CN107056982A - A kind of preparation method of pure organic room temperature phosphorimetry polymeric material without aromatic structure - Google Patents
A kind of preparation method of pure organic room temperature phosphorimetry polymeric material without aromatic structure Download PDFInfo
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- CN107056982A CN107056982A CN201710074852.9A CN201710074852A CN107056982A CN 107056982 A CN107056982 A CN 107056982A CN 201710074852 A CN201710074852 A CN 201710074852A CN 107056982 A CN107056982 A CN 107056982A
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- room temperature
- heavy atom
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- aromatic structure
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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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- 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
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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
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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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- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a kind of preparation method of the pure organic polymer of the room temperature phosphorimetry without aromatic structure, belong to luminous organic material field.This method suppresses the non-radiative relaxation of carbonyl functional group's triplet state in acid amides by the hydrogen bond network of polyacrylamide, hydrogen bond network maintains the heavy atoms effect between bromine atoms and carbonyl simultaneously, carbonyl functional group's phosphorescent emissions ability is enhanced, makes it at room temperature with regard to stronger phosphorescence can be sent.Heavy atom will be contained（Based on bromine）Functional group and double bond functional group modification together with as the polymer monomer containing heavy atom, by simple Raolical polymerizable, by itself and acrylamide copolymerization, you can readily obtain the pure organic polymer with room temperature phosphorimetry transmitting.
Description
Technical field
A kind of preparation method of pure organic room temperature phosphorimetry polymeric material without aromatic structure.
Background technology
Room temperature phosphorimetry material suffers from being widely applied in terms of false proof, bio-imaging, chemical sensitisation.But current room temperature
Phosphor material is based primarily upon noble metal complexes, and noble metal is costly, reserves are limited, and has genotoxic potential to organism,
Therefore develop pure organic room temperature phosphorimetry material and seem and be highly desirable to.Meanwhile, what pure organic room temperature phosphorimetry luminescent material was used
Illuminophore is generally the phosphorescence group with aromatic structure, and it is most increased using intramolecular heavy atoms effect be between shuttle energy
Power.Therefore a kind of easy preparation method and process are required specifically at present, to meet room temperature phosphorimetry material in practice
Application.
In addition to the room temperature phosphorimetry material containing heavy metal, common traditional room temperature phosphor material concentrates on crystal induction phosphorescence hair
Material, film deoxygenation induction phosphorescent emissive material etc. are penetrated, and in the design of illuminophore, is concentrated mainly on by aromatic structure point
Sub- design aspect, most structure contains the aromatic structure of organism more difficult degradation.In order to overcome conventional organic room temperature phosphorimetry material
The shortcoming of material, polymerize by the present invention in that obtaining room temperature phosphorimetry fluorescence with the polymerized monomer containing heavy atom and acrylamide copolymerization
Thing material, what is obtained is unbodied powder, and post processing is simple.Compared with conventional metal-organic complex, adopted in the present invention
It is a purely organic system, and without the synthesis of complicated fragrant phosphorescence group, reduces cost, obtained product is also nontoxic, this
Outside, the material can by the intensity of moisture regulation phosphorescence, so as to reach the change of luminescence generated by light, and its have at room temperature compared with
Strong room temperature phosphorimetry characteristic.This controllable luminous intensity of humidity without aromatic structure room temperature phosphorimetry polymer, advanced significantly
Machine luminescent material is in false proof and biological monitoring field application.
The content of the invention
It is an object of the invention to provide a kind of preparation method without the pure organic polymer material of aromatic structure room temperature phosphorimetry.
Technical scheme：A kind of preparation method of the pure organic polymer material of room temperature phosphorimetry without aromatic structure,
Preparation method is simple, it is not necessary to the synthesis of complicated phosphorescence group.By heavy atom monomer and the simple copolymerization of acrylamide, can be had
There is humidity adjustable without the pure organic polymer material of aromatic structure room temperature phosphorimetry；Comprise the following steps that：
（1）The preparation of heavy atom monomer；
On the basis of the functional group with heavy atom group（There need not be phosphorescence to roll into a ball or potential phosphorescence group）, band alkene in one end in modification
The alkyl chain of hydrocarbon double bond, concrete structure（But it is not limited to following structure）It is as follows：
。
（2）The preparation of heavy atom monomer/acrylamide copolymer；
Heavy atom monomer is dissolved in 2 ~ 5 mL organic solvent with acrylamide, wherein the matter of heavy atom monomer and acrylamide
It is 1 to measure ratio:5~1:50, and azodiisobutyronitrile is added as initiator, the mass ratio of initiator amount and monomer is 1:8~1:
30, the min of system deoxygenation 30,6-8 h are reacted at 65 DEG C.Products therefrom is washed with methanol, and pure organic room temperature phosphorimetry is obtained after drying
Polymeric material.
The step（1）In phosphorescent monomer in position, number and the species of heavy atom do not limit, connect with olefinic double bonds
The length of alkyl chain is not limited, step（2）Middle solvent is DMF or dimethyl sulfoxide (DMSO), and initiator is not limited to azo
Bis-isobutyronitrile.
Compared with prior art, the present invention has following significant advantage：
Room temperature phosphorimetry polymer without aromatic structure prepared by the present invention has stronger luminous intensity at room temperature, and is without fixed
Form, overcomes the shortcoming that conventional pure organic room temperature phosphorimetry material can only light under deoxygenation or crystalline state；The production of amorphous powder
Thing state, beneficial to being processed further；Due to the participation without noble metal, this method greatly reduces synthesis cost；Importantly,
The preparation of the complicated polymerized monomer containing aromatic functional group is not needed in the building-up process, and polymerization and last handling process compare
It is easier；The polymeric water-soluble of generation is good and nontoxic, and changing its luminous intensity with ambient humidity can reversibly regulate and control, anti-
There is relatively broad potential application in the fields such as pseudo- or bio-imaging.
Specific embodiment
With reference to example, the present invention is described in detail：
。
Embodiment one：
A kind of preparation method of pure organic room temperature phosphorimetry polymeric material without aromatic structure, is comprised the following steps that：
Weigh 10 mg compounds 1,150 mg acrylamides 3,5 mg azodiisobutyronitriles and be dissolved in 2 mL N, N- dimethyl formyls
Amine, the min of air-blowing deoxygenation 30 reacts 8 h at 65 DEG C.Gained solid crude product is washed with methanol, and product is obtained after drying.
Under UV illumination, the blue red phosphorescent of polymer solids, increases with humidity under drying condition, luminous to die down.
Embodiment two：
A kind of preparation method of pure organic room temperature phosphorimetry polymeric material without aromatic structure, is comprised the following steps that：
Weigh 10 mg compounds 2,150 mg acrylamides 3,5 mg azodiisobutyronitriles and be dissolved in 2 mL N, N- dimethyl formyls
Amine, the min of air-blowing deoxygenation 30 reacts 8 h at 65 DEG C.Gained solid crude product is washed with methanol, and product is obtained after drying.
Under UV illumination, the blue red phosphorescent of polymer solids, increases with humidity under drying condition, luminous to die down.
Claims (2)
1. the preparation method of the pure organic polymer luminescent material of a kind of room temperature phosphorimetry without aromatic structure, it is characterised in that contain weight
Bond monomer, it is simple free-radical polymerized by being carried out with acrylamide, you can to obtain the room temperature phosphorus of no aromatic structure
The pure organic polymer luminescent material of light；Comprise the following steps that：
（1）The preparation of heavy atom monomer；
On the basis of the functional group with heavy atom, alkyl chain of the one end with olefinic double bonds in modification；
（2）The preparation of heavy atom monomer/acrylamide copolymer；
Heavy atom monomer is dissolved in 2 ~ 5 mL organic solvent together with fluorescent monomer with acrylamide, wherein heavy atom monomer
Amount ratio with the material of acrylamide is 1:5~1：50, and add azodiisobutyronitrile as initiator, initiator amount with again
The mass ratio of atom monomer is 1：8~1：30, the min of system deoxygenation 30, react 6-8 hours, products therefrom is washed with methanol at 65 DEG C
Wash, the pure organic room temperature phosphorimetry polymeric material of thing aromatic structure is obtained after drying.
2. the preparation method without aromatic structure room temperature phosphorimetry polymeric material according to claim 1, it is characterised in that
It is described（1）In heavy atom monomer in the position of heavy atom, number do not limit, the length of the alkyl chain with olefinic double bonds connect is not
Limit, step（2）Middle common solvent is DMF or dimethyl sulfoxide (DMSO), and initiator is not limited to azodiisobutyronitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710074852.9A CN107056982A (en) | 2017-02-12 | 2017-02-12 | A kind of preparation method of pure organic room temperature phosphorimetry polymeric material without aromatic structure |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710074852.9A CN107056982A (en) | 2017-02-12 | 2017-02-12 | A kind of preparation method of pure organic room temperature phosphorimetry polymeric material without aromatic structure |
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| Publication Number | Publication Date |
|---|---|
| CN107056982A true CN107056982A (en) | 2017-08-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710074852.9A Pending CN107056982A (en) | 2017-02-12 | 2017-02-12 | A kind of preparation method of pure organic room temperature phosphorimetry polymeric material without aromatic structure |
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2017
- 2017-02-12 CN CN201710074852.9A patent/CN107056982A/en active Pending
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Application publication date: 20170818 |
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| WD01 | Invention patent application deemed withdrawn after publication |