CN116535650A - Polysulfonimide and preparation method and application thereof - Google Patents
Polysulfonimide and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 125000000732 arylene group Chemical group 0.000 claims abstract description 8
- 230000003287 optical effect Effects 0.000 claims abstract description 8
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- -1 diacetylene compound Chemical class 0.000 claims description 64
- 238000006243 chemical reaction Methods 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 125000004185 ester group Chemical group 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003929 acidic solution Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 abstract description 6
- 238000004220 aggregation Methods 0.000 abstract description 6
- 238000004020 luminiscence type Methods 0.000 abstract description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 238000001228 spectrum Methods 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- HSVFKFNNMLUVEY-UHFFFAOYSA-N sulfuryl diazide Chemical compound [N-]=[N+]=NS(=O)(=O)N=[N+]=[N-] HSVFKFNNMLUVEY-UHFFFAOYSA-N 0.000 description 6
- 229920001002 functional polymer Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 238000000103 photoluminescence spectrum Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 2
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 2
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 2
- 238000012984 biological imaging Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
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- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/30—Polysulfonamides; Polysulfonimides
-
- 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
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1416—Condensed systems
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- 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
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
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- 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
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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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 polysulfonamide, a preparation method and application thereof, wherein the polysulfonamide is shown in a formula I:wherein n is an integer of 2 to 500; r is R 1 、R 2 Each independently is arylene, arylene derivative or alkylene, R 3 、R 4 Each independently is aryl, aryl derivative or alkyl. The polysulfonimide has a brand new structure, has aggregation-induced luminescence or non-traditional luminescence properties, and has potential application value in the fields of optical display and the like.
Description
Technical Field
The invention relates to the technical field of organic high molecular polymers, in particular to polysulfonimide and a preparation method and application thereof.
Background
The non-conjugated polymer rich in hetero atoms can be used as various general polymers and functional polymer materials and is widely used in daily life. In recent years, luminescent high molecular materials based on non-conjugated polymers rich in hetero atoms are paid attention to because of good biocompatibility, special bioactivity, photoelectric properties and the like, and are applied to the fields of fluorescence sensing, stimulus response materials, biological imaging, photoelectric devices and the like. The development of modern technology has increasingly demanded the structure and performance diversity of functional polymers, so that it is needed to prepare hetero atom-rich non-conjugated luminescent polymer materials with brand new structures.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a polysulfonimide, a preparation method and an application thereof, and aims to provide a heteroatom-rich non-conjugated luminescent polymer material with a brand new structure, so as to adapt to the requirements of modern technological development on the structure and performance diversity of functional polymers.
The technical scheme of the invention is as follows:
in a first aspect of the invention, there is provided a polysulfonamide of the formula I:
wherein n is an integer of 2 to 500; r is R 1 、R 2 Each independently is arylene, arylene derivative or alkylene, R 3 、R 4 Each independently is aryl, aryl derivative or alkyl.
Optionally, the R 1 、R 2 Each independently selected from one of the following structures:
wherein, m, h and k are integers from 1 to 20, R, R' is independently hydrogen atom, halogen atom, nitro group, ester group, alkyl group, alkoxy group or aryl group, and X is N, P, O, S or Si.
Optionally, the saidR 3 Selected from one of the following structures:
wherein, is a connection site, m is an integer of 1-20, and R, R' is independently hydrogen atom, halogen atom, nitro group, ester group, alkyl group, alkoxy group or aryl group.
Optionally, the R 4 Selected from one of the following structures:
wherein, is a connection site, m is an integer of 1-20, and R, R' is independently hydrogen atom, halogen atom, nitro group, ester group, alkyl group, alkoxy group or aryl group.
In a second aspect of the present invention, there is provided a method for producing the polysulfonimide according to the present invention as described above, comprising the steps of:
adding a diacetylene compound, a binary sulfonyl azide compound, an aldehyde compound, a hydrazine compound, a monovalent copper catalyst and triethylamine into an organic solvent for reaction, and then filtering to obtain a filtrate;
adding the filtrate into a precipitator for precipitation to obtain the polysulfonimide;
wherein the general structural formula of the diacetylene compound is as follows:
the structural general formula of the binary sulfonyl azide compound is as follows:
the structural general formula of the aldehyde compound is as follows: R3-CHO;
the structural general formula of the hydrazine compound is as follows: R4-NHNH2.
Optionally, the mole ratio of the diacetylene compound to the disulfonyl azide compound to the aldehyde compound to the hydrazine compound is 1:1 (2-3);
and/or the reaction concentration of the diacetylene compound is 0.1-0.4 mol/L;
and/or the molar amount of the monovalent copper catalyst is 2-10% of the molar amount of the dibasic alkyne compound;
and/or the molar quantity of the triethylamine is 1.1-3.3 times of the molar quantity of the binary alkyne compound;
and/or the monovalent copper catalyst comprises at least one of cuprous iodide, cuprous bromide and cuprous chloride;
and/or the precipitant comprises at least one of methanol, diethyl ether, acetone and n-hexane;
and/or the organic solvent comprises at least one of dichloromethane, tetrahydrofuran, N-dimethylformamide and toluene;
and/or the temperature of the reaction is room temperature, and the reaction time is 0.5-24 h.
In a third aspect, the present invention provides the use of a polysulphone-imide according to the present invention as described above or a polysulphone-imide prepared by a preparation method according to the present invention as described above in the field of optical displays.
In a fourth aspect of the invention there is provided the use of a polysulphonamide as described above or as prepared by a method as described above in the preparation of a polysulphonamide.
Optionally, the method of preparing comprises the steps of:
and adding the polysulfonamide into an acidic solution for reaction to obtain the polysulfonamide.
In a fifth aspect of the present invention, there is provided a polysulfonamide of the formula II:
the polysulfonamides are obtained by reacting the polysulfonamides disclosed by the invention or the polysulfonamides prepared by the preparation method disclosed by the invention in an acid solution.
The beneficial effects are that: the invention provides a heteroatom-rich non-conjugated luminescent polymer material with a brand new structure, namely polysulfonamide with a brand new structure, which is used for meeting the requirements of development of modern technology on the structure and performance diversity of functional polymers. The polysulfonimide has aggregation-induced emission or non-traditional emission properties, and has potential application value in the fields of optical display and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the polysulfonimide P1 of example 1 of the invention in deuterated chloroform.
Fig. 2 (a) shows photoluminescence spectra of the polysulfonimide P1 of example 1 according to the present invention at different excitation wavelengths, and (b) shows corresponding color coordinate change patterns.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the polysulfonimide P2 of example 2 of the invention in deuterated chloroform.
FIG. 4 (A) shows photoluminescence spectra of the polysulfonamides P2 of example 2 in tetrahydrofuran/water mixtures with different water contents, and (B) shows luminescence intensity variation trend.
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the polysulfonimide P3 of example 3 of the invention in deuterated chloroform.
FIG. 6 (A) is a graph showing the comparison of the nuclear magnetic resonance hydrogen spectra of the polysulfonamide P1-HCl of example 4, the compound 6, and the polysulfonamide P1 of example 1, and (B) is a graph showing the conversion of the polysulfonamide P1 of example 1 in an acidic solution at various times and the nuclear magnetic resonance hydrogen spectra of the products.
Detailed Description
The invention provides polysulfonamide, a preparation method and application thereof, and the invention is further described in detail below in order to make the purposes, technical schemes and effects 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.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The embodiment of the invention provides a polysulfonimide shown in a formula I:
wherein n is an integer of 2 to 500; r is R 1 、R 2 Each independently is arylene, arylene derivative or alkylene, R 3 、R 4 Each independently is aryl, aryl derivative or alkyl.
The polysulfonamide with the brand new structure provided by the embodiment has aggregation-induced luminescence or non-traditional luminescence properties, and has potential application value in the fields of optical display and the like.
In some embodiments, the R 1 、R 2 Each independently selected from one of the following structures:
wherein, m, h and k are integers from 1 to 20, R, R' is independently hydrogen atom, halogen atom, nitro group, ester group, alkyl group, alkoxy group or aryl group, and X is N, P, O, S or Si. Illustratively, m may be 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; h may be 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.
In some embodiments, the R 3 Selected from one of the following structures:
wherein, is a connection site, m is an integer of 1-20, and R, R' is independently hydrogen atom, halogen atom, nitro group, ester group, alkyl group, alkoxy group or aryl group. Illustratively, m may be 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.
In some embodiments, the R 4 Selected from one of the following structures:
wherein, is a connection site, m is an integer of 1-20, and R, R' is independently hydrogen atom, halogen atom, nitro group, ester group, alkyl group, alkoxy group or aryl group.
The conventional synthesis method of polyimide is often limited to the two-component gradual polymerization reaction of humidity-sensitive imide chloride, diol or dianhydride, diisocyanate and other monomer combinations, and the limitation of the types of reaction substrates severely limits the structural diversity and further functional exploration of the product. In recent years, copper-catalyzed multicomponent click polymerization developed from the front of organic chemistry provides a new opportunity for synthesizing functional polyimide with novel structure, and polysulfonimide derivatives with hetero-chain or heterocyclic structures can be generated through three-component polymerization reaction of alkyne, sulfonyl azide and nucleophilic reagents such as alcohol, amine or salicylaldehyde. However, existing multicomponent polymerization reactions are still mainly focused on three-component polymerization, a great number of heteroatoms and polysubstituted groups are difficult to be introduced simultaneously, and the reactions are carried out smoothly under the condition of nitrogen, and the reactions are still relatively single in terms of product structure and function. These deficiencies limit the preparation and performance studies of polysubstituted polysulfonimide functional polymer materials to a great extent. Based on this, the embodiment of the invention also provides a preparation method of the polysulfonimide according to the embodiment of the invention, which comprises the following steps:
s1, adding a diyne compound, a diyne sulfonyl azide compound, an aldehyde compound, a hydrazine compound, a monovalent copper catalyst and triethylamine into an organic solvent for reaction, and then filtering to obtain a filtrate;
s2, adding the filtrate into a precipitator for precipitation to obtain the polysulfonimide;
wherein the general structural formula of the diacetylene compound is as follows:
the structural general formula of the binary sulfonyl azide compound is as follows:
the structural general formula of the aldehyde compound is as follows: R3-CHO;
the structural general formula of the hydrazine compound is as follows: R4-NHNH2.
The polymerization method provided by the embodiment of the invention adopts cheap and easily available monomers, can be used for efficiently synthesizing a series of polysulfonimides through one-step reaction of four components (a binary alkyne compound, a binary sulfonyl azide compound, an aldehyde compound and a hydrazine compound) in an air environment (without the condition of nitrogen), has good yield, and the obtained polysulfonimides have high molecular weight, relatively high weight average molecular weight of 8 ten thousand and a Polymer Dispersibility Index (PDI) of about 1.3. Meanwhile, the polysulfonamide products are easy to separate, and the polysulfonamide with high purity can be obtained by only one-time precipitation in a precipitator. The polysulfonamide prepared by the invention has aggregation-induced emission or non-traditional emission properties, and has potential application value in the fields of optical display and the like. Therefore, the invention provides a method for conveniently and efficiently preparing the polysulfonamide luminescent material with unique structure and advanced function, which has important value in the fields of academic and industry.
In this example, R in the general structural formula of the diacetylene compound 1 R in structural general formula of binary sulfonyl azide compound 2 R in the structural general formula of aldehyde compound 3 R in the structural general formula of hydrazine compound 4 R in the polysulfonimides respectively 1 、R 2 、R 3 、R 4 The same applies.
In some embodiments, the molar ratio of the alkyne compound, the sulfonyl azide compound, the aldehyde compound, and the hydrazine compound is 1:1 (2-3): 2-3.
In some embodiments, the diacetylene compound has a reaction concentration of 0.1 to 0.4mol/L.
In some embodiments, the molar amount of the monovalent copper catalyst is 2 to 10% of the molar amount of the diacetylene compound.
In some embodiments, the molar amount of triethylamine is 1.1 to 3.3 times the molar amount of the diacetylene compound.
In some embodiments, the monovalent copper catalyst includes at least one of cuprous iodide, cuprous bromide, and cuprous chloride, but is not limited thereto.
In some embodiments, the precipitant includes at least one of methanol, diethyl ether, acetone, and n-hexane, but is not limited thereto.
In some embodiments, the organic solvent includes at least one of dichloromethane, tetrahydrofuran, N-dimethylformamide, toluene, but is not limited thereto.
In some embodiments, the temperature of the reaction is room temperature and the time of the reaction is 0.5 to 24 hours.
In some embodiments, the reaction is carried out at room temperature for 1 hour, that is, the reaction is carried out at room temperature and air, and the conditions are mild, the method is simple, and the reaction can be completed in one hour, so as to prepare the high-yield and high-molecular-weight polysulfonimide.
The embodiment of the invention also provides application of the polysulfonamide disclosed by the embodiment of the invention or the polysulfonamide prepared by adopting the preparation method disclosed by the embodiment of the invention in the field of optical display (such as biological imaging).
The inventors have surprisingly found that polysulfonamides of novel structure can be prepared from the polysulfonamides. Based on the above, the embodiment of the invention also provides an application of the polysulfonamide disclosed by the embodiment of the invention or the polysulfonamide prepared by adopting the preparation method disclosed by the embodiment of the invention in preparation of the polysulfonamide.
In one embodiment, the method of preparation comprises the steps of:
and adding the polysulfonamide into an acidic solution for reaction to obtain the polysulfonamide.
The embodiment of the invention also provides a polysulfonamide shown in the formula II:
the polysulfonamides are obtained by reacting polysulfonamides as described in the examples of the invention or polysulfonamides prepared by the preparation method of the examples of the invention in an acidic solution.
The following is a detailed description of specific examples.
Example 1
The present embodiment provides a linear polysulfonimide P1 having the structural formula:
the synthesis route of the linear polysulfonimide P1 is as follows:
the embodiment also provides a preparation method of the linear polysulfonimide P1, which comprises the following steps:
(1) 15mL of a Schlenk's polymerization tube with a port was taken, and a magnet, a dibasic alkynyl compound la (0.30 mmol,132 mg), a dibasic sulfonyl azide compound 2a (0.30 mmol,114 mg), an aldehyde compound 3 (0.72 mmol, 85. Mu.L), a hydrazine compound 4 (0.72 mmol, 72. Mu.L) and CuI (0.012 mmol,2.4 mg) were sequentially added thereto, 1mL of anhydrous Dichloromethane (DCM) was added thereto by a syringe, the solution was stirred uniformly, triethylamine (0.33 mmo1, 47. Mu.L) was added dropwise by a pipette, and the reaction was stirred at room temperature for 1 hour. After the reaction is completed, the reaction mother solution is diluted by 1mL of dichloromethane, and filtered through a neutral alumina column with the thickness of 1cm to obtain filtrate;
(2) The filtrate was precipitated by adding it to 100mL of diethyl ether, the precipitate was collected, and dried under vacuum at 55℃to a constant weight, giving polysulfonamide P1 in a yield of 77%, a relative weight average molecular weight of 86000g/mol, and a PDI of 1.27.
In the above step, the dibasic alkynyl compound 1a was prepared according to the method disclosed in literature (Macromolecules, 2014,47,1325); dibasic sulfonyl azide 2a was prepared according to the method disclosed in the literature (j. Energy. Mater.,2007,25,79); aldehyde compound 3 and hydrazine compound 4 are commercially available.
The nuclear magnetic resonance hydrogen spectrum of the linear polysulfonimide P1 prepared by the preparation method of the embodiment in deuterated chloroform is shown in figure 1. As can be seen from fig. 1, the characteristic peaks at 7.26 and 1.56ppm (in fig. 1) are the solvent and water peaks, respectively, of deuterated chloroform. In addition, the remaining characteristic peaks are characteristic peaks of hydrogen atom signals in the polysulfonimide, and several hydrogen atom signals of the characteristics can be correspondingly attributed, wherein 2.35ppm (at b in fig. 1) is a characteristic peak of methyl hydrogen atoms in the polysulfonimide P1, and 5.00ppm (at a in fig. 1) is a characteristic peak of methylene hydrogen atoms of the polysulfonimide P1.
FIG. 2 is a photoluminescence spectrum and a color coordinate change of the linear polysulfonamide P1 prepared in the embodiment 1 of the invention at an excitation wavelength of 300-450nm, wherein (A) in FIG. 2 is a photoluminescence spectrum; fig. 2 (B) shows a corresponding color coordinate map. It can be seen that as the excitation wavelength increases, the emission wavelength of the polysulfonimide P1 gradually red shifts, and the corresponding color coordinates also gradually range from blue light to white light, and finally to yellow light.
Example 2
The present embodiment provides a linear polysulfonimide P2 having the structural formula:
the synthesis route of the linear polysulfonimide P2 is as follows:
the embodiment also provides a preparation method of the linear polysulfonimide P2, which comprises the following steps:
(1) 15mL of a Schlenk's polymerization tube with a branch port was taken, and a magneton, a dibasic alkynyl compound lb (0.30 mmol,114 mg), a dibasic sulfonyl azide compound 2b (0.30 mmol,127 mg), an aldehyde compound 3 (0.72 mmol, 85. Mu.L), a hydrazine compound 4 (0.72 mmol, 72. Mu.L) and CuI (0.012 mmol,2.4 mg) were sequentially added thereto, 1mL of anhydrous DCM was added thereto with a syringe, the solution was stirred uniformly, triethylamine (0.33 mmo1, 47. Mu.L) was added dropwise with a pipette, and the reaction was stirred at room temperature for 1 hour. After the reaction was completed, the reaction mother liquor was diluted with 1mL of DCM, and filtered through a 1cm thick neutral alumina column to obtain a filtrate;
(2) The filtrate was precipitated by adding it to 100mL of diethyl ether, the precipitate was collected, and dried under vacuum at 55℃to a constant weight to give polysulfonamide P2 in a yield of 90% with a relative weight average molecular weight of 87700g/mol and a PDI of 1.26.
In this example, dibasic alkynyl compound 1b was prepared according to the method disclosed in literature (polym. Chem.2012,3,1481), and dibasic sulfonyl azide compound 2b was prepared according to the method disclosed in literature (Macromolecules, 2019,52,4526 and j. Energy. Mater.,2007,25,79).
The nuclear magnetic resonance hydrogen spectrum of the polysulfonimide P2 prepared by the preparation method of the embodiment in deuterated chloroform is shown in figure 3. As can be seen from fig. 3, the characteristic peaks at 7.26 and 1.56ppm (in fig. 3) are the solvent and water peaks, respectively, of deuterated chloroform. In addition, the residual characteristic peak-to-peak is the characteristic peak of the hydrogen atom signals in the polysulfonimide, and the characteristic hydrogen atom signals can be correspondingly attributed. Wherein 2.36ppm (at e in FIG. 3) is a characteristic peak of methyl hydrogen atoms in the polysulfonimide P2, and 4.26 and 4.83ppm (at d and c in FIG. 3, respectively) are characteristic peaks of methylene hydrogen atoms in the polysulfonimide.
The photo-induced fluorescence curves of the polysulfonimide P2 prepared by the preparation method of the embodiment in tetrahydrofuran solutions with different water contents are shown in (A) and (B) of FIG. 4. Specifically, tetrahydrofuran and water are respectively prepared according to the volume ratio of 100:0, 90:10 and 80: 20. 70: 30. 60: 40. 50:50, 40: 60. 30: 70. 20: 80. 10: 90. 5:95, the polysulfonamides P2 are dissolved in these solutions while keeping the concentration of the polysulfonamides P2 in the solution at 10. Mu. Mol/L, as can be seen from FIG. 4, the fluorescence intensity of the polymer gradually increases with increasing water content, reaching a maximum at 95% water content. I.e. as the water content of the mixed solution increases, the polysulfonimide P2 aggregates and fluoresces after increasing to a certain extent, i.e. the polysulfonimide P2 exhibits a pronounced aggregation-induced emission phenomenon.
Example 3
The present embodiment provides a linear polysulfonimide P3 having the structural formula:
the synthesis route of the linear polysulfonimide P3 is as follows:
the embodiment of the invention also provides a preparation method of the polysulfonamide P3, which comprises the following steps:
(1) 15mL of a Schlenk's polymerization tube with a branch port was taken, and a magnet, a dibasic alkynyl compound lc (0.30 mmol,61 mg), a dibasic sulfonyl azide compound 2a (0.30 mmol,114 mg), an aldehyde compound 3 (0.72 mmol, 85. Mu.L) and a hydrazine compound 4 (0.72 mmol, 72. Mu.L) were sequentially added thereto, 1mL of anhydrous DCM was added thereto with a syringe, the solution was stirred uniformly, triethylamine (0.33 mmo1, 47. Mu.L) was added dropwise with a pipette, and the reaction was stirred at room temperature for 1 hour. After the reaction was completed, the reaction mother liquor was diluted with 1mL of DCM, and filtered through a 1cm thick neutral alumina column to obtain a filtrate;
(2) The filtrate was precipitated by adding it to 100mL of diethyl ether, the precipitate was collected, and dried under vacuum at 55℃to a constant weight, giving polysulfonamide P3 in a yield of 82% with a relative weight average molecular weight of 55500g/mol and a PDI of 1.35.
The preparation method of the dibasic alkynyl compound lc in this example refers to the dibasic alkynyl compound la in example 1.
The nuclear magnetic resonance hydrogen spectrum of the polysulfonimide P3 of this example in deuterated chloroform is shown in FIG. 5. It can be seen from fig. 5 that the characteristic peaks at 7.26 and 1.56ppm (in fig. 5) are the solvent peak and water peak of deuterated chloroform, respectively, and the characteristic peak at 1.40ppm (in fig. 5) is the impurity cyclohexane peak in the solvent. In addition, the residual characteristic peak average is the characteristic peak of the hydrogen atom signals in the polysulfonimide, and the characteristic hydrogen atom signals can be correspondingly attributed. Wherein 2.36ppm (at g in FIG. 5) is a characteristic peak of methyl hydrogen atoms in the polysulfonimide P3, and 5.00ppm (corresponding to f in FIG. 5) is a characteristic peak of methylene hydrogen atoms in the polysulfonimide P3.
Example 4
The embodiment provides a polysulfonamide P1-HCl, which has the structural formula:
the synthetic route of the polysulfonamide P1-HCl is as follows:
the embodiment also provides a preparation method of the polysulfonamide P1-HCl, which comprises the following steps:
polysulfonamide P1 (30 mg) was added to Tetrahydrofuran (THF) (2 mL), followed by hydrochloric acid (1 mL, 36% HCl concentration) and stirred for 16h to give polysulfonamide P1-HCl having a relative weight average molecular weight of 47300g/mol and a PDI of 1.26.
To verify the structure of the polysulfonamide P1-HCl, a model reaction was performed on the model compound, and model compound 5 (30 mg) was added to THF (2 mL), followed by addition of hydrochloric acid (1 mL, HCl concentration: 36%), and stirring reaction was performed for 1h to obtain compound 6. The synthetic route is as follows:
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the nuclear magnetic resonance hydrogen spectra of polysulfonamide P1, compound 6, and polysulfonamide P1-HCl were compared, as shown in FIG. 6 (A). After conversion under acidic conditions, the characteristic peaks of protons at "a" and "b" of the polysulfonamide P1 shift significantly to new positions or disappear completely in the spectra of compound 6 and polysulfonamide P1-HCl. Furthermore, a new characteristic peak at "i" associated with NH protons was observed in the spectra of compound 6 and polysulfonamide P1-HCl.
Meanwhile, the conversion rate of the polysulfonamide P1 and the nuclear magnetic resonance hydrogen spectrum of the system material at different reaction times after adding hydrochloric acid were examined, and the results are shown in (B) of FIG. 6, which confirm that the polysulfonamide P1 was completely converted into polysulfonamide P1-HCl after 16 hours of reaction. Furthermore, polysulfonamide P1-HCl also has luminescence properties.
In summary, the invention provides a polysulfonamide and a preparation method and application thereof. The polysulfonimide has aggregation-induced emission or non-traditional emission properties, and has potential application value in the fields of optical display and the like. The polymerization method provided by the invention adopts cheap and easily available monomers, can efficiently synthesize a series of polysulfonimides through one-step reaction of four components at room temperature and in an air environment (without nitrogen), has good yield, and the obtained polysulfonimides have high molecular weight, relatively high weight average molecular weight of 8 ten thousand, and Polymer Dispersibility Index (PDI) of about 1.3, short reaction time, mild condition and simple method. Meanwhile, the polysulfonamide products are easy to separate, and the polysulfonamide with high purity can be obtained by only one-time precipitation in a precipitator. Therefore, the invention provides a method for conveniently and efficiently preparing the polysulfonamide luminescent material with unique structure and advanced function, which has important value in the fields of academic and industry.
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. Polysulfonimides of the formula I:
wherein n is an integer of 2 to 500; r is R 1 、R 2 Each independently is arylene, arylene derivative or alkylene, R 3 、R 4 Each independently is aryl, aryl derivative or alkyl.
2. The polysulfonimide according to claim 1, wherein the radicals R 1 、R 2 Each independently selected from one of the following structures:
wherein, m, h and k are integers from 1 to 20, R, R' is independently hydrogen atom, halogen atom, nitro group, ester group, alkyl group, alkoxy group or aryl group, and X is N, P, O, S or Si.
3. The polysulfonimide according to claim 1, wherein the radicals R 3 Selected from one of the following structures:
wherein, is a connection site, m is an integer of 1-20, and R, R' is independently hydrogen atom, halogen atom, nitro group, ester group, alkyl group, alkoxy group or aryl group.
4. The polysulfonimide according to claim 1, wherein the radicals R 4 Selected from one of the following structures:
wherein, is a connection site, m is an integer of 1-20, and R, R' is independently hydrogen atom, halogen atom, nitro group, ester group, alkyl group, alkoxy group or aryl group.
5. A process for the preparation of the polysulfonimides according to any of claims 1 to 4, characterized in that it comprises the steps of:
adding a diacetylene compound, a binary sulfonyl azide compound, an aldehyde compound, a hydrazine compound, a monovalent copper catalyst and triethylamine into an organic solvent for reaction, and then filtering to obtain a filtrate;
adding the filtrate into a precipitator for precipitation to obtain the polysulfonimide;
wherein the general structural formula of the diacetylene compound is as follows:
the structural general formula of the binary sulfonyl azide compound is as follows:
the structural general formula of the aldehyde compound is as follows: r is R 3 -CHO；
The structural general formula of the hydrazine compound is as follows: r is R 4 -NHNH 2 。
6. The preparation method according to claim 5, wherein the molar ratio of the diacetylene compound, the disulfonyl azide compound, the aldehyde compound and the hydrazine compound is 1:1 (2-3): 2-3;
and/or the reaction concentration of the diacetylene compound is 0.1-0.4 mol/L;
and/or the molar amount of the monovalent copper catalyst is 2-10% of the molar amount of the dibasic alkyne compound;
and/or the molar quantity of the triethylamine is 1.1-3.3 times of the molar quantity of the binary alkyne compound;
and/or the monovalent copper catalyst comprises at least one of cuprous iodide, cuprous bromide and cuprous chloride;
and/or the precipitant comprises at least one of methanol, diethyl ether, acetone and n-hexane;
and/or the organic solvent comprises at least one of dichloromethane, tetrahydrofuran, N-dimethylformamide and toluene;
and/or the temperature of the reaction is room temperature, and the reaction time is 0.5-24 h.
7. Use of a polysulphone-imide according to any of claims 1 to 4 or a polysulphone-imide prepared by a preparation method according to any of claims 5 to 6 in the field of optical displays.
8. Use of a polysulphone-mide according to any of claims 1 to 4 or a polysulphone-mide obtainable by a process according to any of claims 5 to 6 for the preparation of a polysulphone-mide.
9. The use according to claim 8, wherein the method of preparation comprises the steps of:
and adding the polysulfonamide into an acidic solution for reaction to obtain the polysulfonamide.
10. Polysulfonamides of the formula II:
the polysulfonamide is obtained by reacting the polysulfonamide according to any one of claims 1 to 4 or the polysulfonamide prepared by the preparation method according to any one of claims 5 to 6 in an acidic solution.
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