CN106188391A - A kind of pure organic room temperature phosphorimetry fluorescence double polymeric material launched of humidity response - Google Patents
A kind of pure organic room temperature phosphorimetry fluorescence double polymeric material launched of humidity response Download PDFInfo
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- CN106188391A CN106188391A CN201610563059.0A CN201610563059A CN106188391A CN 106188391 A CN106188391 A CN 106188391A CN 201610563059 A CN201610563059 A CN 201610563059A CN 106188391 A CN106188391 A CN 106188391A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- 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
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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
- C09K2211/1416—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
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
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Abstract
The present invention relates to a kind of luminescent behavior and can have the room temperature phosphorimetry pure organic polymer material launched double with fluorescence by what humidity responded, belong to luminous organic material field.The method is applicable to major part phosphorescence fluorescent mixed system, the phosphorescence of phosphorescent compound is produced by hydrogen bond in humidity destruction polymer the phenomenon of quencher, controls the variations in light of mixed system.By unit of luminous and acrylamide copolymerization, the room temperature phosphorimetry fluorescence pure organic polymer material of double transmitting with humidity response i.e. can be obtained.This method does not use the heavy metal of costliness, and raw material is simple and easy to get, and preparation method is easy, and obtained material emission function admirable, water-soluble and nontoxic, can apply to a lot of field.
Description
Technical field
The present invention relates to the system of a kind of energy double emitted polymer of pure organic room temperature phosphorimetry fluorescence by humidity response luminescence
Preparation Method, belongs to luminous organic material field.
Background technology
Room temperature phosphorimetry material suffers from being widely applied at the aspect such as false proof, bio-imaging, chemical sensitisation, it is accordingly required in particular to have
The preparation method of a kind of simplicity and the course of processing.Current room temperature phosphor material is concentrated mainly on noble metal complexes aspect, and expensive
Metal cost intensive, reserves are limited, and organism is had genotoxic potential, therefore develop pure organic room temperature phosphorimetry material and seem very
It is necessary.Traditional double emissive materials are many based on fluorescent material, its variations in light many based on the electron transfer between fluorogen or
Energy shifts, and is incorporated into by phosphor material in double emissive material, owing to fluorescent emission and phosphorescent emissions are based respectively on singletstate
With two kinds of different mechanism of triplet state, both combinations can significantly expand luminescence system for the responding ability of environmental stimuli or
Widen internal electron transfer or the viable mechanism of energy transfer, in addition by TIME RESOLVED TECHNIQUE, phosphorescence letter can be read respectively
Breath and fluorescence information so that the double emissive material of phosphorescence, fluorescence is expected to expand the application in the fields such as false proof and bio-imaging.
In addition to the room temperature phosphorimetry material containing heavy metal, common traditional room temperature phosphor material concentrates on crystal induction phosphorescence and sends out
Penetrate material, thin film deoxygenation induction phosphorescent emissive material etc., in order to overcome the shortcoming of conventional organic room temperature phosphorimetry material, and consider wet
Spending special nature phosphor material being produced to quencher, the present invention is mainly by using pure organic room temperature phosphorimetry fluorescent monomer and third
Acrylamide copolymerization obtains room temperature phosphorimetry fluorescent polymer materials, and obtain is unbodied powder, and post processing is simple.With conventional
Metal-organic complex is compared, and uses a purely organic system, reduce cost in the present invention, and the product obtained is the most nontoxic, this
Outward, this material by the transmitting of humidity regulation phosphorescence fluorescent, thus can reach the change of color, and it at room temperature has relatively
Strong room temperature luminous characteristic.On the basis of proposing and preparing pure organic room temperature phosphorimetry luminescent material, fluorogen is introduced by we
In this system.By introducing fluorogen, the luminescent behavior of system can be expanded from the conventional single phosphorescence cancellation that can only produce
To producing the change of continuous print glow color, thus expand the potential application of this material.The controlled phosphorescence of this humidity is glimmering
The double emitted polymer of light, advances luminous organic material significantly in false proof and biological monitoring field application.
Summary of the invention
For the characteristic of phosphorescence fluorescent, it is an object of the invention to provide that Tong Guo the humidity of a kind of uniqueness responds pure has
The preparation method of the double emissive polymeric materials of unit room temperature phosphorescence fluorescent.
Technical scheme: one can respond the double emissive polymeric materials of pure organic room temperature phosphorimetry fluorescence by humidity
Preparation method, it is applicable to major part phosphorescence fluorescent mixed system, by water for the Quenching of phosphorescence, thus controls mixed
The variations in light of fit system.By unit of luminous and the simple copolymerization of acrylamide, can obtain that there is the adjustable room temperature phosphorimetry of humidity
The double pure organic polymer material launched of fluorescence；Specifically comprise the following steps that
(1) preparation of phosphorescent monomer；
On the basis of the aromatic rings with heavy atom group, in modification, the alkyl chain of one end band olefinic double bonds, specifically ties
Structure (but being not limited to following structure) is as follows:
(2) preparation of fluorescent monomer；
On the basis of aromatic rings, the alkyl chain of one end band olefinic double bonds in modification, concrete structure (but it is not limited to following knot
Structure) as follows:
(3) preparation of phosphorescence fluorescent monomer/acrylamide copolymer；
Phosphorescent monomer is dissolved in the organic solvent of 2 ~ 5 mL with acrylamide together with fluorescent monomer, wherein phosphorescent monomer and third
The mass ratio of acrylamide is 1:5 ~ 1:50, and adds azodiisobutyronitrile as initiator, initiator amount and phosphorescent monomer
Mass ratio is 1:8 ~ 1:30, system drum noble gas deoxygenation 30 min, reacts 6 h at 70 DEG C.Products therefrom methanol is washed
Wash, dried pure organic room temperature phosphorimetry polymeric material.
In phosphorescent monomer in described step (1), the position of heavy atom, number and kind do not limit, the band olefinic double bonds connect
The length of alkyl chain does not limits, and the length of the alkyl chain of the band olefinic double bonds that the fluorescent monomer in step (2) connects does not limits, step (3)
Middle common solvent is DMF or dimethyl sulfoxide, and initiator is not limited to azodiisobutyronitrile.
Compared with prior art, the present invention has a following significantly advantage:
The double emitted polymer of pure organic room temperature phosphorimetry fluorescence prepared by the present invention at room temperature has stronger luminous intensity, and is
Amorphous state, overcomes the shortcoming that conventional pure organic room temperature phosphorimetry material can only be luminous under deoxygenation or crystalline state；Amorphous powder
Product state, be beneficial to be processed further；Owing to not having the participation of noble metal, the method greatly reduces synthesis cost；Phosphorescence
Preparation and the polymerization of fluorescent monomer are the easiest with last handling process；The polymeric water-soluble generated is good and nontoxic, in conjunction with
Fluorophor can reach the color change that humidity is controlled, have in fields such as false proof or bio-imagings relatively broad potential should
With.
Specific embodiments
Below in conjunction with example, the present invention is described in detail:
Embodiment one:
The preparation method of the double polymeric material launched of pure organic room temperature phosphorimetry fluorescence of a kind of humid control, concrete steps are such as
Under:
Weigh 0.008 g compound 1,0.016 g compound 2,0.150 g acrylamide, 0.005 g azodiisobutyronitrile is dissolved in
2ml DMF, drum noble gas deoxygenation 30 min, reacts 6 h at 70 DEG C.Products therefrom methanol washs,
Dried product.
Under UV illumination, wet condition exhibits blue light, drying condition issues orange-red light.
Embodiment two:
The preparation method of the double polymeric material launched of pure organic room temperature phosphorimetry fluorescence of a kind of humid control, concrete steps are such as
Under:
Weigh 0.004 g compound 2,0.025 g compound 4,0.150 g acrylamide, 0.005 g azodiisobutyronitrile is dissolved in
2ml DMF, drum noble gas deoxygenation 30 min, reacts 6 h at 70 DEG C.Products therefrom methanol washs,
Dried product.
Under UV illumination, glow green under wet condition, drying condition issues orange-red light.
Claims (2)
1. a preparation method for the double pure organic polymer luminescent material launched of the room temperature phosphorimetry fluorescence of humidity response, its feature
Being phosphorescence fluorescent monomer, by copolymerization simple with acrylamide, obtaining can be by the luminous room temperature changed of humidity regulation
The pure organic polymer material of phosphorescence fluorescent；Specifically comprise the following steps that
(1) preparation of phosphorescent monomer；
On the basis of the aromatic rings with heavy atom group, the alkyl chain of one end band olefinic double bonds in modification；
(2) preparation of fluorescent monomer；
On the basis of there is the aromatic rings of fluorescent emission, the alkyl chain of one end band olefinic double bonds in modification；
(3) preparation of phosphorescence fluorescent monomer/acrylamide copolymer；
Phosphorescent monomer is dissolved in the organic solvent of 2 ~ 5 mL with acrylamide together with fluorescent monomer, wherein phosphorescent monomer and third
The mass ratio of acrylamide is 1:5 ~ 1:50, and adds azodiisobutyronitrile as initiator, initiator amount and phosphorescent monomer
Mass ratio is 1:8 ~ 1:30, system drum noble gas deoxygenation 30 min, reacts 6 h at 70 DEG C, and products therefrom methanol is washed
Wash, dried pure organic room temperature phosphorimetry polymeric material.
2. the preparation of the double emissive polymeric materials of pure organic room temperature phosphorimetry fluorescence responded according to the humidity described in claim 1
Method, it is characterised in that in the phosphorescent monomer in described (1), the position of heavy atom, number and kind do not limit, the band alkene connect is double
The length of the alkyl chain of key does not limits, and the length of the alkyl chain of the band olefinic double bonds that the fluorescent monomer in step (2) connects does not limits, step
Suddenly in (3), common solvent is DMF or dimethyl sulfoxide, and initiator is not limited to azodiisobutyronitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610563059.0A CN106188391B (en) | 2016-07-18 | 2016-07-18 | A kind of polymer material of the double transmittings of pure organic room temperature phosphorimetry fluorescence of humidity response |
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| CN201610563059.0A CN106188391B (en) | 2016-07-18 | 2016-07-18 | A kind of polymer material of the double transmittings of pure organic room temperature phosphorimetry fluorescence of humidity response |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109283162A (en) * | 2018-09-21 | 2019-01-29 | 华东理工大学 | A method of using pure organic room temperature phosphorimetry material tests latent fingerprint |
| CN109957106A (en) * | 2019-03-13 | 2019-07-02 | 北京大学 | A kind of room temperature phosphorimetry nylon copolymer and preparation method thereof |
| CN111253933A (en) * | 2020-03-27 | 2020-06-09 | 中山大学 | Room-temperature phosphorescent anti-counterfeiting material with timeliness, and preparation method and application thereof |
| CN111410790A (en) * | 2020-04-29 | 2020-07-14 | 广东圆融新材料有限公司 | Humidity-sensitive fluorescent modified polypropylene material and preparation method thereof |
| CN111848947A (en) * | 2020-07-24 | 2020-10-30 | 中国科学技术大学 | Naphthalene ring-based precise self-degradation amphiphilic block oligomer, and synthesis method and application thereof |
| CN113735772A (en) * | 2021-09-22 | 2021-12-03 | 四川羽玺新材料股份有限公司 | Fluorescent functional monomer, pressure-sensitive adhesive capable of timely discovering coating defects and preparation method thereof |
| CN113968928A (en) * | 2021-12-08 | 2022-01-25 | 西北工业大学 | X-ray responsive polymer phosphorescent scintillator and preparation method and application thereof |
| CN115433427A (en) * | 2022-08-10 | 2022-12-06 | 华东理工大学 | Light-activated circular polarization phosphorescent material and preparation method and application thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109283162B (en) * | 2018-09-21 | 2021-02-02 | 华东理工大学 | Method for detecting potential fingerprints by using pure organic room temperature phosphorescent material |
| CN109283162A (en) * | 2018-09-21 | 2019-01-29 | 华东理工大学 | A method of using pure organic room temperature phosphorimetry material tests latent fingerprint |
| CN109957106A (en) * | 2019-03-13 | 2019-07-02 | 北京大学 | A kind of room temperature phosphorimetry nylon copolymer and preparation method thereof |
| CN111253933A (en) * | 2020-03-27 | 2020-06-09 | 中山大学 | Room-temperature phosphorescent anti-counterfeiting material with timeliness, and preparation method and application thereof |
| CN111410790B (en) * | 2020-04-29 | 2022-10-25 | 广东圆融新材料有限公司 | Humidity-sensitive fluorescent modified polypropylene material and preparation method thereof |
| CN111410790A (en) * | 2020-04-29 | 2020-07-14 | 广东圆融新材料有限公司 | Humidity-sensitive fluorescent modified polypropylene material and preparation method thereof |
| CN111848947A (en) * | 2020-07-24 | 2020-10-30 | 中国科学技术大学 | Naphthalene ring-based precise self-degradation amphiphilic block oligomer, and synthesis method and application thereof |
| CN111848947B (en) * | 2020-07-24 | 2021-10-01 | 中国科学技术大学 | Naphthalene ring-based precise self-degradation amphiphilic block oligomer, and synthesis method and application thereof |
| CN113735772A (en) * | 2021-09-22 | 2021-12-03 | 四川羽玺新材料股份有限公司 | Fluorescent functional monomer, pressure-sensitive adhesive capable of timely discovering coating defects and preparation method thereof |
| CN113735772B (en) * | 2021-09-22 | 2024-04-09 | 四川羽玺新材料股份有限公司 | Fluorescent functional monomer, pressure-sensitive adhesive capable of finding coating defects in time and preparation method of pressure-sensitive adhesive |
| CN113968928A (en) * | 2021-12-08 | 2022-01-25 | 西北工业大学 | X-ray responsive polymer phosphorescent scintillator and preparation method and application thereof |
| CN115433427A (en) * | 2022-08-10 | 2022-12-06 | 华东理工大学 | Light-activated circular polarization phosphorescent material and preparation method and application thereof |
| CN115433427B (en) * | 2022-08-10 | 2024-01-26 | 华东理工大学 | Optically activated circularly polarized phosphorescent material, and preparation method and application thereof |
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