CN102477146B - Organic porous material and preparation method thereof - Google Patents
Organic porous material and preparation method thereof Download PDFInfo
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- CN102477146B CN102477146B CN201010562462.4A CN201010562462A CN102477146B CN 102477146 B CN102477146 B CN 102477146B CN 201010562462 A CN201010562462 A CN 201010562462A CN 102477146 B CN102477146 B CN 102477146B
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Abstract
The invention discloses an organic porous material. According to the material, rigid tetraphenyl germanium with a tetrahedron structure is adopted as a primitive for constructing the porous material, the material of the present invention has diamond structure units, has characteristics of high specific surface area and excellent photoelectric performance, and has good application prospects in fields of catalysis, optics, electricity, separation and the like. The invention further discloses a method for preparing the organic porous material.
Description
Technical field
The present invention relates to field of functional materials, high-specific surface area organic porous material particularly with photoelectric properties and preparation method thereof.
Background technology
Along with the high speed development of China's industry, exploitation and the research of advanced function material are paid attention to widely, and its function and significance is self-evident.In the middle of the various material be constantly developed and apply, porous material enjoys the concern of whole world researcher due to the skeleton structure of its spaciousness always, and in ion-exchange, adsorb and be all widely used with fields such as host-guest chemistries with being separated.Originally, porous material research has specific pore passage structure material for what constructed by inorganic species.This comprises the poromerics that aperture is less than 2nm, and aperture is greater than the large pore material of 50nm at the mesoporous material of 2 to 50nm and aperture.In recent years, the metal-organic framework compound MOFs (metal-organic-frameworks) with periodic network structure that organic ligand and metal are formed by self assembling process causes people's interest widely.It typically refers to the metal-organic framework crystalline material with periodic network structure that organic ligand and metal are formed by self assembling process.On the one hand because it has advantage not available for a large amount of conventional molecular sieve, as uncommon geometries, gentleer synthesis condition and the potential controllability to hole size and size; On the other hand because it has the feature such as unique, structure diversification, uncommon optical, electrical, magnetic effect.Therefore, metal-organic framework compound has huge application potential in many-sides such as absorption, catalysis, optics, electricity and magnetics.In addition, the hole characteristic of metal-organic framework compound also combines with several functions such as optical, electrical, magnetic by investigator, designs the compound molecular material with two or more function of some novelties.But the MOFs obtained is after removal guest molecule, its ordered structure is just destroyed thereupon, therefore MOFs stability also needs to improve, in addition because constructing of MOF structure needs metallic element to participate in usually, this adds increased the proportion of material itself, and this using become its as gas storage or liquid absorption material application critical defect.2005, O.M.Yaghi reported the organic backbone porous material COFs (covalent organic frameworks) connected by covalent linkage constructed by light element (carbon, hydrogen, oxygen, boron).These organic porous polymer materials possess MOF porous controlled, adjustable just, comparatively MOFs can be modified outside advantage stablize, and there is larger specific surface area, less density, simultaneously can by the chemical property regulating reaction monomers to control porous material, make it in catalysis, optics, electricity, there is good application prospect the aspects such as separation.
But the performance of organic porous polymer material still needs to be further improved.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of high-specific surface area organic porous material with photoelectric properties.
For solving the problems of the technologies described above, technical scheme provided by the invention is: organic porous material, for having the poly-four benzene germanium of formula [1] structural unit.
Organic porous material of the present invention is to have the primitive of four benzene germanium as structure porous material of tetrahedral structure and rigidity, there is the diamond lattic structure unit shown in Fig. 1, can be regarded as and by biphenyl, the germanium atom of diamond topology node is connected, there are high-specific surface area and excellent photoelectric properties, in catalysis, optics, electricity, there is good application prospect the aspects such as separation.
Another technical problem that the present invention will solve is to provide one and prepares above-mentioned organic porous material method.
For solving the problems of the technologies described above, technical scheme provided by the invention is the method for preparing organic porous material described in claim 1, carry out Yamamoto type Liv Ullmann (Yamamoto Type Ullmann) linked reaction by reaction monomers to obtain, wherein, the general formula of described reaction monomers is as follows:
Wherein:
X is Cl, Br, I;
R is:
The position that indicates of numeral 1 ~ 10 for C, N, CH or H by methyl, ethyl, amido, carboxyl, methoxyl group, hydroxyl or ester group the CH that replaces; The position of letter represented by a, b is C, N
+or B
-.
The present invention, by Yamamoto type Liv Ullmann (Yamamoto type Ullmann reaction) linked reaction, makes reaction monomers self-polymerization that have tetrahedral structure, that have above-mentioned general formula prepare the high-specific surface area organic porous material with photoelectric properties.Wherein, the preparation method with the reaction monomers of the above-mentioned general formula of tetrahedral structure is known, illustrate, can according to Joseph B.Lambert, * Zhongqiang Liu and ChunqingLiu at " Metal-Organic Frameworks from Silicon-andGermanium-Centered Tetrahedral Ligands " (J.B.Lambert, Z.Liu, C.Liu, Organometallics, 2008,27,1464-1469.) disclosed in method obtain.
The present invention to prepare in the method for organic porous material preferred reaction monomers to be R in general formula be:
illustrate: reaction monomers can be four (X-halogeno-benzene) germanium, four (X-naphthalene halide) germanium, four (X-haloperidid) germanium or four (X-halogenated biphenyl) germanium, the corresponding organic porous material generated is respectively poly-four (X-benzene) germanium, poly-four (X-naphthalene) germanium, poly-four (X-pyridine) germanium or poly-four (X-biphenyl) germanium.Preferred again, reaction monomers can be to bromine four benzene germanium or to iodine four benzene germanium.The organic porous material performance selecting these reaction monomers obtained is comparatively excellent, and comparatively easily obtains because of it, and cost also has superiority.
Preferred technical scheme is that the method preparing organic porous material comprises the steps:
Step 1: catalyzer and catalyst ligand are joined in anhydrous aprotic organic solvent, then they are placed in the oil bath being preheating to 20 ~ 140 DEG C, make catalyst aging 0.5 ~ 3 hour, wherein catalyzer is selected from zero-valent nickel organic coordination compound or nickelous organic coordination compound; Catalyst ligand is 2, the mixture of any one or they in 2 '-dipyridyl, 1,5-cyclooctadiene; Catalyzer is (0.2 ~ 1.5) with the ratio of the amount of substance of catalyst ligand: 1;
Step 2: the solution adding the aprotic organic solvent of reaction monomers in the product of described step 1, when making reaction initial, the concentration of reaction monomers remains between 0.001M ~ 5M, and the ratio of the amount of substance of catalyzer and reaction monomers is (4-12): 1;
Step 3: solution step 2 obtained remains on 20 ~ 140 DEG C, reacts 10 minutes to 120 hours, stopped reaction;
Step 4, adds concentrated acid, destroys remaining catalyzer, and filtered out by the fluffy solid of precipitation in the product that step 3 obtains;
Step 5, use the product of the hot solution washing step 4 of water, methyl alcohol (or acetone) and chloroform respectively, but the organism removing inorganic salt and can dissolve, the product obtained, 80 ~ 200 DEG C of vacuum-dryings 4 ~ 40 hours, obtains the polymkeric substance with repeating unit shown in formula [1].
Aforesaid method prepares organic porous material by the polycondensation of organo-metallic nickel catalysis, and yield is higher, substantially can reach more than 90%.
In the present invention, aprotic organic solvent can be any in DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, benzene or toluene.The boiling point of these aprotic organic solvents is higher, all higher than temperature of reaction of the present invention.In addition, these aprotic organic solvents are good to the solvability of reaction monomers of the present invention.Further, at the reaction temperatures, reaction monomers of the present invention is more stable in these aprotic organic solvents, and the side reaction outside Yamamoto type Ullmann reaction can not occur usually.
In the present invention, catalyzer can be zero-valent nickel organic coordination compound or nickelous organic coordination compound.Citing, zero-valent nickel complexes can be four (triphenyl phosphorus) nickel, two (1,5-cyclooctadiene) nickel, and nickelous organic coordination compound can be two (triphenyl phosphorus) nickelous chloride, two (triphenyl phosphorus) nickelous bromide.Preferred catalyzer is two (1,5-cyclooctadiene) nickel, and it not only can improve reaction efficiency, and in price more dominant.In the step 1 of aforesaid method, catalyzer preferred concentration range in aprotic organic solvent can be: 0.005M-20M.
In the present invention, catalyst ligand can be 1,5-cyclooctadiene, 2,2 '-dipyridyl or triphenyl phosphorus or their mixtures of any two kinds.Preferably, catalyst ligand is 1,5-cyclooctadiene and 2,2 '-dipyridyl or their mixture, and wherein, 1,5-cyclooctadiene is double bond and nickel coordination, 2, and 2 '-dipyridyl is atom N and nickel coordination, and the two all effectively can promote the polycondensation of monomer.Preferred, catalyst ligand is the mixture of 1,5-cyclooctadiene and 2,2 '-dipyridyl, and when 1,5-cyclooctadiene and 2, when 2 '-dipyridyl all exists, polymerization yield rate is higher.Also preferred, when 1,5-cyclooctadiene and 2, when 2 '-dipyridyl exists simultaneously, 1,5-cyclooctadiene and 2, the ratio of the amount of substance of 2 '-dipyridyl, catalyzer is 1: (0.8 ~ 1.3): (1 ~ 1.5), and polymerization yield rate can reach the highest, substantially can reach 100%.
Preferably, can being obtained by path reaction formula [1] Suo Shi of organic porous material of the present invention, comprises the following steps:
Step 1, by 1,5-cyclooctadiene, 2,2-dipyridyls and two 1,5-cyclooctadiene nickel joins N, in dinethylformamide or toluene solution, inserted in the oil bath being preheating to 20 DEG C-140 DEG C, made catalyst aging 0.5-3 hour, wherein, 1,5-cyclooctadiene and 2, the ratio of the amount of substance of 2 '-dipyridyl, catalyzer is 1: (0.8 ~ 1.3): (1 ~ 1.5);
Step 2, add corresponding mole number to bromine four benzene germanium or the N to iodine four benzene germanium, dinethylformamide or toluene solution, make to bromine four benzene germanium or to iodine four benzene germanium concentration remain between 0.001M-5M, ensure two 1,5-cyclooctadiene nickel simultaneously and be (4-12) to bromine four benzene germanium or to the ratio of the amount of substance of iodine four benzene germanium: 1;
Step 3, keeps the temperature identical with step 1 by above-mentioned solution, reacts 10 minutes to 5 days, stopped reaction;
Step 4, adds concentrated hydrochloric acid in reaction system, destroys remaining two 1,5-cyclooctadiene nickel, and is filtered out by the fluffy solid of precipitation;
Step 5, use the organism that the hot solution eccysis of water, methyl alcohol (or acetone) and chloroform is removed inorganic salt and can be dissolved respectively, final product, 80 ~ 200 DEG C of vacuum-dryings 4 ~ 40 hours, obtains polymkeric substance: poly-four benzene germanium.
Preferably, step 5 can also comprise the steps:
Step 5.1, each with 10-100 milliliter 50-100 DEG C of water treatment 3-5 time, filter;
Step 5.2, processes 3-5 time with 10-100 milliliter 20-70 DEG C of methyl alcohol (or acetone) at every turn, filters;
Step 5.3, each with 10-100 milliliter 20-60 DEG C of chloroform process 3-5 time, filter;
Step 5.4, under 80-200 DEG C of condition, vacuumize process 4-40 hour by common oil pump, vacuum tightness is less than 10-3mmHg, obtains polymkeric substance.
Reaction formula [I] is as follows, and wherein X is bromine or iodine, n be more than or equal to 2 integer.
Reaction formula [1]
Accompanying drawing explanation
Figure 1A is the porous material structural unit schematic diagram with diamond topological framework;
Figure 1B is the diamond lattic structure cell schematics of organic porous material of the present invention;
Fig. 2 A, 2B are the organic porous material of the embodiment of the present invention 1 synthesis and the infrared contrast spectrogram of reaction monomers;
Fig. 3 is the thermogravimetric spectrogram of the embodiment of the present invention 1 organic porous material under dry air;
Fig. 4 is XRD spectra and the simulation XRD contrast figure of the measuring of the embodiment of the present invention 1 organic porous material;
Fig. 5 is the embodiment of the present invention 1 organic porous material
13c solid state nmr spectrogram;
Fig. 6 is the transmission electron microscope picture of the embodiment of the present invention 1 organic porous material;
Fig. 7 is the scanning electron microscope (SEM) photograph of the embodiment of the present invention 1 organic porous material;
Fig. 8 is the N of the embodiment of the present invention 1 organic porous material
2adsorption-desorption isothermal.
Fig. 9 is the graph of pore diameter distribution of the embodiment of the present invention 1 organic porous material according to DFT method;
Figure 10 is the fluorescence excitation-emission spectrogram of the embodiment of the present invention 1 organic porous material;
Figure 11 is the fluorescence photo of the embodiment of the present invention 1 organic porous material;
Figure 12 is the I-V curve of the embodiment of the present invention 1 organic porous material.
Figure 13 is the electric current on-off curve of the embodiment of the present invention 1 organic porous material.
Embodiment
For further setting forth the technique means and decorative effect thereof that the present invention takes, be described in detail below in conjunction with the preferred embodiments of the present invention and accompanying drawing thereof.But each preferred embodiment and accompanying drawing are not limitation of the present invention.
Embodiment 1
By the poly-four benzene germanium of following steps preparation:
(1) by two for 0.758g 1,5-cyclooctadiene nickel, 0.215g 2,2-dipyridyl and 0.2mL 1,5-cyclooctadiene join in the DMF solution of 5mL, are inserted in the oil bath being preheated to 80 DEG C, make catalyst aging 0.5-3 hour;
(2) adding the DMF solution to bromine four benzene germanium subsequently, make the DMF cumulative volume in system be 29mL, is 0.1M to the concentration of bromine four benzene germanium;
(3) step (2) gained solution is reacted 60 hours at 80 DEG C of temperature, stopped reaction;
(4) in reaction system, add 12mol/L concentrated hydrochloric acid 35mL, destroy 1,5-excessive cyclooctadiene nickel, filter and obtain faint yellow flocculent precipitate;
(5) respectively with the hot solution washing of 100mL water, 100mL methyl alcohol and 100mL chloroform, removing inorganic salt and the organism that can dissolve, final product is in 10 ~ 40 hours (vacuum tightness is less than 10-3mmHg) of 80 ~ 200 DEG C of vacuum-dryings, obtain polymer poly four benzene germanium, productive rate is 96%.
Fig. 2 A, 2B are the infrared contrast spectrogram of the organic porous material that synthesizes of the present invention and reaction monomers, and wherein Fig. 2 A is the organic porous material of preparation and the 4000cm of reaction monomers
-1to 400cm
-1the full spectrogram of infrared contrast, Fig. 2 B is the organic porous material of preparation and the 2000cm of reaction monomers
-1to 400cm
-1spectrogram is amplified in infrared contrast.The infrared spectrum that figure center line 1 (line above) is reaction monomers, line 2 (line below) is the infrared spectrum of the organic porous material of preparation, amplifies the 484cm marked in infrared spectrum
-1for C-Br charateristic avsorption band, after polyreaction, the C-Br charateristic avsorption band of correspondence position obviously disappears, and proves that polyreaction is very thorough.Measurement uses Shimadzu Corporation IRAffinity-1 Fu Li leaf transform infrared spectroscopy.
Fig. 3 is the thermal multigraph of organic porous material of the present invention, and by heat weight research, polymkeric substance 5% quality in dry air is weightless at 443 DEG C, shows that the organic porous material synthesized has good stability.Surveyed the thermogravimetric curve of product by Shimadzu DTG-60 differential thermal-thermogravimetric analyzer, heat-up rate is 10 DEG C/min, and crucible is aluminum oxide, and atmosphere is dry air.
Fig. 4 is experiment XRD (line 1) and simulation XRD (line 2) of the mensuration of organic porous material of the present invention, it is the X-ray diffraction spectrogram of the powder being surveyed product by Riguku D/MAX2550X x ray diffractometer x, copper target, test condition is 40.0kV, 200mA, sweep velocity 0.3 °/minute (2 θ), main peak position in experiment XRD spectra (line 1) is coincide with the peak position in simulation XRD spectra (line 2), illustrates that product structure of the present invention is consistent with project organization.
Fig. 5 is organic porous material of the present invention
13c solid state nmr spectrogram.Corresponding embodiment 1: have four peaks in this spectrogram, four kinds of carbon respectively in corresponding polymer network structure on phenyl ring.The experiment of this nuclear-magnetism uses Varian Infinity-plus 400 nuclear magnetic resonance spectrometer, and magneticstrength is 9.4T.The resonant frequency pair in this magnetic field
13c is 100.6MHz.For
1h-
13the experiment of C CP/MAS nuclear-magnetism uses hexamethyl-benzene (HMB) to reach Hartmann-Hahn condition, and the time of response is 4.0 milliseconds, 2.0 seconds repetition times.Chemical shift in spectrogram is all the value relative to HMB.CP-
13on C-NMR spectrogram, peak is from left to right corresponding in turn to the signal of 1,2,3,4 these four kinds of carbon in the structure of the upper left corner.
Fig. 6 is the transmission electron microscope picture of organic porous material of the present invention.System by a small amount of sample dispersion of organic porous material of the present invention in ethanol, drips on the copper mesh of porous carbon covering.With 200kV JEM-2100F transmissioning electric mirror test, and by High Resolution G atan Ultrascan100CCD cameras record transmission electron microscope picture.Clearly can be observed the pore structure of the organic porous material of synthesis by the transmission plot of Fig. 6, but not have sequence structure.
Fig. 7 is the scanning electron microscope (SEM) photograph of organic porous material of the present invention.Be by by a small amount of sample dispersion of organic porous material of the present invention in ethanol, drip on silicon chip, obtain with JEOSJSM 6700 sem test.Can find out in the product obtained only have homogeneous globular solids one phase by the scanning electron microscope (SEM) photograph of Fig. 7, product process is very thorough, and purity is very high.
Fig. 8 be by organic porous material of the present invention at 77K, record nitrogen adsorption-desorption isotherm under 0 ~ 1atm, wherein real point is adsorption curve, and ignore is desorption curve, passes through N
2adsorption-desorption isothermal, the BET specific surface area obtaining organic porous material reaches 2246m
2/ g.
Fig. 9 is the graph of pore diameter distribution that organic porous material of the present invention calculates according to DFT method, and organic porous material pore size distribution is at about 1.2nm.
Figure 10 is the fluorescent emission spectrogram of organic porous material of the present invention.First by sample dispersion in ethanol, sample preparation, in black back end, obtains fluorescent emission spectrogram at 25 DEG C with JASCO model FPLS55.Very narrow fluorescence excitation and emission spectrum peak illustrate that the form of energy transmitted in this kind of material molecule is unique, and the special construction of this kind of material effectively prevents between phenyl ring due to fluorescent quenching that pi-pi accumulation causes.
Figure 11 is the fluorescence photo of organic porous material OlympusBX51 fluorescent microscope of the present invention shooting.Figure 11 illustrates this material blue light-emitting under laser radiation, is a kind of blue light material.
Figure 12 is the I-V curve adopting sample after organic porous material of the present invention and I2 doping thereof, and its center line 1 be blank, and line 2 (blue line) is polymkeric substance I-V curve, and line 3 (red line) is the I-V curve of iodine post-consumer polymer of adulterating.Figure 12 illustrates that this material itself has electroconductibility, and after doping iodine, electroconductibility increases, and illustrates that this material is P-type semiconductor material.
Figure 13 is the current switch curve adopting organic porous material of the present invention.Give 5V voltage to material discontinuity, the electric current of polymkeric substance does not have considerable change.Multiple switching, material conductivity is without obvious decay, and illustrative material conductive stable, favorable repeatability, illustrates that it has excellent electric property.The electrical properties of its excellence has potential using value by making it at photoelectric field.
Above data acknowledgement the present invention has successfully prepared the poly-four benzene germanium of target product, it has photoelectric properties, high thermal stability (443 DEG C can be reached), excellent pore passage structure (there is the 3 D pore canal that diameter is about 1.2nm), porous material after activation, has larger specific surface area (BET specific surface area 2246m
2/ g).This has photoelectric properties and high stability, high-ratio surface material, can have a wide range of applications at photoelectric field.
Embodiment 2:
The present embodiment is substantially the same manner as Example 1, and difference is the mixing solutions in embodiment 1 step (1) to move in stainless-steel vacuum reactor, and temperature of reaction changes into 80 DEG C, and other conditions are constant, obtains the material identical with example 1.
Embodiment 3:
The present embodiment is substantially the same manner as Example 1, and difference is that the reaction monomers in embodiment 1 step (2) being changed is that other conditions are constant, obtain the material identical with example 1, and productive rate is 90% to iodine four benzene germanium.
Embodiment 4:
Reaction soln in embodiment 1 step (1) is become toluene by the present embodiment and embodiment 1, and other conditions are constant, obtains the material identical with described in example 1.
Embodiment 5:
Method is as embodiment 1, and digestion time is extended for 10 hours, other are constant, obtains the material identical with embodiment 1.Productive rate: 93.0%.
Embodiment 6:
The present embodiment is substantially the same manner as Example 1, difference to be in step (1) two 1,5-cyclooctadiene nickel, 2,2-dipyridyls and, the ratio of the amount of substance of 1,5-cyclooctadiene is 1: 1: 1, other are constant, obtain the material identical with embodiment 1.
Embodiment 7:
The present embodiment is substantially the same manner as Example 1, and difference is that the temperature in step (1) and step 3 all controls at 100 DEG C, and other are constant, obtain the material identical with embodiment 1.
Embodiment 8:
The present embodiment is substantially the same manner as Example 1, and difference is that the temperature in step (1) and step 3 all controls at 60 DEG C, and other are constant, obtain the material identical with embodiment 1.
Specific form based on the present invention's spirit or principal character is not limited in above-described embodiment, when describing of the present invention with reference to some preferred embodiments, persons skilled in the art will recognize that: do not departing under spiritual principles of the present invention, various different amendment, change, omission and replacement may be made, also can there be multiple combination or change, as: the concentration changing catalyzer and reaction monomers, change the proportion relation of reaction monomers, catalyzer and catalyst ligand, like this etc., these change acquired by effect be identical with above embodiment.Therefore, no matter from which point, above-mentioned embodiment of the present invention all can only be thought explanation of the present invention and can not limit the present invention, any change in the implication suitable with claims of the present invention and scope, all should think to be included in the scope of claims.
Claims (6)
1. organic porous material, is characterized in that: described organic porous material is for having the poly-four benzene germanium of formula [1] structural unit:
2. organic porous material according to claim 1, is characterized in that:
The BET of described organic porous material amasss as 2600-2000 meters squared per gram than table.
3. prepare the method for organic porous material described in claim 1, it is characterized in that: described organic porous material carries out Yamamoto type Liv Ullmann linked reaction by reaction monomers to obtain, and wherein, the general formula of described reaction monomers is as follows:
Wherein:
X is Cl, Br, I;
R is:
4. the method preparing organic porous material according to claim 3, is characterized in that: comprise the steps:
Step 1: catalyzer and catalyst ligand are joined in anhydrous aprotic organic solvent, then the mixture of described catalyzer, described catalyst ligand and described anhydrous aprotic organic solvent is placed in the oil bath being preheating to 20 ~ 140 DEG C, make described catalyst aging 0.5 ~ 3 hour, wherein said catalyzer is selected from zero-valent nickel organic coordination compound or nickelous organic coordination compound; Described catalyst ligand is selected from 2, the mixture of any one or they of 2 '-dipyridyl, 1,5-cyclooctadiene or triphenyl phosphorus; Described catalyzer is (0.2 ~ 1.5) with the ratio of the amount of substance of described catalyst ligand: 1;
Step 2: the solution adding the aprotic organic solvent of described reaction monomers in the product of described step 1, when making reaction initial, the concentration of described reaction monomers remains between 0.001M ~ 5M, and the ratio of the amount of substance of described catalyzer and described reaction monomers is (4-12): 1;
Step 3: the solution that described step 2 obtains is remained on 20 ~ 140 DEG C, reacts 10 minutes to 120 hours, stopped reaction;
Step 4, adds concentrated acid, destroys remaining catalyzer, and filtered out by the fluffy solid of precipitation in the product that described step 3 obtains;
Step 5, the product of described step 4 is washed respectively by the hot solution of water, methyl alcohol or acetone and chloroform, the organism removed inorganic salt and can dissolve, the product obtained, 80 ~ 200 DEG C of vacuum-dryings 4 ~ 40 hours, obtains the polymkeric substance with the repeating unit shown in formula [1].
5. the method preparing organic porous material according to claim 4, is characterized in that:
Described aprotic organic solvent be selected from DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, benzene or toluene any one.
6. the method preparing organic porous material according to claim 4, is characterized in that:
Described catalyst ligand is the mixture of 1,5-cyclooctadiene and 2,2 '-dipyridyl, 1,5-cyclooctadiene and 2, and the ratio of the amount of substance of 2 '-dipyridyl, described catalyzer is 1: (0.8 ~ 1.3): (1 ~ 1.5).
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| C. A. Terraza,et al."Synthesis and characterization of poly(urethanes) containing sulfone and silarylene or germarylene moieties".《Polym. Bull.》.2009,第63卷第663–672页. * |
| Frederic Lerouge,et al."Hydrophobic induced supramolecular self-organization of tetrahedral units based on van der Waals interactions".《Journal of Materials Chemistry》.2005,第16卷第90-95页. * |
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