CN114957659B - Polyoxadiazole and preparation method and application thereof - Google Patents
Polyoxadiazole and preparation method and application thereof Download PDFInfo
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- CN114957659B CN114957659B CN202210627246.6A CN202210627246A CN114957659B CN 114957659 B CN114957659 B CN 114957659B CN 202210627246 A CN202210627246 A CN 202210627246A CN 114957659 B CN114957659 B CN 114957659B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- -1 dialdehyde compound Chemical class 0.000 claims abstract description 21
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 18
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000000241 respiratory effect Effects 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims abstract description 6
- 239000012716 precipitator Substances 0.000 claims abstract description 6
- 238000012800 visualization Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000000732 arylene group Chemical group 0.000 claims description 10
- 150000002527 isonitriles Chemical class 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 150000003628 tricarboxylic acids Chemical group 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000003384 imaging method Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000000059 patterning Methods 0.000 claims 1
- 238000000799 fluorescence microscopy Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 22
- 238000001228 spectrum Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000010413 mother solution Substances 0.000 description 5
- 239000003755 preservative agent Substances 0.000 description 5
- 230000002335 preservative effect Effects 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 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 4
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 3
- IRMCTFUJDWPQGS-UHFFFAOYSA-N N(=C=O)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound N(=C=O)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 IRMCTFUJDWPQGS-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 3
- FQJXYULOQZUKBZ-UHFFFAOYSA-N 4-[6-(4-carboxyphenoxy)hexoxy]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OCCCCCCOC1=CC=C(C(O)=O)C=C1 FQJXYULOQZUKBZ-UHFFFAOYSA-N 0.000 description 2
- LUQVCHRDAGWYMG-UHFFFAOYSA-N 4-phenylbenzamide Chemical compound C1=CC(C(=O)N)=CC=C1C1=CC=CC=C1 LUQVCHRDAGWYMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- KQOATKAFTRNONV-UHFFFAOYSA-N oxolan-2-amine Chemical compound NC1CCCO1 KQOATKAFTRNONV-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002192 fatty aldehydes Chemical class 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- NIDTXBFHPXMXTR-UHFFFAOYSA-N isocyanoimino(triphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=N[N+]#[C-])C1=CC=CC=C1 NIDTXBFHPXMXTR-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/08—Polyhydrazides; Polytriazoles; Polyaminotriazoles; Polyoxadiazoles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1475—Heterocyclic containing nitrogen and oxygen as heteroatoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a polyoxadiazole, a preparation method and application thereof, wherein the method comprises the following steps: respectively adding an aldehyde monomer, a carboxylic acid monomer, an amine monomer and (isocyanido) triphenylphosphine into an organic solvent for reaction to obtain a reaction solution; the aldehyde monomer is a dialdehyde compound, and the carboxylic acid monomer is a dicarboxylic acid compound; and adding the reaction solution into a precipitator, filtering and drying to obtain the polyoxadiazole. The structure general formula of the polyoxadiazole is as follows:
Description
Technical Field
The invention relates to the technical field of organic heterocyclic polymers, in particular to a polyoxadiazole and a preparation method and application thereof.
Background
Polyoxadiazole (POD) is an important class of functional polymers. Because the macromolecule chain contains oxadiazole rings, the POD has excellent heat resistance and thermal stability; meanwhile, the oxadiazole ring also has a photoelectric effect and is a good electrophilic group, so that the POD also has good application in the aspect of photoelectric materials. In addition, the POD has good film forming and fiber forming properties, and the fiber is widely applied to high-temperature filter materials, protective products, insulating materials and the like. However, the oxadiazole structure-containing polymers which are currently and reported are relatively single in structure and function, and it is difficult to achieve multifunctionality. Therefore, the construction of POD materials with unique structures and advanced functions has important value in both academic and industrial fields, and has received extensive attention from scientists.
Existing POD materials are typically prepared by polymerizing dicarboxylic acid and hydrazine salts in solution or by solid state cyclodehydration of polyhydrazide. This typically requires a cumbersome synthesis procedure.
Accordingly, the prior art is still further developed and improved.
Disclosure of Invention
The invention aims to solve the technical problem that the existing preparation process of the polyoxadiazole is complex.
The invention solves the technical problems by the following technical proposal:
in a first aspect, a polyoxadiazole is provided, wherein the polyoxadiazole has the following structural formula:
wherein n is an integer of 2 to 500; r is R 1 、R 2 Are the same or different organic groups; r is R 3 Is an organic group.
In a second aspect, a polyoxadiazole is provided, wherein the polyoxadiazole has the structural formula:
wherein R is 1 、R 3 Arylene, arylene derivatives, and alkylene radicals, which may be the same or differentA substituent; r is R 4 Selected from any one of the following structural formulas:
R 5 any one selected from the following structural formulas;
* R is hydrogen, halogen atom, nitro, alkyl or alkoxy.
Optionally, the polyoxadiazole wherein R 1 、R 2 Arylene, arylene derivatives, alkylene substituents, which may be the same or different; r is R 3 Is aryl, aryl derivative or alkyl substituent.
Optionally, the polyoxadiazole wherein R 1 、R 2 Selected from any one of the following structural formulas:
，
* Is a joint; r, R', which are identical or different, are independently hydrogen, a halogen atom, an alkyl group or an alkoxy group, X being selected from the group consisting of oxygen, sulfur or selenium; m, p, q, s, t is an integer of 1-20.
In a third aspect, a method for preparing the polyoxadiazole described above, wherein the method includes:
respectively adding an aldehyde monomer, a carboxylic acid monomer, an amine monomer and (isocyanido) triphenylphosphine into an organic solvent for reaction to obtain a reaction solution; the aldehyde monomer is a dialdehyde compound, and the carboxylic acid monomer is a dicarboxylic acid compound;
and adding the reaction solution into a precipitator, filtering and drying to obtain the polyoxadiazole.
A fourth aspect, a method for preparing the polyoxadiazole described above, wherein the method includes:
respectively adding an aldehyde monomer, a carboxylic acid monomer, an amine monomer and (isocyanido) triphenylphosphine into an organic solvent for reaction to obtain a reaction solution; the aldehyde monomer is a dialdehyde compound, and the carboxylic acid monomer is a tri-or tetra-carboxylic acid compound;
adding the reaction solution into a precipitator, filtering and drying to obtain the polyoxadiazole
Optionally, the preparation method of the polyoxadiazole comprises the step that the organic solvent is selected from one or more of dichloromethane, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide and tetrahydrofuran; the precipitant is at least one selected from methanol, diethyl ether, ethanol and acetone.
Optionally, the method for preparing polyoxadiazole, wherein the aldehyde monomer: carboxylic acid monomer: amine monomer: the molar ratio of the isonitrile monomer is 1:1 (2-3) to (2-3).
Optionally, the preparation method of the polyoxadiazole, wherein the amine monomer is selected from one of the following structural formulas:
，
wherein k is an integer of 1 to 20.
In a fifth aspect, the use of the polyoxadiazole described above, wherein the polyoxadiazole is used in the fields of respiratory pattern preparation, visualization and cytofluorescence imaging.
The beneficial effects are that: compared with the prior art, the preparation method provided by the invention has the advantages that the used monomer is cheap and easy to obtain, the yield is good, and the molecular weight of the obtained polymer is high (the absolute weight average molecular weight is up to 5 ten thousand, and the PDI is 1.4-2.1); a series of polyoxadiazoles are efficiently synthesized in one step through a four-component reaction without any catalyst; the polymerization method can be carried out at normal temperature and under air condition, and good results are obtained; the polyoxadiazole product is easy to separate, the polymer with high purity can be obtained only by one-time precipitation in the precipitant, and meanwhile, the prepared polyoxadiazole has good film forming property and unique application value in the fields of respiratory pattern preparation, visualization and cell fluorescence imaging.
Drawings
FIG. 1 is a nuclear magnetic spectrum of polyoxadiazole P1 obtained in example 1 in deuterated dimethyl sulfoxide;
FIG. 2 is a nuclear magnetic spectrum of the polyoxadiazole P2 obtained in example 2 in deuterated dimethyl sulfoxide;
FIG. 3 is a graph showing the photo-induced fluorescence of the polyoxadiazole P2 obtained in example 2 in tetrahydrofuranamine solutions of different water contents;
fig. 4 is a fluorescence photograph of the respiratory pattern prepared by polyoxadiazole P2 obtained in example 2.
Fig. 5 is an SEM photograph of the respiratory pattern prepared from polyoxadiazole P2 obtained in example 2.
FIG. 6 is a nuclear magnetic spectrum of polyoxadiazole P3 in deuterated dimethyl sulfoxide obtained in example 3;
FIG. 7 is a nuclear magnetic spectrum of the polyoxadiazoles P4, P5, P6 obtained in examples 4, 5, 6 in deuterated dimethyl sulfoxide;
FIG. 8 is a graph showing the photo-induced fluorescence of the polyoxadiazole P6 obtained in example 6 in tetrahydrofuranamine solutions of different water contents;
fig. 9 is a plot of fluorescence intensity curves of the resulting polyoxadiazoles P2, P6 of examples 2 and 6 in tetrahydrofuran solutions of different water contents.
Fig. 10 is a confocal image of 4T1 cells stained with lystatter Red (1 μm,30 minutes) and a combined image thereof, and superimposed field images of fluorescent and bright images, respectively, of polyoxadiazoles P2, P6 (10 μm,4 hours) obtained in example 2 and example 6.
Detailed Description
The invention provides a polyoxadiazole, a preparation method and application thereof, and the invention is further described in detail below in order to make the purposes, technical schemes and advantages of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. It should be noted that the process parameters not specifically mentioned can be performed by referring to conventional techniques.
The polyoxadiazole provided by the invention comprises linear polyoxadiazole with the structural general formula shown in the formula (1), hyperbranched polyoxadiazoles with the structural general formulas shown in the formulas (6) and (7),
wherein n is an integer of 2 to 500, such as 100, 300, 500, and the polyoxadiazole having a specific weight average molecule is obtained by controlling the size of n. R is R 1 、R 2 Arylene, arylene derivatives, alkylene substituents, which may be the same or different; r is R 3 Is aryl, aryl derivative or alkyl substituent.
The polyoxadiazole provided by the invention has good film forming property and unique application value in the fields of respiratory pattern preparation, visualization and cell fluorescence imaging. In other words, the polyoxadiazole can be applied to the fields of respiratory pattern preparation, visualization and cytofluorescence imaging.
The polyoxadiazole can be prepared by the following preparation method,
s10, respectively adding an aldehyde monomer, a carboxylic acid monomer, an amine monomer and (isocyanido) triphenylphosphine into an organic solvent for reaction to obtain a reaction solution;
and S20, adding the reaction solution into a precipitator, filtering and drying to obtain the polyoxadiazole.
Specifically, an aldehyde monomer, a carboxylic acid monomer, an amine monomer and an isonitrile are dissolved in a solvent and fully reacted at a proper temperature; after the reaction is completed, the mixture is filtered by neutral alumina, added into a large amount of precipitants for precipitation, filtered and collected, and dried to constant weight, thus obtaining the polyoxadiazole derivative.
In this embodiment, the precipitating agent may be methanol, and the use of methanol as the precipitating agent may well precipitate polyoxadiazole. The aldehyde: carboxylic acid: amine: the molar ratio of the isonitrile monomers is 1:1:2:2. the room temperature is also a general temperature, and means 25 ℃. The reaction time may be 24 hours.
In this embodiment, the structural general formulas of the dialdehyde compound and the dicarboxylic acid compound are shown in formula (2) and formula (3):
OHC-R 1 -CHO formula (2);
HOOC-R 2 -COOH (3)
The structural general formula of the amine compound is shown as formula (4):
the structural formula of the isonitrile compound is shown as formula (5):
the structural general formulas of the tri-and tetra-carboxylic acid compounds are respectively shown as a formula (8) and a formula (9):
it is easy to understand that when the aldehyde monomer is a dialdehyde compound and the carboxylic acid monomer is a dicarboxylic acid compound, linear polyoxadiazole is obtained by the reaction; when the aldehyde monomer is a dialdehyde compound and the carboxylic acid monomer is a ternary or quaternary carboxylic acid compound, hyperbranched polyoxadiazole is obtained by the reaction.
The polyoxadiazole and the preparation method thereof provided by the invention are further explained below through specific preparation examples.
Example 1
A method for preparing linear polyoxadiazole by multicomponent polymerization of binary aromatic aldehyde, binary aromatic carboxylic acid, amine and isonitrile comprises the following steps:
(1) 27.0mg of terephthalaldehyde, 33.0mg of terephthalic acid and 121mg of (isocyanato) triphenylphosphine are added into 1mL of dry dimethyl sulfoxide to be dissolved, 77 mu L of dibenzylamine is added under stirring, and the mixture is stirred at room temperature for reaction for 24 hours;
(2) After the reaction was completed, the reaction mother liquor was diluted with 2mL of methylene chloride, filtered through a 2cm thick neutral alumina column, and directly precipitated in 200mL of methanol solution, and the precipitate was collected and dried under vacuum (drying temperature: 55 ℃) to constant weight to obtain polyoxadiazole. The product yield of this example was 57%, the absolute weight average molecular weight was 14200g/mol and the PDI was 1.4.
The experimental monomers of this example were all obtained by direct purchase.
The polyoxadiazole obtained in this example has a structural formula shown as P1:
the reaction equation according to this example is as follows:
the nuclear magnetic spectrum of hydrogen spectrum of the polyoxadiazole P1 in the deuterated dimethyl sulfoxide is shown in figure 1. As can be seen from FIG. 1, the solvent and water peaks of deuterated dimethyl sulfoxide are at 2.50 and 3.30ppm, respectively. In addition, the signals are all hydrogen atom signals in the polyoxadiazole, and the signals of several hydrogen atoms can be correspondingly attributed. Wherein 3.70ppm is a characteristic peak of a methylene hydrogen atom in the polymer P1, 5.30ppm is a hydrogen atom of a methine group, and 8.10ppm is a characteristic peak of a hydrogen atom on a benzene ring.
Example 2
A method for preparing polyoxadiazole containing tetraphenyl ethylene structure by multicomponent polymerization of aromatic dibasic aldehyde, aromatic dibasic carboxylic acid, amine and isonitrile containing tetraphenyl ethylene comprises the following steps:
(1) 78.0mg of 4,4' - (1, 2-diphenyl-1, 2-vinylidene) dibenzoaldehyde, 72.0mg of 1, 6-bis (p-carboxyphenoxy) hexane and 121mg of (isocyanatoimino) triphenylphosphine were added to 1mL of dry dimethyl sulfoxide for dissolution, 77. Mu.L of dibenzylamine was added with stirring, and the mixture was stirred at room temperature for reaction for 24 hours;
(2) After the reaction was completed, the reaction mother solution was diluted with 2mL of tetrahydrofuran, filtered through an alumina column having a thickness of 2cm, and directly precipitated in 200mL of methanol solution, and the precipitate was collected and dried under vacuum (drying temperature: 55 ℃) to constant weight to obtain polyoxadiazole. The product yield of this example was 57%, the absolute weight average molecular weight was 12000g/mol and the PDI was 1.5.
The 4,4' - (1, 2-diphenyl-1, 2-vinylidene) dibenzoaldehyde and 1, 6-bis (p-carboxyphenoxy) hexane of this example were prepared according to literature (Karaburu, A.; lafzi, F.; bayindir, S.; sevigili,orak, I., the synthesis, current transformer mechanism and structural properties of novel rhodanine-based Al/Bis (Rh) -Ph/p-Si and Al/Bis (Rh) -TPE/p-Si heterojunctions. Journal of Molecular Structure 2021,1231.).
The polyoxadiazole obtained in this example has a structural formula shown as P2:
the reaction equation according to this example is as follows:
the nuclear magnetic spectrum of hydrogen spectrum of the polyoxadiazole P2 in the deuterated dimethyl sulfoxide is shown in figure 2.
The photo-fluorescence curves of the polyoxadiazole P2 of this example in tetrahydrofuran solutions of different water contents are shown in FIG. 3. As can be seen from fig. 3, the fluorescence of the polymer gradually increases with increasing water content, reaching a maximum at 80% water content. The polymer shows a remarkable aggregation-induced emission phenomenon.
Fig. 4 and 5 are a fluorescence photograph and an SEM photograph of the respiratory pattern prepared from polyoxadiazole P2 obtained in example 2, respectively. The specific operation steps are as follows: dissolving a certain amount of polyoxadiazole in CHCl 3 The solution forms a solution with quantitative concentration, and the polymer is completely dissolved in the solvent by vibrating and ultrasonic for 30 minutes. At room temperature, a clean and pollution-free glass dish is taken, 10mL of deionized water is added, a bracket with a certain height is placed in the glass dish, the surface of the bracket is about 5 mm higher than the liquid level of the deionized water, a clean silicon wafer is placed on the bracket, the whole device is sealed by a plastic preservative film, and the glass dish is placed at room temperature for 2 hours, so that water vapor in a weighing bottle is saturated. Taking 50 microliters of polyoxadiazole solution by using a pinhole injector, penetrating a preservative film, dripping the preservative film on a silicon wafer, immediately sticking pinholes on the preservative film by using a transparent adhesive tape, standing for 30 minutes, and taking out the preservative film to obtain the white polyoxadiazole porous film.
Example 3
A method for preparing linear polyoxadiazole by multicomponent polymerization of dibasic fatty aldehyde, dibasic aromatic carboxylic acid, amine and isonitrile comprises the following steps:
(1) 22.0mg of glutaraldehyde, 33.0mg of terephthalic acid and 121mg of (isocyanimino) triphenylphosphine are added into 1mL of dry dimethyl sulfoxide for dissolution, 77 mu L of dibenzylamine are added under stirring, and the reaction is stirred at room temperature for 24 hours;
(2) After the reaction was completed, the reaction mother solution was diluted with 2mL of tetrahydrofuran, filtered through an alumina column having a thickness of 2cm, and directly precipitated in 200mL of methanol solution, and the precipitate was collected and dried under vacuum (drying temperature: 55 ℃) to constant weight to obtain polyoxadiazole. The product yield of this example was 70%, the absolute weight average molecular weight was 12100g/mol and the PDI was 1.6.
The polyoxadiazole obtained in this example has a structural formula shown in P3:
the reaction equation according to this example is as follows:
the nuclear magnetic spectrum of the hydrogen spectrum of the polyoxadiazole P3 in the deuterated dimethyl sulfoxide is shown in fig. 6.
Example 4
A method for preparing three-arm hyperbranched polyoxadiazole by multicomponent polymerization of dialdehyde, tricarboxylic acid, amine and isonitrile comprises the following steps:
(1) 13.4mg of terephthalaldehyde, 60.5mg of tris (4-biphenylcarboxamide) and 60.5mg of (isocyanato) triphenylphosphine were added to 1mL of dried dimethyl sulfoxide to dissolve, 38.5. Mu.L of dibenzylamine was added under stirring, and the mixture was stirred at room temperature to react for 24 hours;
(2) After the reaction was completed, the reaction mother solution was diluted with 2mL of tetrahydrofuran, filtered through an alumina column having a thickness of 2cm, and directly precipitated in 200mL of methanol solution, and the precipitate was collected and dried under vacuum (drying temperature: 55 ℃) to constant weight to obtain polyoxadiazole. The product yield of this example was 70%, the absolute weight average molecular weight was 12100g/mol and the PDI was 1.6.
The polyoxadiazole obtained in this example has a structural formula shown in P4:
the reaction equation according to this example is as follows:
the nuclear magnetic spectrum of hydrogen spectrum of polyoxadiazole P4 in deuterated dimethyl sulfoxide of this example is shown in FIG. 7 (A).
Example 5
A method for preparing three-arm hyperbranched polyoxadiazole containing tetraphenyl ethylene structure by multicomponent polymerization of dialdehyde, tricarboxylic acid containing tetraphenyl ethylene, amine and isonitrile comprises the following steps:
(1) 39.0mg of 4,4' - (1, 2-diphenyl-1, 2-vinylidene) dibenzoaldehyde, 60.5mg of tris (4-biphenylcarboxamide) and 60.5mg of (isocyanatoimino) triphenylphosphine were added to 1mL of dry dimethyl sulfoxide for dissolution, and 38.5. Mu.L of dibenzylamine was added with stirring, and the mixture was stirred at room temperature for reaction for 24 hours;
(2) After the reaction was completed, the reaction mother solution was diluted with 2mL of tetrahydrofuran, filtered through an alumina column having a thickness of 2cm, and directly precipitated in 200mL of methanol solution, and the precipitate was collected and dried under vacuum (drying temperature: 55 ℃) to constant weight to obtain polyoxadiazole. The product yield of this example was 70%, the absolute weight average molecular weight was 12100g/mol and the PDI was 1.6.
The polyoxadiazole obtained in this example has a structural formula shown in P5:
the reaction equation according to this example is as follows:
the nuclear magnetic spectrum of hydrogen spectrum of polyoxadiazole P5 in deuterated dimethyl sulfoxide of this example is shown in FIG. 7 (B).
Example 6
A method for preparing four-arm hyperbranched polyoxadiazole by multicomponent polymerization of dialdehyde, tetracarboxylic acid, amine and isonitrile comprises the following steps:
(1) 13.4mg of terephthalaldehyde, 81.2mg of tetra- (4-carboxyl- (1, 1-biphenyl)) ethylene and 60.5mg of (isocyanato) triphenylphosphine are added into 1mL of dry dimethyl sulfoxide for dissolution, 38.5 mu L of dibenzylamine are added under stirring, and the reaction is stirred at room temperature for 24 hours;
(2) After the reaction was completed, the reaction mother solution was diluted with 2mL of tetrahydrofuran, filtered through an alumina column having a thickness of 2cm, and directly precipitated in 200mL of methanol solution, and the precipitate was collected and dried under vacuum (drying temperature: 55 ℃) to constant weight to obtain polyoxadiazole. The product yield of this example was 65%, the absolute weight average molecular weight was 65000g/mol and the PDI was 1.4.
The polyoxadiazole obtained in this example has a structural formula shown in P6:
the reaction equation according to this example is as follows:
the nuclear magnetic spectrum of the hydrogen spectrum of the polyoxadiazole P6 in the deuterated dimethyl sulfoxide is shown in fig. 7 (C).
The photo-fluorescence curves of the polyoxadiazole P6 of this example in tetrahydrofuran solutions of different water contents are shown in FIG. 8. As can be seen from fig. 8, the fluorescence of the polymer gradually increased with increasing water content, reaching a maximum at 70% water content. The polymer shows a remarkable aggregation-induced emission phenomenon.
Fig. 9 is a plot of fluorescence intensity curves of the resulting polyoxadiazoles P2, P6 of examples 2 and 6 in tetrahydrofuran solutions of different water contents.
Fig. 10 is a confocal image of 4T1 cells stained with lystatter Red (1 μm,30 min) and a combined image thereof, and superimposed field images of fluorescent and bright images, respectively, of polyoxadiazoles P2, P6 (10 μm,4 h) obtained in example 2 and example 6.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (10)
1. The polyoxadiazole is characterized by having the following structural general formula:
，
wherein n is an integer of 100 to 500; r is R 1 、R 2 Arylene, arylene derivatives, alkylene substituents, which may be the same or different; r is R 3 Is aryl, aryl derivative or alkyl substituent.
2. The polyoxadiazole is characterized by having a structural general formula:
or->，
Wherein R is 1 Arylene, arylene derivatives, alkylene substituents, which may be the same or different; r is R 3 Is aryl, aryl derivative or alkyl substituent; r is R 4 Selected from any one of the following structural formulas:
R 5 any one selected from the following structural formulas;
，
* R is hydrogen, halogen atom, nitro, alkyl or alkoxy.
3. The polyoxadiazole according to claim 1, wherein R 1 、R 2 Selected from any one of the following structural formulas:
，
* Is a joint; r, R', which are identical or different, are independently hydrogen, a halogen atom, an alkyl group or an alkoxy group, X being selected from the group consisting of oxygen, sulfur or selenium; m, p, q, s, t is an integer of 1-20.
4. The polyoxadiazole of claim 2, wherein R 1 Selected from any one of the following structural formulas:
，
* Is a joint; r, R', which are identical or different, are independently hydrogen, a halogen atom, an alkyl group or an alkoxy group, X being selected from the group consisting of oxygen, sulfur or selenium; m, p, q, s, t is an integer of 1-20.
5. A process for the preparation of polyoxadiazole according to claim 1, comprising:
respectively adding an aldehyde monomer, a carboxylic acid monomer, an amine monomer and (isocyanido) triphenylphosphine into an organic solvent for reaction to obtain a reaction solution; the aldehyde monomer is a dialdehyde compound, and the carboxylic acid monomer is a dicarboxylic acid compound;
and adding the reaction solution into a precipitator, filtering and drying to obtain the polyoxadiazole.
6. A process for the preparation of polyoxadiazole according to claim 2, comprising:
respectively adding an aldehyde monomer, a carboxylic acid monomer, an amine monomer and (isocyanido) triphenylphosphine into an organic solvent for reaction to obtain a reaction solution; the aldehyde monomer is a dialdehyde compound, and the carboxylic acid monomer is a tri-or tetra-carboxylic acid compound;
and adding the reaction solution into a precipitator, filtering and drying to obtain the polyoxadiazole.
7. The process for preparing polyoxadiazole according to claim 5 or 6, characterized in that the organic solvent is selected from dichloromethane, dimethyl sulfoxide,N,N-a solvent of the type dimethylformamide, which is chosen,N,N-one or more of dimethylacetamide, tetrahydrofuran; the precipitant is at least one selected from methanol, diethyl ether, ethanol and acetone。
8. The method for producing polyoxadiazole according to claim 5 or 6, characterized in that the aldehyde monomer: carboxylic acid monomer: amine monomer: the molar ratio of the isonitrile monomer is 1:1 (2-3) to (2-3).
9. The method for preparing polyoxadiazole according to claim 5 or 6, characterized in that the amine monomer is selected from one of the following structural formulas:
，
wherein k is an integer of 1 to 20.
10. Use of the polyoxadiazole according to claim 1 or 2, characterized in that it is used in the fields of respiratory patterning, visualization and cytofluorescence imaging.
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| CN101384346A (en) * | 2006-02-16 | 2009-03-11 | 巴斯夫欧洲公司 | Catalytic process for the phosphonylation of high-temperature polymers |
| CN103261275A (en) * | 2010-12-16 | 2013-08-21 | 纳幕尔杜邦公司 | Preparation of sulfonated polyoxadiazole polymers |
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| CN101384346A (en) * | 2006-02-16 | 2009-03-11 | 巴斯夫欧洲公司 | Catalytic process for the phosphonylation of high-temperature polymers |
| CN103261275A (en) * | 2010-12-16 | 2013-08-21 | 纳幕尔杜邦公司 | Preparation of sulfonated polyoxadiazole polymers |
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