CN111607069B - Conjugated microporous organic polymer based on spiro [3.3] heptane-2, 6-spirofluorene and preparation thereof - Google Patents
Conjugated microporous organic polymer based on spiro [3.3] heptane-2, 6-spirofluorene and preparation thereof Download PDFInfo
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Abstract
The invention discloses a spiro [3,3] based structural formula shown in formula (I)]The conjugated microporous organic heptane-2, 6-spirofluorene polymer is spiro [3.3]]Heptane-2, 6-di- (2 ', 2 ', 7 ' -tetrabromo) spirofluorene is used as a first construction monomer, and is respectively prepared by SuZuki coupling reaction or Sonogashira cross-coupling reaction with a second construction monomer with different connecting bonds. The repeating unit of the conjugated microporous organic polymer has three distorted spiro atom centers, so that the polymer chain can be effectively prevented from being stacked, the synthesis of the conjugated microporous organic polymer can be better realized, the pore size of the polymer is regulated and controlled by changing the second construction monomer, the polymer has permanent holes, the stability is good, and the conjugated microporous organic polymer can be used as a light-emitting layer material of an organic electroluminescent device.
Description
Technical Field
The invention belongs to the technical field of porous organic polymer preparation, and relates to a spiro [3.3] heptane-2, 6-spirofluorene-based conjugated microporous organic polymer and a preparation method thereof.
Background
Microporous Organic Polymers (MOPs) are a new class of porous materials interconnected by light elements (C, H, O, N, B, etc.) through covalent bonds.
MOPs have the unique properties of high specific surface area, low framework density, high porosity, and the like. Meanwhile, most of MOPs have good stability under severe conditions such as acid-base, solvent, moisture, high temperature and the like. In addition, the MOPs can regulate and control the structure, the size and the functionalization of micropores by selecting reaction monomers with different functional groups and different synthesis means.
Currently, MOPs mainly include four types, namely Polymers with micropores (PIMs), hypercrosslinked Polymers (HCPs), Covalent Organic networks (COFs) and Conjugated Microporous Polymers (CMPs), and are widely applied to the fields of adsorption, separation, photoelectron, heterogeneous catalysis, gas storage and the like.
Among them, the Conjugated Microporous Polymers (CMPs) have excellent physical and chemical properties, and have the advantages of high porosity, large specific surface area, permanent pore channels, and the like. The synthesis of CMPs is diverse, and CMPs with specific functions can be formed and applied to different fields by changing the synthesis strategy, selecting building elements with different functional groups and changing the reaction conditions.
Firstly, CMPs are beneficial to introducing unique optical, electrical and other properties into a porous organic framework, and have good application prospects in the aspects of electrons and electroluminescence. The polymer has an open pore channel, so that the transfer of holes and electrons in the material is facilitated, and the integral skeleton of the polymer has a conjugated structure, so that photoelectrons can be effectively captured and efficiently transmitted in the skeleton, and the polymer is convenient to act with guest molecules doped in the pore channel.
Secondly, CMPs have potential applications in gas adsorption and storage. Currently, the problems of continuous consumption and exhaustion of fossil fuels and global warming caused by greenhouse gas emission in the world are serious, so that the sustainable energy source is urgently needed to be searched. H2The byproduct of energy combustion is only water, is green and environment-friendly, and is undeniably a perfect energy source, namely H2By storing H by physical reversible adsorption using materials having a high specific surface area2。CO2Is the main greenhouse gas, produces over 60% of the temperatureChamber effect, capture of CO by adsorptive separation using porous materials with high specific surface area2It is considered to be one of the more promising technologies.
Thirdly, the application of CMPs in the field of heterogeneous catalysis has also been recently reported. Jiang et al report that a CMPs type ferriporphyrin network FeP-CMPs with high specific surface area is prepared by Suzuki-Miyaura coupling reaction of an iron (III) derivative and p-phenylboronic acid (PDBA), and O is used for preparing the FeP-CMPs2When the catalyst is an oxidant, FeP-CMP has good catalytic activity and selectivity for the reaction of oxidizing sulfide into sulfone.
Given the unique advantages of CMPs, it has attracted considerable attention from researchers. However, most of the currently studied CMPs have a substantially planar structure, and have a strong coplanarity, and are likely to cause interchain aggregation. The CMPs with the three-dimensional structure can effectively prevent polymer chains from being accumulated, and can increase pore channels beneficial to electron transmission in the synthesis process, so that the carrier mobility of the polymer is improved, and excellent application prospects are shown in the fields of organic photoelectricity, lithium batteries and the like.
Disclosure of Invention
The invention aims to provide a conjugated microporous organic polymer based on spiro [3,3] heptane-2, 6-spirofluorene and having a three-dimensional twisted structure.
It is another object of the present invention to provide a method for preparing the conjugated microporous organic polymer.
The spiro [3,3] heptane-2, 6-spirofluorene-based conjugated microporous organic polymer has a structural formula shown in the formula (I).
Wherein the linking group R is any one of the following first group and second group.
A first group:
、
、
、
、
、
。
second group:
、
、
、
。
furthermore, the invention also provides a preparation method of the conjugated microporous organic polymer based on spiro [3,3] heptane-2, 6-spirofluorene. The invention selects the first group or the second group according to the connecting group R and adopts different preparation methods.
When the connecting group R is a first group, spiro [3.3] heptane-2, 6-bis- (2 ', 2 ', 7 ' -tetrabromo) spirofluorene (TBrSDF) is used as a first building monomer, and the first building monomer and a second building monomer with a structural formula shown in a formula (II) are subjected to SuZuki coupling reaction in the presence of a catalyst of tetrakis (triphenylphosphine) palladium and a phase transfer catalyst of methyl trioctyl ammonium chloride to prepare the conjugated microporous organic polymer with the structural formula shown in the formula (I).
Specifically, the SuZuki coupling reaction is carried out by heating to 60-120 ℃ in toluene solvent containing potassium carbonate under the protection of inert gas for reflux reaction.
More specifically, the reflux reaction time is preferably 36-96 h.
Furthermore, according to the invention, 10-100 mL of solvent toluene and 2mol/L of potassium carbonate solution with the volume of 30-100% of toluene are preferably added according to each gram of monomer.
In the preparation method, the addition amount of the catalyst tetrakis (triphenylphosphine) palladium is preferably 1-5% of the molar amount of the structural monomer reaction functional group.
In the preparation method, the addition amount of the phase transfer catalyst methyl trioctyl ammonium chloride is preferably 1-5% of the molar amount of the structural monomer reaction functional group.
When the connecting group R is selected from a second group of groups, spiro [3.3] heptane-2, 6-bis- (2 ', 2 ', 7 ' -tetrabromo) spirofluorene (TBrSDF) is used as a construction monomer, and in the presence of a catalyst of tetrakis (triphenylphosphine) palladium and cuprous iodide, the construction monomer and a second construction monomer with two terminal alkynyl groups are subjected to Sonogashira cross coupling reaction to prepare the conjugated microporous organic polymer with the structural formula shown in the formula (I).
Specifically, the second building monomer having two terminal alkynyl groups may be 1, 4-diethynylbenzene, 4' -diethynylbiphenyl, 2, 7-diethynyl-9, 9-dioctylfluorene, or 3, 6-diethynylcarbazole.
Specifically, the Sonogashira cross-coupling reaction is carried out by heating to 60-120 ℃ under the protection of inert gas for reflux reaction.
More specifically, the reflux reaction time is preferably 36-96 h.
The Sonogashira cross-coupling reaction of the invention is preferably carried out in a mixed solvent of triphenylamine and N, N-dimethylformamide. More preferably, the volume ratio of N, N-dimethylformamide to triphenylamine in the mixed solvent is 7: 3.
More specifically, the invention preferably adds 10-100 mL of mixed solvent in terms of monomer per gram.
In the above preparation method of the present invention, preferably, the amount of the tetrakis (triphenylphosphine) palladium catalyst added is 1 to 5% by mole of the amount of the building monomer reaction functional group, and the amount of the cuprous iodide catalyst added is 1 to 10% by mole of the amount of the building monomer reaction functional group.
The invention adopts any preparation method to prepare the conjugated microporous organic polymer with the structural formula shown in the formula (I), and can further purify the conjugated microporous organic polymer.
One typical purification method is: adding water into the reaction solution after the reaction is finished, adding toluene for extraction, collecting a liquid organic phase, removing most of solvent through vacuum rotary evaporation, adding anhydrous methanol for alcohol precipitation, filtering out a precipitated solid product, putting the solid product into a Soxhlet purifier, purifying with acetone for 48-72 hours, and drying in a vacuum drying oven for 12 hours to obtain the purified conjugated microporous organic polymer.
It should be understood that the above is not the only purification method for the conjugated microporous organic polymer, and other conventional purification methods, such as recrystallization, column chromatography, etc., can be used.
The conjugated microporous organic polymer is prepared by taking spiro [3,3] heptane-2, 6-spirofluorene as a core repeating unit of the polymer and regulating and controlling the pore size of the microporous polymer by changing a connecting unit. Furthermore, the spiro [3,3] heptane-2, 6-spirofluorene as the core repeating unit of the conjugated microporous organic polymer has three distorted spiro atom centers, so that the accumulation of polymer chains can be effectively prevented, and the synthesis of the conjugated microporous organic polymer can be better realized.
Therefore, the constructed conjugated microporous organic polymer has permanent holes and good stability, and the thermal decomposition temperature is 350-400 ℃.
The conjugated microporous organic polymer constructed by the invention has potential application prospects in the fields of photoelectric technology, heterogeneous catalysis, gas adsorption and separation, gas storage and the like. For example, the conjugated microporous organic polymer constructed by the invention can be used as a material for preparing a light emitting layer of an organic electroluminescent device.
Drawings
FIG. 1 is an infrared spectrum of the conjugated microporous organic polymer prepared in examples 1 to 6.
FIG. 2 is an XRD spectrum of the conjugated microporous organic polymer prepared in examples 1-6.
FIG. 3 is a nitrogen adsorption curve and a pore size distribution diagram of the conjugated microporous organic polymer prepared in examples 1 to 3.
FIG. 4 is a nitrogen adsorption curve and a pore size distribution diagram of the conjugated microporous organic polymer prepared in examples 4 to 6.
FIG. 5 is an atomic force microscope photograph of the conjugated microporous organic polymer prepared in examples 1 to 3.
FIG. 6 is an atomic force microscope photograph of the conjugated microporous organic polymers prepared in examples 4 to 6.
FIG. 7 is an SEM spectrum of the conjugated microporous organic polymer prepared in examples 1-6.
FIG. 8 is a spectrum of ultraviolet absorption and fluorescence emission spectra of the conjugated microporous organic polymer solutions prepared in examples 1-3.
FIG. 9 shows UV absorption and fluorescence emission spectra of the conjugated microporous organic polymer thin films prepared in examples 1-3.
FIG. 10 is a graph showing UV absorption and fluorescence emission spectra of the conjugated microporous organic polymer solutions prepared in examples 4-6.
FIG. 11 is a graph showing UV absorption and fluorescence emission spectra of the conjugated microporous organic polymer thin films prepared in examples 4-6.
FIG. 12 is a thermogravimetric plot of the conjugated microporous organic polymers prepared in examples 1-6.
FIG. 13 is a DSC chart of the conjugated microporous organic polymers prepared in examples 1 to 6.
FIG. 14 is an electrochemical spectrum of the conjugated microporous organic polymer prepared in examples 1 to 6.
Detailed Description
The following examples further describe embodiments of the present invention. The following examples are only for illustrating the technical solutions of the present invention more clearly, and do not limit the scope of the present invention. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.
Example 1.
320mg (0.45mmol) of TBrSDF and 160mg (0.94mmol) of 1, 4-benzenediboronic acid were weighed, mixed and introduced into a 250ml two-necked flask, and the flask was evacuated and purged with nitrogen gas 3 times each to exhaust the atmosphere.
30ml of toluene previously dehydrated was added to the two-necked flask and stirred for 10 min. 3g of potassium carbonate are weighed out and dissolved in 10ml of water, 1ml of Aliquant 336 phase transfer catalyst is weighed out and dissolved in 5ml of anhydrous toluene, the solution is respectively added into a two-neck flask under the protection of nitrogen, and the two-neck flask is vacuumized and is respectively introduced with nitrogen for 1 time.
Finally, 0.026g of tetrakis (triphenylphosphine) palladium was weighed into a two-necked flask, heated to 110 ℃ and refluxed for 4 days, and then the reaction was stopped.
Cooling the reaction liquid to room temperature, adding water for dilution, extracting with toluene, removing the solvent by rotary evaporation of the extract, adding 300ml of anhydrous methanol for alcohol precipitation, stirring for 30min, performing suction filtration to obtain powder in a solid form, wrapping the powder with filter paper, placing the wrapped powder in a Soxhlet purifier, purifying with acetone for 72h, and drying to obtain the conjugated microporous organic polymer, which is recorded as SDFB-CMP.
FIG. 1 (a) is an infrared spectrum of the produced polymer, and it can be seen that 1125cm-1The C-B stretching vibration peak is obviously weakened, which indicates that the SDFB-CMP is successfully polymerized.
Example 2.
360mg (0.5mmol) of TBrSDF and 260mg (1.05mmol) of 4, 4' -biphenyldiboronic acid were weighed out and mixed into a 250ml two-necked flask, and the flask was evacuated and purged with nitrogen 3 times each to exhaust the air.
30ml of toluene previously dehydrated was added to the two-necked flask and stirred for 10 min. 3g of potassium carbonate are weighed out and dissolved in 10ml of water, 1ml of Aliquant 336 phase transfer catalyst is weighed out and dissolved in 5ml of anhydrous toluene, the solution is respectively added into a two-neck flask under the protection of nitrogen, and the two-neck flask is vacuumized and is respectively introduced with nitrogen for 1 time.
Finally, 0.03g of tetrakis (triphenylphosphine) palladium was weighed into a two-necked flask, heated to 110 ℃ and refluxed for 4 days, and then the reaction was stopped.
Cooling the reaction liquid to room temperature, adding water for dilution, extracting with toluene, removing the solvent by rotary evaporation of the extract, adding 300ml of anhydrous methanol for alcohol precipitation, stirring for 30min, performing suction filtration to obtain powder in a solid form, wrapping the powder with filter paper, placing the wrapped powder in a Soxhlet purifier, purifying with acetone for 72h, and drying to obtain the conjugated microporous organic polymer, which is recorded as SDFBp-CMP.
FIG. 1 (b) is an infrared spectrum of the resulting polymer, and it can be seen that 1175cm-1The C-B stretching vibration peak is obviously weakened, and the SDFBp-CMP is successfully polymerized.
Example 3.
360mg (0.5mmol) of TBrSDF and 502mg (1.05mmol) of 9, 9-dioctylfluorene-2, 7-diboronic acid are weighed, mixed and introduced into a 250ml two-necked flask, and the flask is evacuated and purged with nitrogen 3 times each to exhaust the air.
30ml of toluene previously dehydrated was added to the two-necked flask and stirred for 10 min. 3g of potassium carbonate are weighed out and dissolved in 10ml of water, 1ml of Aliquant 336 phase transfer catalyst is weighed out and dissolved in 5ml of anhydrous toluene, the solution is respectively added into a two-neck flask under the protection of nitrogen, and the two-neck flask is vacuumized and is respectively introduced with nitrogen for 1 time.
Finally, 0.03g of tetrakis (triphenylphosphine) palladium was weighed into a two-necked flask, heated to 110 ℃ and refluxed for 4 days, and then the reaction was stopped.
Cooling the reaction liquid to room temperature, adding water for dilution, extracting with toluene, removing the solvent by rotary evaporation of the extract, adding 300ml of anhydrous methanol for alcohol precipitation, stirring for 30min, performing suction filtration to obtain powder in a solid form, wrapping the powder with filter paper, placing the wrapped powder in a Soxhlet purifier, purifying with acetone for 72h, and drying to obtain the conjugated microporous organic polymer, which is recorded as SDFDoF-CMP.
FIG. 1 (c) is an infrared spectrum of the resulting polymer, and it can be seen that 1150cm-1The peak of C-B stretching vibration is obviously weakened, which indicates that the SDFDoF-CMP is successfully polymerized.
Example 4.
360mg (0.5mmol) of TBrSDF and 140mg (1.05mmol) of 1, 4-diethynylbenzene were weighed out and mixed in a 250ml two-necked flask, and the flask was evacuated and purged with nitrogen gas 3 times each to exhaust the air in the flask.
70ml of N, N-dimethylformamide previously dehydrated and 30ml of toluene previously dehydrated were put in a two-necked flask and stirred for 10 min. 0.03g of tetrakis (triphenylphosphine) palladium and 0.01g of cuprous iodide are weighed, respectively added into a two-neck flask under the protection of nitrogen, vacuumized, introduced with nitrogen for 1 time respectively, heated to 90 ℃, refluxed for 4 days, and stopped.
Cooling the reaction liquid to room temperature, adding water for dilution, extracting with toluene, removing the solvent by rotary evaporation of the extract, adding 300ml of anhydrous methanol for alcohol precipitation, stirring for 30min, performing suction filtration to obtain powder in a solid form, wrapping the powder with filter paper, placing the wrapped powder in a Soxhlet purifier, purifying with acetone for 72h, and drying to obtain the conjugated microporous organic polymer, which is recorded as SDFBy-CMP.
FIG. 1 (d) is an infrared spectrum of the resulting polymer, and it can be seen that 634cm-1The bending vibration peak of the terminal hydrogen of the alkynyl is obviously weakened, and the SDFBy-CMP is proved to be successfully polymerized.
Example 5.
360mg (0.5mmol) of TBrSDF and 220mg (1.05mmol) of 4, 4' -diacetylbiphenyl were weighed out and mixed in a 250ml two-necked flask, and the flask was evacuated and purged with nitrogen 3 times each to exhaust the air.
70ml of N, N-dimethylformamide previously dehydrated and 30ml of toluene previously dehydrated were put in a two-necked flask and stirred for 10 min. 0.03g of tetrakis (triphenylphosphine) palladium and 0.01g of cuprous iodide are weighed, respectively added into a two-neck flask under the protection of nitrogen, vacuumized, introduced with nitrogen for 1 time respectively, heated to 90 ℃, refluxed for 4 days, and stopped.
Cooling the reaction liquid to room temperature, adding water for dilution, extracting with toluene, removing the solvent by rotary evaporation of the extract, adding 300ml of anhydrous methanol for alcohol precipitation, stirring for 30min, performing suction filtration to obtain powder in a solid form, wrapping the powder with filter paper, placing the wrapped powder in a Soxhlet purifier, purifying with acetone for 72h, and drying to obtain the conjugated microporous organic polymer, which is recorded as SDFBpy-CMP.
FIG. 1 (e) is an infrared spectrum of the resulting polymer, and it can be seen that 640cm-1The bending vibration peak of the terminal hydrogen of the alkynyl is obviously weakened, which indicates that the SDFBpy-CMP is successfully polymerized.
Example 6.
360mg (0.5mmol) of TBrSDF and 460mg (1.05mmol) of 2, 7-diacetylene-9, 9-dioctylfluorene are weighed out and mixed into a 250ml two-neck flask, which is evacuated and purged with nitrogen 3 times each to exhaust the air from the flask.
70ml of N, N-dimethylformamide previously dehydrated and 30ml of toluene previously dehydrated were put in a two-necked flask and stirred for 10 min. 0.03g of tetrakis (triphenylphosphine) palladium and 0.01g of cuprous iodide are weighed, respectively added into a two-neck flask under the protection of nitrogen, vacuumized, introduced with nitrogen for 1 time respectively, heated to 90 ℃, refluxed for 4 days, and stopped.
Cooling the reaction liquid to room temperature, adding water for dilution, extracting with toluene, removing the solvent by rotary evaporation of the extract, adding 300ml of anhydrous methanol for alcohol precipitation, stirring for 30min, performing suction filtration to obtain powder in a solid form, wrapping the powder with filter paper, placing the wrapped powder in a Soxhlet purifier, purifying with acetone for 72h, and drying to obtain the conjugated microporous organic polymer, which is recorded as SDFDoFy-CMP.
FIG. 1 (f) is an infrared spectrum of the produced polymer, and it can be seen that 653cm is-1The bending vibration peak of the terminal hydrogen of the alkynyl is obviously weakened, and the SDFDoFy-CMP is successfully polymerized.
Fig. 2 shows XRD patterns of 6 conjugated microporous organic polymers prepared in the above 6 examples. As can be seen from the figure, except that the polymer SDFB-CMP has a sharp peak and has certain crystallinity, the other polymers have a broad peak at about 20 ℃, which proves that the structure of the conjugated microporous organic polymer is amorphous.
FIGS. 3 and 4 provide nitrogen adsorption curves and pore size distribution diagrams for the conjugated microporous organic polymers prepared in examples 1-3 and 4-6, respectively. As can be seen from the figure, the pore sizes of the 6 polymers are mainly distributed in the range of 1-20 nm, and 70% of the pore sizes are concentrated in the range of 1-2 nm.
FIG. 5 is an atomic force microscope photograph of the conjugated microporous organic polymer prepared in examples 1 to 3. The surface Roughness (RMS) of the polymers SDFB-CMP (a), SDFBp-CMP (b) and SDFDoF-CMP (c) are shown to be 3.22, 8.65 and 1.84nm, respectively. Among them, SDFDoF-CMP has a smaller RMS because introduction of fluorene group improves film-forming property.
FIG. 6 is an atomic force microscope photograph of the conjugated microporous organic polymers prepared in examples 4-6, in which the polymers SDFBy-CMP (d), SDFBpy-CMP (e), and SDFDoFy-CMP (f) have surface Roughness (RMS) of 0.81, 0.32, and 0.46nm, respectively. As can be seen, the surface of the polymer SDFBy-CMP had some small protrusions, probably due to the introduction of alkynyl groups, which increased the rigidity of the polymer and made the solubility worse.
FIG. 7 is a field emission scanning electron microscope image of the 6 conjugated microporous organic polymers. The surface topography of the polymers SDFB-CMP, SDFBp-CMP and SDFDoF-CMP is nano fiber, and the polymers SDFBy-CMP, SDFBpy-CMP and SDFDoFy-CMP are formed by aggregating irregular microspheres with different particle sizes. In addition, some holes formed by the polymer accumulation can be clearly seen in the figure.
FIG. 8 shows the UV-visible absorption spectrum and fluorescence emission (PL) spectrum of the conjugated microporous organic polymer prepared in examples 1-3 in tetrahydrofuran (10 mg/mL). As can be seen from the figure, the absorption maxima of the polymers SDFB-CMP and SDFBp-CMP are around 330nm, while the absorption maxima of the polymer SDFDoF-CMP are at 370nm, and obvious red shift occurs, because the fluorene group is introduced, and the carbon chain and the fluorenyl group form a co-planar pi conjugated conformation. The main fluorescence emission peaks and electron vibration shoulders of the polymers SDFB-CMP, SDFBp-CMP and SDFDoF-CMP are located near 420nm and 440 nm.
FIG. 9 shows the UV-visible absorption spectrum and the fluorescence emission spectrum of the conjugated microporous organic polymer thin films prepared in examples 1 to 3. In the film, all polymers showed a similar absorption maximum as in the solution, and the polymer SDFDoF-CMP showed a similar absorption maximum around 380nm as typical polyfluorenes. Further, in the PL spectrum, each polymer did not undergo a significant red shift, and the result indicates that the three-dimensional chain structure can effectively prevent aggregation of the polymer main chain, so that no significant red shift occurred.
FIG. 10 shows the UV-visible absorption spectrum and fluorescence emission (PL) spectrum of the conjugated microporous organic polymer prepared in examples 4-6 in tetrahydrofuran (10 mg/mL). Wherein the ultraviolet absorption peak of the polymer is about 360nm, the main fluorescence emission peak and electronic vibration shoulder peak of the polymers SDFBy-CMP and SDFBpy-CMP are about 410nm and 460nm, but the main fluorescence emission peak and electronic vibration shoulder peak of the polymer SDFDoFy-CMP are respectively at 420nm and 504nm, and the peak intensity is enhanced at 504 nm. The reason is that the polymer is too rigid after the alkynyl is introduced, certain stacking is formed, and meanwhile, the degree of inhibition of the interaction between alkyl chains in the fluorenyl is weakened, so that the band gap is narrowed, and the fluorescence emission peak is red-shifted.
FIG. 11 shows the UV-visible absorption spectrum and the fluorescence emission spectrum of the conjugated microporous organic polymer thin films prepared in examples 4-6. In the thin film state, the ultraviolet absorption peaks of the polymer are around 340nm and 500 nm. The fluorescence emission peaks of the three polymers are located at about 500nm and are red-shifted by about 40nm compared with a solvent, and the reason is that after alkynyl is introduced, the aperture of the conjugated microporous organic polymer is increased, polymer chains connected with spirobifluorene are closely arranged, and the interaction among the chains is enhanced, so that the spectrum is red-shifted compared with that in a solution.
FIG. 12 is a thermogravimetric analysis graph of the conjugated microporous organic polymers prepared in examples 1-6. The test protective gas is nitrogen, the gas flow is 10ml/L, and the temperature rise speed is 10 ℃/min. As can be seen from the figure, the decomposition temperatures at 10% weight loss of the 6 polymers were all around 350 ℃, indicating that the 6 polymers all have very good thermal stability.
Further, according to the Differential Scanning Calorimetry (DSC) graph of the 6 conjugated microporous organic polymers of FIG. 13, the glass transition temperature of the polymer is around 200 ℃, indicating that the polymer has good morphological stability.
FIG. 14 is an electrochemical test chart of the conjugated microporous organic polymers prepared in examples 1 to 6. The first redox peaks of the polymers SDFB-CMP, SDFBp-CMP, SDFDoF-CMP, SDFBy-CMP, SDFBpy-CMP and SDFDoFy are respectively 1.05, 1.07, 1.08, 1.28, 1.18 and 1.22V, and the HOMO energy levels are calculated to be respectively-5.55, -5.57, -5.58, -5.78, -5.68 and-5.72 eV.
Claims (6)
1. A spiro [3,3] heptane-2, 6-spirofluorene-based conjugated microporous organic polymer having a structural formula shown in formula (I):
wherein the linking group R is any one of the following first and second groups:
a first group:
、
、
、
、
、
；
second group:
、
、
、
。
2. the method for preparing spiro [3,3] heptane-2, 6-spirofluorene-based conjugated microporous organic polymer according to claim 1, wherein spiro [3.3] heptane-2, 6-bis- (2 ', 2 ", 7', 7" -tetrabromo) spirofluorene is used as a first constitutional monomer, and the spiro [3.3] heptane-2, 6-bis- (2 ', 2 ", 7', 7" -tetrabromo) spirofluorene and a second constitutional monomer with the structural formula shown in formula (II) are subjected to SuZuki coupling reaction in the presence of a catalyst of tetrakis (triphenylphosphine) palladium and a phase transfer catalyst of methyltrioctylammonium chloride to prepare the conjugated microporous organic polymer with the structural formula shown in formula (I) and the connecting group R as a first group:
3. the preparation method of claim 2, wherein the SuZuki coupling reaction is performed by heating to 60-120 ℃ in toluene containing potassium carbonate under the protection of inert gas for reflux reaction for 36-96 h.
4. The method for preparing spiro [3,3] heptane-2, 6-spirofluorene-based conjugated microporous organic polymer according to claim 1, wherein spiro [3.3] heptane-2, 6-bis- (2 ', 2 ", 7', 7" -tetrabromo) spirofluorene is used as the first monomer, in the presence of catalysts of palladium tetrakis (triphenylphosphine) and cuprous iodide, performing Sonogashira cross coupling reaction with a second construction monomer with two terminal alkynyl groups to prepare a conjugated microporous organic polymer with a connecting group R as a second group and a structural formula shown in a formula (I), wherein the second building monomer with two terminal alkynyl groups is 1, 4-diacetylene benzene, 4' -diacetylene biphenyl, 2, 7-diacetylene-9, 9-dioctyl fluorene or 3, 6-diacetylene carbazole.
5. The preparation method of claim 4, wherein the Sonogashira cross-coupling reaction is performed by heating to 60-120 ℃ under the protection of inert gas and performing reflux reaction for 36-96 h.
6. Use of the spiro [3,3] heptane-2, 6-spirofluorene-based conjugated microporous organic polymer as claimed in claim 1 as a material for preparing a light emitting layer of an organic electroluminescent device.
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