CN107083237A - A kind of ligand functionalized polymer rare earth complex luminescent material of Phen - Google Patents
A kind of ligand functionalized polymer rare earth complex luminescent material of Phen Download PDFInfo
- Publication number
- CN107083237A CN107083237A CN201710314339.2A CN201710314339A CN107083237A CN 107083237 A CN107083237 A CN 107083237A CN 201710314339 A CN201710314339 A CN 201710314339A CN 107083237 A CN107083237 A CN 107083237A
- Authority
- CN
- China
- Prior art keywords
- phen
- rare
- functionalized polymer
- ligand functionalized
- rare earth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of ligand functionalized polymer rare earth complex luminescent material of Phen, belong to macromolecule rare-earth compound luminescent material technical field, the problem of scattered inequality of prior art luminescent material rare earth compounding, polymer substrate poor performance can be solved, the present invention will have coordination to rare earth ion and introduce polymer pendant groups with being sensitized the Phen aglucon of difunctional effect, obtain the ligand functionalized polymer of Phen, then with rare-earth ion coordination, the ligand functionalized polymer rare earth complex luminescent material of Phen is obtained.The present invention not only develops a kind of new red fluorescence material, and they have good heat endurance and luminous intensity, and technical process is easily realized, open new way to prepare novel high polymer rare earth luminescent material, there is potential application in terms of luminescent material.
Description
Technical field
The invention belongs to macromolecule-rare-earth compound luminescent material technical field, and in particular to a kind of Phen aglucon work(
Can fluidized polymer-rare-earth complexes luminous material.
Background technology
Rare earth compounding has very narrow emission peak and very long fluorescence lifetime, in light emitting diode, laser, light
The fluorescent material had a great attraction is considered in terms of fibre.It is numerous in order to be widely used on light-emitting device
Researcher begins to use different materials to be used as the matrix of rare earth compounding, and wherein macromolecule has low cost, easy processing, machine
The advantages of tool performance is good.Bonding type macromolecule-rare-earth complexes luminous material, had both remained small molecule rare earth compounding excellent
Luminescent properties, have the advantages that high polymer material again, are the excellent luminescent materials of a class, can be used in Organic Light Emitting Diode, light
In terms of catalysis material, organic fluorescence sensor.
Most common rare earth organic complex is roughly divided into three major types：Aromatic carboxylic acids class, beta-diketon class, bipyridyliumses.Will
These parts are bonded in high molecular side base, then then form with rare-earth ion coordination bonding type macromolecule-rare earth compounding hair
Luminescent material.Researcher also develops the bonding type that some contain N, N- bidentates schiff bases or N, O- bidentate schiff bases aglucon in recent years
Macromolecule-rare-earth complexes luminous material, these materials all have excellent luminescent properties and good heat endurance and machinery
Performance.
As bidentate ligand, two nitrogen-atoms above 1,10- Phen can very easily and metallic ion coordination,
The central ion of metal is set to be in highly stable state.The rigid conjugate planes structure of three rings of 1,10- Phens is added
Nitrogen-atoms cloud density on ring so that the transmission of electron energy is more effective between atom.1,10- Phens pass through
Strong light absorbs-intramolecular energy, can effectively be sensitized the fluorescent emission of rare earth ion, launch complex strong glimmering
Light, therefore, Phen functionalized macromolecular-rare-earth complexes luminous material have very good development prospect.
The content of the invention
The problem of present invention scattered for rare earth compounding in the prior art uneven, polymer substrate poor performance there is provided：
（1）A kind of ligand functionalized polymer-rare-earth complexes luminous material of Phen；（2）A kind of Phen is ligand functionalized
The preparation method of polymer-rare-earth complexes luminous material.
Benzaldehyde modified polysulfones BA-PSF used can [Chen Pinghong, Gao Baojiao, Xu Di change according to document in the present invention
Learn research and application, 2014,26 (12)：1904-1911] described in method prepare.
Chloromethyl polysulphone CMPSF used can [Zhang Dandan looks into aobvious space, Gao Baojiao, application according to document in the present invention
Chemistry, 2016,33 (1):53-62] described in method prepare.
The present invention is adopted the following technical scheme that：
A kind of ligand functionalized polymer-rare-earth complexes luminous material of Phen, will to rare earth ion have coordination with it is quick
The Phen aglucon for changing difunctional effect introduces polymer pendant groups, the ligand functionalized polymer of Phen is obtained, then by neighbour
The ligand functionalized polymer of phenanthroline and rare-earth ion coordination, obtain the ligand functionalized polymer of Phen-rare earth compounding hair
Luminescent material.
A kind of preparation method of the ligand functionalized polymer-rare-earth complexes luminous material of Phen, including following step
Suddenly：
The first step, 0.16-0.55g polymer is added in 20-25mL solvents, fully after dissolving, adds 10-25mL dissolvings
There is the solution of the above-mentioned solvent of 0.05-0.25g Phens, be warming up to 65-75 DEG C, add 0.05-0.35g catalyst, constant temperature
7-10h is reacted, reaction goes out reaction product after terminating with ethanol precipitation, then is alternately washed with watery hydrochloric acid, ethanol and distilled water, vacuum
Dry to constant weight, produce the ligand functionalized polymer of Phen；
Second step, weighs the ligand functionalized polymer of 0.40-0.50 g Phens and is dissolved in 40-50mL solvents, use NaOH
Solution adjusts pH to 6-7, adds rare earth crystal, is warming up to 55-65 DEG C, isothermal reaction 8-10 h, reaction uses ethanol after terminating
Reaction product is settled out, then is alternately washed with ethanol and distilled water, the ligand functionalized polymer of Phen-rare earth is produced and coordinates
Thing luminescent material.
Solvent described in first and second step is any in dimethyl sulfoxide (DMSO), dimethyl acetamide or dimethylformamide
It is a kind of.
Catalyst described in the first step is one kind in sodium hydroxide, natrium carbonicum calcinatum, anhydrous sodium bicarbonate or KI
Or two kinds.
Rare earth crystal described in second step is europium chloride crystal, the amount of the material of Phen aglucon and rare earth ion
The ratio between be 3-3.5:1.
The polymer is benzaldehyde modified polysulfones, and the Phen is 5- amino -1,10- Phens, and gained is adjacent
The ligand functionalized polymer of phenanthroline is 5- schiff bases -1,10- Phen modified polysulfones, its structure such as formula（Ⅰ）It is shown,
Formula（Ⅰ）,
Ligand functionalized polymer-the rare-earth complexes luminous material of gained Phen is that 5- schiff bases -1,10- Phens change
Property polysulfones-rare earth ion complex thing luminescent material, its structure such as formula（Ⅱ）It is shown,
Formula（Ⅱ）,
Wherein, M3+For rare earth ion.
The polymer is chloromethyl polysulphone, and the Phen is 4,7- dihydroxy -1,10- Phens, gained
The ligand functionalized polymer of Phen is 4- hydroxyl -1,10- Phen modified polysulfones, its structure such as formula（III）It is shown,
Formula（III）,
Ligand functionalized polymer-the rare-earth complexes luminous material of gained Phen is modified for 4- hydroxyls -1,10- Phen
Polysulfones-rare earth ion complex luminescent material, its structure such as formula（IV）It is shown,
Formula（IV）,
Wherein, M3+For rare earth ion.
The bonded amount of 5- schiff bases -1,10- Phens is 1.12-1.22 mmol/g.
The bonded amount of 4- hydroxyl -1,10- Phens is 0.96-1.05 mmol/g.
Ligand functionalized polysulfones-the rare-earth complexes luminous material of Phen to illustrate the invention, one is entered with reference to accompanying drawing
Step is described as follows：
Fig. 1 is red for benzaldehyde modified polysulfones BA-PSF's and 5- schiff bases -1,10- Phen modified polysulfone Phen-PSF (I)
External spectrum figure.Infrared spectrum contrast with BA-PSF understands that in Phen-PSF (I) infrared spectrum, aldehyde radical is in 1692cm-1Place
Absworption peak and 2735cm-1The absworption peak at place weakens significantly even to disappear, while in 1657 cm-1Place occurs in that schiff bases
The stretching vibration absworption peak of imine linkage C=N double bonds.This is absolutely proved, neighbour has successfully been bonded by schiff base reaction in polysulfones side chain
Phenanthroline, forms Phen-PSF (I).
Fig. 2 is red for chloromethyl polysulphone CMPSF and 4- hydroxyl -1,10- Phen modified polysulfone Phen-PSF's (II)
External spectrum figure.In Phen-PSF (II) infrared spectrum, compared with CMPSF infrared spectrum, 1444 cm-1With 670 cm-1The characteristic absorption peak for locating chloromethyl substantially weakens even disappearance, and in 1170 cm-1Place occurs in that the characteristic absorption of fragrant ehter bond
Peak, in 1630 cm-1The peak that place occurs is the vibration absorption peak of C=N double bonds on 4,7- dihydroxy-Phen ring, 3370
cm-1Place occurs in that the vibration performance absworption peak of hydroxyl on 4,7- dihydroxy-Phen ring, and above-mentioned change is proved, CMPSF and 4,
Nucleophilic substitution occurs for 7- dihydroxy-Phen, generates Phen-PSF (II).
Fig. 3 is 5- schiff bases -1,10- Phen modified polysulfone Phen-PSF (I), 5- schiff bases -1,10- Phens
Modified polysulfone-rare earth ion complex luminescent material Eu (III)-(Phen)3- PSF (I) and europium chloride EuCl3DMF solution
Fluorescence emission spectrogram of compound.Fig. 4 is 4- hydroxyl -1,10- Phen modified polysulfone Phen-PSF (II), the adjacent phenanthrene of 4- hydroxyls -1,10-
Sieve quinoline modified polysulfone-rare earth ion complex luminescent material Eu (III)-(Phen)3- PSF (II) and europium chloride EuCl3DMF
The fluorescence emission spectrogram of compound of solution.From Fig. 3 and Fig. 4, Phen-PSF (I) and Phen-PSF (II) itself also launch by force
Strong fluorescence（As produced by the big pi bond system of bonded ligand Phen conjugation）, with Eu（Ⅲ）Ion coordination formation Eu (III)-
(Phen)3- PSF (I) and Eu (III)-(Phen)3After-PSF (II), the fluorescent emission intensity of its part in itself greatly weakens, together
When launch the characteristic fluorescence of Eu (III) ion, and fluorescent emission intensity compares EuCl3 About 60 times and 5 times have been respectively increased.
Fig. 5 be 5- schiff bases -1,10- Phen modified polysulfone-rare earth ion complex luminescent material Eu (III) -
(Phen)3- PSF (I) and 4- hydroxyls -1,10- Phen modified polysulfone-rare earth ion complex luminescent material Eu (III) -
(Phen)3- PSF (II) thermogravimetric curve figure.As seen from the figure, the obvious weightless temperature of both luminescent materials is at 280 DEG C
Left and right, illustrates that both macromolecule-rare-earth complexes luminous materials all have good heat endurance.
The present invention compared with prior art, its remarkable advantage：（1）The preparation method will to rare earth ion have coordination with it is quick
The Phen aglucon for changing difunctional effect introduces polymer lateral chain, and the aglucon can not only form stable between rare earth ion
Macromolecule-rare earth compounding, and with larger conjugate rigid plane, polymer can be strengthened significantly and match somebody with somebody basal orientation rare earth ion
Transfer of energy, strengthens luminescent properties；（2）Present invention obtains two kinds of new bonding type functionalized polymers-rare earth luminous
Material, and open the new way and new raw material for preparing the luminescent material.
Brief description of the drawings
Fig. 1 is benzaldehyde modified polysulfones BA-PSF and 5- schiff bases -1,10- Phen modified polysulfone Phen-PSF (I)
Infrared spectrogram；
Fig. 2 is chloromethyl polysulphone CMPSF and 4- hydroxyl -1,10- Phen modified polysulfone Phen-PSF (II) infrared light
Spectrogram；
Fig. 3 is 5- schiff bases -1,10- Phen modified polysulfone Phen-PSF (I), the modification of 5- schiff bases -1,10- Phen
Polysulfones-rare earth ion complex luminescent material Eu (III)-(Phen)3- PSF (I) and EuCl3DMF solution fluorescence emission spectrum
Figure；
Fig. 4 is 4- hydroxyl -1,10- Phen modified polysulfone Phen-PSF (II), 4- hydroxyls -1,10- Phen is modified and gathered
Sulfone-rare earth ion complex luminescent material Eu (III)-(Phen)3- PSF (II) and EuCl3DMF solution fluorescence emission spectrum
Figure；
Fig. 5 is 5- schiff bases -1,10- Phen modified polysulfone-rare earth ion complex luminescent material Eu (III)-(Phen)3-
PSF (I) and 4- hydroxyls -1,10- Phen modified polysulfone-rare earth ion complex luminescent material Eu (III)-(Phen)3-PSF
(II) thermogravimetric curve figure.
Embodiment
A kind of ligand functionalized polymer-rare-earth complexes luminous material of Phen, will have coordination to rare earth ion
Phen aglucon introducing polymer pendant groups with being sensitized difunctional effect, obtain the ligand functionalized polymer of Phen, then
By the ligand functionalized polymer of Phen and rare-earth ion coordination, obtain the ligand functionalized polymer of Phen-rare earth and coordinate
Thing luminescent material.
A kind of preparation method of the ligand functionalized polymer-rare-earth complexes luminous material of Phen, it is characterised in that：
Comprise the following steps：
The first step, 0.16-0.55g polymer is added in 20-25mL solvents, fully after dissolving, adds 10-25mL dissolvings
There is the solution of the above-mentioned solvent of 0.05-0.25g Phens, be warming up to 65-75 DEG C, add 0.05-0.35g catalyst, constant temperature
7-10h is reacted, reaction goes out reaction product after terminating with ethanol precipitation, then is alternately washed with watery hydrochloric acid, ethanol and distilled water, vacuum
Dry to constant weight, produce the ligand functionalized polymer of Phen；
Second step, weighs the ligand functionalized polymer of 0.40-0.50 g Phens and is dissolved in 40-50mL solvents, use NaOH
Solution adjusts pH to 6-7, adds rare earth crystal, is warming up to 55-65 DEG C, isothermal reaction 8-10 h, reaction uses ethanol after terminating
Reaction product is settled out, then is alternately washed with ethanol and distilled water, the ligand functionalized polymer of Phen-rare earth is produced and coordinates
Thing luminescent material.
Solvent described in first and second step is any in dimethyl sulfoxide (DMSO), dimethyl acetamide or dimethylformamide
It is a kind of.
Catalyst described in the first step is one kind in sodium hydroxide, natrium carbonicum calcinatum, anhydrous sodium bicarbonate or KI
Or two kinds.
Rare earth crystal described in second step is europium chloride crystal, the amount of the material of Phen aglucon and rare earth ion
The ratio between be 3-3.5:1.
The polymer is benzaldehyde modified polysulfones, and the Phen is 5- amino -1,10- Phens, and gained is adjacent
The ligand functionalized polymer of phenanthroline is 5- schiff bases -1,10- Phen modified polysulfones, its structure such as formula（Ⅰ）It is shown,
Formula（Ⅰ）,
Ligand functionalized polymer-the rare-earth complexes luminous material of gained Phen is that 5- schiff bases -1,10- Phens change
Property polysulfones-rare earth ion complex thing luminescent material, its structure such as formula（Ⅱ）It is shown,
Formula（Ⅱ）,
Wherein, M3+For rare earth ion.
The polymer is chloromethyl polysulphone, and the Phen is 4,7- dihydroxy -1,10- Phens, gained
The ligand functionalized polymer of Phen is 4- hydroxyl -1,10- Phen modified polysulfones, its structure such as formula（III）It is shown,
Formula（III）,
Ligand functionalized polymer-the rare-earth complexes luminous material of gained Phen is modified for 4- hydroxyls -1,10- Phen
Polysulfones-rare earth ion complex luminescent material, its structure such as formula（IV）It is shown,
Formula（IV）,
Wherein, M3+For rare earth ion.
The bonded amount of 5- schiff bases -1,10- Phens is 1.12-1.22 mmol/g.
The bonded amount of 4- hydroxyl -1,10- Phens is 0.96-1.05 mmol/g.
Embodiment 1, in four-hole boiling flask, adds 0.5 g BA-PSF and 22 mL DMF, fully after dissolving, adds
22mL is warming up to 70 DEG C dissolved with the DMF solution of 0.23g 5- amino -1,10- Phens, adds 0.2g NaOH, and constant temperature is anti-
8h, reaction is answered to go out polymer with ethanol precipitation after terminating, polymer watery hydrochloric acid, ethanol and distilled water are alternately washed, and vacuum is done
It is dry to constant weight, produce 5- schiff bases -1,10- Phen modified polysulfone Phen-PSF (I).Wherein, 5- schiff bases -1,10- is adjacent
The mmol/g of bonded amount 1.22 of phenanthroline.
Weigh 0.40 g Phen-PSF (I) to be dissolved in 40mL DMF, adjust pH to 6-7 with NaOH solution, add
0.056g rare earths EuCl3•6H2O crystal（The amount of material is 0.16mmol), it is warming up to 55 DEG C, isothermal reaction 8h, after reaction terminates
Go out polymer with ethanol precipitation, polymer ethanol and distilled water are alternately washed, and obtain the modification of 5- schiff bases -1,10- Phen
Polysulfones-rare earth ion complex luminescent material Eu (III)-(Phen)3-PSF(I)。
Embodiment 2, in four-hole boiling flask, adds 0.16 g CMPSF and 20 mLDMF, fully after dissolving, adds 10mL
Dissolved with 0.05g 4, the DMF solution of 7- dihydroxy -1,10- Phens is warming up to 70 DEG C, add 0.3 g natrium carbonicum calcinatums and
0.05 g KIs, isothermal reaction 10h, reaction goes out polymer after terminating with ethanol precipitation, polymer watery hydrochloric acid, ethanol and
Distilled water is alternately washed, and is dried under vacuum to constant weight, is produced 4- hydroxyl -1,10- Phen modified polysulfone Phen-PSF (II).Its
In, the mmol/g of bonded amount 1.05 of 4- hydroxyl -1,10- Phens.
Weigh 0.40 g Phen-PSF (II) to be dissolved in 40mL DMF, adjust pH to 6-7 with NaOH solution, add
0.049g rare earths EuCl3•6H2O crystal（The amount of material is 0.14mmol), it is warming up to 55 DEG C, isothermal reaction 8h, after reaction terminates
Go out polymer with ethanol precipitation, polymer ethanol and distilled water are alternately washed, obtain 4- hydroxyls -1,10- Phen and be modified and gather
Sulfone-rare earth ion complex luminescent material Eu (III)-(Phen)3-PSF(II)。
Embodiment 3：In four-hole boiling flask, 0.45 g BA-PSF and 20mL DMAC are added, fully after dissolving, are added
20mL is warming up to 75 DEG C dissolved with the DMAC solution of 0.20g 5- amino -1,10- Phens, adds 0.15g Carbon Dioxides
Sodium, isothermal reaction 10h, reaction goes out polymer after terminating with ethanol precipitation, and polymer watery hydrochloric acid, ethanol and distilled water are alternately washed
Wash, be dried under vacuum to constant weight, produce 5- schiff bases -1,10- Phen modified polysulfone Phen-PSF (I).Wherein, 5- Schiffs
The mmol/g of bonded amount 1.20 of alkali -1,10- Phen.
Weigh 0.50 g Phen-PSF (I) to be dissolved in 50mL DMAC, adjust pH to 6-7 with NaOH solution, add
0.065g rare earths EuCl3•6H2O crystal（The amount of material is 0.188mmol), 65 DEG C are warming up to, isothermal reaction 10h, reaction terminates
Go out polymer with ethanol precipitation afterwards, polymer ethanol and distilled water alternately wash, obtains 5- schiff bases -1,10- Phens and change
Property polysulfones-rare earth ion complex luminescent material Eu (III)-(Phen)3-PSF(I)。
Embodiment 4, in four-hole boiling flask, adds 0.20 g CMPSF and 25 mLDMAC, fully after dissolving, adds
15mL is warming up to 75 DEG C, adds the anhydrous carbon of 0.35 g dissolved with 0.07g 4, the DMAC solution of 7- dihydroxy -1,10- Phens
Sour sodium and 0.06 g KIs, isothermal reaction 9h, reaction go out polymer, polymer watery hydrochloric acid, second after terminating with ethanol precipitation
Alcohol and distilled water are alternately washed, and are dried under vacuum to constant weight, are produced 4- hydroxyl -1,10- Phen modified polysulfones Phen-PSF
(II).Wherein, the mmol/g of bonded amount 1.00 of 4- hydroxyls -1,10- Phen.
Weigh 0.50gPhen-PSF (II) to be dissolved in 50mLDMAC, adjust pH to 6-7 with NaOH solution, add
0.054g rare earths EuCl3•6H2O crystal（The amount of material is 0.156mmol), 65 DEG C are warming up to, isothermal reaction 10h, reaction terminates
Go out polymer with ethanol precipitation afterwards, polymer ethanol and distilled water are alternately washed, and obtain the modification of 4- hydroxyls -1,10- Phen
Polysulfones-rare earth ion complex luminescent material Eu (III)-(Phen)3-PSF(II)。
Embodiment 5：In four-hole boiling flask, 0.55 g BA-PSF and 25 mL DMSO are added, fully after dissolving, are added
25 mL are warming up to 65 DEG C dissolved with the DMSO solution of 0.25 g 5- amino -1,10- Phens, add 0.25g Carbon Dioxides
Hydrogen sodium, isothermal reaction 7h, reaction goes out polymer, polymer watery hydrochloric acid, ethanol and distilled water alternating after terminating with ethanol precipitation
Washing, is dried under vacuum to constant weight, produces 5- schiff bases -1,10- Phen modified polysulfone Phen-PSF (I).Wherein, 5- Schiffs
The mmol/g of bonded amount 1.12 of alkali -1,10- Phen.
Weigh 0.45 g Phen-PSF (I) to be dissolved in 45mL DMSO, adjust pH to 6-7 with NaOH solution, add
0.05g rare earths EuCl3•6H2O crystal（The amount of material is 0.144mmol), it is warming up to 60 DEG C, isothermal reaction 9h, after reaction terminates
Go out polymer with ethanol precipitation, polymer ethanol and distilled water are alternately washed, and obtain the modification of 5- schiff bases -1,10- Phen
Polysulfones-rare earth ion complex luminescent material Eu (III)-(Phen)3-PSF(I)。
Embodiment 6, in four-hole boiling flask, adds 0.18 g CMPSF and 23mL DMSO, fully after dissolving, adds
13mL is warming up to 65 DEG C, adds the anhydrous carbon of 0.32 g dissolved with 0.06g 4, the DMSO solution of 7- dihydroxy -1,10- Phens
Sour hydrogen sodium and 0.055 g KIs, isothermal reaction 7h, reaction go out polymer after terminating with ethanol precipitation, polymer watery hydrochloric acid,
Ethanol and distilled water are alternately washed, and are dried under vacuum to constant weight, are produced 4- hydroxyl -1,10- Phen modified polysulfones Phen-PSF
(II).Wherein, the mmol/g of bonded amount 0.96 of 4- hydroxyls -1,10- Phen.
Weigh 0.45 g Phen-PSF (II) to be dissolved in 45mL DMSO, adjust pH to 6-7 with NaOH solution, then add
Enter 0.042g rare earths EuCl3•6H2O crystal（The amount of material is 0.12mmol), 60 DEG C are warming up to, isothermal reaction 9h, reaction terminates
Go out polymer with ethanol precipitation afterwards, polymer ethanol and distilled water are alternately washed, and 4- hydroxyls -1,10- Phen is modified poly-
Sulfone-rare earth ion complex luminescent material Eu (III)-(Phen)3-PSF(II)。
Claims (9)
1. a kind of ligand functionalized polymer-rare-earth complexes luminous material of Phen, it is characterised in that：Phen is matched somebody with somebody
Base introduce polymer pendant groups, obtain the ligand functionalized polymer of Phen, then by the ligand functionalized polymer of Phen with
Rare-earth ion coordination, obtains the ligand functionalized polymer-rare-earth complexes luminous material of Phen.
2. the ligand functionalized polymer-rare-earth complexes luminous material of a kind of Phen according to claim 1, it is special
Levy and be：Its preparation method comprises the following steps：
The first step, 0.16-0.55g polymer is added in 20-25mL solvents, fully after dissolving, adds 10-25mL dissolvings
There is the solution of the above-mentioned solvent of 0.05-0.25g Phens, be warming up to 65-75 DEG C, add 0.05-0.35g catalyst, constant temperature
7-10h is reacted, reaction goes out reaction product after terminating with ethanol precipitation, then is alternately washed with watery hydrochloric acid, ethanol and distilled water, vacuum
Dry to constant weight, produce the ligand functionalized polymer of Phen；
Second step, weighs the ligand functionalized polymer of 0.40-0.50 g Phens and is dissolved in 40-50mL solvents, use NaOH
Solution adjusts pH to 6-7, adds rare earth crystal, is warming up to 55-65 DEG C, isothermal reaction 8-10 h, reaction uses ethanol after terminating
Reaction product is settled out, then is alternately washed with ethanol and distilled water, the ligand functionalized polymer of Phen-rare earth is produced and coordinates
Thing luminescent material.
3. the ligand functionalized polymer-rare-earth complexes luminous material of a kind of Phen according to claim 2, it is special
Levy and be：Solvent described in first and second step is any one in dimethyl sulfoxide (DMSO), dimethyl acetamide or dimethylformamide
Kind.
4. the ligand functionalized polymer-rare-earth complexes luminous material of a kind of Phen according to claim 2, it is special
Levy and be：Catalyst described in the first step be sodium hydroxide, natrium carbonicum calcinatum, anhydrous sodium bicarbonate or KI in one kind or
Two kinds.
5. the ligand functionalized polymer-rare-earth complexes luminous material of a kind of Phen according to claim 2, it is special
Levy and be：Rare earth crystal described in second step is europium chloride crystal, the amount of the material of Phen aglucon and rare earth ion
The ratio between be 3-3.5:1.
The material 6. the ligand functionalized polymer-rare earth compounding of a kind of Phen according to one of claim 1-5 lights
Material, it is characterised in that：The polymer is benzaldehyde modified polysulfones, and the Phen is 5- amino -1,10- Phens,
The ligand functionalized polymer of gained Phen is 5- schiff bases -1,10- Phen modified polysulfones, its structure such as formula（Ⅰ）Institute
Show,
1.jpgFormula（Ⅰ）,
Ligand functionalized polymer-the rare-earth complexes luminous material of gained Phen is that 5- schiff bases -1,10- Phens change
Property polysulfones-rare earth ion complex thing luminescent material, its structure such as formula（Ⅱ）It is shown,
2.jpgFormula（Ⅱ）,
Wherein, M3+For rare earth ion.
The material 7. the ligand functionalized polymer-rare earth compounding of a kind of Phen according to one of claim 1-5 lights
Material, it is characterised in that：The polymer is chloromethyl polysulphone, and the Phen is the adjacent Féraud of 4,7- dihydroxy -1,10-
Quinoline, the ligand functionalized polymer of gained Phen is 4- hydroxyl -1,10- Phen modified polysulfones, its structure such as formula（III）
It is shown,
3.jpgFormula（III）,
Ligand functionalized polymer-the rare-earth complexes luminous material of gained Phen is modified for 4- hydroxyls -1,10- Phen
Polysulfones-rare earth ion complex luminescent material, its structure such as formula（IV）It is shown,
4.jpgFormula（IV）,
Wherein, M3+For rare earth ion.
8. the ligand functionalized polymer-rare-earth complexes luminous material of a kind of Phen according to claim 6, it is special
Levy and be：The bonded amount of 5- schiff bases -1,10- Phens is 1.12-1.22 mmol/g.
9. the ligand functionalized polymer-rare-earth complexes luminous material of a kind of Phen according to claim 7, it is special
Levy and be：The bonded amount of 4- hydroxyl -1,10- Phens is 0.96-1.05 mmol/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710314339.2A CN107083237A (en) | 2017-05-06 | 2017-05-06 | A kind of ligand functionalized polymer rare earth complex luminescent material of Phen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710314339.2A CN107083237A (en) | 2017-05-06 | 2017-05-06 | A kind of ligand functionalized polymer rare earth complex luminescent material of Phen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107083237A true CN107083237A (en) | 2017-08-22 |
Family
ID=59612674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710314339.2A Pending CN107083237A (en) | 2017-05-06 | 2017-05-06 | A kind of ligand functionalized polymer rare earth complex luminescent material of Phen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107083237A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292411A (en) * | 2021-12-17 | 2022-04-08 | 广东省科学院化工研究所 | Organic rare earth luminescent material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004039913A2 (en) * | 2002-10-30 | 2004-05-13 | Ciba Specialty Chemicals Holding Inc. | Process for incorporation of uv-luminescent compounds in polymeric materials |
| JP2005048137A (en) * | 2003-07-31 | 2005-02-24 | Nippon Kayaku Co Ltd | Europium compound and ink composition containing the same |
| CN103013494A (en) * | 2012-11-21 | 2013-04-03 | 中北大学 | Bonding type polymer-rare earth ternary complex luminescent material and preparation method thereof |
| CN104829639A (en) * | 2015-04-24 | 2015-08-12 | 嘉兴学院 | Hyperbranched polyester rare earth complex containing nitrogen heterocyclic terminal group, and preparation method and use thereof |
| CN105218818A (en) * | 2015-09-11 | 2016-01-06 | 中北大学 | Functionalization polysulfones-Tb (III) ionic complex luminescent material preparation method |
| CN106243355A (en) * | 2016-07-08 | 2016-12-21 | 中北大学 | Amino phenolic bidentate Schiff's base ligand functionalized polymer rare earth complex luminescent material and preparation method thereof |
-
2017
- 2017-05-06 CN CN201710314339.2A patent/CN107083237A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004039913A2 (en) * | 2002-10-30 | 2004-05-13 | Ciba Specialty Chemicals Holding Inc. | Process for incorporation of uv-luminescent compounds in polymeric materials |
| JP2005048137A (en) * | 2003-07-31 | 2005-02-24 | Nippon Kayaku Co Ltd | Europium compound and ink composition containing the same |
| CN103013494A (en) * | 2012-11-21 | 2013-04-03 | 中北大学 | Bonding type polymer-rare earth ternary complex luminescent material and preparation method thereof |
| CN104829639A (en) * | 2015-04-24 | 2015-08-12 | 嘉兴学院 | Hyperbranched polyester rare earth complex containing nitrogen heterocyclic terminal group, and preparation method and use thereof |
| CN105218818A (en) * | 2015-09-11 | 2016-01-06 | 中北大学 | Functionalization polysulfones-Tb (III) ionic complex luminescent material preparation method |
| CN106243355A (en) * | 2016-07-08 | 2016-12-21 | 中北大学 | Amino phenolic bidentate Schiff's base ligand functionalized polymer rare earth complex luminescent material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| XUPING LI等: "Novel polyimide containing 1,10-phenanthroline and its europium(III) complex: synthesis, characterization,and luminescence properties", 《J MATER SCI》 * |
| 陈萍虹等: "双齿席夫碱配基功能化的聚砜与 Eu(III) 离子所形成的高分子稀土配合物的制备及其荧光发射特性", 《化学通报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292411A (en) * | 2021-12-17 | 2022-04-08 | 广东省科学院化工研究所 | Organic rare earth luminescent material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109385273B (en) | Ultra-long-life room temperature phosphorescent material, and preparation method and application thereof | |
| TWI708777B (en) | Pyrrolomethylene boron complex, color conversion composition, color conversion film, light source unit, display and lighting device | |
| CN108530423B (en) | Water-soluble aggregation-induced emission quinoxaline compound and preparation method and application thereof | |
| US10767109B2 (en) | Method for manufacturing carbonaceous luminescent material | |
| CN1867528A (en) | Compounds based on fluoranthene and use thereof | |
| WO2021232578A1 (en) | Organic-inorganic hybrid perovskite capable of emitting room-temperature phosphorescence, preparation method therefor, and use thereof | |
| CN107108862B (en) | Conjugated polymer, the mixture comprising it, composition, organic electronic device and its application of the crosslinked group containing acetenyl | |
| JP6455884B2 (en) | Light up-conversion illuminator | |
| CN110240699A (en) | One kind has the side chain liquid crystalline polymer and preparation method thereof of circular polarised luminescence performance | |
| CN110156962B (en) | Macromolecule with aggregation-induced emission characteristic, covalent modification carbon nanotube thereof and preparation method | |
| CN107083237A (en) | A kind of ligand functionalized polymer rare earth complex luminescent material of Phen | |
| CN108358957B (en) | Preparation method of rare earth-polymer nanospheres emitting white light | |
| CN110818834B (en) | Room-temperature phosphorescent material based on polymer hydrogen bonds and preparation method thereof | |
| CN112011098B (en) | Supermolecule luminescent gel system constructed by sulfonated cyclodextrin-bromophenyl picolinate-amino clay and preparation method thereof | |
| CN110845479B (en) | Guest material of phosphorescent luminescent material and pure organic room temperature phosphorescent luminescent material excited by visible light | |
| JP2018004928A (en) | Color conversion sheet, and light source unit, display and illumination containing the same | |
| CN109369726B (en) | Preparation and application of binuclear cyclometalated platinum (III) complex near-infrared luminescent material | |
| CN106243355B (en) | Ligand functionalized polymer-rare-earth complexes luminous material of amino phenolic bidentate schiff bases and preparation method thereof | |
| CN105176520B (en) | One kind is based on 4,4′The preparation and application of the luminous and material of main part of substitution benzil core | |
| CN113527708B (en) | Bridged tetraphenyl vinyl based supramolecular polymer light capture system, preparation and application | |
| CN114956973A (en) | Organic porous material based on tetraphenylethylene, and preparation method and application thereof | |
| CN115160588A (en) | Full-spectrum luminescent nanoscale zirconium-based metal organic framework material and preparation method thereof | |
| CN110105337B (en) | Quinoline triarylamine and preparation method thereof | |
| CN110452364B (en) | Method for preparing solid film optical limiter from high-molecular covalent modified graphene composite material with aggregation-induced emission characteristic | |
| CN106833617B (en) | Ligand functionalized polymer-rare-earth complexes luminous material of furfural contracting amine type bidentate schiff bases and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170822 |
|
| RJ01 | Rejection of invention patent application after publication |