CN117229450A - Fluorescent copolymer with high quantum yield, preparation method and application - Google Patents
Fluorescent copolymer with high quantum yield, preparation method and application Download PDFInfo
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- 229920001114 fluorescent copolymer Polymers 0.000 title claims abstract description 49
- 238000006862 quantum yield reaction Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000000178 monomer Substances 0.000 claims abstract description 51
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 40
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 25
- QOJXAPSXKQKFKS-UHFFFAOYSA-N (4-ethenylphenyl)methanethiol Chemical compound SCC1=CC=C(C=C)C=C1 QOJXAPSXKQKFKS-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 13
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 9
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000012984 biological imaging Methods 0.000 claims description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- -1 4-vinylphenyl Chemical group 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000000977 initiatory effect Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 abstract 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 229920001109 fluorescent polymer Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- QVDBRPUWNAGCFI-UHFFFAOYSA-N 2-(4-ethenylphenyl)ethanethiol Chemical compound SCCC1=CC=C(C=C)C=C1 QVDBRPUWNAGCFI-UHFFFAOYSA-N 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical group C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 229920005605 branched copolymer Polymers 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 2
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 231100000135 cytotoxicity Toxicity 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a fluorescent copolymer with high quantum yield, a preparation method and application thereof, and belongs to the technical field of high polymer materials. The fluorescent copolymer is a branched maleic anhydride copolymer prepared by solution polymerization. The preparation method of the high quantum yield fluorescent copolymer comprises the steps of dissolving maleic anhydride, vinyl monomers and branched monomers in a solvent according to a certain proportion, and polymerizing under the initiation of an initiator to obtain the high quantum yield branched fluorescent copolymer. The excitation range of the prepared fluorescent copolymer is 340-590nm, the emission range is 450-620nm, the fluorescence quantum yield can reach 30%, the raw material price is low, the method is simple, and the fluorescent copolymer has wide application prospect in the aspects of light conversion agricultural film, anti-counterfeiting, fluorescent dye and the like.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a high quantum yield fluorescent copolymer, a preparation method and application thereof.
Background
Fluorescence is that the substances reach an excited state after absorbing high energy, and finally, the substances return to a ground state to emit long waves with lower energy. Due to the unique optical characteristics, the fluorescent substance has wide application prospect in the fields of light emitting diodes, chemical sensing, medical treatment and the like. The fluorescent material can be divided into inorganic and organic luminescent materials, and compared with inorganic fluorescent agents, the organic luminescent material has the advantages of low price, easy adjustment and the like, and has wide application value in a plurality of fields such as photoelectric devices, chemical probes, anti-counterfeiting and the like. However, conventional organic fluorescent materials often have large unsaturated conjugated groups such as benzene rings, thiophenes, carbazole and the like, which are limited in application in the fields of biology and the like due to conjugated structures with cytotoxicity, and on the other hand, fluorescence quenching often occurs in a high concentration or aggregation state.
In recent years, more and more experimental researches show that some novel materials without conjugated groups also have fluorescence properties. These non-conventional fluorescent materials often contain electron-rich heteroatoms (N, O, S, P) or unsaturated bonds (c= O, C = N, S =o) that form clusters through spatial interactions, and thus become a fluorescent material that emits light from the clusters. Compared with the traditional fluorescent substance, the cluster luminous polymer has the advantages of low biotoxicity, low production cost and simple preparation, and has wide application in the fields of biological imaging, anti-counterfeiting, medicine carrying, photoelectric devices and the like.
However, the current cluster luminescent polymers are not perfect due to the mechanism, most luminescent polymers are only in blue emission, and the fluorescence quantum yield is very low. Paper macromol. Chem. Phys. 2019,220,1900324-1900330 by varying the flexibility of the polymer chains, the quantum yield of the synthesized 1-octene-itaconic anhydride copolymer can reach 21.0% but the maximum emission wavelength is in the blue region of 430 nm. Paper J.Mater.chem.C 2020,8 (3), 1017-1024 gives itaconic anhydride-vinyl caprolactam copolymer by free radical polymerization with a maximum emission wavelength up to 630nm but a quantum yield of only 3.09%. Therefore, the preparation of the red light-emitting fluorescent copolymer with high quantum yield by adopting a simple method has important significance.
Disclosure of Invention
Aiming at the problems of short emission wavelength and low quantum yield of the current cluster light-emitting copolymer, the invention provides a preparation method of a fluorescent copolymer with high quantum yield. Adding branching monomer into the copolymerization system of maleic anhydride and vinyl monomer, polymerizing under the initiation of initiator, and obtaining high quantum yield branching fluorescent copolymer after reaction, and regulating emission wavelength and quantum yield by regulating branching degree of copolymer. The method has simple synthesis process, is economical and efficient, and is suitable for industrial production.
The specific technical scheme of the invention is as follows:
in one aspect, a high quantum yield fluorescent copolymer is provided comprising maleic anhydride, vinyl monomer, and branching monomer, wherein the molar ratio of maleic anhydride, vinyl monomer, and branching monomer is 100 (50-100): 1-20.
In an alternative embodiment, the branched fluorescent copolymer has a degree of branching of 1-30%, an emission wavelength of which is tunable, and an emission wavelength of 450-620nm, and a quantum yield of up to 30%.
In an alternative embodiment, the branched monomer has the general structural formula:
wherein R is a saturated alkyl group, preferably one of 4-vinylbenzyl mercaptan, 1- (4-vinylphenyl) -1-mercaptoethane, more preferably 4-vinylbenzyl mercaptan.
In an alternative embodiment, the high quantum yield fluorescent copolymer, the vinyl monomer is one of vinyl acetate, vinyl propionate, vinyl butyrate, styrene, methyl styrene, more preferably vinyl acetate.
In another aspect, a method for preparing a high quantum yield fluorescent copolymer is provided, comprising the steps of:
adding maleic anhydride, vinyl monomer, branching monomer and initiator into solvent, ultrasonic dissolving, mixing uniformly to obtain reaction system, reacting under inert gas protection, centrifuging or filtering, purifying, drying to obtain high quantum yield fluorescent copolymer.
Further, the concentration of maleic anhydride in the reaction system is 0.1-1.0mol/L, the concentration of vinyl monomer is 0.05-1.0mol/L, the branched monomer accounts for 1-20% of the mole number of the maleic anhydride monomer, the initiator is used in an amount of 0.5-2% by weight of the total mass of the maleic anhydride, the branched monomer and the vinyl monomer, the reaction temperature is 70-90 ℃, and the reaction time is 6-12h.
In an alternative embodiment, the solvent in the preparing step is one or more than two of 1, 4-dioxane, tetrahydrofuran, ethyl acetate, acetone, butanone, N-dimethylformamide and dimethyl sulfoxide.
In an alternative embodiment, the initiator in the preparing step is one of azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, more preferably azobisisobutyronitrile.
On the other hand, the application of the fluorescent copolymer with high quantum yield or the application of the preparation method is provided, and the fluorescent polymer can be applied to the fields of light conversion agricultural film materials, anti-counterfeiting materials, fluorescent dyes and biological imaging.
The invention has the beneficial effects that:
1. compared with other cluster luminous anhydride copolymers, the branched copolymer prepared by the invention has the advantages that the branched structure reduces the rigidity of polymer chains, and the quantum yield can reach 30% by enhancing the inter-molecular-chain interaction.
2. Compared with the traditional method for improving the quantum yield of the cluster light-emitting polymer, the method can directly obtain the copolymer with improved quantum yield by adding the branching monomer before the reaction, has simple steps and is suitable for mass production.
3. The branched fluorescent copolymer prepared by the invention can regulate the branching degree by using different branching monomer addition amounts, thereby regulating the emission wavelength and quantum yield of the fluorescent copolymer.
Drawings
FIG. 1 is a 3D fluorescence spectrum of the fluorescent polymer of example 1;
FIG. 2 is a 3D fluorescence spectrum of the fluorescent polymer of example 3;
FIG. 3 is a 3D fluorescence spectrum of the fluorescent polymer of example 5;
FIG. 4 is a 3D fluorescence spectrum of the fluorescent polymer of example 6;
FIG. 5 is a 3D fluorescence spectrum of the fluorescent polymer of example 7;
detailed description of the preferred embodiments
The sources of reagents used in the examples of the present invention may be commercially available, except where otherwise specified.
It should be understood that what is described hereinA kind of electronic deviceThe detailed description is merely illustrative and explanatory of the invention, and is not intended to limit the invention. The raw material components which are equivalent to or contain the same structural units as the functional groups contained in the raw materials used in the examples except the raw materials used in the examples are included in the protection scope of the invention. The invention is further illustrated below with reference to specific examples.
The present invention provides the test result drawings of the embodiments, other comparative examples adopt the same test method, and a person skilled in the art can directly and unambiguously determine the content of the embodiments of the present invention through the test method provided by the present invention.
Example 1
4.90g of maleic anhydride, 4.30g of vinyl acetate, 0.225g of branched monomer 4-vinylbenzyl mercaptan (molar ratio 100:100:3) and 0.047g of azobisisobutyronitrile are weighed and added into 50ml of 1, 4-dioxane, and the mixture is ultrasonically dissolved, and a reaction system is obtained after uniform mixing, wherein the concentration of the maleic anhydride and the vinyl acetate in the reaction system is 1.0mol/L, the 4-vinylbenzyl mercaptan accounts for 3% of the mole number of the maleic anhydride monomer, and the azobisisobutyronitrile accounts for 0.5wt% of the total mass of the maleic anhydride, the vinyl acetate and the 4-vinylbenzyl mercaptan. The reaction system is reacted for 10 hours at 70 ℃ under the protection of nitrogen gas, after the reaction is completed, the product is precipitated by petroleum ether and washed for three times, and the product is dried in vacuum until the weight is constant, so that the branched fluorescent copolymer is obtained, and the fluorescent properties are shown in table 1.
Example 2
4.90g of maleic anhydride, 5.0g of vinyl propionate, 0.225g of branched monomer 4-vinylbenzyl mercaptan (molar ratio 100:100:3) and 0.05g of azobisisobutyronitrile are weighed and added into 50ml of 1, 4-dioxane, the mixture is ultrasonically dissolved and uniformly mixed to obtain a reaction system, wherein the concentration of the maleic anhydride and the vinyl propionate in the reaction system is 1.0mol/L, the 4-vinylbenzyl mercaptan accounts for 3% of the mole number of the maleic anhydride monomer, and the azobisisobutyronitrile accounts for 0.5wt% of the total mass of the maleic anhydride, the vinyl propionate and the 4-vinylbenzyl mercaptan. The reaction system is reacted for 10 hours at 70 ℃ under the protection of nitrogen gas, after the reaction is completed, the product is precipitated by petroleum ether and washed for three times, and the product is dried in vacuum until the weight is constant, so that the branched fluorescent copolymer is obtained, and the fluorescent properties are shown in table 1.
Example 3
4.90g of maleic anhydride, 4.30g of vinyl acetate, 0.375g of branched monomer 4-vinylbenzyl mercaptan (molar ratio 100:100:5) and 0.096g of azobisisobutyronitrile are weighed and added into 50ml of 1, 4-dioxane, and the mixture is ultrasonically dissolved, and the reaction system is obtained after uniform mixing, wherein the concentration of the maleic anhydride and the vinyl acetate in the reaction system is 1.0mol/L, the 4-vinylbenzyl mercaptan accounts for 5% of the mole number of the maleic anhydride monomer, and the azobisisobutyronitrile accounts for 1wt% of the total mass of the maleic anhydride, the vinyl acetate and the 4-vinylbenzyl mercaptan. The reaction system is reacted for 10 hours at 70 ℃ under the protection of nitrogen gas, after the reaction is completed, the product is precipitated by petroleum ether and washed for three times, and the product is dried in vacuum until the weight is constant, so that the branched fluorescent copolymer is obtained, and the fluorescent properties are shown in table 1.
Example 4
4.90g of maleic anhydride, 4.30g of vinyl acetate, 0.41g of branched monomer 4-vinyl phenethyl mercaptan (molar ratio 100:100:5) and 0.096g of azobisisobutyronitrile are weighed and added into 50ml of 1, 4-dioxane, and are ultrasonically dissolved and uniformly mixed to obtain a reaction system, wherein the concentration of the maleic anhydride and the vinyl acetate in the reaction system is 1.0mol/L, the 4-vinyl phenethyl mercaptan accounts for 5% of the mole number of the maleic anhydride monomer, and the azobisisobutyronitrile accounts for 1wt% of the total mass of the maleic anhydride, the vinyl acetate and the 4-vinyl phenethyl mercaptan. The reaction system is reacted for 10 hours at 70 ℃ under the protection of nitrogen gas, after the reaction is completed, the product is precipitated by petroleum ether and washed for three times, and the product is dried in vacuum until the weight is constant, so that the branched fluorescent copolymer is obtained, and the fluorescent properties are shown in table 1.
Example 5
0.98g of maleic anhydride, 0.43g of vinyl acetate, 0.150g of branched monomer 4-vinylbenzyl mercaptan (molar ratio 100:50:10) and 0.016g of azobisisobutyronitrile are weighed and added into 50ml of 1, 4-dioxane, and the mixture is ultrasonically dissolved, and a reaction system is obtained after uniform mixing, wherein the concentrations of the maleic anhydride and the vinyl acetate in the reaction system are respectively 0.2mol/L and 0.1mol/L, the 4-vinylbenzyl mercaptan accounts for 10% of the mole number of the vinyl monomer, and the azobisisobutyronitrile accounts for 1wt% of the total mass of the maleic anhydride, the vinyl acetate and the 4-vinylbenzyl mercaptan. The reaction system is reacted for 10 hours at 70 ℃ under the protection of nitrogen gas, after the reaction is completed, the product is precipitated by petroleum ether and washed for three times, and the product is dried in vacuum until the weight is constant, so that the branched fluorescent copolymer is obtained, and the fluorescent properties are shown in table 1.
Example 6
4.90g of maleic anhydride, 4.30g of vinyl acetate, 0.750g of branched monomer 4-vinylbenzyl mercaptan (molar ratio 100:100:10) and 0.1g of azobisisobutyronitrile are weighed and added into 50ml of 1, 4-dioxane, and the mixture is ultrasonically dissolved and uniformly mixed to obtain a reaction system, wherein the concentration of the maleic anhydride and the vinyl acetate in the reaction system is 1.0mol/L, the 4-vinylbenzyl mercaptan accounts for 10% of the mole number of the maleic anhydride monomer, and the azobisisobutyronitrile accounts for 1wt% of the total mass of the maleic anhydride, the vinyl acetate and the 4-vinylbenzyl mercaptan. The reaction system is reacted for 10 hours at 70 ℃ under the protection of nitrogen gas, after the reaction is completed, the product is precipitated by petroleum ether and washed for three times, and the product is dried in vacuum until the weight is constant, so that the branched fluorescent copolymer is obtained, and the fluorescent properties are shown in table 1.
Example 7
2.45g of maleic anhydride, 1.94g of vinyl acetate, 0.563g of branched monomer 4-vinylbenzyl mercaptan (molar ratio 100:90:15) and 0.05g of azobisisobutyronitrile are weighed and added into 50ml of 1, 4-dioxane, and the mixture is ultrasonically dissolved to obtain a reaction system, wherein the concentration of the maleic anhydride and the concentration of the vinyl acetate in the reaction system are respectively 0.5mol/L and 0.45mol/L, the concentration of the 4-vinylbenzyl mercaptan accounts for 15% of the mole number of the maleic anhydride monomers, and the azobisisobutyronitrile accounts for 1wt% of the total mass of the maleic anhydride, the vinyl acetate and the 4-vinylbenzyl mercaptan. The reaction system is reacted for 10 hours at 70 ℃ under the protection of nitrogen gas, after the reaction is completed, the product is precipitated by petroleum ether and washed for three times, and the product is dried in vacuum until the weight is constant, so that the branched fluorescent copolymer is obtained, and the fluorescent properties are shown in table 1.
Comparative example 1
4.90g of maleic anhydride, 4.30g of vinyl acetate (molar ratio 100:100) and 0.047g of azobisisobutyronitrile are weighed and added into 50ml of 1, 4-dioxane, and the mixture is ultrasonically dissolved and uniformly mixed to obtain a reaction system, wherein the concentration of the maleic anhydride and the concentration of the vinyl acetate in the reaction system are 1.0mol/L. The reaction system is reacted for 10 hours at 70 ℃ under the protection of nitrogen gas, after the reaction is completed, the product is precipitated by petroleum ether and washed for three times, and the product is dried in vacuum until the weight is constant, so that the branched fluorescent copolymer is obtained, and the fluorescent properties are shown in table 1.
Comparative example 2
2.45g of maleic anhydride, 1.94g of vinyl acetate (molar ratio 100:90) and 0.05g of azobisisobutyronitrile were weighed and added into 50ml of 1, 4-dioxane, and the mixture was subjected to ultrasonic dissolution and uniform mixing to obtain a reaction system, wherein the concentrations of maleic anhydride and vinyl acetate in the reaction system were 0.5mol/L and 0.45mol/L, respectively. The reaction system is reacted for 10 hours at 70 ℃ under the protection of nitrogen gas, after the reaction is completed, the product is precipitated by petroleum ether and washed for three times, and the product is dried in vacuum until the weight is constant, so that the branched fluorescent copolymer is obtained, and the fluorescent properties are shown in table 1.
Comparative example 3
4.90g of maleic anhydride, 5.0g of vinyl propionate (molar ratio 100:100) and 0.05g of azobisisobutyronitrile are weighed and added into 50ml of 1, 4-dioxane, and the mixture is ultrasonically dissolved and uniformly mixed to obtain a reaction system, wherein the concentration of the maleic anhydride and the concentration of the vinyl propionate in the reaction system are 1.0mol/L. The reaction system is reacted for 10 hours at 70 ℃ under the protection of nitrogen gas, after the reaction is completed, the product is precipitated by petroleum ether and washed for three times, and the product is dried in vacuum until the weight is constant, so that the branched fluorescent copolymer is obtained, and the fluorescent properties are shown in table 1.
TABLE 1
It can be seen from comparative examples 1 and 1, comparative examples 2 and 7, and comparative examples 3 and 2 that the resulting fluorescent copolymer is only linear without the addition of a branching monomer, and the interactions between groups in the molecular chain are small, so that clusters are not easily generated, resulting in short-wavelength emission and low quantum yield. By adding the branching monomer, branched chains can be formed in the polymerization process, stronger inter-molecular-chain interaction and more cluster production can be realized, so that the emission of the fluorescent copolymer can be red shifted, and the quantum yield of the fluorescent copolymer can be improved. At a certain degree of branching, i.e. when the inter-molecular-chain interactions and the non-radiative transitions reach equilibrium, the quantum yield of the branched fluorescent copolymer reaches a maximum.
The branched copolymer prepared by the invention can enhance the inter-molecular interaction by reducing the rigidity of the polymer chain, so that the quantum yield can reach 30 percent. Compared with the traditional method for improving the quantum yield of the cluster light-emitting polymer, the method can directly obtain the copolymer with improved quantum yield by directly adding the branching monomer before the polymerization reaction starts, has simple steps and is suitable for mass production. In addition, the branching degree can be regulated by using different branching monomer addition amounts, so that the emission wavelength and quantum yield of the fluorescent copolymer can be regulated.
In conclusion, compared with the traditional method, the method for improving the quantum yield of the fluorescent copolymer has obvious advantages, and the branched fluorescent copolymer has good application prospects in the fields of light conversion agricultural film materials, anti-counterfeiting materials, fluorescent dyes, biological imaging and the like.
Those of ordinary skill in the art will appreciate that: the foregoing description of the embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A high quantum yield fluorescent copolymer, characterized in that the high quantum yield fluorescent copolymer comprises maleic anhydride, vinyl monomer and branching monomer, wherein the molar ratio of maleic anhydride, vinyl monomer and branching monomer is 100 (50-100): 1-20.
2. The high quantum yield fluorescent copolymer of claim 1, wherein the high quantum yield fluorescent copolymer is a branched polymer having a degree of branching of 1 to 30%; the emission wavelength is adjustable, and is 450-620nm; the maximum quantum yield can reach 30%.
3. The high quantum yield fluorescent copolymer of claim 1, wherein the branched monomer has the structural formula:
wherein R is a saturated alkyl group.
4. A high quantum yield fluorescent copolymer as claimed in claim 3 wherein said branching monomer is one of 4-vinylbenzyl mercaptan, 1- (4-vinylphenyl) -1-thiol ethane.
5. The high quantum yield fluorescent copolymer of claim 1, wherein the vinyl monomer is one of vinyl acetate, vinyl propionate, vinyl butyrate, styrene, and methyl styrene.
6. A method for preparing a high quantum yield fluorescent copolymer according to any of claims 1-5, characterized in that the preparation steps are as follows:
adding maleic anhydride, vinyl monomer, branching monomer and initiator into solvent, ultrasonic dissolving, mixing uniformly to obtain reaction system, reacting under inert gas protection, centrifuging or filtering, purifying, drying to obtain high quantum yield fluorescent copolymer.
7. The preparation method according to claim 6, wherein the concentration of maleic anhydride in the reaction system is 0.1-1.0mol/L, the concentration of vinyl monomer is 0.05-1.0mol/L, the branched monomer accounts for 1-20% of the mole number of the maleic anhydride monomer, the initiator is used in an amount of 0.5-2% by weight of the total mass of the maleic anhydride, the branched monomer and the vinyl monomer, the reaction temperature is 70-90 ℃, and the reaction time is 6-12h.
8. The method according to claim 6, wherein the solvent is one or more of 1, 4-dioxane, tetrahydrofuran, ethyl acetate, acetone, butanone, N-dimethylformamide, and dimethyl sulfoxide.
9. The method of claim 6, wherein the initiator is one of azobisisobutyronitrile, benzoyl peroxide, and potassium persulfate.
10. Use of a high quantum yield fluorescent copolymer according to any one of claims 1 to 5 or a high quantum yield fluorescent copolymer obtained by a method according to any one of claims 6 to 9, characterized in that the high quantum yield fluorescent copolymer is used in the field of light-converting agricultural film materials, anti-counterfeit materials, fluorescent dyes or biological imaging.
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