CN113736068B - Pyridine and thiazole dual-functionalized conjugated microporous polymer and preparation method and application thereof - Google Patents
Pyridine and thiazole dual-functionalized conjugated microporous polymer and preparation method and application thereof Download PDFInfo
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- CN113736068B CN113736068B CN202111220397.1A CN202111220397A CN113736068B CN 113736068 B CN113736068 B CN 113736068B CN 202111220397 A CN202111220397 A CN 202111220397A CN 113736068 B CN113736068 B CN 113736068B
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000013317 conjugated microporous polymer Substances 0.000 title claims abstract description 75
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Natural products ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 70
- 238000006243 chemical reaction Methods 0.000 claims description 33
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims description 28
- JYGHBDIKJOYWLT-UHFFFAOYSA-N 2,4,6-tris(4-bromophenyl)pyridine Chemical compound C1=CC(Br)=CC=C1C1=CC(C=2C=CC(Br)=CC=2)=NC(C=2C=CC(Br)=CC=2)=C1 JYGHBDIKJOYWLT-UHFFFAOYSA-N 0.000 claims description 26
- 238000005886 esterification reaction Methods 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 239000007983 Tris buffer Substances 0.000 claims description 18
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 18
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 16
- 239000004327 boric acid Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 claims description 11
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 claims description 10
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 9
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 9
- 239000005695 Ammonium acetate Substances 0.000 claims description 9
- 229940043376 ammonium acetate Drugs 0.000 claims description 9
- 235000019257 ammonium acetate Nutrition 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 claims description 8
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 8
- 230000001588 bifunctional effect Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000006303 photolysis reaction Methods 0.000 claims description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 abstract description 5
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 20
- 238000010521 absorption reaction Methods 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000007872 degassing Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000005885 boration reaction Methods 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 125000006416 CBr Chemical group BrC* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- VBXDEEVJTYBRJJ-UHFFFAOYSA-N diboronic acid Chemical compound OBOBO VBXDEEVJTYBRJJ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention belongs to the technical field of conjugated microporous polymersThe invention provides a pyridine and thiazole dual-functional conjugated microporous polymer and a preparation method and application thereof. The pyridine and thiazole dual-functionalized conjugated microporous polymer provided by the invention has a structural unit shown as the following formula. The pyridine and thiazole dual-functionalized conjugated microporous polymer provided by the invention widens the types of the conjugated microporous polymer. Meanwhile, the pyridine and thiazole difunctional conjugated microporous polymer provided by the invention contains a pyridine group and a benzothiazole group, so that the polymer possibly has the performance of photolyzing water to produce hydrogen.
Description
Technical Field
The invention relates to the technical field of conjugated microporous polymers, in particular to a pyridine and thiazole dual-functionalized conjugated microporous polymer and a preparation method and application thereof.
Background
With the development of times, the use of fossil fuels in human life and production causes serious pollution to the living environment of human beings, so that the development of novel energy sources is reluctant. Hydrogen energy is widely advocated as a new energy source, but hydrogen storage methods are not widespread due to lack of economy and safety. Microporous polymers have received attention from a number of researchers as a potential novel hydrogen storage material.
Conjugated Microporous Polymers (CMPs) as a microporous material have the following unique properties compared to other organic porous materials: (1) adjustability of the structure: it can build up units that are linked in pi-conjugated form to form a three-dimensional network structure. Cooper studies have demonstrated that CMPs can be adjusted for specific surface area and pore size by altering the structure of the monomers. (2) The CMPs have large specific surface areas, typically close to 1000m 2 The characteristic of the catalyst enables the catalyst to have potential application markets in gas adsorption and separation, heterogeneous catalysis and photocatalysis.
At present, the conjugated microporous polymer takes pyrene as a basic construction unit, and a series of novel conjugated microporous polymer photocatalysts are synthesized through ternary polymerization. However, the conjugated microporous polymers are of a few kinds, limiting the applications of the conjugated microporous polymers.
Disclosure of Invention
In view of the above, the present invention aims to provide a pyridine and thiazole bifunctional conjugated microporous polymer, and a preparation method and an application thereof. The pyridine and thiazole dual-functionalized conjugated microporous polymer provided by the invention widens the types of the conjugated microporous polymer, and has the performance of photolyzing water to produce hydrogen.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a pyridine and thiazole dual-functionalized conjugated microporous polymer, which has a structural unit shown as a formula I:
the invention also provides a preparation method of the pyridine and thiazole difunctional conjugated microporous polymer, which comprises the following steps:
4-bromoacetophenone, 4-bromobenzaldehyde and ammonium acetate are subjected to polymerization reaction to obtain 2,4,6-tri (4-bromophenyl) pyridine;
carrying out Miyaura boric acid esterification reaction on 2,4,6-tri (4-bromophenyl) pyridine and pinacol diboron under alkaline condition to obtain 2,4,6-tri (4-phenylboronic acid pinacol ester) pyridine;
and (3) carrying out Suzuik reaction on the 2,4,6-tri (4-phenylboronic acid pinacol ester) pyridine and 4,7-dibromo-2,1,3-benzothiadiazole under an alkaline condition to obtain the pyridine and thiazole bifunctional conjugated microporous polymer.
Preferably, the molar ratio of the 4-bromoacetophenone to the 4-bromobenzaldehyde to the ammonium acetate is (1.8-2.2): (0.8-1.2): (36 to 38).
Preferably, the temperature of the polymerization reaction is 200-250 ℃, and the holding time is 30-60 min.
Preferably, the 2,4,6-tris (4-bromophenyl) pyridine and pinacol diboron are in a molar ratio of (0.8-1.2): (4-6).
Preferably, the Miyaura boric acid esterification reaction further comprises a catalyst, wherein the catalyst is a mixed catalyst comprising [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride dichloromethane complex and tetrakis (triphenylphosphine) palladium; in the mixed catalyst, the molar ratio of the [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride dichloromethane complex to the tetrakis (triphenylphosphine) palladium is (1.8-2.2): (0.8-1.2).
Preferably, the temperature of the Miyaura boric acid esterification reaction is 70-100 ℃, and the holding time is 36-72 h.
Preferably, the molar ratio of 4,7-dibromo-2,1,3-benzothiadiazole to 2,4,6-tris (4-phenylboronic acid pinacol ester) pyridine is 0.704:0.486.
preferably, the temperature of the Suzuik reaction is 120-200 ℃, and the heat preservation time is 36-48 h.
The invention also provides the application of the pyridine and thiazole difunctional conjugated microporous polymer in the technical scheme or the pyridine and thiazole difunctional conjugated microporous polymer prepared by the preparation method in the technical scheme in the hydrogen production by photolysis of water.
The invention provides a pyridine and thiazole dual-functionalized conjugated microporous polymer, which has a structural unit shown as a formula I:
the pyridine and thiazole dual-functionalized conjugated microporous polymer provided by the invention widens the types of the conjugated microporous polymer. Meanwhile, the pyridine and thiazole difunctional conjugated microporous polymer provided by the invention contains a pyridine group and a benzothiazole group, so that the polymer possibly has the performance of photolysis of water to produce hydrogen.
The invention also provides a preparation method of the pyridine and thiazole dual-functionalized conjugated microporous polymer, which comprises the following steps: 4-bromoacetophenone, 4-bromobenzaldehyde and ammonium acetate are subjected to polymerization reaction to obtain 2,4,6-tri (4-bromophenyl) pyridine; carrying out Miyaura boric acid esterification reaction on 2,4,6-tri (4-bromophenyl) pyridine and pinacol diboron under alkaline condition to obtain 2,4,6-tri (4-phenylboronic acid pinacol ester) pyridine; and (3) carrying out Suzuik reaction on the 2,4,6-tri (4-phenylboronic acid pinacol ester) pyridine and 4,7-dibromo-2,1,3-benzothiadiazole under an alkaline condition to obtain the pyridine and thiazole bifunctional conjugated microporous polymer. The preparation method provided by the invention has the advantages of short process flow, simple operation and easy industrialization.
The invention also provides the application of the pyridine and thiazole difunctional conjugated microporous polymer in the technical scheme in the hydrogen production by photolysis of water. The conjugated microporous polymer of the invention contains pyridine groups and benzothiazole groups, and may have the performance of photolyzing water to produce hydrogen.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 2,4,6-tris (4-bromophenyl) pyridine;
FIG. 2 is an IR spectrum of 2,4,6-tris (4-bromophenyl) pyridine;
FIG. 3 is a nuclear magnetic hydrogen spectrum of 2,4,6-tris (4-phenylboronic acid pinacol ester) pyridine;
FIG. 4 is an IR spectrum of 2,4,6-tris (pinacol 4-phenylboronate) pyridine;
FIG. 5 is an infrared spectrum of a pyridine and thiazole bi-functionalized conjugated microporous polymer (ZJM-CMP);
FIG. 6 is a UV spectrum of a dual functionalized conjugated microporous polymer with pyridine and thiazole (ZJM-CMP);
FIG. 7 is a thermogravimetric analysis of a pyridine and thiazole bi-functionalized conjugated microporous polymer (ZJM-CMP);
FIG. 8 is an XRD scanning analysis of a pyridine and thiazole bi-functionalized conjugated microporous polymer (ZJM-CMP);
FIG. 9 is a scanning electron microscope image of pyridine and thiazole bi-functionalized conjugated microporous polymer (ZJM-CMP).
Detailed Description
The invention provides a pyridine and thiazole dual-functionalized conjugated microporous polymer, which has a structural unit shown as a formula I:
the invention also provides a preparation method of the pyridine and thiazole dual-functionalized conjugated microporous polymer, which comprises the following steps:
4-bromoacetophenone, 4-bromobenzaldehyde and ammonium acetate are subjected to polymerization reaction to obtain 2,4,6-tri (4-bromophenyl) pyridine;
carrying out Miyaura boric acid esterification reaction on 2,4,6-tri (4-bromophenyl) pyridine and pinacol diboron under alkaline condition to obtain 2,4,6-tri (4-phenylboronic acid pinacol ester) pyridine;
and (3) carrying out Suzuik reaction on the 2,4,6-tri (4-phenylboronic acid pinacol ester) pyridine and 4,7-dibromo-2,1,3-benzothiadiazole under an alkaline condition to obtain the pyridine and thiazole bifunctional conjugated microporous polymer.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
The invention carries out polymerization reaction on 4-bromoacetophenone, 4-bromobenzaldehyde and ammonium acetate to obtain 2,4,6-tri (4-bromophenyl) pyridine.
In the invention, the molar ratio of the 4-bromoacetophenone, the 4-bromobenzaldehyde and the ammonium acetate is preferably (1.8-2.2): (0.8-1.2): (36 to 38), more preferably 2:1:37.
in the present invention, the reaction medium of the polymerization reaction preferably comprises glacial acetic acid; the dosage ratio of the 4-bromoacetophenone to the reaction medium is preferably (9-11) mmol:7.3mL, more preferably 10mmol:7.3mL.
In the present invention, the temperature of the polymerization reaction is preferably 200 to 250 ℃, and more preferably 220 ℃; the heat-retaining time is preferably 30 to 60min, and more preferably 45min.
In the present invention, the polymerization reaction is preferably carried out in an oven.
In the present invention, the reaction formula of the polymerization reaction is shown in formula 1:
after the polymerization reaction, the invention preferably further comprises the steps of cooling the polymerization reaction feed liquid obtained by the polymerization reaction to room temperature, and diluting with water to obtain diluted reaction feed liquid; adjusting the diluted reaction liquid to be neutral to obtain neutral reaction liquid; extracting the neutral reaction liquid by using dichloromethane, and removing dichloromethane in a dichloromethane phase to obtain an extraction product; and washing the extracted product with water, drying the obtained washed product, and then recrystallizing to obtain the 2,4,6-tris (4-bromophenyl) pyridine.
In the present invention, the water is preferably deionized water; the volume ratio of the polymerization reaction feed liquid to water is preferably 1:1. in the present invention, the reagent for adjusting the diluted reaction feed solution preferably comprises a saturated sodium bicarbonate solution. In the present invention, the method for removing dichloromethane in the dichloromethane phase is preferably rotary evaporation, and the parameters of the rotary evaporation are not particularly limited as long as dichloromethane in the dichloromethane phase can be completely removed. The present invention does not specifically limit the drying parameters, as long as water can be completely removed. In the present invention, the recrystallization reagent is preferably acetone; the specific operation of the recrystallization preferably includes: heating the dried washing product to slight boiling, adding acetone until the dried washing product is completely dissolved, pouring clear liquid into a beaker, cooling and crystallizing.
After 2,4,6-tris (4-phenylboronic acid pinacol ester) pyridine is obtained, the 2,4,6-tris (4-bromophenyl) pyridine and the diboronic acid pinacol ester are subjected to Miyaura boric acid esterification reaction under the alkaline condition to obtain 2,4,6-tris (4-phenylboronic acid pinacol ester) pyridine.
In the present invention, the molar ratio of 2,4,6-tris (4-bromophenyl) pyridine to pinacol diboron is preferably (0.8 to 1.2): (4 to 6), more preferably 1:5. in the present invention, the pH value of the alkaline condition is preferably 6 to 8; the alkaline conditions are preferably provided by potassium acetate; the amount of potassium acetate used in the present invention is not particularly limited as long as the pH value under alkaline conditions can be adjusted to 6 to 8.
In the present invention, the Miyaura boric acid esterification reaction preferably further comprises a catalyst, preferably a mixed catalyst comprising [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride dichloromethane complex and tetrakis (triphenylphosphine) palladium; the molar ratio of the [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride dichloromethane complex to the tetrakis (triphenylphosphine) palladium catalyst in the mixed catalyst is preferably (1.8-2.2): (0.8 to 1.2), more preferably 2:1. in the present invention, the ratio of the amounts of 2,4,6-tris (4-bromophenyl) pyridine and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride dichloromethane complex is preferably 1.6mmol:0.1570g.
In the present invention, the reaction medium of the Miyaura boration reaction preferably comprises tetrahydrofuran; the ratio of 2,4,6-tris (4-bromophenyl) pyridine to tetrahydrofuran is preferably 1.6mmol:50mL.
In the present invention, before carrying out Miyaura boric acid esterification reaction, it is preferable to further include: the reaction system of the Miyaura boric acid esterification reaction is degassed, and the degassing operation is not particularly limited in the invention and can be a degassing operation well known to those skilled in the art.
In the invention, the temperature of the Miyaura boric acid esterification reaction is preferably 70-100 ℃, and is further preferably 80 ℃; the holding time is preferably 36 to 72 hours, and more preferably 48 hours.
In the invention, the reaction formula of the Miyaura boric acid esterification reaction is shown as formula 2
After the Miyaura boric acid esterification reaction, the invention preferably further comprises the steps of cooling the esterification reaction material liquid obtained by the Miyaura boric acid esterification reaction, and diluting the esterification reaction material liquid with water to obtain diluted esterification reaction material liquid; extracting the diluted esterification reaction liquid by using dichloromethane, drying the obtained dichloromethane phase, and removing an extracting agent in the dichloromethane phase to obtain an extraction product; and washing and drying the extracted product to obtain 2,4,6-tri (4-phenylboronic acid pinacol ester) pyridine.
In the present invention, the volume ratio of the esterification reaction feed liquid to water is preferably 1:1. in the present invention, the dried reagent preferably includes anhydrous sodium sulfate. In the present invention, the manner of removing the extractant in the methylene chloride phase is preferably rotary evaporation; the parameters of the rotary evaporation are not particularly limited, as long as the extractant in the dichloromethane phase can be completely removed. In the present invention, the washing agent preferably includes water.
After 2,4,6-tri (4-phenylboronic acid pinacol ester) pyridine is obtained, the invention carries out Suzuik reaction on 2,4,6-tri (4-phenylboronic acid pinacol ester) pyridine and 4,7-dibromo-2,1,3-benzothiadiazole under alkaline conditions to obtain the pyridine and thiazole dual-functionalized conjugated microporous polymer.
In the present invention, the molar ratio of 4,7-dibromo-2,1,3-benzothiadiazole to 2,4,6-tris (4-phenylboronic acid pinacol ester) pyridine is preferably 0.704:0.486.
in the present invention, the pH value of the alkaline condition is preferably 7 to 9; the alkaline condition is preferably provided by potassium carbonate, and the amount of potassium carbonate used is not particularly limited in the present invention as long as the pH value under the alkaline condition can be 7 to 9.
In the present invention, the reaction medium of the Suzuik reaction preferably comprises N, N-Dimethylformamide (DMF); the dosage ratio of 4,7-dibromo-2,1,3-benzothiadiazole to N, N-dimethylformamide is preferably 0.704mmol:40mL.
In the present invention, the Suzuik reaction preferably further comprises a catalyst, which preferably comprises tetrakis (triphenylphosphine) palladium; the dosage ratio of 4,7-dibromo-2,1,3-benzothiadiazole to catalyst is preferably 0.704mmol:0.1g.
In the present invention, before the Suzuik reaction, it is preferable to further include: the reaction system of the Suzuik reaction is degassed, and the degassing operation is not particularly limited in the present invention, and may be a degassing operation known to those skilled in the art.
In the invention, the temperature of the Suzuik reaction is preferably 120-200 ℃, and more preferably 150 ℃; the holding time is preferably 36 to 48 hours, and more preferably 48 hours.
In the present invention, the reaction formula of the Suzuik reaction is shown in formula 3:
after the Suzuik reaction, the invention preferably further comprises cooling the Suzuik reaction feed liquid obtained by the Suzuik reaction to room temperature, and diluting with water to obtain diluted Suzuik reaction feed liquid; and washing and drying the diluted Suzuik reaction feed liquid to obtain the dual-functional conjugated microporous polymer of pyridine and thiazole.
In the present invention, the volume ratio of the Suzuik reaction feed liquid to water is preferably 1:1. in the present invention, the washing preferably includes sequentially performing an anhydrous methanol washing, a deionized water washing, an acetone washing, and a dichloromethane washing. The drying parameters are not particularly limited, as long as the drying is ensured to be constant weight.
The invention also provides application of the pyridine and thiazole double-functionalized conjugated microporous polymer in the technical scheme or the pyridine and thiazole double-functionalized conjugated microporous polymer prepared by the preparation method in the technical scheme in hydrogen production through visible light decomposition.
The pyridine and thiazole bifunctional conjugated microporous polymers provided by the present invention, the preparation method and applications thereof are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparation of 2,4,6-tris (4-bromophenyl) pyridine
4-bromoacetophenone (2.1322g, 10mmol), 4-bromobenzaldehyde (0.9871g, 5mmol), ammonium acetate 14.2375g, and glacial acetic acid 7.3mL were added to the reaction vessel. The contents were heated in an oven at 220 ℃ for 45min under autogenous pressure. After heating, cooling the polymerization reaction feed liquid to room temperature, and adding deionized water with the same volume as the reaction feed liquid to obtain diluted polymerization reaction feed liquid; then neutralizing the diluted polymerization reaction feed liquid by using a saturated sodium bicarbonate solution to obtain a neutral reaction feed liquid; and (3) extracting the neutral reaction liquid by using dichloromethane, screwing out a product from the obtained dichloromethane phase by using a rotary evaporator, and adding a proper amount of deionized water for elution. After suction filtration, a solid was obtained, the dried solid was placed in a round bottom flask, recrystallized with acetone (about 70 ℃), the solution in the flask was slightly boiled, acetone was slowly added until the solid in the flask was dissolved, and the clear liquid was poured into a beaker for cooling and crystallization to give the pure product 2,4,6-tris (4-bromophenyl) pyridine as a white solid (0.9258g, 31.9%).
FIG. 1 is a nuclear magnetic hydrogen spectrum of 2,4,6-tris (4-bromophenyl) pyridine, as seen in FIG. 1:1. proton peaks at 2, 13 and 14 are represented at δ = 8.04; proton peaks at 3 and 12 are represented at δ = 7.82; 4. proton peaks at 5, 6, 7, 8, 9, 10 and 11 are represented at δ = 7.66; which indicates that 2,4,6-tris (4-bromophenyl) pyridine has been successfully synthesized.
FIG. 2 is an IR spectrum of 2,4,6-tris (4-bromophenyl) pyridine as seen in FIG. 2: 3061cm -1 The absorption peak is the stretching vibration of unsaturated C-H; 1597cm -1 、1485cm -1 The absorption peak is the skeleton vibration of the pyridine ring; 1072cm -1 The absorption peak is unsaturated = C-Br stretching vibration; 816cm -1 Out-of-plane bending vibration having an absorption peak at C-H; 496cm -1 The absorption peak is C-N stretching vibration. Description of the drawings: the product meets the characteristic absorption band of 2,4,6-tris (4-bromophenyl) pyridine.
Preparation of 2,4,6-tris (4-phenylboronic acid pinacol ester) pyridine
2,4,6-tris (4-bromophenyl) pyridine (0.8561g, 1.6 mmol), pinacol diboron (2.0267g, 8.0 mmol), potassium acetate 0.6917g, [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride dichloromethane complex (0.1570g, 0.2mmol), tetrakis (triphenylphosphine) palladium (0.12g, 0.1mmol) and anhydrous tetrahydrofuran (50 mL) were added to a round bottom flask, respectively. The reaction solution was degassed by bubbling nitrogen three times with stirring and subjected to Miyaura boration reaction at 80 ℃ for 48h. Then cooling the obtained Miyaura boric acid esterification reaction feed liquid to room temperature and adding deionized water with the same volume to obtain diluted esterification reaction feed liquid; and (3) extracting the diluted esterification reaction liquid by using dichloromethane, adding a proper amount of anhydrous sodium sulfate into the lower dichloromethane layer, drying, then, spinning out a product by using a rotary evaporator, and adding a proper amount of anhydrous methanol to cover the surface of a reactant for elution. After suction filtration a solid was obtained which after drying gave the pure product 2,4,6-tris (4-phenylboronic acid pinacol ester) pyridine as a grey solid (0.8357g, 77.5%).
FIG. 3 is a nuclear magnetic hydrogen spectrum of 2,4,6-tris (4-phenylboronic acid pinacol ester) pyridine, as seen in FIG. 3: 5. proton peaks at 6, 25 and 26 are represented at δ = 8.21; 8. proton peaks at 9, 14, 15, 16, 17, 22 and 23 are represented at δ = 7.94; proton peaks at 7 and 24 are represented at δ = 7.75; 1. proton peaks at 2, 3, and 4 are represented at δ = 3.81; 10. the proton peaks at 11, 12, 13, 18, 19, 20 and 21 are represented at δ = 1.06. It is demonstrated that 2,4,6-tris (pinacol 4-phenylboronate) pyridine has been successfully synthesized.
FIG. 4 is an IR spectrum of 2,4,6-tris (pinacol 4-phenylboronate) pyridine, as seen in FIG. 4: 2978cm -1 The absorption peak is saturated C-H stretching vibration; 1599cm -1 The absorption peak is the skeleton vibration of the pyridine ring; 1144cm -1 The absorption peak is C-O stretching vibration; 858cm -1 Out-of-plane bending vibration having an absorption peak at C-H; 436cm -1 The absorption peak is C-N stretching vibration. Description of the drawings: the product meets the characteristic absorption band of 2,4,6-tris (4-phenylboronic acid pinacol ester) pyridine.
Preparation of pyridine and thiazole dual-functionalized conjugated microporous polymer (ZJM-CMP)
A2 mol/L potassium carbonate solution is prepared (6.9317 g potassium carbonate is weighed and added into 25mL deionized water, and ultrasonic dissolution is carried out for standby).
Weighing 4,7-dibromo-2,1,3-benzothiadiazole (0.2070g, 0.704mmol), 2,4,6-tris (4-phenylboronic acid pinacol ester) pyridine (0.3215g, 0.486mmol), measuring potassium carbonate solution (6mL), N-Dimethylformamide (DMF) 40mL and tetrakis (triphenylphosphine) palladium (0.1 g) in a round-bottomed flask, and degassing the reaction solution by bubbling nitrogen three times and stirring; the reaction was carried out at 150 ℃ for 48h. The reaction mixture was then cooled to room temperature and an equal volume of deionized water was added. Finally, covering the surface of the reactant with a proper amount of anhydrous methanol, deionized water, acetone and dichloromethane respectively, washing, and performing suction filtration to obtain a solid, wherein the color of the dried solid is green (0.3128g, 59.2%).
FIG. 5 is an infrared spectrum of a pyridine and thiazole bi-functionalized conjugated microporous polymer (ZJM-CMP), and it can be seen from FIG. 5 that: comparing and judging the infrared absorption peak of 2,4,6-tri (4-bromophenyl) pyridine (L1), 2,4,6-tri (4-phenylboronic acid pinacol ester) pyridine (L2) and ZJM-CMP; it can be seen that: ZJM-CMP at 1144cm -1 The C-O characteristic absorption peak disappears at 1599cm -1 The absorption peak of the skeleton vibration having a pyridine ring did not disappear at 2978cm -1 The absorption peak of C-H stretching vibration at saturation disappears. In conclusion, the characteristic absorption band of ZJM-CMP is met.
FIG. 6 is a UV spectrum of a pyridine and thiazole double-functionalized conjugated microporous polymer (ZJM-CMP), as can be seen from FIG. 6: ZJM-CMP showed a broadening of the absorption band compared to 2,4,6-tris (4-phenylboronic acid pinacol ester) pyridine (L2), indicating an increased degree of ZJM-CMP conjugation.
FIG. 7 is a thermogravimetric analysis plot of 2,4,6-tris (pinacol ester 4-phenylboronate) pyridine (ZJM-CMP) as seen in FIG. 7: the slope is larger in the range of RT-71.9 ℃, which shows that the ZJM-CMP loses weight rapidly in the stage, and the weight loss is mainly caused by the absorption of water on the surface and the loss of structural water. At the stage of 71.9-600 ℃, the weight loss curve almost tends to level, which shows that the weight loss is very small in the temperature range, and the polymer structure has better thermal stability in the temperature range. At the 600-1000 ℃ stage, weight loss is relatively fast, indicating that the polymer structure has collapsed and the structure is damaged in this temperature range. Therefore, the ZJM-CMP has better thermal stability at the stage of 71.9-600 ℃.
FIG. 8 is an XRD scanning analysis of 2,4,6-tris (4-phenylboronic acid pinacol ester) pyridine (ZJM-CMP) as seen in FIG. 8: ZJM-CMP has no diffraction peak, and its structure is amorphous.
FIG. 9 is a scanning electron micrograph of 2,4,6-tris (4-phenylboronic acid pinacol ester) pyridine (ZJM-CMP) showing that: the ZJM-CMP is granular with different shapes, and the structure of the ZJM-CMP is amorphous.
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 (10)
1. A pyridine and thiazole dual-functionalized conjugated microporous polymer is characterized by comprising a structural unit shown as a formula I:
2. the method for preparing the pyridine and thiazole bi-functionalized conjugated microporous polymer according to claim 1, comprising the following steps:
4-bromoacetophenone, 4-bromobenzaldehyde and ammonium acetate are subjected to polymerization reaction to obtain 2,4,6-tri (4-bromophenyl) pyridine;
carrying out Miyaura boric acid esterification reaction on 2,4,6-tri (4-bromophenyl) pyridine and pinacol diboron under alkaline condition to obtain 2,4,6-tri (4-phenylboronic acid pinacol ester) pyridine;
and (3) carrying out Suzuik reaction on the 2,4,6-tri (4-phenylboronic acid pinacol ester) pyridine and 4,7-dibromo-2,1,3-benzothiadiazole under an alkaline condition to obtain the pyridine and thiazole bifunctional conjugated microporous polymer.
3. The preparation method according to claim 2, characterized in that the molar ratio of 4-bromoacetophenone, 4-bromobenzaldehyde and ammonium acetate is (1.8-2.2): (0.8-1.2): (36 to 38).
4. The method according to claim 2 or 3, wherein the polymerization reaction temperature is 200 to 250 ℃ and the holding time is 30 to 60min.
5. The method of claim 2, wherein the molar ratio of 2,4,6-tris (4-bromophenyl) pyridine to pinacol diboron is (0.8-1.2): (4-6).
6. The method of claim 2, wherein the Miyaura boronation reaction further comprises a catalyst, the catalyst being a mixed catalyst comprising [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride dichloromethane complex and tetrakis (triphenylphosphine) palladium; in the mixed catalyst, the molar ratio of the [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride dichloromethane complex to the tetrakis (triphenylphosphine) palladium is (1.8-2.2): (0.8-1.2).
7. The preparation method of claim 2, 5 or 6, wherein the temperature of the Miyaura boric acid esterification reaction is 70-100 ℃, and the holding time is 36-72 h.
8. The method of claim 2, wherein the molar ratio of 4,7-dibromo-2,1,3-benzothiadiazole to 2,4,6-tris (4-phenylboronic acid pinacol ester) pyridine is 0.704:0.486.
9. the method according to claim 2 or 8, wherein the temperature of the Suzuik reaction is 120 to 200 ℃ and the holding time is 36 to 48 hours.
10. Use of the pyridine and thiazole double-functionalized conjugated microporous polymer according to claim 1 or the pyridine and thiazole double-functionalized conjugated microporous polymer prepared by the preparation method according to any one of claims 2 to 9 in hydrogen production by photolysis of water.
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