CN111909370A - High-performance fluorescent functionalized poly (arylene ether nitrile) and preparation method and application thereof - Google Patents
High-performance fluorescent functionalized poly (arylene ether nitrile) and preparation method and application thereof Download PDFInfo
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 85
- -1 poly (arylene ether nitrile Chemical class 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
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- 239000007787 solid Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 230000018044 dehydration Effects 0.000 claims abstract description 9
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 9
- 239000000376 reactant Substances 0.000 claims abstract description 9
- 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 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229920000412 polyarylene Polymers 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229920000090 poly(aryl ether) Polymers 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- VKOUCJUTMGHNOR-UHFFFAOYSA-N Diphenolic acid Chemical compound C=1C=C(O)C=CC=1C(CCC(O)=O)(C)C1=CC=C(O)C=C1 VKOUCJUTMGHNOR-UHFFFAOYSA-N 0.000 claims description 5
- QRFMXBKGNQEADL-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 QRFMXBKGNQEADL-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- 238000003745 diagnosis Methods 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- VANWLQWTNYDIRX-UHFFFAOYSA-N 2-[2-(2-hydroxyphenyl)ethyl]-3,4,5,6-tetraphenylphenol Chemical compound C1(=CC=CC=C1)C1=C(C(=C(C(=C1O)CCC1=C(C=CC=C1)O)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 VANWLQWTNYDIRX-UHFFFAOYSA-N 0.000 claims 1
- ZYIGFXHZSKIVOO-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)-1,2-diphenylethenyl]phenol Chemical group C1=CC(O)=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC(O)=CC=1)C1=CC=CC=C1 ZYIGFXHZSKIVOO-UHFFFAOYSA-N 0.000 claims 1
- 230000002776 aggregation Effects 0.000 abstract description 21
- 238000004220 aggregation Methods 0.000 abstract description 21
- 239000002861 polymer material Substances 0.000 abstract description 6
- 238000001228 spectrum Methods 0.000 abstract description 3
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- 229920001002 functional polymer Polymers 0.000 abstract 1
- 230000001939 inductive effect Effects 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 33
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 24
- 238000012360 testing method Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 15
- 239000010408 film Substances 0.000 description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 7
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- 238000004020 luminiscence type Methods 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
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4031—(I) or (II) containing nitrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
The invention discloses a high-performance fluorescence functionalized poly (arylene ether nitrile) and a preparation method and application thereof, relating to the field of functional polymer materials, wherein the preparation method comprises the following steps: placing 2, 6-dichlorobenzonitrile, a tetraphenyl ethylene bisphenol derivative monomer, an aromatic dihydric phenol monomer, a catalyst, an organic solvent and a water-carrying agent into a reactor together, stirring to mix and dissolve reactants, heating to 130-150 ℃ for azeotropic dehydration for 2 hours, gradually raising the temperature to 180-200 ℃ for reaction for 2-3 hours, after the reaction is finished, slowly pouring the obtained viscous product into a dilute hydrochloric acid solution to separate out a strip poly (arylene ether nitrile) solid, crushing the poly (arylene ether nitrile) solid, purifying and drying to obtain a poly (arylene ether nitrile) polymer with a main chain containing a tetraphenyl ethylene structure; according to the invention, the aggregation inducing monomer is introduced into the molecular main chain, so that the luminous efficiency of the polymer is enhanced, the fluorescence intensity is enhanced by 1.5-15.9 times, the emission peak is red-shifted from about 420nm to about 460nm, the spectrum is widened, and meanwhile, the polymer has good film forming property, thermal stability and mechanical property, and is simple in synthesis method and convenient and fast to operate.
Description
Technical Field
The invention relates to the field of functional high polymer materials, in particular to high-performance fluorescent functional poly (arylene ether nitrile) and a preparation method and application thereof.
Background
The poly (arylene ether nitrile) (PEN) is a novel special polymer material which has excellent heat resistance, radiation resistance and corrosion resistance, excellent mechanical strength, good electrical appliance insulation and flame retardance and is easy to process. The method is applied to high and new technical fields of aerospace, special equipment, electrical equipment and the like at present. In recent years, with the direction of innovation and improvement of the technical content and the additional value of materials, the poly (arylene ether nitrile) serving as a special high polymer material with excellent comprehensive performance is gradually developed and applied to functional materials, and the poly (arylene ether nitrile) is proved to be a high-performance functional material not only serving as a high-performance special engineering plastic but also serving as a high-performance functional material in the fields of dielectrics, adsorption resins, proton exchange membranes and the like. The poly (arylene ether nitrile) has a large number of conjugated aromatic rings in the structure, can emit blue fluorescence under the excitation of ultraviolet light, is used as a high-molecular fluorescent material, and is applied to the fields of flexible display devices, visual monitoring, biological diagnosis and treatment and the like. However, recent research reports show that the poly (arylene ether nitrile) fluorescence functionalization still has the defects of single emission spectrum, only in a deep blue region, low luminous efficiency and the like, and the progress of the application research of the light functionalization is hindered.
Chinese patent CN109593826A discloses a method for preparing high-performance carboxyl-functionalized polyarylether nitrile, which takes phenolphthalein containing carboxyl as a bisphenol monomer, and the phenolphthalein containing carboxyl is copolymerized with other monomers such as bisphenol A, biphenyl bisphenol and the like respectively to synthesize the high-performance carboxyl-functionalized polyarylether nitrile copolymer. Phenolphthalein serving as a functional monomer is introduced into a molecular main chain, so that the original high glass transition temperature, excellent thermal stability, good mechanical strength and good solubility of a polar solvent of the polyarylether are ensured, and blue fluorescence can be emitted under the excitation of ultraviolet light. Provides a material foundation for the poly (arylene ether nitrile) to prepare a functional composite material by utilizing the reactivity of the poly (arylene ether nitrile) and develop the application in the optical field. But the phenolphthalein functional monomer used is not a fluorescent small molecule with high quantum yield, cannot improve the light-emitting waveband of the poly (arylene ether nitrile), and the emission peak of the phenolphthalein functional monomer is still in a deep blue region (about 420 nm) which is difficult to observe by naked eyes; and the light-emitting efficiency of the poly (arylene ether nitrile) is low.
Disclosure of Invention
The invention aims to: the high-performance fluorescent functionalized poly (arylene ether nitrile) and the preparation method and the application thereof are provided, the luminous efficiency of the polymer is enhanced and the emission spectrum is widened by means of the luminous characteristic of the aggregation-induced monomer, and meanwhile, the high-performance fluorescent functionalized poly (arylene ether nitrile) has good film forming property, thermal stability and mechanical property, the synthesis method is simple, and the operation is convenient.
The technical scheme adopted by the invention is as follows:
in order to achieve the above object, the present invention provides a high-performance fluorescence functionalized poly (arylene ether nitrile), having the following structural formula:
wherein x is more than 0 and less than 1, n is the polymerization degree, and n is more than 0.
The invention also provides a preparation method of the high-performance fluorescence functionalized poly (arylene ether nitrile), which comprises the following steps:
placing 2, 6-dichlorobenzonitrile, a tetraphenyl ethylene bisphenol derivative monomer, an aromatic dihydric phenol monomer, a catalyst, an organic solvent and a water-carrying agent into a reactor together, mechanically stirring to mix and dissolve reactants, heating to 130-150 ℃ for azeotropic dehydration for 2 hours, gradually raising the temperature to 180-200 ℃ for reaction for 2-3 hours, after the reaction is finished, slowly pouring the obtained viscous product into a dilute hydrochloric acid solution to separate out a strip poly (arylene ether nitrile) solid, crushing the strip poly (arylene ether nitrile) solid into powder, and purifying and drying to obtain the poly (arylene ether nitrile) polymer with the main chain containing a tetraphenyl ethylene structure, wherein the polymer is high-performance fluorescent functionalized poly (arylene ether nitrile).
Preferably, the purification step is: and boiling and washing the powdery polymer for 3-5 times by using absolute ethyl alcohol and deionized water respectively.
Preferably, the drying step is carried out at 80 ℃ for 24 h.
Preferably, the tetraphenyl ethylene bisphenol-derived monomer is 1, 2-bis (4-hydroxyphenyl) -1, 2-stilbene.
Preferably, the aromatic dihydric phenol monomer is selected from any one of biphenyl bisphenol, p-phenyl bisphenol, bisphenol a, phenolphthalein, and diphenolic acid.
Preferably, the organic solvent is N-methylpyrrolidone.
Preferably, the water-carrying agent is toluene or xylene.
The invention also provides application of the high-performance fluorescence functionalized poly (arylene ether nitrile) in flexible thin film display devices, fluorescence sensors and biological diagnosis and treatment.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the invention introduces tetraphenyl ethylene bisphenol derivative monomer into the main molecular chain, utilizes the aggregation-induced luminescence characteristic of the tetraphenyl ethylene bisphenol derivative monomer to adjust the emission spectrum of the poly (arylene ether nitrile), so that the poly (arylene ether nitrile) is in a solid state, by means of aggregation-induced emission characteristics, the light-emitting efficiency of the poly (arylene ether nitrile) copolymer is enhanced, and experiments prove that the fluorescence intensity of the poly (arylene ether nitrile) copolymer in an aggregation state is obviously enhanced by 1.5 to 15.9 times, the emission peak of the blue-green light spectrum is shifted from about 420nm which is difficult to be observed by naked eyes to about 460nm bright blue-green light band, the spectrum is widened, meanwhile, compared with other fluorescent materials, the high-performance fluorescent functional poly (arylene ether nitrile) has better film forming property, thermal stability and mechanical property, is a fluorescent high polymer material with excellent comprehensive performance, and has the potential of being applied to the fields of flexible thin film display devices, fluorescent sensors, biological diagnosis and treatment and the like.
2. The method adopts a one-time feeding method, introduces tetraphenyl ethylene bisphenol derivative monomers with aggregation-induced fluorescence characteristics into a molecular main chain by virtue of nucleophilic substitution stepwise polymerization reaction, synthesizes the poly (arylene ether nitrile) copolymer, and has the advantages of few synthesis steps and simple and convenient operation.
Drawings
The invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a chart showing an infrared absorption spectrum of a tetraphenylethylene-type polyarylene ether nitrile copolymer prepared in examples 1 to 6;
FIG. 2 shows the tetraphenylethylene-type polyarylene ether nitrile copolymer PEN-TPE/PPL prepared in example 5 in different ratios of good-poor mixed solvent (DMF-H)2Fluorescence emission spectrum in O);
FIG. 3 shows the good-poor mixed solvent (DMF-H) at different ratios of the PEN-TPE/PPL copolymer of tetraphenylethylene type prepared in example 52Fluorescence photograph of the real object in O);
FIG. 4 is a comparative photograph of fluorescence of a film made of the tetraphenyl ethylene type poly (arylene ether nitrile) PEN-TPE/PPL copolymer prepared in example 5 and a film made of pure poly (arylene ether nitrile) PEN-PPL polymerized with phenolphthalein under excitation of ultraviolet light (365 nm).
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example provides a tetraphenyl ethylene poly (arylene ether nitrile) copolymer PEN-TPE/BP, which has the following structural formula:
the embodiment also provides a synthetic method of the copolymer PEN-TPE/BP, which comprises the following steps:
adding 0.20mmol of tetraphenyl ethylene bisphenol derivative monomer, 19.80mmol of biphenyl bisphenol, 20.00mmol of 2, 6-dichlorobenzonitrile, 30.00mmol of anhydrous potassium carbonate, 16.00mL of methyl pyrrolidone and 6.00mL of toluene into a 100mL three-neck flask provided with a mechanical stirring device, a thermometer, a water separator and a condensing device; mechanically stirring to mix and dissolve reactants, heating to 130-150 ℃ for azeotropic dehydration for 2h, and gradually raising the temperature to 180-200 ℃ for reaction for 2-3 h; after the reaction is finished, slowly pouring the obtained viscous product into a dilute hydrochloric acid solution to separate out a strip-shaped poly (arylene ether nitrile) solid, crushing a polymer into powder, and boiling and washing the powder for 3-5 times by using absolute ethyl alcohol and deionized water respectively to remove small molecules which do not participate in the reaction, the residual potassium carbonate catalyst, the residual organic solvent and the like; and finally, placing the purified poly (arylene ether nitrile) powder in a vacuum oven, and drying for 24h at the temperature of 80 ℃ to obtain the PEN-TPE/BP poly (arylene ether nitrile) copolymer.
Example 2
This example provides a tetraphenylethylene-type poly (arylene ether nitrile) copolymer PEN-TPE/HQ, which has the following structural formula:
the present embodiment also provides a method for synthesizing the copolymer PEN-TPE/HQ, comprising the following steps:
adding 0.20mmol of tetraphenyl ethylene bisphenol derivative monomer, 19.80mmol of p-phenyl bisphenol, 20.00mmol of 2, 6-dichlorobenzonitrile, 30.00mmol of anhydrous potassium carbonate, 14.00mL of methyl pyrrolidone and 4.70mL of toluene into a 100mL three-neck flask provided with a mechanical stirring device, a thermometer, a water separator and a condensing device; mechanically stirring to mix and dissolve reactants, heating to 130-150 ℃ for azeotropic dehydration for 2h, and gradually raising the temperature to 180-200 ℃ for reaction for 2-3 h; after the reaction is finished, slowly pouring the obtained viscous product into a dilute hydrochloric acid solution to separate out a strip-shaped poly (arylene ether nitrile) solid, crushing a polymer into powder, and boiling and washing the powder for 3-5 times by using absolute ethyl alcohol and deionized water respectively to remove small molecules which do not participate in the reaction, the residual potassium carbonate catalyst, the residual organic solvent and the like; and finally, placing the purified poly (arylene ether nitrile) powder in a vacuum oven, and drying for 24h at the temperature of 80 ℃ to obtain the PEN-TPE/HQ poly (arylene ether nitrile) copolymer.
Example 3
This example provides a tetraphenyl ethylene poly (arylene ether nitrile) copolymer PEN-TPE/BPA, which has the following structural formula:
the embodiment also provides a synthesis method of the copolymer PEN-TPE/BPA, which comprises the following steps:
adding 0.20mmol of tetraphenyl ethylene bisphenol derivative monomer, 19.80mmol of bisphenol A, 20.00mmol of 2, 6-dichlorobenzonitrile, 30.00mmol of anhydrous potassium carbonate, 20.00mmol of methyl pyrrolidone and 6.70mL of toluene into a 100mL three-neck flask provided with a mechanical stirring device, a thermometer, a water separator and a condensing device; mechanically stirring to mix and dissolve reactants, heating to 130-150 ℃ for azeotropic dehydration for 2h, and gradually raising the temperature to 180-200 ℃ for reaction for 2-3 h; after the reaction is finished, slowly pouring the obtained viscous product into a dilute hydrochloric acid solution to separate out a strip-shaped poly (arylene ether nitrile) solid, crushing a polymer into powder, and boiling and washing the powder for 3-5 times by using absolute ethyl alcohol and deionized water respectively to remove small molecules which do not participate in the reaction, the residual potassium carbonate catalyst, the residual organic solvent and the like; and finally, placing the purified poly (arylene ether nitrile) powder in a vacuum oven, and drying for 24h at the temperature of 80 ℃ to obtain the PEN-TPE/BPA poly (arylene ether nitrile) copolymer.
Example 4
This example provides a tetraphenyl ethylene poly (arylene ether nitrile) copolymer PEN-TPE/PP, which has the following structural formula:
the embodiment also provides a synthetic method of the copolymer PEN-TPE/PP, which comprises the following steps:
adding 0.10mmol of tetraphenyl ethylene bisphenol derivative monomer, 9.90mmol of phenolphthalein, 10.00mmol of 2, 6-dichlorobenzonitrile, 15.00mmol of anhydrous potassium carbonate, 10.00mL of methyl pyrrolidone and 3.30mL of toluene into a 100mL three-neck flask provided with a mechanical stirring device, a thermometer, a water separator and a condensing device; mechanically stirring to mix and dissolve reactants, heating to 130-150 ℃ for azeotropic dehydration for 2h, and gradually raising the temperature to 180-200 ℃ for reaction for 2-3 h; after the reaction is finished, slowly pouring the obtained viscous product into a dilute hydrochloric acid solution to separate out a strip-shaped poly (arylene ether nitrile) solid, crushing a polymer into powder, and boiling and washing the powder for 3-5 times by using absolute ethyl alcohol and deionized water respectively to remove small molecules which do not participate in the reaction, the residual potassium carbonate catalyst, the residual organic solvent and the like; and finally, placing the purified poly (arylene ether nitrile) powder in a vacuum oven, and drying for 24h at the temperature of 80 ℃ to obtain the PEN-TPE/PP poly (arylene ether nitrile) copolymer.
Example 5
This example provides a tetraphenyl ethylene poly (arylene ether nitrile) copolymer PEN-TPE/PPL, which has the following structural formula:
the embodiment also provides a synthetic method of the copolymer PEN-TPE/PPL, which comprises the following steps:
adding 0.05mmol of tetraphenyl ethylene bisphenol derivative monomer, 4.95mmol of phenolphthalein, 5.00mmol of 2, 6-dichlorobenzonitrile, 11.21mmol of anhydrous potassium carbonate, 12.00mL of N-methylpyrrolidone and 4.00mL of toluene into a 100mL three-neck flask provided with a mechanical stirring device, a thermometer, a water separator and a condensing device; mechanically stirring to mix and dissolve reactants, heating to 130-150 ℃ for azeotropic dehydration for 2h, and gradually raising the temperature to 180-200 ℃ for reaction for 2-3 h; after the reaction is finished, slowly pouring the obtained viscous product into a dilute hydrochloric acid solution to separate out a strip-shaped poly (arylene ether nitrile) solid, crushing a polymer into powder, and boiling and washing the powder for 3-5 times by using absolute ethyl alcohol and deionized water respectively to remove small molecules which do not participate in the reaction, the residual potassium carbonate catalyst, the residual organic solvent and the like; and finally, placing the purified poly (arylene ether nitrile) powder in a vacuum oven, and drying for 24h at the temperature of 80 ℃ to obtain the PEN-TPE/PPL poly (arylene ether nitrile) copolymer.
Example 6
This example provides a tetraphenylethylene-type poly (arylene ether nitrile) copolymer PEN-TPE/DPA, which has the following structural formula:
the present embodiment also provides a method for synthesizing the copolymer PEN-TPE/DPA, which comprises the following steps:
adding 0.10mmol of tetraphenyl ethylene bisphenol derivative monomer, 9.90mmol of diphenolic acid, 10.00mmol of 2, 6-dichlorobenzonitrile, 22.42mmol of anhydrous potassium carbonate, 15.00mL of methyl pyrrolidone and 5.00mL of toluene into a 100mL three-neck flask provided with a mechanical stirring device, a thermometer, a water separator and a condensing device; mechanically stirring to mix and dissolve reactants, heating to 130-150 ℃ for azeotropic dehydration for 2h, and gradually raising the temperature to 180-200 ℃ for reaction for 2-3 h; after the reaction is finished, slowly pouring the obtained viscous product into a dilute hydrochloric acid solution to separate out a strip-shaped poly (arylene ether nitrile) solid, crushing a polymer into powder, and boiling and washing the powder for 3-5 times by using absolute ethyl alcohol and deionized water respectively to remove small molecules which do not participate in the reaction, the residual potassium carbonate catalyst, the residual organic solvent and the like; and finally, placing the purified poly (arylene ether nitrile) powder in a vacuum oven, and drying for 24h at the temperature of 80 ℃ to obtain the PEN-TPE/DPA poly (arylene ether nitrile) copolymer.
Test example 1
In this test example, infrared absorption spectrum tests were performed on the tetraphenylethylene-type polyarylene ether nitrile copolymers prepared in examples 1 to 6, and the results of the tests were shown in fig. 1.
As can be seen from FIG. 1, all polymers were in the 2230cm range-1The expansion vibration peak of the cyano-group appears at the left and the right, 1242cm-1And 1017cm-1The left and the right of the asymmetric and symmetric stretching vibration peak of ether bond appears, 1575cm-1，1500cm-1And 1460cm-1The absorption peak of the skeleton vibration of the benzene ring appears on the left and right. 2970cm of PEN-TPE/BPA and PEN-TPE/DPA exist-1The vibration peak of the methyl in the structures of bisphenol A and diphenolic acid appears. The concentration of PEN-TPE/PPL and PEN-TPE/DPA is 1720cm-1The absorption peaks of carbonyl groups in side chain carboxyl of phenolphthalein and diphenolic acid appear. PEN-TPE/PP at 1773cm-1The absorption peak of carbonyl in the lactone structure of phenolphthalein appears. It was shown that the obtained polyarylene ether nitriles of examples 1 to 6 were all of the expected structures.
Test example 2
In this test example, the tetraphenylethylene-type polyarylene ether nitrile copolymers prepared in examples 1 to 6 were subjected to a thermal mechanical property test, and the results are shown in table one.
TABLE I, thermal resistance test data
As can be seen from Table 1, the 5% thermal decomposition temperature of the obtained tetraphenylethylene-type polyaryl ether nitrile copolymer is between 385-552 ℃, which shows that the polymer has very excellent heat resistance.
Test example 3
This test example the tetraphenylethylene-type polyarylene ether nitrile copolymer prepared in example 5 was subjected to fluorescence property test.
Adopts DMF as a good solvent, H2O is a poor solvent, and the poor solvent is utilized to promote the aggregation of the poly (arylene ether nitrile) in the solution. The concentration of the solution is configured to be 1mg/mL, H2The content of O (volume ratio, vol%) is increased from 0% to 90% and is the sameThe emission spectrum was measured at an excitation wavelength (365nm), and the results are shown in FIG. 2.
From the results shown in FIG. 2, it can be seen that the poor solvent (H) is accompanied by2O) the volume ratio of the polymer in the mixed solvent is increased, the fluorescence emission peak of the polymer is red-shifted, the emission peak of 408nm in the good solvent (DMF) is finally red-shifted to 462nm after aggregation, which shows that the introduction of aggregation-induced fluorescence monomer enables PEN-TPE/PPL to be aggregated under the promotion of the poor solvent, and the fluorescence emission peak in an aggregation state generates 54nm red-shift. Meanwhile, the fluorescence intensity is increased and then reduced, the peak value is reached when the content of the poor solvent is 50%, and the fluorescence intensity is enhanced by 10.6 times compared with that in the good solvent. The ratio of the maximum fluorescence intensity in the aggregated state to the fluorescence intensity in the good solvent is called the AIE factor, i.e. the AIE factor of PEN-TPE/PPL is 10.6.
Test example 4
This experimental example was conducted to visualize the aggregation-induced fluorescence enhancement of the tetraphenylethylene-type polyarylene ether nitrile copolymer prepared in example 5.
The different H configured in test example 42PEN-TPE/PPL solutions with O content (0, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%) were subjected to ultraviolet light (365nm) excitation for comparison, and the fluorescence photographs of the resulting samples are shown in FIG. 3.
As can be seen from the results of the real fluorescence of the solutions shown in FIG. 3 at different contents of the poor solvent, the fluorescence intensity gradually increases with the increase of the content of the poor solvent, and bright fluorescence is emitted after the content exceeds 30%. At higher levels, the solution appeared cloudy to the naked eye, indicating H2The too high O content promotes excessive aggregation of the polyarylene ether nitrile, resulting in precipitation of large-sized aggregates. This is also the fluorescence intensity at H2The reason for the decrease after the O content was 50%.
Test example 5
In this test example, the thin film was prepared from the tetraphenylethylene-type polyarylene ether nitrile copolymer (PEN-TPE/PPL) prepared in example 5, and the thin film was prepared by the following method:
dissolving PEN-TPE/PPL powder in an N-methyl pyrrolidone solvent to prepare a solution with the concentration of 0.1g/mL, mechanically stirring the solution at the temperature of 80-100 ℃ for 30min to fully dissolve the poly (arylene ether nitrile), then forming a film by adopting a tape casting method, horizontally placing a glass plate in an oven, heating the glass plate to 80 ℃, and then pouring the poly (arylene ether nitrile) solution on the horizontal glass plate while the temperature is high. The temperature program was set at 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ for 2h each to completely remove the solvent. And finally, naturally cooling and demolding to obtain the flexible fluorescent PEN-TPE/PPL film.
(1) The obtained PEN-TPE/PPL film was compared with a PEN-PPL film prepared by synthesizing phenolphthalein without adding tetraphenylethylene bisphenol derivative monomer under excitation of ultraviolet light (365nm), and the fluorescence photograph of the obtained product is shown in FIG. 4.
As shown in FIG. 4, the comparison between PEN-PPL and PEN-TPE/PPL films shows that PEN-PPL without addition of aggregation-induced emission monomer (tetraphenyl ethylene bisphenol derived monomer) has weak fluorescence, while PEN-TPE/PPL films with addition of aggregation-induced emission monomer emit bright fluorescence.
(2) The mechanical property test of the thin film of the tetraphenylethylene type poly (arylene ether nitrile) (PEN-TPE/PPL) prepared by the method is shown in the table II.
TABLE II PEN-TPE/PPL film mechanical property data
As can be seen from Table two, PEN-TPE/PPL has an elongation at break of 9.3%, a tensile strength of 81.6MPa and an elastic modulus of 1.9 GPa. The introduction of the aggregation-induced fluorescent monomer is shown, the luminous efficiency of the poly (arylene ether nitrile) in the film state is improved, and the originally good mechanical properties of the special high polymer material are also preserved, so that the poly (arylene ether nitrile) has the property of being capable of being called a flexible fluorescent film material and being applied to the optical field.
Test example 6
In this test example, the tetraphenylethylene type obtained in examples 1 to 6 was usedRespectively adopting poor solvent (H) for the poly (arylene ether nitrile) copolymer2O) means for promoting aggregation for characterization of aggregation-induced emission properties, the results of which are shown in table three.
Fluorescence property data of epi-tri and tetraphenyl ethylene type poly (arylene ether nitrile) copolymer
As can be seen from the results shown in Table III, the polyarylene ether nitriles obtained in examples 1 to 6 were dissolved in a poor solvent H after addition of the aggregation-induced emission monomer2After the O promotes aggregation, the luminous intensity is enhanced, and the maximum luminous intensity can be enhanced by 15.9 times; meanwhile, the emission peak wavelength is subjected to red shift of different degrees, and the maximum red shift degree is 61 nm. The introduction of aggregation-induced emission monomers is shown, so that the light-emitting efficiency of the poly (arylene ether nitrile) in an aggregation state is improved, the fluorescence emission peak originally located in a deep blue light region of about 420nm, which is difficult to observe by naked eyes, is red-shifted to a blue-green light region of about 460nm, which is easy to observe, and the light-emitting waveband of the poly (arylene ether nitrile) is widened.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; these modifications and substitutions do not cause the essence of the corresponding technical solution to depart from the scope of the technical solution of the embodiments of the present invention, and are intended to be covered by the claims and the specification of the present invention.
Claims (9)
1. A high-performance fluorescent functionalized poly (arylene ether nitrile) is characterized by having the following structural formula:
wherein x is more than 0 and less than 1, n is the polymerization degree, and n is more than 0.
2. The method for preparing the high-performance fluorescent functionalized polyarylethernitrile according to claim 1, characterized by comprising the following steps:
placing 2, 6-dichlorobenzonitrile, a tetraphenyl ethylene bisphenol derivative monomer, an aromatic dihydric phenol monomer, a catalyst, an organic solvent and a water-carrying agent into a reactor together, mechanically stirring to mix and dissolve reactants, heating to 130-150 ℃ for azeotropic dehydration for 2 hours, gradually raising the temperature to 180-200 ℃ for reaction for 2-3 hours, after the reaction is finished, slowly pouring the obtained viscous product into a dilute hydrochloric acid solution to separate out a strip poly (arylene ether nitrile) solid, crushing the strip poly (arylene ether nitrile) solid into powder, and purifying and drying to obtain the poly (arylene ether nitrile) polymer with the main chain containing a tetraphenyl ethylene structure, wherein the polymer is high-performance fluorescent functionalized poly (arylene ether nitrile).
3. The method for preparing high-performance fluorescent functionalized polyarylene ether nitrile according to claim 2, wherein the purification step is: and boiling and washing the powdery polymer for 3-5 times by using absolute ethyl alcohol and deionized water respectively.
4. The method for preparing high-performance fluorescent functionalized polyarylene ether nitrile according to claim 2, wherein the drying step is carried out at 80 ℃ for 24 h.
5. The method for preparing the high-performance fluorescent functionalized polyarylethernitrile according to claim 2, wherein the tetraphenylethylenebisphenol-derived monomer is 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene.
6. The method of claim 2, wherein the aromatic dihydric phenol monomer is selected from any one of biphenyl bisphenol, p-phenyl bisphenol, bisphenol a, phenolphthalein, and diphenolic acid.
7. The method for preparing high-performance fluorescent functionalized polyarylethernitrile according to claim 2, wherein the organic solvent is N-methylpyrrolidone.
8. The method for preparing high-performance fluorescent functionalized polyarylethernitrile according to claim 2, wherein the water-carrying agent is toluene or xylene.
9. The high-performance fluorescence functionalized polyarylether nitrile in claim 1 or the high-performance fluorescence functionalized polyarylether nitrile prepared by the preparation method in any one of claims 2 to 8 is applied to flexible thin film display devices, fluorescence sensors and biological diagnosis and treatment.
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| Title |
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| PAN WANG ET AL.: "《Ca2+ Induced Crosslinking of AIE-Active Polyarylene EtherNitrile into Fluorescent Polymeric Nanoparticles for Cellular Bioimaging》", 《MACROMOLECULAR RAPID COMMUNICATION》 * |
| 王盼: "《荧光聚芳醚腈的结构与性能研究》", 《中国博士学位论文全文数据库 工程科技I辑》 * |
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