CN109485868B - 1,3,6,8-tetra (ethynyl) pyrene-based polymer and preparation method thereof - Google Patents
1,3,6,8-tetra (ethynyl) pyrene-based polymer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polymer based on 1,3,6,8-tetra (ethynyl) pyrene and a preparation method thereof, belonging to the technical field of porous organic framework polymeric materials. The 1,3,6,8-tetra (ethynyl) pyrene-based polymer provided by the invention is spherically stacked, and has the advantages of low bulk density of the whole structure, high thermal stability and strong ultraviolet visible absorption.
Description
Technical Field
The invention relates to the technical field of porous organic framework polymeric materials, in particular to a polymer based on 1,3,6,8-tetra (ethynyl) pyrene and a preparation method thereof.
Background
In recent years, porous organic framework polymeric materials (POFs) have attracted general attention and research by researchers due to their special pore arrangement, low bulk density, high specific surface area, and high thermal stability. Due to the unique pore channel structure and high specific surface area, the adsorbent is widely applied to the aspects of adsorption, storage and separation. With the intensive research on porous organic framework materials, the porous organic framework is more stable by introducing heteroatoms into the framework or using covalent bonds to connect organic moieties in chemical reactions, and meanwhile, the synthesis method, the process and the like are continuously improved.
Porous organic framework materials have been developed and can now be classified into Metal Organic Frameworks (MOFs) and Covalent Organic Frameworks (COFs). As a novel porous polymeric material, the covalent organic framework material has remarkable advantages compared with other porous materials due to extremely low density, higher thermal stability, good structure cutting property, larger specific surface area and the like, is widely applied to the aspects of adsorption separation, sensing, photoelectricity, catalysis and the like, and has wide development prospect.
The organic fluorescent dyes are various in types, wherein rhodamine and fluorescein are two types which are reported most, and actually, pyrene dyes, coumarin dyes, naphthalimide dyes, cyanine dyes, fluorescent dyes containing tetrapyrrole groups, thiazine dyes, oxazine dyes, rare earth complex fluorescent dyes and the like are also included. Among them, the fluorescence property of the pyrene dye parent is general, and when the parent structure is conjugated with an electron-donating group, the fluorescence property of the pyrene dye is enhanced (the fluorescence quantum yield can reach more than 50%). The four six-membered rings in the pyrene dye precursor are coplanar, and this structure determines the pyrene dye to have an accumulating effect. The pyrene dye has fluorescence emission at 470nm due to the accumulation effect, and based on the characteristic of the pyrene dye, a fluorescent probe can be designed by utilizing the pyrene dye, and the currently reported pyrenyl excimer fluorescent probe is prepared by utilizing the characteristic of the pyrene dye. This planar structural property of pyrene dyes can also be used as a DNA intercalating probe. The pyrene dye also has a plurality of excellent characteristics, but the synthesis of the difunctional conjugated microporous organic polymer is not realized by co-introducing pyrene and benzothiazole into a covalent organic framework material in the prior art.
Disclosure of Invention
In view of the above, the present invention aims to provide a polymer based on 1,3,6,8-tetra (ethynyl) pyrene and a preparation method thereof, wherein the polymer based on 1,3,6,8-tetra (ethynyl) pyrene provided by the present invention is spherically stacked, and has a low bulk density of the whole structure, high thermal stability and strong ultraviolet visible absorption.
The invention provides a polymer based on 1,3,6,8-tetra (ethynyl) pyrene, which is prepared by taking 1,3,6,8-tetra (ethynyl) pyrene and 4, 7-dibromo-2, 1, 3-benzothiadiazole as monomers according to the molar ratio of1,3,6,8-tetra (ethynyl) pyrene to 4, 7-dibromo-2, 1, 3-benzothiadiazole of 1:2 and has a structure shown in a formula I:
The invention also provides a preparation method of the polymer based on 1,3,6,8-tetra (ethynyl) pyrene, which comprises the following steps:
mixing 1,3,6,8-tetra (ethynyl) pyrene, 4, 7-dibromo-2, 1, 3-benzothiadiazole, an organic solvent and a catalyst, and then carrying out sonogashira coupling reaction in a protective atmosphere to obtain a polymer based on 1,3,6,8-tetra (ethynyl) pyrene; the molar ratio of the 1,3,6,8-tetra (ethynyl) pyrene to the 4, 7-dibromo-2, 1, 3-benzothiadiazole is 1: 2.
Preferably, the organic solvent is one or more of toluene, diisopropylamine and tetrahydrofuran.
Preferably, the catalyst is one or more of tetrakis (triphenylphosphine) palladium, palladium chloride, palladium acetate or cuprous iodide.
Preferably, the mass of the catalyst is 0.5-3% of that of1,3,6,8-tetra (ethynyl) pyrene.
Preferably, the temperature of the sonogashira coupling reaction is 60-100 ℃ and the time is 12-48 h.
Preferably, after the sonogashira coupling reaction is completed, the solid-liquid separation is carried out on the sonogashira coupling reaction liquid, and the obtained solid product is sequentially subjected to acetone soaking, soxhlet extraction, dichloromethane soaking and vacuum drying to obtain the polymer of1,3,6,8-tetra (ethynyl) pyrene.
Preferably, the soxhlet extraction is performed with methanol and dichloromethane in sequence.
The beneficial technical effects are as follows: the invention provides a polymer based on 1,3,6,8-tetra (ethynyl) pyrene and a preparation method thereof, wherein the polymer based on 1,3,6,8-tetra (ethynyl) pyrene is stacked in a spherical shape, and has the advantages of low bulk density of the whole structure, high thermal stability and high absorption intensity of ultraviolet short waves.
Description of the drawings:
FIG. 1 is an infrared spectrum of1,3,6, 8-tetrabromopyrene obtained in example 1;
FIG. 2 is an infrared spectrum of1,3,6,8-tetrakis (trimethylsilylethynyl) pyrene obtained in example 1;
FIG. 3 is a NMR chart of1,3,6,8-tetrakis (trimethylsilylethynyl) pyrene obtained in example 1;
FIG. 4 is an infrared spectrum of1,3,6,8-tetra (ethynyl) pyrene obtained in example 1;
FIG. 5 is a NMR spectrum of 3,6,8-tetra (ethynyl) pyrene obtained in example 1;
FIG. 6 is an infrared spectrum of a 1,3,6,8-tetra (ethynyl) pyrene-based polymer obtained in example 1;
FIG. 7 is a thermogravimetric analysis chart of the 1,3,6,8-tetra (ethynyl) pyrene-based polymer obtained in example 1;
FIG. 8 is an XRD pattern of the 1,3,6,8-tetra (ethynyl) pyrene based polymer obtained in example 1;
FIG. 9 is an ultraviolet analysis spectrum of a 1,3,6,8-tetra (ethynyl) pyrene-based polymer obtained in example 1;
FIG. 10 is an electron micrograph of a 1,3,6,8-tetra (ethynyl) pyrene based polymer obtained in example 1, with a 100 μm scale;
FIG. 11 is an electron micrograph of a 1,3,6,8-tetra (ethynyl) pyrene based polymer obtained in example 1, with a 20 μm scale.
Detailed Description
The invention provides a polymer based on 1,3,6,8-tetra (ethynyl) pyrene, which is prepared by taking 1,3,6,8-tetra (ethynyl) pyrene and 4, 7-dibromo-2, 1, 3-benzothiadiazole as monomers according to the molar ratio of 1:2 of1,3,6,8-tetra (ethynyl) pyrene and 4, 7-dibromo-2, 1, 3-benzothiadiazole, and has a structure shown in a formula I:
The invention also provides a preparation method of the polymer based on 1,3,6,8-tetra (ethynyl) pyrene, which comprises the following steps:
mixing 1,3,6,8-tetra (ethynyl) pyrene, 4, 7-dibromo-2, 1, 3-benzothiadiazole, an organic solvent and a catalyst, and then carrying out sonogashira coupling reaction in a protective atmosphere to obtain a polymer based on 1,3,6,8-tetra (ethynyl) pyrene; the molar ratio of the 1,3,6,8-tetra (ethynyl) pyrene to the 4, 7-dibromo-2, 1, 3-benzothiadiazole is 1: 2.
In the present invention, the 1,3,6,8-tetra (ethynyl) Pyrene is preferably prepared in the laboratory by the methods of the literature (Pyrene as Chromophore and Electrophor: Encapsulation in a structured Polyphenylene Shell, chem. Eur. J.2006,12, 6117-6128) and by the literature (Effects of catalysis on silicon atoms adsorption and fluorescence properties of1,3,6,8-tetra (thionyl) pyres, Tetrahedron Letters,2017, 58(46),
4372-4376; ) The preparation process disclosed in (1).
In the present invention, the organic solvent is preferably one or more of toluene, diisopropylamine, tetrahydrofuran, more preferably toluene and diisopropylamine; the dosage of the organic solvent is preferably 40-60 mL, and more preferably 50 mL; in the present invention, when the solvent is preferably toluene and diisopropylamine, the volume ratio of toluene and diisopropylamine is preferably 1: 1.
In the present invention, the catalyst is preferably one or more of tetrakis (triphenylphosphine) palladium, palladium acetate, palladium chloride or cuprous iodide, more preferably tetrakis (triphenylphosphine) palladium and cuprous iodide; the mass of the catalyst is preferably 0.5-3%, more preferably 1-2.5%, and most preferably 1.5-2% of the mass of1,3,6,8-tetra (ethynyl) pyrene. In the present invention, when the catalyst is preferably tetrakis (triphenylphosphine) palladium and cuprous iodide, the mass ratio of tetrakis (triphenylphosphine) palladium to cuprous iodide is preferably 0.5: 1.5, more preferably 1: 1. The tetrakis (triphenylphosphine) palladium is preferably newly prepared in a laboratory, and the preparation method of the tetrakis (triphenylphosphine) palladium is not particularly limited, and can be selected from preparation methods well known to those skilled in the art.
In the invention, the temperature of the sonogashira coupling reaction is preferably 60-100 ℃, and more preferably 80-90 ℃; the time of the sonogashira coupling reaction is preferably 24-48h, more preferably 30-45 h, and most preferably 35-40 h.
In the present invention, the protective atmosphere is preferably a nitrogen atmosphere.
In the invention, after the sonogashira coupling reaction is completed, the solid-liquid separation of the sonogashira coupling reaction liquid is preferably performed, and the obtained solid product is sequentially subjected to acetone soaking, soxhlet extraction, dichloromethane soaking and vacuum drying to obtain the polymer of1,3,6,8-tetra (ethynyl) pyrene.
The method for solid-liquid separation in the present invention is not particularly limited, and a method known to those skilled in the art may be used. The present invention is preferably suction filtration under reduced pressure.
In the invention, the time for soaking in acetone is preferably 4-10 h, more preferably 5-8 h, and the frequency for soaking in acetone is preferably 3-5 times.
In the present invention, the soaking in acetone preferably further comprises filtering and drying, and the filtering and drying method is not particularly limited, and a drying method known to those skilled in the art may be selected.
In the present invention, the soxhlet extraction is preferably performed on the dried sonogashira coupling reaction liquid. The Soxhlet extraction is preferably carried out by sequentially using methanol and dichloromethane, and the Soxhlet extraction time of the methanol and the dichloromethane is preferably 12-36 h independently, and more preferably 24 h. The invention adopts methanol and dichloromethane to carry out Soxhlet extraction on the obtained dry material, and aims to ensure that the solvent and unreacted monomers on the surface of the polymer and in the pore canal are fully removed.
The method of vacuum drying in the present invention is not particularly limited, and a vacuum drying method known to those skilled in the art may be selected.
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
Preparation of1,3,6,8-tetra (ethynyl) pyrene
1) 5.06g of pyrene and 125mL of nitro groupAdding benzene into a three-neck flask, starting a magnetic stirrer, exhausting to vacuum, heating to 80 ℃ under the protection of nitrogen, then slowly adding 5.6mL of liquid bromine into a reaction system by using a constant-pressure separating funnel, heating to 120 ℃, and carrying out condensation reflux for 12 hours. After the reaction is finished, adding a sodium hydroxide solution into a three-neck flask, carrying out vacuum filtration, washing with sodium hydroxide and ethanol in sequence, and drying in a constant-temperature drying oven at 50 ℃ to obtain a light yellow-green solid. The infrared spectrum is shown in figure 1. The infrared characteristic absorption peak of1,3,6, 8-tetrabromopyrene comprises C-Br, C-C in benzene ring, C ═ C in benzene ring, etc., and is 673.16cm when analyzed from FIG. 1-1C-Br absorption peak of (1); has a length of 873.75cm-1C-C absorption peak in the benzene ring of (1); and 1591.21cm-1The yellow-green solid is proved to be 1,3,6, 8-tetrabromopyrene.
2) 2.8117g of1,3,6, 8-tetrabromophyrene, 0.73g of bis (triphenylphosphine) palladium dichloride, 0.4411g of cuprous iodide and 0.6267g of triphenylphosphine were added into a three-necked flask, then 110mL of triethylamine and 20mL of toluene were poured, a magnetic stirrer was started to evacuate, the temperature was raised to 60 ℃ under the protection of nitrogen, 6mL of trimethylsilylacetylene was slowly added by a syringe, and after 15min of reaction, the temperature was raised to 80 ℃ for 12 h. And after the reaction is finished, adding 120mL of dichloromethane, then extracting for 2-3 times by using water, adding anhydrous magnesium sulfate, filtering, and washing by using dichloromethane. Mixing silica gel and n-hexane, loading into a separation chromatographic column, pouring the filtrate into the upper layer, adding n-hexane, purifying by the column until the color of the solution becomes light, finally obtaining the orange-red (1, 3,6,8-tetra (trimethylsilylethynyl) pyrene) solution, adding absolute ethyl alcohol into the orange-red solid obtained by rotary evaporation, carrying out ultrasonic oscillation, carrying out vacuum filtration and ethanol immersion washing, and drying to obtain the bright and bright orange-red solid. The infrared spectrogram and the nuclear magnetic hydrogen spectrogram are respectively shown as figure 2 and figure 3.
The infrared characteristic absorption peak of the 1,3,6,8-tetra (trimethylsilylethynyl) pyrene has Si (CH)3)3The medium Si-C, C ≡ C, C-H, etc., as can be derived from FIG. 2, has 840.96cm-1Si (CH)3)3Middle Si-C absorption peak of 2152.56cm-1Has a C.ident.C absorption peak of 2958.80cm-1The C-H absorption peak of (a) proves that the compound is 1,3,6,8-Tetra (trimethylsilylethynyl) pyrene.
As can be seen from FIG. 3, there are three hydrogen sites, the absorption peak at 0.38ppm corresponds to the proton peak at silicon site, the absorption peak at 8.317ppm corresponds to the proton peaks at the upper and lower tips of the benzene ring, the absorption peak at 8.612ppm corresponds to the proton peaks at the left and right sides of the benzene ring, and the peaks appearing at other sites are the proton peaks on water and a dissolving agent, further illustrating that the synthesized compound is 1,3,6,8-tetrakis (trimethylsilylethynyl) pyrene.
3) 6.0857g of1,3,6,8-tetra (trimethylsilylethynyl) pyrene, 50mL of tetrahydrofuran and 3mL of tetrabutylammonium fluoride were added to a round-bottom flask, a magnetic stirrer was started to evacuate, and the temperature was raised to 32 ℃ under nitrogen protection for reaction for 48 h. After the reaction is finished, pouring the mixture into distilled water, stirring, carrying out vacuum filtration, washing with anhydrous methanol for multiple times, and drying to obtain a light yellow solid. The nuclear infrared characterization spectrum and the nuclear magnetic resonance hydrogen spectrum are shown in fig. 4 and fig. 5.
1,3,6,8-tetra (ethynyl) pyrene has an infrared characteristic absorption peak of C-H, C ≡ C, etc., and can be obtained from FIG. 4, which has 3278.99cm-1、2958.80cm-1Has a C-H absorption peak of 2150.63cm-1The absorption peak of C.ident.C proves that the compound is 1,3,6,8-tetra (ethynyl) pyrene.
As can be seen from FIG. 5, there are two hydrogen sites, the absorption peak at 4.97ppm corresponds to the proton peak at the alkyne site, the absorption peak at 8.39ppm corresponds to the proton peaks at the upper and lower tips of the benzene ring, the absorption peak at 8.66ppm corresponds to the proton peaks at the left and right of the benzene ring, and the peaks appearing at the other sites are mass peaks on water and the solubilizing agent. The description further proves that the compound is 1,3,6,8-tetra (ethynyl) pyrene.
Preparation of1,3,6,8-tetra (ethynyl) pyrene based polymers
0.6176g of1,3,6,8-tetra (ethynyl) pyrene, 1.2029g of 4, 7-dibromo-2, 1, 3-benzothiadiazole, 50mL of toluene and 50mL of diisopropylamine are started to be stirred to be completely dissolved, then fresh tetrakis (triphenylphosphine) palladium and 0.0279g of cuprous iodide are added, the mixture is exhausted to vacuum, and the temperature is raised to 90 ℃ under the protection of nitrogen to react for 48 hours (the reaction time needs to be accurate). And after the reaction is finished, carrying out vacuum filtration, soaking for one day by using acetone (the acetone is replaced for 3-5 times), filtering and drying, sequentially carrying out Soxhlet extraction for one day by using methanol and dichloromethane, soaking for filtration by using dichloromethane, and carrying out vacuum drying to obtain a black solid product. The infrared spectrum is shown in FIG. 6.
The preparation method of the novel tetrakis (triphenylphosphine) palladium comprises the following steps:
0.0505g palladium chloride, 0.3075g triphenylphosphine and 6mL dimethyl sulfoxide were added to the round bottom flask, the magnetic stirrer was started and vented to vacuum and the temperature was raised to 130 ℃ for 1h under nitrogen. After the reaction is finished, 2mL of hydrazine hydrate is added while the solution is hot, and the solution is quickly filtered and washed by ethanol and ether to obtain a bright green solid, namely the tetrakis (triphenylphosphine) palladium.
The infrared characteristic absorption peaks of the 1,3,6,8-tetra (ethynyl) pyrene-based polymer include C-C in the benzene ring, C-C, C ═ N, C ≡ C and C-H in the benzene ring, etc., and 832.32cm in fig. 6-1Has a C-C absorption peak of 1476.57cm-1Has a C-C absorption peak of 1579.77cm-1Has a C-N absorption peak of 2081.28cm-1Has a C.ident.C absorption peak of 2969.54cm-1C-H absorption peak of (a), it was confirmed that the compound was a polymer based on 1,3,6,8-tetra (ethynyl) pyrene.
Thermogravimetric analysis was performed on the obtained 1,3,6,8-tetra (ethynyl) pyrene based polymer, and the results are shown in fig. 7, wherein the mass was significantly reduced at a temperature of 15.29-100 ℃, indicating that the sample may contain moisture and is not completely dried; then the mass fraction curve of about 300 ℃ is basically leveled, which shows that the structure of the sample is not changed completely; the mass decreases but plateaus smoothly at temperatures between 300 ℃ and 984.65 ℃, indicating that there is some change in the structure of the sample but no change overall. Indicating that the sample had good stability before 984.65 ℃.
XRD analysis was performed on the obtained 1,3,6,8-tetra (ethynyl) pyrene-based polymer, and the result is shown in FIG. 8. As can be seen from FIG. 8, the obtained polymer of1,3,6,8-tetra (ethynyl) pyrene was of amorphous structure.
The obtained 1,3,6,8-tetra (ethynyl) pyrene-based polymer was subjected to ultraviolet spectrum analysis, and the result is shown in FIG. 9. As is clear from FIG. 9, the sample had a high light absorption intensity at a wavelength of 300nm to 600 nm.
The obtained 1,3,6,8-tetra (ethynyl) pyrene-based polymer was subjected to electron microscope scanning, and the results are shown in fig. 10 and 11. As can be seen from fig. 10 and 11, the samples are stacked in a spherical shape, and the overall structure is relatively loose.
Example 2
0.6176g of1,3,6,8-tetra (ethynyl) pyrene obtained in example 1, 1.2029g of 4, 7-dibromo-2, 1, 3-benzothiadiazole and 100mL of dioxane were stirred by a magnetic stirrer until the materials were completely dissolved, 0.0279g of palladium acetate was added, the mixture was evacuated, and the temperature was raised to 60 ℃ under nitrogen protection for 24 hours (the reaction time was accurate). And after the reaction is finished, carrying out vacuum filtration, soaking for one day by using acetone (the acetone is replaced for 3-5 times), filtering, drying, sequentially carrying out Soxhlet extraction for one day by using methanol and dichloromethane, soaking for filtration by using dichloromethane, and carrying out vacuum drying to obtain a black solid product 1,3,6,8-tetra (ethynyl) pyrene. The characterization results were similar to those of example 1.
Example 3
0.6176g of1,3,6,8-tetra (ethynyl) pyrene obtained in example 1, 1.2029g of 4, 7-dibromo-2, 1, 3-benzothiadiazole and 100mL of tetrahydrofuran are stirred by a magnetic stirrer until the palladium chloride is completely dissolved, 0.0279g of palladium chloride is added, the mixture is exhausted to vacuum, the temperature is raised to 100 ℃ under the protection of nitrogen, and the reaction is carried out for 12 hours (the reaction time is accurate). And after the reaction is finished, carrying out vacuum filtration, soaking for one day by using acetone (the acetone is replaced for 3-5 times), filtering, drying, sequentially carrying out Soxhlet extraction for one day by using methanol and dichloromethane, soaking for filtration by using dichloromethane, and carrying out vacuum drying to obtain a black solid product 1,3,6,8-tetra (ethynyl) pyrene. The characterization results were similar to those of example 1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A polymer based on 1,3,6,8-tetra (ethynyl) pyrene is prepared by taking 1,3,6,8-tetra (ethynyl) pyrene and 4, 7-dibromo-2, 1, 3-benzothiadiazole as monomers according to a molar ratio of 1:2 of1,3,6,8-tetra (ethynyl) pyrene and 4, 7-dibromo-2, 1, 3-benzothiadiazole, and has a structure shown in a formula I:
2. The method for preparing 1,3,6,8-tetra (ethynyl) pyrene based polymer of claim 1 comprising the steps of:
mixing 1,3,6,8-tetra (ethynyl) pyrene, 4, 7-dibromo-2, 1, 3-benzothiadiazole, an organic solvent and a catalyst, and then carrying out sonogashira coupling reaction in a nitrogen atmosphere to obtain a polymer based on 1,3,6,8-tetra (ethynyl) pyrene; the molar ratio of the 1,3,6,8-tetra (ethynyl) pyrene to the 4, 7-dibromo-2, 1, 3-benzothiadiazole is 1: 2.
3. The method according to claim 2, wherein the organic solvent is one or more of toluene, diisopropylamine, THF, or dioxane.
4. The method of claim 2, wherein the catalyst is one or more of tetrakis (triphenylphosphine) palladium, cuprous iodide, palladium acetate, and palladium chloride.
5. The production method according to claim 2 or 4, characterized in that the mass of the catalyst is 0.5% to 3% of the mass of1,3,6,8-tetra (ethynyl) pyrene.
6. The preparation method according to claim 2, wherein the temperature of the sonogashira coupling reaction is 60 to 100 ℃ and the time is 12 to 48 hours.
7. The preparation method according to claim 2, wherein the sonogashira coupling reaction is completed and then solid-liquid separation is performed on the sonogashira coupling reaction liquid, and the obtained solid product is sequentially subjected to acetone soaking, soxhlet extraction, dichloromethane soaking and vacuum drying to obtain the polymer of1,3,6,8-tetra (ethynyl) pyrene.
8. The method according to claim 7, wherein the Soxhlet extraction is performed by sequentially using methanol and dichloromethane.
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