normal pressure, carbonic acid gas is all had to stronger absorption property, can be used as sorbing material and is used widely.
Brief description of the drawings
Fig. 1 is the hydrogen adsorption figure of organic capillary copolymer material of making of embodiment 1.
Fig. 2 is the carbonic acid gas absorption figure of organic capillary copolymer material of making of embodiment 1.
Embodiment
Embodiment 1:
A preparation for the organic capillary copolymer material of rich nitrogen, comprises the steps:
1) 4 mmole phenyl aldehydes are joined in the there-necked flask of 50 milliliters, under argon shield, add 1 mmole p-6,6 '-bis-(2,4-diaminostilbene, 3,5-triazine) base benzene, the dimethylsulfoxide solvent that then adds 25 milliliters of drying treatment to cross, is stirred to solid and dissolves completely;
2) under argon shield agitation condition, be heated to 453K reaction 72 hours; subsequent filtration falls solution; wash successively after solid with 5 milliliters of methyl-sulphoxides and 20 milliliters of methylene dichloride; the pale solid obtaining is extracted 48 hours with methylene dichloride and tetrahydrofuran (THF) respectively successively in apparatus,Soxhlet's, can make organic capillary copolymer material of pale powder shape.
The prepared organic capillary copolymer material of rich nitrogen, with the sorbing material of doing hydrogen and carbonic acid gas.
Fig. 1 is the hydrogen adsorption figure of the organic capillary copolymer material of rich nitrogen that makes, shows: the adsorptive capacity of hydrogen can reach 1.80wt% under 900mmHg and 77K in figure.
Fig. 2 is the carbonic acid gas absorption figure of organic capillary copolymer material of making, in figure, shows: the adsorptive capacity of carbonic acid gas can reach respectively 105 and 67.7cm under 900mmHg and 273K, 900mmHg and 298K 3g -1.
Embodiment 2:
A preparation for the organic capillary copolymer material of rich nitrogen, comprises the steps:
1) 4 mmole salicylic aldehydes are joined in the there-necked flask of 50 milliliters, under argon shield, add 1 mmole p-6,6 '-bis-(2,4-diaminostilbene, 3,5-triazine) base benzene, the dimethylsulfoxide solvent that then adds 25 milliliters of drying treatment to cross, is stirred to solid and dissolves completely;
2) under argon shield agitation condition, be heated to 453K reaction 72 hours; subsequent filtration falls solution; wash successively after solid with 5 milliliters of methyl-sulphoxides and 20 milliliters of methylene dichloride; the pale solid obtaining is extracted 48 hours with methylene dichloride and tetrahydrofuran (THF) respectively successively in apparatus,Soxhlet's, can make organic capillary copolymer material of pale powder shape.
Embodiment 3:
A preparation for the organic capillary copolymer material of rich nitrogen, comprises the steps:
1) 4 mmole 4-hydroxy benzaldehydes are joined in the there-necked flask of 50 milliliters, under argon shield, add 1 mmole p-6,6 '-bis-(2,4-diaminostilbene, 3,5-triazine) base benzene, the dimethylsulfoxide solvent that then adds 25 milliliters of drying treatment to cross, is stirred to solid and dissolves completely;
2) under argon shield agitation condition, be heated to 453K reaction 72 hours; subsequent filtration falls solution; wash successively after solid with 5 milliliters of methyl-sulphoxides and 20 milliliters of methylene dichloride; the pale solid obtaining is extracted 48 hours with methylene dichloride and tetrahydrofuran (THF) respectively successively in apparatus,Soxhlet's, can make organic capillary copolymer material of pale powder shape.
Embodiment 4:
A preparation for the organic capillary copolymer material of rich nitrogen, comprises the steps:
1) 4 milli 2-fluorobenzaldehydes are joined in the there-necked flask of 50 milliliters, under argon shield, add 1 mmole p-6,6 '-bis-(2,4-diaminostilbene, 3,5-triazine) base benzene, the dimethylsulfoxide solvent that then adds 25 milliliters of drying treatment to cross, is stirred to solid and dissolves completely;
2) under argon shield agitation condition, be heated to 453K reaction 72 hours; subsequent filtration falls solution; wash successively after solid with 5 milliliters of methyl-sulphoxides and 20 milliliters of methylene dichloride; the pale solid obtaining is extracted 48 hours with methylene dichloride and tetrahydrofuran (THF) respectively successively in apparatus,Soxhlet's, can make organic capillary copolymer material of pale powder shape.
Embodiment 5:
A preparation for the organic capillary copolymer material of rich nitrogen, comprises the steps:
1) 4 mmole 4-fluorobenzaldehydes are joined in the there-necked flask of 50 milliliters, under argon shield, add 1 mmole p-6,6 '-bis-(2,4-diaminostilbene, 3,5-triazine) base benzene, the dimethylsulfoxide solvent that then adds 25 milliliters of drying treatment to cross, is stirred to solid and dissolves completely;
2) under argon shield agitation condition, be heated to 453K reaction 72 hours; subsequent filtration falls solution; wash successively after solid with 5 milliliters of methyl-sulphoxides and 20 milliliters of methylene dichloride; the pale solid obtaining is extracted 48 hours with methylene dichloride and tetrahydrofuran (THF) respectively successively in apparatus,Soxhlet's, can make organic capillary copolymer material of pale powder shape.
Embodiment 6:
A preparation for the organic capillary copolymer material of rich nitrogen, comprises the steps:
1) 4 mmole 9-anthracene aldehyde are joined in the there-necked flask of 50 milliliters, under argon shield, add 1 mmole p-6,6 '-bis-(2,4-diaminostilbene, 3,5-triazine) base benzene, the dimethylsulfoxide solvent that then adds 25 milliliters of drying treatment to cross, is stirred to solid and dissolves completely;
2) under argon shield agitation condition, be heated to 453K reaction 72 hours; subsequent filtration falls solution; wash successively after solid with 5 milliliters of methyl-sulphoxides and 20 milliliters of methylene dichloride; the pale solid obtaining is extracted 48 hours with methylene dichloride and tetrahydrofuran (THF) respectively successively in apparatus,Soxhlet's, can make organic capillary copolymer material of pale powder shape.

Claims (4)

1. the preparation method of the organic capillary copolymer material of rich nitrogen, it is characterized in that: by [6,6 '-bis-(2,4-diaminostilbene, 3,5-triazine)] base benzene and aromatic aldehyde carry out condensation reaction, and extract and remove small molecules and low-molecular(weight)polymer and obtain through Soxhlet, its preparation method comprises the steps:
1) under argon shield, will be dissolved in methyl-sulphoxide [6,6 '-bis-(2,4-diamino-1,3,5-triazines)] base benzene and aromatic aldehyde, and be stirred to solid and dissolve completely;
2) under argon shield agitation condition, react 72 hours in 433-458K; after filtration; wash successively after solid with methyl-sulphoxide and methylene dichloride; the pale solid obtaining is extracted 48 hours with methylene dichloride and tetrahydrofuran (THF) respectively successively in apparatus,Soxhlet's, obtain pulverous organic capillary copolymer material.
2. the preparation method of the organic capillary copolymer material of rich nitrogen according to claim 1, is characterized in that: described aromatic aldehyde is phenyl aldehyde, salicylic aldehyde, 4-hydroxy benzaldehyde, 2-fluorobenzaldehyde, 4-fluorobenzaldehyde or 9-anthracene aldehyde.
3. the preparation method of the organic capillary copolymer material of rich nitrogen according to claim 1, is characterized in that: the described mol ratio to [6,6 '-bis-(2,4-diamino-1,3,5-triazines)] base benzene and aromatic aldehyde is 1:3-6.
4. an application for the organic capillary copolymer material of rich nitrogen as prepared in claim 1, is characterized in that: with the sorbing material of doing hydrogen and carbonic acid gas.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1044474A (en) * 1989-01-13 1990-08-08 阿克佐公司 Composition based on the low-temperature curable of the polyamino compound of compound that contains many aromatic aldehydes base and ketoimineization
EP1416005A1 (en) * 2002-10-31 2004-05-06 AMI Agrolinz Melamine International GmbH Aminotriazine copolymers with improved water solubility, their use and process for the preparation thereof

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JP2007169440A (en) * 2005-12-21 2007-07-05 Toyo Ink Mfg Co Ltd Method for producing fine thermosetting resin particle

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1044474A (en) * 1989-01-13 1990-08-08 阿克佐公司 Composition based on the low-temperature curable of the polyamino compound of compound that contains many aromatic aldehydes base and ketoimineization
EP1416005A1 (en) * 2002-10-31 2004-05-06 AMI Agrolinz Melamine International GmbH Aminotriazine copolymers with improved water solubility, their use and process for the preparation thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP特开2007-169440A 2007.07.05

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