CN116769159A - Polyarylpyridine and preparation method and application thereof - Google Patents
Polyarylpyridine and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- -1 poly aryl pyridine Chemical compound 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 119
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 59
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 38
- 239000005695 Ammonium acetate Substances 0.000 claims description 38
- 229940043376 ammonium acetate Drugs 0.000 claims description 38
- 235000019257 ammonium acetate Nutrition 0.000 claims description 38
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 23
- 238000001514 detection method Methods 0.000 claims description 20
- 239000002360 explosive Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 3
- 229940107816 ammonium iodide Drugs 0.000 claims description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 3
- 230000001404 mediated effect Effects 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000005841 biaryl group Chemical group 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000002776 aggregation Effects 0.000 abstract description 32
- 238000004220 aggregation Methods 0.000 abstract description 32
- 125000000524 functional group Chemical group 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract 1
- 239000004033 plastic Substances 0.000 abstract 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 67
- 229920000642 polymer Polymers 0.000 description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 52
- 238000005227 gel permeation chromatography Methods 0.000 description 29
- 239000000243 solution Substances 0.000 description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 24
- 229920000742 Cotton Polymers 0.000 description 17
- 239000011521 glass Substances 0.000 description 17
- 238000010790 dilution Methods 0.000 description 16
- 239000012895 dilution Substances 0.000 description 16
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000001345 alkine derivatives Chemical class 0.000 description 4
- 150000005347 biaryls Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920000412 polyarylene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OBQRODBYVNIZJU-UHFFFAOYSA-N (4-acetylphenyl)boronic acid Chemical compound CC(=O)C1=CC=C(B(O)O)C=C1 OBQRODBYVNIZJU-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- XXZCIYUJYUESMD-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(morpholin-4-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCOCC1 XXZCIYUJYUESMD-UHFFFAOYSA-N 0.000 description 1
- 229940073735 4-hydroxy acetophenone Drugs 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
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- 235000013399 edible fruits Nutrition 0.000 description 1
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 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 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
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- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
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- 150000003967 siloles Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a poly aryl pyridine and a preparation method and application thereof. The reaction raw materials disclosed by the invention are easy to obtain, and the reaction conditions are mild; the polymerization reaction has wide substrate applicability and good functional group compatibility, and can conveniently introduce various functional groups; the polyarylpyridine prepared by the invention has good processability, higher thermal stability and aggregation-induced emission performance, and has application value in the aspects of optical plastics, biomedical materials, fluorescence sensing and the like.
Description
Technical Field
The invention relates to the technical field of polymer synthesis and materials, in particular to a polyarylpyridine and a preparation method and application thereof.
Background
The development of new polymerization reaction and the preparation of polymer materials with new structures have important application values. In recent years, a method for synthesizing functional polymers has been developed, and multicomponent polymerization has been receiving attention for the advantages of high synthesis efficiency, simple operation, structural diversity of products, high atomic economy, and the like. In addition, the in situ construction of new functional groups such as heterocycles in multicomponent polymerizations is difficult to achieve with other polymerization methods. Meanwhile, in the multicomponent polymerization reaction, a plurality of reaction steps can be completed according to a specific sequence by a one-pot method, wherein the intermediate formed in the first step is directly added with new components for subsequent reaction without separation and purification, and a product with high efficiency and good specificity can be obtained. For example, a multicomponent polymerization consisting of a modified Sonogashira coupling reaction and a sequential addition-cyclization reaction of alkyne/carbonyl chloride can readily yield conjugated polythiophenes (Macromolecules 2014,47,4920-4929) and polypyrazoles (Macromolecules 2016,49,9291-9300) of well-defined structure, high molecular weight, and high yield. In addition, the multi-component polymerization can also effectively control the order of functional groups on the polymer backbone, for example, a structurally tunable and sequence-controllable polytetrahydrofyrimidine can be obtained by a metal-free multi-component polymerization of activated alkynes, aromatic diamines and formaldehyde (polym. Chem.2015,6, 4436-4446). Most of these multicomponent polymerizations are based on terminal alkynes, which are rarely used for the preparation of heterocyclic polymers due to their high steric hindrance and relatively low reactivity. In the multicomponent polymerization reaction reported at present, a transition metal catalyst is often used to reduce the activation energy of the reaction, however, the residual catalyst can influence the mechanical property and the photoelectric property of the polymer functional material. In 2021, the trofimiov group reported a reaction to produce 2,4, 6-triarylpyridine in situ from potassium tert-butoxide catalyzed by a multicomponent one pot process of methyl ketone, active alkyne and ammonium acetate (org. Biomol. Chem.2021,19, 2703-2715.). The reaction is expected to develop into a polymerization reaction for preparing the polyarylpyridine.
Conventional organic and polymeric luminescent materials emit intense light in solution, while they emit reduced or no light in the aggregated or solid state, limiting the use of such materials in the solid state. In 2001, the hong Kong university of science and technology Tang group reported a novel photophysical phenomenon, aggregation-induced emission (AIE): little luminescence was observed in solution with small organic molecule silole derivatives, while fluorescence intensity showed a significant increase once nanoparticles were formed or after film formation (chem. Commun.2001, 1740-1741). Materials possessing AIE properties have been widely used in the fields of display, chemical detection, biosensing, and the like (chem. Rev.2015,115, 11718-11940). AIE-active polymeric materials have been reported to be less frequently than small molecule materials (prog. Polym. Sci.2020,100, 101176). The AIE polymer with a new structure prepared based on the novel polymerization reaction has important application value.
Disclosure of Invention
In order to solve the technical problems, the invention provides a polyarylpyridine and a preparation method and application thereof. The invention takes binary aryl ketone monomer, binary aryl acetylenic ketone monomer and ammonium acetate as raw materials, and obtains the poly aryl pyridine through reaction in the presence of potassium tert-butoxide and polar aprotic solvent. The preparation method is simple, has wide substrate applicability and good functional group compatibility, is convenient for introducing various functional groups, and realizes the preparation of different polymer functional materials.
A first object of the present invention is to provide a polyarylpyridine having the structural formula:
wherein n is 2-200;
r1 is one of the groups 1-20, R2 is one of the groups 1-20, and the structural formula of the groups 1-20 is as follows:
m is an integer from 1 to 18, and is the substitution position.
The second object of the present invention is to provide a method for preparing a polyarylpyridine, comprising the steps of:
with biaryl ethanone monomersWith a biaryl alkynone monomer->And (3) taking ammonium acetate or ammonium iodide as a raw material, and obtaining the polyarylpyridine through solution polymerization reaction in a reaction solvent.
R 1 Is one of the groups 1 to 20, R 2 Is one of the groups 1 to 20, and the structural formula of the groups 1 to 20 is as follows:
m is an integer from 1 to 18, and is the substitution position.
In one embodiment of the invention, the polymerization is carried out under air atmosphere and under potassium tert-butoxide mediated conditions.
In one embodiment of the invention, the polymerization conditions are: the reaction temperature is 30-120 ℃, preferably 80-110 ℃; the reaction time is 3 to 15 hours, preferably 4 to 12 hours.
In one embodiment of the present invention, the reaction solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and toluene. The solvent may be a conventional high boiling point solvent.
In one embodiment of the invention, the molar ratio of the biaryl ethanone monomer to the biaryl alkynone monomer is 1:1.1 to 1:3.
in one embodiment of the invention, the concentration of the biaryl ethanone monomer is 0.02 to 1mol/L. Further, it is preferably 0.05 to 0.33mol/L.
In one embodiment of the invention, the concentration of the biaryl alkynone monomer is 0.02 to 1mol/L. Further, it is preferably 0.05 to 0.33mol/L.
Further, the polymerization reaction is finished, and the method further comprises post-treatment, preferably, the post-treatment is as follows: and diluting the polymerization reaction solution by the first organic solvent, then dripping the diluted polymerization reaction solution into the second organic solvent, and precipitating to obtain the polyarylpyridine.
Further, the first organic solvent is tetrahydrofuran or chloroform.
Further, the second organic solvent is methanol, petroleum ether or n-hexane.
Further, the preparation method of the polyarylpyridine specifically comprises the following steps:
mixing a biaryl ethanone monomer, a biaryl alkynone monomer and ammonium acetate with a reaction solvent to obtain a mixed solution, and then carrying out solution polymerization to obtain the poly aryl pyridine.
The third object of the present invention is to provide a fluorescence sensor, which comprises the polyarylpyridine or the polyarylpyridine prepared by the preparation method.
The fourth object of the invention is to provide the fluorescent sensor for detecting polynitro aromatic explosives.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the invention takes biaryl ethanone, biacetylene ketone and ammonium acetate as reaction raw materials, and synthesizes the poly aryl pyridine through reaction under the mediation of potassium tert-butoxide. The polyarylpyridine prepared by the invention has good thermal stability, good solubility in organic solvents such as chloroform, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and the like, and good processability and film forming property. In addition, the polyarylpyridine containing AIE active units (such as tetraphenyl ethylene and the like) prepared by the method has AIE performance and can be used as a fluorescence sensor for detecting polynitro aromatic explosives.
2. The invention develops the potassium tert-butoxide mediated polymerization reaction, has mild reaction conditions, easily available reaction raw materials, direct purchase or synthesis by simple reaction, does not need to use a transition metal catalyst, and can avoid the influence of the residue of the transition metal catalyst on the biological and optical properties of the polymer material; the polymerization reaction has wide substrate applicability and good functional group compatibility, and can conveniently introduce various functional groups. Therefore, the polymerization reaction has important application value in the aspect of high molecular synthesis and polymer functional materials.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings, in which
Fig. 1 is a structural diagram of a polyarylpyridine of the present invention (n=4);
FIG. 2 shows the preparation of the polyarylene pyridines and their corresponding monomers in CDCl according to example 1 of the present invention 3 Hydrogen nuclear magnetic resonance spectra ("x" represents solvent peak) plot;
FIG. 3 is a graph showing the thermal weight loss of the polyarylene pyridines prepared in examples 1, 13, 14, 15, 16 according to the present invention, under test conditions: the temperature rising rate is 10 ℃/min under the nitrogen atmosphere;
FIG. 4 is an AIE graph of a polyarylpyridine prepared in example 1 of the present invention;
FIG. 5 is a fluorescence spectrum of Picric Acid (PA) under the aggregation state of the polyarylpyridine prepared in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it. In the present invention, unless otherwise indicated,only the molecular connection relationship is shown.
Example 1
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
(1) Preparation of binary acetophenone
The first monomer, binary acetophenone, is a commercial chemical and is commercially available.
(2) Preparation of a diyne monomer
The synthesis of the second monomer, the diketene monomer, was synthesized by reference to published literature (Acta chim. Sinica 2016,74, 885-892) preparation methods.
The compound diynyltetraphenyl ethylene (0.76 g,2.0 mmol), benzoyl chloride (0.56 g,4.0 mmol), bis (triphenylphosphine) palladium dichloride (56 mg,0.08 mmol) and cuprous iodide (64 mg,0.32 mmol) were weighed into a 100mL double-necked flask, evacuated, and purged with nitrogen to remove oxygen and water vapor from the flask. Tetrahydrofuran (50 mL) and triethylamine (0.6 mL) were then sequentially injected into the flask, the reaction was stirred at room temperature for 4h, after the completion of the reaction, the organic layer was extracted with dichloromethane and water, concentrated by rotary evaporation, and purified by silica gel column chromatography with a mixed solvent of petroleum ether/ethyl acetate (20:1, v/v) as a eluent to give 0.96g of a yellowish green solid with a yield of 82%. The nuclear magnetic characterization data are as follows: 1 H NMR(400MHz,CDCl 3 ),δ(TMS,ppm):8.26–8.14(m,4H),7.67–7.40(m,10H),7.23–6.92(m,14H).
(3) Preparation of ammonium acetate
The third component, ammonium acetate, is a commercial chemical and is available directly.
(4) Preparation of polyarylpyridines
To a 10mL polymerization tube with side arms was added first monomer binary acetophenone (16.2 mg,0.10 mmol), second monomer binary alkynone monomer (88.2 mg,0.15 mmol), potassium tert-butoxide (22.4 mg,0.2 mmol) and DMSO (1.0 mL). After reacting for 0.5h in a constant temperature oil bath at 60 ℃, adding a third component ammonium acetate (38.5 mg,0.5 mmol), continuing the reaction for 11.5h in the constant temperature oil bath at 90 ℃, adding 3mL of tetrahydrofuran for dilution after polymerization, then dripping the diluted solution into stirring absolute methanol (120 mL) through a glass tube filled with cotton, standing, filtering by a funnel, and obtaining a polymer which is dried to constant weight.
Characterization data: yellow solid with a yield of 70.1%. GPC results showed that: weight average molecular weight (M) w ) 13400 and a molecular weight distribution (PDI) of 3.00. 1 H NMR(400MHz,CDCl 3 ),δ(TMS,ppm):7.86,7.79,7.25,6.69,2.50.
The nuclear magnetic resonance hydrogen spectrum of the polymer and the corresponding monomer is shown in figure 2, the polymer is determined to be polyarylpyridine from the figure, the peak at delta 2.58 (6) is a proton resonance peak on the binary acetophenone methyl of the first monomer, the intensity is obviously reduced on the nuclear magnetic resonance hydrogen spectrum of the polymer, and the reaction of the monomers is shown. Meanwhile, a new resonance peak of delta 7.85 appears, and the new resonance peak is compared with a model product to attribute the new resonance peak to hydrogen on a newly generated pyridine ring, and meanwhile, the newly generated pyridine ring in the polymer can be determined to be in a single 2,4, 6-configuration, so that the multicomponent reaction has regioselectivity.
Performance study and application:
(1) Solubility of
The polyarylpyridine prepared by the embodiment is easy to dissolve in common organic solvents such as chloroform, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and the like at room temperature, and has good processability and film forming property.
(2) Thermal stability
The polyarylpyridine prepared in this example was subjected to thermogravimetric analysis and the test results are shown in fig. 3, and the polyarylpyridine polymer was heated to 460 ℃ to lose only 5% weight, which also indicates that the polyarylpyridine prepared in this example has good thermal stability.
(3) AIE performance
The polyarylpyridine prepared in this example was dispersed in tetrahydrofuran solutions having different water contents, and as shown in fig. 4, the polymer showed extremely weak luminescence in tetrahydrofuran solution, significantly enhanced fluorescence after addition of poor solvent water, and enhanced with increasing water content, exhibiting excellent aggregation-induced emission properties.
(4) Application of polyarylpyridine in detection of nitroaromatic explosives
Detecting PA (picric acid, PA) by taking picric acid as a model explosive: first prepare 10 -5 A tetrahydrofuran aqueous solution of the polyarylpyridine (the volume fraction of water is 90%) with mol/L is taken as a detection object, different amounts of the detection object PA are sequentially added, and fluorescence spectra are rapidly tested. As shown in fig. 4, when PA is not added, the detection object has stronger fluorescence; the fluorescence was decreased when PA was added, and the fluorescence intensity was gradually decreased as the PA content was gradually increased. The result shows that the polyarylpyridine prepared by the invention can be used as a sensor for detecting the nitrateAnd (3) base aromatic explosives.
Example 2
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
the binary acetophenone monomer, the binary alkynone monomer and the ammonium acetate were the same as in example 1. To a 10mL polymerization tube with side arms was added first monomer binary acetophenone (16.2 mg,0.10 mmol), second monomer binary alkynone monomer (88.2 mg,0.15 mmol), potassium tert-butoxide (22.4 mg,0.2 mmol) and DMSO (1.0 mL). After reacting for 0.5h in a constant temperature oil bath at 60 ℃, ammonium acetate (38.5 mg,0.5 mmol) was added, the reaction was continued for 5.5h in a constant temperature oil bath at 80 ℃, 3mL of tetrahydrofuran was added for dilution after the polymerization was completed, then the diluted solution was added dropwise to stirred absolute methanol (120 mL) through a glass tube filled with cotton, and after standing, filtration was carried out with a funnel, and the polymer was dried to constant weight. The yield was 64.7%. Gel permeation chromatography GPC results showed: weight average molecular weight (M) w ) 9300 and a molecular weight distribution (PDI) of 2.23.
The polymer prepared by the embodiment also has better solubility and thermal stability; the polymer also has aggregation-induced emission properties due to the inclusion of the aggregation-induced photoactive tetraphenyl vinyl group, and can be used for nitroaromatic explosives detection, as in example 1.
Example 3
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
the binary acetophenone monomer, the binary alkynone monomer and the ammonium acetate were the same as in example 1. To a 10mL polymerization tube with side arms was added first monomer binary acetophenone (16.2 mg,0.10 mmol), second monomer binary alkynone monomer (88.2 mg,0.15 mmol), potassium tert-butoxide (22.4 mg,0.2 mmol) and DMSO (1.0 mL). After reacting for 0.5h in a constant temperature oil bath at 60 ℃, ammonium acetate (38.5 mg,0.5 mmol) was added, the reaction was continued for 5.5h in a constant temperature oil bath at 100 ℃, 3mL of tetrahydrofuran was added for dilution after the polymerization was completed, then the diluted solution was added dropwise to stirred absolute methanol (120 mL) through a glass tube filled with cotton, and after standing, filtration was carried out with a funnel, and the polymer was dried to constant weight. The yield was 84.0%. Gel permeation chromatography GPC junctionThe fruit display: weight average molecular weight (M) w ) 26800, molecular weight distribution (PDI) of 4.22.
The polymer prepared by the embodiment also has better solubility and thermal stability; the polymer also has aggregation-induced emission properties due to the inclusion of the aggregation-induced photoactive tetraphenyl vinyl group, and can be used for nitroaromatic explosives detection, as in example 1.
Example 4
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
the binary acetophenone monomer, the binary alkynone monomer and the ammonium acetate were the same as in example 1. To a 10mL polymerization tube with side arms was added first monomer binary acetophenone (16.2 mg,0.10 mmol), second monomer binary alkynone monomer (88.2 mg,0.15 mmol), potassium tert-butoxide (22.4 mg,0.2 mmol) and DMSO (1.0 mL). After reacting for 0.5h in a constant temperature oil bath at 60 ℃, ammonium acetate (38.5 mg,0.5 mmol) was added, the reaction was continued for 5.5h in a constant temperature oil bath at 110 ℃, 3mL of tetrahydrofuran was added for dilution after the polymerization was completed, then the diluted solution was added dropwise to stirred absolute methanol (120 mL) through a glass tube filled with cotton, and after standing, filtration was carried out with a funnel, and the polymer was dried to constant weight. The yield was 67.6%. Gel permeation chromatography GPC results showed: weight average molecular weight (M) w ) 26800, molecular weight distribution (PDI) of 4.53.
The polymer prepared by the embodiment also has better solubility and thermal stability; the polymer also has aggregation-induced emission properties due to the inclusion of the aggregation-induced photoactive tetraphenyl vinyl group, and can be used for nitroaromatic explosives detection, as in example 1.
Example 5
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
to a 10mL polymerization tube with side arms was added first monomer binary acetophenone (16.2 mg,0.10 mmol), second monomer binary alkynone monomer (88.2 mg,0.15 mmol), potassium tert-butoxide (22.4 mg,0.2 mmol) and DMSO (2.0 mL). After 0.5h of reaction in a 60℃constant temperature oil bath, ammonium acetate (38.5 mg,0.5 mmol) was added to the reaction vessel, and the reaction vessel was heated at 90℃constant temperatureThe reaction was continued for 5.5 hours, 3mL of tetrahydrofuran was added to dilute after the polymerization was completed, then the diluted solution was added dropwise to stirred absolute methanol (120 mL) through a glass tube filled with cotton, and after standing, the mixture was filtered with a funnel to obtain a polymer which was dried to constant weight. The yield was 66.7%. Gel permeation chromatography GPC results showed: weight average molecular weight (M) w ) 7000 and a molecular weight distribution (PDI) of 2.21.
The polymer prepared by the embodiment also has better solubility and thermal stability; the polymer also has aggregation-induced emission properties due to the inclusion of the aggregation-induced photoactive tetraphenyl vinyl group, and can be used for nitroaromatic explosives detection, as in example 1.
Example 6
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
the binary acetophenone monomer, the binary alkynone monomer and the ammonium acetate monomer were the same as in example 1. To a 10mL polymerization tube with side arms was added first monomer binary acetophenone (16.2 mg,0.10 mmol), second monomer binary alkynone monomer (88.2 mg,0.15 mmol), potassium tert-butoxide (22.4 mg,0.2 mmol) and DMSO (1.5 mL). After reacting for 0.5h in a constant temperature oil bath at 60 ℃, ammonium acetate (38.5 mg,0.5 mmol) was added, the reaction was continued for 5.5h in a constant temperature oil bath at 90 ℃, 3mL of tetrahydrofuran was added for dilution after the polymerization was completed, then the diluted solution was added dropwise to stirred absolute methanol (120 mL) through a glass tube filled with cotton, and after standing, filtration was carried out with a funnel, and the polymer was dried to constant weight. The yield was 75.0%. Gel permeation chromatography GPC results showed: weight average molecular weight (M) w ) 8700 and a molecular weight distribution (PDI) of 2.30.
The polymer prepared by the embodiment also has better solubility and thermal stability; the polymer also has aggregation-induced emission properties due to the inclusion of the aggregation-induced photoactive tetraphenyl vinyl group, and can be used for nitroaromatic explosives detection, as in example 1.
Example 7
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
binary acetophenone monomerThe diyne ketone monomer and the ammonium acetate monomer were as in example 1. To a 10mL polymerization tube with side arms was added first monomer binary acetophenone (16.2 mg,0.10 mmol), second monomer binary alkynone monomer (88.2 mg,0.15 mmol), potassium tert-butoxide (22.4 mg,0.2 mmol) and DMSO (0.5 mL). After reacting for 0.5h in a constant temperature oil bath at 60 ℃, ammonium acetate (38.5 mg,0.5 mmol) was added, the reaction was continued for 5.5h in a constant temperature oil bath at 90 ℃, 3mL of tetrahydrofuran was added for dilution after the polymerization was completed, then the diluted solution was added dropwise to stirred absolute methanol (120 mL) through a glass tube filled with cotton, and after standing, filtration was carried out with a funnel, and the polymer was dried to constant weight. The yield was 70.0%. Gel permeation chromatography GPC results showed: weight average molecular weight (M) w ) 8200 and a molecular weight distribution (PDI) of 1.86.
The polymer prepared by the embodiment also has better solubility and thermal stability; the polymer also has aggregation-induced emission properties due to the inclusion of the aggregation-induced photoactive tetraphenyl vinyl group, and can be used for nitroaromatic explosives detection, as in example 1.
Example 8
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
the binary acetophenone monomer, the binary alkynone monomer and the ammonium acetate monomer were the same as in example 1. To a 10mL polymerization tube with side arms was added first monomer binary acetophenone (16.2 mg,0.10 mmol), second monomer binary alkynone monomer (88.2 mg,0.15 mmol), potassium tert-butoxide (22.4 mg,0.2 mmol) and DMSO (0.3 mL). After reacting for 0.5h in a constant temperature oil bath at 60 ℃, ammonium acetate (38.5 mg,0.5 mmol) was added, the reaction was continued for 5.5h in a constant temperature oil bath at 90 ℃, 3mL of tetrahydrofuran was added for dilution after the polymerization was completed, then the diluted solution was added dropwise to stirred absolute methanol (120 mL) through a glass tube filled with cotton, and after standing, filtration was carried out with a funnel, and the polymer was dried to constant weight. The yield was 13.9%. Gel permeation chromatography GPC results showed: weight average molecular weight (M) w ) 3200 and a molecular weight distribution (PDI) of 1.24.
The polymer prepared by the embodiment also has better solubility and thermal stability; the polymer also has aggregation-induced emission properties due to the inclusion of the aggregation-induced photoactive tetraphenyl vinyl group, and can be used for nitroaromatic explosives detection, as in example 1.
Example 9
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
the binary acetophenone monomer, the binary alkynone monomer and the ammonium acetate monomer were the same as in example 1. To a 10mL polymerization tube with side arms was added first monomer binary acetophenone (16.2 mg,0.10 mmol), second monomer binary alkynone monomer (88.2 mg,0.15 mmol), potassium tert-butoxide (11.2 mg,0.1 mmol), and DMSO (1.0 mL). After reacting for 0.5h in a constant temperature oil bath at 60 ℃, ammonium acetate (38.5 mg,0.5 mmol) was added, the reaction was continued for 5.5h in a constant temperature oil bath at 90 ℃, 3mL of tetrahydrofuran was added for dilution after the polymerization was completed, then the diluted solution was added dropwise to stirred absolute methanol (120 mL) through a glass tube filled with cotton, and after standing, filtration was carried out with a funnel, and the polymer was dried to constant weight. The yield was 47.2%. Gel permeation chromatography GPC results showed: weight average molecular weight (M) w ) 3100, a molecular weight distribution (PDI) of 1.35.
The polymer prepared by the embodiment also has better solubility and thermal stability; the polymer also has aggregation-induced emission properties due to the inclusion of the aggregation-induced photoactive tetraphenyl vinyl group, and can be used for nitroaromatic explosives detection, as in example 1.
Example 10
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
the binary acetophenone monomer, the binary alkynone monomer and the ammonium acetate monomer were the same as in example 1. To a 10mL polymerization tube with side arms was added first monomer binary acetophenone (16.2 mg,0.10 mmol), second monomer binary alkynone monomer (88.2 mg,0.15 mmol), potassium tert-butoxide (16.8 mg,0.15 mmol), and DMSO (1.0 mL). After 0.5h of reaction in a 60 ℃ constant temperature oil bath, ammonium acetate (38.5 mg,0.5 mmol) is added, the reaction is continued for 5.5h in a 90 ℃ constant temperature oil bath, 3mL of tetrahydrofuran is added for dilution after the polymerization is completed, then the diluted solution is dripped into the stirred absolute methanol (120 mL) through a glass tube filled with cotton,after standing, the polymer was filtered through a funnel and dried to constant weight. The yield was 55.6%. Gel permeation chromatography GPC results showed: weight average molecular weight (M) w ) 4100, a molecular weight distribution (PDI) of 1.60.
The polymer prepared by the embodiment also has better solubility and thermal stability; the polymer also has aggregation-induced emission properties due to the inclusion of the aggregation-induced photoactive tetraphenyl vinyl group, and can be used for nitroaromatic explosives detection, as in example 1.
Example 11
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
the binary acetophenone monomer, the binary alkynone monomer and the ammonium acetate monomer were the same as in example 1. To a 10mL polymerization tube with side arms was added first monomer binary acetophenone (16.2 mg,0.10 mmol), second monomer binary alkynone monomer (88.2 mg,0.15 mmol), potassium tert-butoxide (28.0 mg,0.25 mmol), and DMSO (1.0 mL). After reacting for 0.5h in a constant temperature oil bath at 60 ℃, ammonium acetate (38.5 mg,0.5 mmol) was added, the reaction was continued for 5.5h in a constant temperature oil bath at 90 ℃, 3mL of tetrahydrofuran was added for dilution after the polymerization was completed, then the diluted solution was added dropwise to stirred absolute methanol (120 mL) through a glass tube filled with cotton, and after standing, filtration was carried out with a funnel, and the polymer was dried to constant weight. The yield was 75.0%. Gel permeation chromatography GPC results showed: weight average molecular weight (M) w ) 13600 and a molecular weight distribution (PDI) of 3.79.
The polymer prepared by the embodiment also has better solubility and thermal stability; the polymer also has aggregation-induced emission properties due to the inclusion of the aggregation-induced photoactive tetraphenyl vinyl group, and can be used for nitroaromatic explosives detection, as in example 1.
Example 12
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
the binary acetophenone monomer, the binary alkynone monomer and the ammonium acetate monomer were the same as in example 1. Into a 10mL polymerization tube with side arms was added a first monomer, dibasic acetophenone (16.2 mg,0.10 mmol), a second monomerBinary alkynone monomer (88.2 mg,0.15 mmol), potassium tert-butoxide (33.6 mg,0.30 mmol) and DMSO (1.0 mL) were added. After reacting for 0.5h in a constant temperature oil bath at 60 ℃, ammonium acetate (38.5 mg,0.5 mmol) was added, the reaction was continued for 5.5h in a constant temperature oil bath at 90 ℃, 3mL of tetrahydrofuran was added for dilution after the polymerization was completed, then the diluted solution was added dropwise to stirred absolute methanol (120 mL) through a glass tube filled with cotton, and after standing, filtration was carried out with a funnel, and the polymer was dried to constant weight. The yield was 76.4%. Gel permeation chromatography GPC results showed: weight average molecular weight (M) w ) 9100 and a molecular weight distribution (PDI) of 2.42.
The polymer prepared by the embodiment also has better solubility and thermal stability; the polymer also has aggregation-induced emission properties due to the inclusion of the aggregation-induced photoactive tetraphenyl vinyl group, and can be used for nitroaromatic explosives detection, as in example 1.
Example 12-1
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
the binary acetophenone monomer and the binary alkynone monomer were the same as in example 1. To a 10mL polymerization tube with side arms was added first monomer binary acetophenone (16.2 mg,0.10 mmol), second monomer binary alkynone monomer (88.2 mg,0.15 mmol), potassium tert-butoxide (33.6 mg,0.30 mmol), and DMSO (1.0 mL). After reacting for 0.5h in a constant temperature oil bath at 60 ℃, ammonium iodide (72.5 mg,0.5 mmol) is added, the reaction is continued for 11.5h in the constant temperature oil bath at 90 ℃, 3mL of tetrahydrofuran is added for dilution after the polymerization is completed, then the diluted solution is dripped into the stirred absolute methanol (120 mL) through a glass tube filled with cotton, and the mixture is filtered by a funnel after standing, so that a polymer is obtained and dried to constant weight. The yield was 68.4%. Gel permeation chromatography GPC results showed: weight average molecular weight (M) w ) 6400, a molecular weight distribution (PDI) of 6.19.
The polymer prepared by the embodiment also has better solubility and thermal stability; the polymer also has aggregation-induced emission properties due to the inclusion of the aggregation-induced photoactive tetraphenyl vinyl group, and can be used for nitroaromatic explosives detection, as in example 1.
Example 13
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
(1) Synthesis of a biaryl ethanone monomer:
synthesis of the first monomer, the biaryl ethanone monomer, was synthesized by reference to published literature (Polym. Adv. Technology.2021, 33 (1), 427-439.).
Into a 250mL three-necked round bottom flask was charged 6.6g (0.04 mol) of 4-hydroxyacetophenone, 13.5g (0.09 mol) of potassium carbonate, 6g (0.02 mol) of 1, 6-dibromohexane and 25mL of N, N-Dimethylformamide (DMF). The contents were stirred at 110 ℃ under nitrogen atmosphere at room temperature for 24 hours. After the reaction was completed, the resultant product was extracted with ethyl acetate and washed twice in sodium hydroxide solution. The resulting organic layer was dried over anhydrous sodium sulfate and the organic layer was evaporated under vacuum to give 1,1- ((hexane-1, 6-diylbis (oxy)) bis (4, 1-phenylene)) diethyl ketone as a yellow solid (80% yield). 1 H NMR(400MHz,CDCl 3 ),δ(TMS,ppm):7.92(d,J＝8.4Hz,4H),6.92(d,J＝8.4Hz,4H),4.04(t,J＝6.4Hz,4H),2.55(s,6H),1.84(q,J＝6.5Hz,4H),1.54(s,4H).
(2) The second monomer, the diacetylenone monomer, was the same as in example 1.
(3) The third component ammonium acetate was as in example 1.
(4) Preparation of polyarylpyridine:
to a 10mL polymerization tube with side arms was added first monomer binary acetophenone (35.4 mg,0.10 mmol), second monomer binary alkynone monomer (88.2 mg,0.15 mmol), potassium tert-butoxide (22.4 mg,0.2 mmol), and DMSO (1.0 mL). After 0.5h of reaction in a 60 ℃ constant temperature oil bath, ammonium acetate (38.5 mg,0.5 mmol) is added, the reaction is continued for 11.5h in a 90 ℃ constant temperature oil bath, 3mL of tetrahydrofuran is added for dilution after the polymerization is completed, then the diluted solution is dripped into the stirred absolute methanol (120 mL) through a glass tube filled with cotton, and the mixture is filtered by a funnel after standing, thus obtaining polymer dryDrying to constant weight. Characterization data: yellow solid with a yield of 55.4%. GPC results showed that: weight average molecular weight (M) w ) 18800 and a molecular weight distribution (PDI) of 3.07. 1 H NMR(400MHz,CDCl 3 ),δ(TMS,ppm):8.02,7.92,7.58,7.51,7.42,7.29,7.10,6.91,6.76,6.71,4.08,2.5,1.86,1.75.
The polymer prepared by the embodiment also has better solubility and thermal stability; the polymer also has aggregation-induced emission properties due to the inclusion of the aggregation-induced photoactive tetraphenyl vinyl group, and can be used for nitroaromatic explosives detection, as in example 1.
Example 14
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
(1) Synthesis of a biaryl ethanone monomer:
1, 4-dibromo-tetraphenylene (2.46 g,5 mmol), potassium carbonate (2.07 g,15 mmol), tetrakis triphenylphosphine palladium (0.13 g,0.15 mmol), 4-acetylphenylboronic acid (3.28 g,20 mmol) were weighed into a 250mL dry two-port bottle, the apparatus was evacuated and nitrogen-filled three times, fresh THF (102 mL) was added, water (10.2 mL) was reacted in a 70℃constant temperature oil bath pot for 6h, the TLC plate confirmed that the starting materials had reacted completely, the reaction was completed and cooled to room temperature, extraction was performed with methylene chloride, the combined organic phases were dried with anhydrous magnesium sulfate, the filtered filtrate was concentrated by distillation under reduced pressure, and purified by silica gel column chromatography using a mixed solvent of petroleum ether and ethyl acetate (15:1) as an eluent. And drying to obtain grey solid which is the first monomer binary acetophenone monomer. The yield was 50.4% (1.43 g). 1 H NMR(400MHz,CDCl 3 ),δ(TMS,ppm):7.99(d,J＝8.0Hz,4H),7.65(d,J＝8.0Hz,4H),7.42(d,J＝7.9Hz,4H),7.23–6.96(m,12H),2.62(s,4H).
(2) The second monomer, the diacetylenone monomer, was the same as in example 1.
(3) The third component ammonium acetate was as in example 1.
(4) Preparation of polyarylpyridine:
to a 10mL polymerization tube with side arms was added first monomer binary acetophenone (56.9 mg,0.10 mmol), second monomer binary alkynone monomer (88.2 mg,0.15 mmol), potassium tert-butoxide (22.4 mg,0.2 mmol), and DMSO (1.0 mL). After reacting for 0.5h in a constant temperature oil bath at 60 ℃, ammonium acetate (38.5 mg,0.5 mmol) was added, the reaction was continued for 11.5h in a constant temperature oil bath at 90 ℃, 3mL of tetrahydrofuran was added for dilution after the polymerization was completed, then the diluted solution was added dropwise to stirred absolute methanol (120 mL) through a glass tube filled with cotton, and after standing, filtration was carried out with a funnel, and the polymer was dried to constant weight. Characterization data: yellow solid with a yield of 84.1%. GPC results showed that: weight average molecular weight (M) w ) 11600 and a molecular weight distribution (PDI) of 3.30. 1 HNMR(400MHz,CDCl 3 ),δ(TMS,ppm):δ8.03,7.90,7.74,7.58,7.53,7.47,7.19,7.22,7.13,7.07,6.84,6.76,2.52.
The polymer prepared by the embodiment also has better solubility and thermal stability; the polymer also has aggregation-induced emission properties due to the inclusion of the aggregation-induced photoactive tetraphenyl vinyl group, and can be used for nitroaromatic explosives detection, as in example 1.
Example 15
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
the method specifically comprises the following steps:
(1) First monomer binary acetophenone monomer same as in example 13
(2) Synthesis of binary alkynone monomer
The synthesis of the second monomer, the diketene monomer, was synthesized by the preparation method of published literature (macromol. Rapid Commun.2012,33 (16), 1356-1361).
PdCl was added to a 250mL double neck round bottom flask under nitrogen atmosphere 2 (PPh 3 )(281mg，0.4ⅹ10 -3 mol)、CuI(152mg，0.8ⅹ10 -3 mol)、PPh 3 (105mg，0.40ⅹ10 -3 mol), THF (60 mL) and triethylamine (20 mL). Then, 1, 4-dialkynylbenzene (10 x 10) was injected by syringe -3 mol,1.32 mL). The mixture was cooled to 0℃in an ice-water bath, after which benzoyl chloride (2.783 mL,24 x 10) was added dropwise -3 mol). After stirring at room temperature for 12 hours, the mixture was poured into ice water. The aqueous solution was extracted three times with 50mL of dichloromethane. The organic phases were combined and then dried over anhydrous magnesium sulfate overnight. After filtration and evaporation of the solvent, the crude product was purified by a silica gel column using a petroleum ether/chloroform mixture (1:1, v:v) as eluent. A grey powder (3.145 g) was obtained in 94.2% yield. 1 H NMR(400MHz,CDCl 3 ),δ(TMS,ppm):8.25–8.17(m,4H),7.73(s,4H),7.69–7.61(m,2H),7.57–7.49(m,4H).
(3) The third component ammonium acetate was as in example 1.
(4) Preparation of polyarylpyridine:
to a 10mL polymerization tube with side arms was added first monomer binary acetophenone (35.4 mg,0.10 mmol), second monomer binary alkynone monomer (50.1 mg,0.15 mmol), potassium tert-butoxide (22.4 mg,0.2 mmol), and DMSO (1.0 mL). After reacting for 0.5h in a constant temperature oil bath at 60 ℃, ammonium acetate (38.5 mg,0.5 mmol) was added, the reaction was continued for 11.5h in a constant temperature oil bath at 90 ℃, 3mL of tetrahydrofuran was added for dilution after the polymerization was completed, then the diluted solution was added dropwise to stirred absolute methanol (120 mL) through a glass tube filled with cotton, and after standing, filtration was carried out with a funnel, and the polymer was dried to constant weight. Characterization data: brown solid, yield 61.4%. GPC results showed that: weight average molecular weight (M) w ) 6700 and a molecular weight distribution (PDI) of 2.13. 1 H NMR(400MHz,CDCl 3 ),δ(TMS,ppm):8.23,7.86,7.81,7.68,7.64,7.50,7.45,7.35,7.26,7.01,6.96,6.89,6.64,4.00,3.93,2.571.85,1.27.
Example 16
The embodiment provides a preparation method of polyarylpyridine, which specifically comprises the following steps:
the method specifically comprises the following steps:
(1) First monomer binary acetophenone monomer As in example 14
(2) Synthesis of a second monomer, a binary alkynone monomer, was performed as in example 14
(3) The third component ammonium acetate was as in example 1.
(4) Preparation of polyarylpyridine:
to a 10mL polymerization tube with side arms was added first monomer binary acetophenone (56.9 mg,0.10 mmol), second monomer binary alkynone monomer (50.1 mg,0.15 mmol), potassium tert-butoxide (22.4 mg,0.2 mmol), and DMSO (1.0 mL). After reacting for 0.5h in a constant temperature oil bath at 60 ℃, ammonium acetate (38.5 mg,0.5 mmol) was added, the reaction was continued for 11.5h in a constant temperature oil bath at 90 ℃, 3mL of tetrahydrofuran was added for dilution after the polymerization was completed, then the diluted solution was added dropwise to stirred absolute methanol (120 mL) through a glass tube filled with cotton, and after standing, filtration was carried out with a funnel, and the polymer was dried to constant weight. Characterization data: brown solid, yield 57.8%. GPC results showed that: weight average molecular weight (M) w ) 7400 has a molecular weight distribution (PDI) of 2.70. 1 H NMR(400MHz,CDCl 3 ),δ(TMS,ppm):8.26,8.03,7.76,7.66,7.53,7.49,7.24,7.15,2.53.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A polyarylpyridine, wherein the polyarylpyridine has the structural formula:
wherein n is 2-200;
R 1 is one of the groups 1 to 20, R 2 Is one of the groups 1 to 20, and the structural formula of the groups 1 to 20 is as follows:
m is an integer from 1 to 18, and is the substitution position.
2. A process for the preparation of a polyarylpyridine according to claim 1, comprising the steps of:
with biaryl ethanone monomersWith a biaryl alkynone monomer->And (3) taking ammonium acetate or ammonium iodide as a raw material, and obtaining the polyarylpyridine through solution polymerization reaction in a reaction solvent.
3. The process according to claim 2, wherein the polymerization is carried out under air atmosphere and under potassium tert-butoxide-mediated conditions.
4. The method of claim 2, wherein the polymerization conditions: the reaction temperature is 30-120 ℃ and the reaction time is 3-15 hours.
5. The method according to claim 2, wherein the reaction solvent is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and toluene.
6. The method of claim 2, wherein the molar ratio of the biaryl ethanone monomer to the biaryl alkynone monomer is 1:1 to 1.3.
7. The method of claim 2, wherein the concentration of the biaryl ethanone monomer is 0.02 to 1mol/L.
8. The method of claim 2, wherein the concentration of the biaryl alkynone monomer is 0.02 to 1mol/L.
9. A fluorescence sensor, characterized in that it comprises a polyarylpyridine as described in claim 1 or a polyarylpyridine produced by the production method as described in any one of claims 2 to 8.
10. The fluorescence sensor of claim 9 for detection of polynitro aromatic explosives.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1747748A (en) * | 2003-05-23 | 2006-03-15 | 尼克塔治疗亚拉巴马公司 | Polymer derivatives having particular atom arrangements |
| US20060073607A1 (en) * | 2003-12-05 | 2006-04-06 | Massachusetts Institute Of Technology | Organic materials able to detect analytes |
| CN104094435A (en) * | 2011-09-02 | 2014-10-08 | 巴斯夫欧洲公司 | Diketopyrrolopyrrole oligomers and compositions, comprising diketopyrrolopyrrole oligomers |
| CN104817691A (en) * | 2015-04-24 | 2015-08-05 | 浙江大学 | Polyene ether compounds and preparation method thereof |
| CN106243352A (en) * | 2016-07-29 | 2016-12-21 | 苏州大学 | A kind of polyphenylene triazole formic acid esters and preparation method and application |
| WO2018076595A1 (en) * | 2016-10-28 | 2018-05-03 | 华南理工大学 | Narrow-range polyacetylene ester compound and preparation method therefor |
| CN110650947A (en) * | 2017-05-26 | 2020-01-03 | 免疫医疗有限责任公司 | Methods and molecules |
| WO2021017214A1 (en) * | 2019-07-31 | 2021-02-04 | 华南理工大学 | Electroluminescent polymer, preparation method and application thereof |
| WO2021031818A1 (en) * | 2019-08-22 | 2021-02-25 | 苏州大学 | Polyvinyl thioether ester, preparation method therefor and use thereof |
| CN113461914A (en) * | 2021-06-21 | 2021-10-01 | 上饶师范学院 | D-pi-A type polymer fluorescent material containing 2, 6-diphenyl-4-aryl pyridine structure and synthetic method thereof |
| CN113512050A (en) * | 2021-04-30 | 2021-10-19 | 中国计量大学 | Cuprous iodide complex-based pyridine VOC (volatile organic Compounds) fluorescent sensing material |
| CN114436948A (en) * | 2022-01-19 | 2022-05-06 | 上海工程技术大学 | Dipyridyl triphenylamine aldehyde fluorescent material with aggregation-induced emission effect and preparation method and application thereof |
| CN114835747A (en) * | 2022-06-02 | 2022-08-02 | 中国计量大学 | Cu2I2 binuclear cluster complex luminescent material and pyridine fluorescence sensor thereof |
| CN115124715A (en) * | 2021-03-29 | 2022-09-30 | 华南理工大学 | Preparation method of pyridyl polythioamide |
-
2023
- 2023-05-12 CN CN202310534131.7A patent/CN116769159A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1747748A (en) * | 2003-05-23 | 2006-03-15 | 尼克塔治疗亚拉巴马公司 | Polymer derivatives having particular atom arrangements |
| US20060073607A1 (en) * | 2003-12-05 | 2006-04-06 | Massachusetts Institute Of Technology | Organic materials able to detect analytes |
| CN104094435A (en) * | 2011-09-02 | 2014-10-08 | 巴斯夫欧洲公司 | Diketopyrrolopyrrole oligomers and compositions, comprising diketopyrrolopyrrole oligomers |
| CN104817691A (en) * | 2015-04-24 | 2015-08-05 | 浙江大学 | Polyene ether compounds and preparation method thereof |
| CN106243352A (en) * | 2016-07-29 | 2016-12-21 | 苏州大学 | A kind of polyphenylene triazole formic acid esters and preparation method and application |
| WO2018076595A1 (en) * | 2016-10-28 | 2018-05-03 | 华南理工大学 | Narrow-range polyacetylene ester compound and preparation method therefor |
| CN110650947A (en) * | 2017-05-26 | 2020-01-03 | 免疫医疗有限责任公司 | Methods and molecules |
| WO2021017214A1 (en) * | 2019-07-31 | 2021-02-04 | 华南理工大学 | Electroluminescent polymer, preparation method and application thereof |
| WO2021031818A1 (en) * | 2019-08-22 | 2021-02-25 | 苏州大学 | Polyvinyl thioether ester, preparation method therefor and use thereof |
| CN115124715A (en) * | 2021-03-29 | 2022-09-30 | 华南理工大学 | Preparation method of pyridyl polythioamide |
| CN113512050A (en) * | 2021-04-30 | 2021-10-19 | 中国计量大学 | Cuprous iodide complex-based pyridine VOC (volatile organic Compounds) fluorescent sensing material |
| CN113461914A (en) * | 2021-06-21 | 2021-10-01 | 上饶师范学院 | D-pi-A type polymer fluorescent material containing 2, 6-diphenyl-4-aryl pyridine structure and synthetic method thereof |
| CN114436948A (en) * | 2022-01-19 | 2022-05-06 | 上海工程技术大学 | Dipyridyl triphenylamine aldehyde fluorescent material with aggregation-induced emission effect and preparation method and application thereof |
| CN114835747A (en) * | 2022-06-02 | 2022-08-02 | 中国计量大学 | Cu2I2 binuclear cluster complex luminescent material and pyridine fluorescence sensor thereof |
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