CN106243355A - Amino phenolic bidentate Schiff's base ligand functionalized polymer rare earth complex luminescent material and preparation method thereof - Google Patents
Amino phenolic bidentate Schiff's base ligand functionalized polymer rare earth complex luminescent material and preparation method thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 116
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 112
- 239000000463 material Substances 0.000 title claims abstract description 90
- 239000003446 ligand Substances 0.000 title claims abstract description 66
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000013589 supplement Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 114
- 239000002585 base Substances 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 62
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 47
- 229920002492 poly(sulfone) Polymers 0.000 claims description 40
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 29
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 25
- 238000010792 warming Methods 0.000 claims description 24
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 23
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 238000013329 compounding Methods 0.000 claims description 15
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 12
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 claims description 12
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 10
- 238000004020 luminiscence type Methods 0.000 claims description 9
- 229940018563 3-aminophenol Drugs 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- ADMXIMIGWLFCTJ-UHFFFAOYSA-N chloromethylbenzene formaldehyde Chemical compound C(C1=CC=CC=C1)Cl.C=O ADMXIMIGWLFCTJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 4
- 206010070834 Sensitisation Diseases 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- -1 rare-earth compound Chemical class 0.000 abstract description 2
- 230000008313 sensitization Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 15
- 229910016644 EuCl3 Inorganic materials 0.000 description 14
- 239000007787 solid Substances 0.000 description 12
- 238000002189 fluorescence spectrum Methods 0.000 description 11
- 238000007306 functionalization reaction Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000005284 excitation Effects 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 150000002466 imines Chemical group 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 5
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 description 3
- 230000021615 conjugation Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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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
- 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
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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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
-
- 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
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to macromolecule rare-earth compound luminescent material field, be specifically related to a kind of amino phenolic bidentate Schiff's base ligand functionalized polymer rare earth complex luminescent material and preparation method thereof.This preparation method introduces polymer pendant groups by having the coordination amino phenolic bidentate Schiff's base aglucon with the difunctional effect of sensitization to rare earth ion, then with rare-earth ion coordination, amino phenolic bidentate Schiff's base ligand functionalized polymer rare earth two-element match luminescent material is obtained.Again by this coordination compound respectively with smaller ligand Phen or 2,2 bipyridyls supplement coordination, obtain amino phenolic bidentate Schiff's base ligand functionalized polymer rare earth ternary complex luminescent material.The method easily realizes, and solves the problems such as prior art middle rare earth coordination compound dispersion inequality, polymeric matrix poor performance, opens new way for preparing novel high polymer rare earth luminescent material.
Description
Technical field
The invention belongs to macromolecule-rare-earth compound luminescent material technical field, be specifically related to a kind of amino phenolic bidentate seat
Ligand functionalized polymer-rare-earth complexes luminous material of husband's alkali and preparation method thereof.
Background technology
In electroluminescent material field, the macromolecule-rare earth compounding launching fluorescence is a kind of high performance material.Such material
Material had both had the luminescent properties that little molecule rare earth compounding is excellent, and such as, luminous intensity is high, launch and carry narrow (monochromaticity is good), glimmering
Light life-span length and Stokes shift are big；The most also with the premium properties that high polymer is numerous, such as, excellent mechanical property
Energy, good physical and chemical stability, homogeneous speciality, speciality the most easily processed into type.These characteristics are advantageous to
The actual application of this type of material, at luminescence generated by light and the high-tech area such as electroluminescent and solar energy conversion, macromolecule-rare earth
Complex luminescent material suffers from the most wide, potential application prospect.But, up to the present, more successfully this type of
Material report is the fewest, and for meeting the demand of scientific technological advance, macromolecule-rare-earth complexes luminous material needs to be ground energetically
Study carefully and development.
Prepare macromolecule-rare-earth complexes luminous material and mainly have two kinds of approach: (1) first synthesizes containing rare earth compounding knot
The monomer of structure, then makes function monomer generation polyreaction；(2) manage to make the side chain of polymer macromolecule contain aglucon, make this
A little aglucons are directly coordinated with rare earth ion and obtain product.But the monomer synthesis more difficulty containing rare earth compounding structure, and position
Inhibition effect makes polyreaction be difficult to carry out, and products therefrom molecular weight is the highest, therefore comparatively speaking, the second way is to prepare high score
The effective way of son-rare-earth complexes luminous material.But, for being successfully obtained this type of functional material, need to carry out meticulous dividing
Son designs and by effective macromolecular reaction approach, and the side base of macromolecular chain just can be made really to become effective aglucon.Gao Bao
Spoiling and wait by macromolecular reaction, managing will be to rare earth ion with coordination chelating and the aglucon (benzene of sensitized luminescence dual-use function
Formic acid, naphthoic acid etc.) it is bonded in polymer lateral chain, then make function macromole and Eu (III) and the coordination of Tb (III) ion chelating,
Be prepared for multiple macromolecule-rare-earth complexes luminous material of good performance [Mingjuan WANG, Gao Baojiao, Du Junmei, functional material,
2013,44(S1): 142；Hou Xiaodong, Gao Baojiao, Xu Zeqing, chemical research and application, 2013,25(12): 1639].Schiff's base
Compound is an important aglucon of class of metal ion, in its molecule in addition to imines atom N, also tends to join atom containing other, i.e. it
Can be multiple tooth aglucon, stable chelate can be formed with rare earth ion by chelating ligands；The more important thing is that Schiff alkalizes
Mostly containing conjugation aromatic ring in adduct molecule, by strong light absorption-intramolecular energy, can effective sensitization rare earth ion
Fluorescent emission, make coordination compound launch hyperfluorescence, therefore, schiff's base type macromolecule-rare-earth complexes luminous material has ten
Divide good development prospect.
Summary of the invention
The present invention is directed to prior art middle rare earth coordination compound and there is the problems such as dispersion inequality, polymeric matrix poor performance, carry
Supply: (1) a kind of novel amino ligand functionalized polymer-rare-earth complexes luminous material of phenolic bidentate Schiff's base, enhance and send out
Optical property；(2) preparation of a kind of novel amino ligand functionalized polymer-rare-earth complexes luminous material of phenolic bidentate Schiff's base
Method.
The modified polysulfone PSF-AL of functionalized polymer used in the present invention-side chain bonding acetaldehyde (AL) group can be by
Prepare according to method described in document [Zhang Dandan, looks into aobvious space, Gao Baojiao, applied chemistry, 2016,33 (1): 53-62].
The present invention adopts the following technical scheme that realization:
A kind of amino ligand functionalized polymer-rare-earth complexes luminous material of phenolic bidentate Schiff's base, by amino phenolic bidentate
Schiff's base aglucon introduces the side base of polymer, then with rare-earth ion coordination, obtains amino phenolic bidentate Schiff's base ligand functionalized
Polymer-rare earth complex luminescent material；Again by the amino ligand functionalized polymer of phenolic bidentate Schiff's base-rare earth binary
Complex luminescent material respectively with smaller ligand Phen or 2,2-bipyridyl supplement coordination, obtain amino phenolic bidentate seat
The ligand functionalized polymer of husband's alkali-rare earth ternary complexes luminescent material.
Described polymer is polysulfones (PSF) or polystyrene (PS), the amino phenolic bidentate Schiff's base aglucon merit of gained
Can fluidized polymer-rare earth complex luminescent material structure as shown in the formula (I), the amino phenolic bidentate Schiff's base aglucon of gained
Functionalized polymer-rare earth ternary complexes luminescent material structure as shown in the formula (II),
Formula (I) formula (II),
M in formula3+For rare earth ion.
The preparation method of the described amino ligand functionalized polymer-rare-earth complexes luminous material of phenolic bidentate Schiff's base,
Comprise the steps:
The first step, joins 0.40-0.50 g polymer in 50 mL solvents and fully dissolves, add 0.85-0.95 g couple
Chloromethylbenzene formaldehyde and 0.14-0.16 mL catalyst, be warming up to 60-80 DEG C, N2Isothermal reaction 10-12 h under atmosphere, reaction knot
Shu Houyong ethanol is settled out polymer, the alternately washing of polymer dilute hydrochloric acid, ethanol and distilled water, is dried under vacuum to constant weight, i.e.
Obtain the polymer-modified of side chain bonding benzaldehyde (BA) aglucon；
Second step, the side chain 0.40-0.50g first step prepared is bonded the polymer-modified or direct of benzaldehyde (BA) aglucon
Use 0.40-0.50g side chain bonding acetaldehyde (AL) group polymer-modified (according to document [Zhang Dandan, looks into aobvious space, Gao Baojiao,
Applied chemistry, 2016,33 (1): 53-62] described in prepared by method) it is dissolved in 50 mL solvents, add 0.16-0.19 g
Amino-phenol, be warming up to 60-70 DEG C, N2Isothermal reaction 8-10h under atmosphere, reaction is settled out polymer with ethanol after terminating,
The alternately washing of polymer ethanol and distilled water, is dried under vacuum to constant weight, obtains side chain and be bonded with amino phenolic bidentate Schiff's base
The functionalized polymer of aglucon；
3rd step, the functionalized polymer that the side chain of 0.30-0.50g is bonded with amino phenolic bidentate Schiff's base aglucon is dissolved in 50
In mL solvent, regulate pH=7 ~ 8 by NaOH solution, add a certain amount of rare earth crystal, be warming up to 55-65 DEG C, isothermal reaction
8-10h, reaction is settled out polymer with ethanol after terminating, and polymer is washed, and is dried, obtains amino phenolic bidentate Schiff's base aglucon merit
Can fluidized polymer-rare earth complex luminescent material；
4th step, the functionalized polymer that 0.30-0.50g side chain is bonded with amino phenolic bidentate Schiff's base aglucon is dissolved in 50
In mL solvent, add a certain amount of rare earth crystal, be warming up to 55-65 DEG C, isothermal reaction 4-6 h, add little molecule and join
Body, constant temperature continues reaction 8-10 h, and reaction is settled out polymer with ethanol after terminating, and polymer is washed, and is dried, obtains amino phenols
The ligand functionalized polymer of type bidentate Schiff's base-rare earth ternary complexes luminescent material.
Catalyst described in the first step is anhydrous stannic chloride, aluminum trichloride (anhydrous) or anhydrous titanium tetrachloride.
Amino-phenol described in second step is o-aminophenol (OAP) or m-aminophenol (MAP).
Rare earth crystal described in 3rd step and the 4th step is terbium trichloride crystal (TbCl3·6H2Or europium chloride is brilliant O)
Body (EuCl3·6H2O)；Schiff's base aglucon in functionalized polymer is 3:1 with the thing mass ratio of rare earth ion.
Smaller ligand described in 4th step is Phen (Phen) or 2,2-bipyridyl (Bipy)；Functional poly
Schiff's base aglucon in compound is 3:1 with the thing mass ratio of rare earth ion；The material amount of smaller ligand and rare earth ion it
Ratio is 1:1.
First, second and third and four solvent described in step is dimethyl sulfoxide (DMSO), dimethyl acetylamide (DMAC) or two
Any one in methylformamide (DMF).
For the amino ligand functionalized polymer-rare-earth complexes luminous material of phenolic bidentate Schiff's base of the present invention is described,
It is further described below in conjunction with accompanying drawing:
Functionalization polysulfones PSF-AO, the coordination compound PSF-(AO) that Fig. 1 is modified polysulfone PSF-AL, prepared by PSF-AL3-Tb
And PSF-(AO) (III)3-Tb(Ⅲ)-(Phen)1Infrared spectrum.In the spectrogram of Fig. 1 modified polysulfone PSF-AL, except display is poly-
Outside whole characteristic absorption of sulfone, at 1675 cm-1 For the characteristic absorption peak of aldehyde radical, 2726 cm-1 Place stretches for C-H key on aldehyde radical
Contracting vibration absorption peak；At 1730 cm-1Stretching vibration absworption peak for the C=O key on ester group.The spectrum of functionalization polysulfones PSF-AO
In figure, 1675 cm-1With 2726 cm-1 The aldehyde radical characteristic absorption at place the most substantially weakens or disappears, and the aldehyde radical of PSF-AL has been described
Almost all converts；Meanwhile, at 1662 cm-1Place occurs in that the stretching vibration of C=N key absorbs, at 3456 cm-1Place occurs
The stretching vibration of phenolic hydroxyl group, shows that polysulfones side chain has been bonded o-aminophenol, forms the functionalization polysulfones of bidentate Schiff's base aglucon
PSF-AO。
At two-element match PSF-(AO)3In the spectrogram of-Tb (III), coordination compound occurring in that, new weak absorbing peak is positioned at
415cm-1With 526 cm-1ν should be belonged toTb-NAnd νTb-OStretching vibration peak, Schiff's base imines C=N key with stretching vibration absorb
Peak is from 1662 original cm-1Red shift is to 1658 cm-1, part Schiff's base imines C=N key and O H and Tb of phenol are described3+
Coordination forms chela ring, makes on ring electron cloud to Tb3+Transfer, causes original C=N bond energy to be tied by the resonance of C N Tb key
Structure weakens, therefore νC=NFrequency low frequency displacement.Bonded ligand AO indicated above sends out with Tb (III) ion with the form of bidentate aglucon
Give birth to sequestration coordination, define binary macromolecule-rare earth compounding PSF-(AO)3-Tb (III), simultaneously at 3254 cm-1Feature
Peak becomes wider, shows the existence having water of coordination.
At ternary complex PSF-(AO)3-Tb(Ⅲ)-(Phen)1Spectrogram in, also occur in that new weak absorbing peak is positioned at
419 cm-1With 528 cm-1ν should be belonged toTb-NAnd νTb-OStretching vibration peak, and the stretching vibration of Schiff's base imines C=N key absorbs
Peak is from 1662 original cm-1Red shift is to 1655 cm-1, this is due to addition (its of complex molecule small molecular aglucon Phen
The characteristic absorption peak of imines C=N key is also at 1650 cm-1Near), coordination compound ligancy increases, and energy reduces, and makes Schiff's base imines
C=N key stretching vibration absworption peak red shift degree is bigger, from 1662 original cm-1Red shift is to 1655cm-1, absolutely prove Schiff
The atom N of the atom N on alkali imines C=N key, the O atom on phenol ring and Phen all there occurs coordination with Tb (III) ion
Effect, defines ternary macromolecule-rare earth compounding PSF-(AO)3-Tb(Ⅲ)-(Phen)1。
Fig. 2 gives polysulfones PSF, benzaldehyde modified polysulfones PSF-BA and the infrared spectrum of functionalization polysulfones PSF-BAOP.
In the spectrogram of benzaldehyde modified polysulfones PSF-BA, in addition to whole characteristic absorption of display polysulfones, 1679 cm-1 Place occurs in that aldehyde
The characteristic absorption of base C=O key；2735 cm-1 Place occurs in that c h bond stretching vibration absworption peak on aldehyde radical.At functionalization polysulfones
In the spectrogram of PSF-BAOP, 1679 cm-1With 2735 cm-1The aldehyde radical characteristic absorption at place disappears the most substantially, meanwhile,
1643cm-1Place occurs in that the stretching vibration of Schiff's base group Central Asia amine-CH=N key absorbs, and at 3452 cm-1There is phenol in place
The stretching vibration of hydroxyl, fully shows that benzaldehyde modified polysulfones PSF-BA there occurs that with o-aminophenol Schiff base is anti-
Should, define the functionalization polysulfones PSF-BAOP of bidentate Schiff's base aglucon.
Additionally for the amino ligand functionalized polymer-rare-earth complexes luminous material of phenolic bidentate Schiff's base of the present invention is described
The characteristics of luminescence, use fluorescence emission spectrum to study the luminescent properties of this material, will the amino phenolic bidentate Schiff's base of preparation
Ligand functionalized polymer-rare-earth complexes luminous material is configured to DMF solution, surveys its fluorescence emission spectrum.And respectively by two
Unit's coordination compound and ternary complex are dissolved in chloroform, prolong stream film forming, be placed in the baking oven that temperature is 40 DEG C in culture dish, remove
Solvent, drying and forming-film, prepare the thin film (thickness of film is about 60 μm) of two-element match and ternary complex respectively, measure thin film
Fluorescence emission spectrum.
Fig. 3 is with 350nm as excitation wavelength, measures rare earth luminescent material TbCl3, part PSF-AO, two-element match
PSF-(AO)3-Tb (III) and ternary complex PSF-(AO)3-Tb(Ⅲ)-(Phen)1Fluorescence emission spectrum in DMF solution
Figure.As seen from the figure, prepared functionalization polysulfones PSF-AO itself also occurs the strongest fluorescence (by being total to of bonded ligand AO
Yoke big π key system is produced), form two-element match PSF-(AO) with Tb (III) ion coordination3After-Tb (III), itself
Fluorescent emission greatly weakens, and the position of the fluorescent emission bands of a spectrum of this two-element match is identical with Tb (III) ion with shape, table
Bright coordination compound launches the characteristic fluorescence of Tb (III) ion, and fluorescent emission intensity compares TbCl3 Improve by force about 10 times；Form three
Unit coordination compound PSF-(AO)3-Tb(Ⅲ)-(Phen)1After, coordination compound launches the characteristic fluorescence of Tb (III) ion, and fluorescent emission
Strength ratio TbCl3 Intensity improves about 18 times, and it is bigger that the fluorescent emission of part itself weakens degree, or even almost without, show
The dynamics of intramolecular energy is bigger.
Fig. 4 is to prolong two-element match PSF-(AO) prepared by stream membrane formation process3-Tb (III) and ternary complex PSF-(AO)3-
Tb(Ⅲ)-(Phen)1The fluorescence emission spectrum of solid film.Figure shows, two-element match PSF-(AO)3-Tb (III) with
Ternary complex PSF-(AO)3-Tb(Ⅲ)-(Phen)1Solid film launch the characteristic fluorescence of Tb (III) ion equally, and
And there is higher fluorescent emission intensity, i.e. present higher sensibilization.
Fig. 5 is with 335nm as excitation wavelength, measures rare earth luminescent material EuCl3, part PSF-BAOP, two-element match
PSF-(BAOP)3-Eu (III) and ternary complex PSF-(BAOP)3-Eu(Ⅲ)-(Phen)1Fluorescent emission in DMF solution
Spectrogram.As seen from the figure, prepared functionalization polysulfones PSF-BAOP itself also occurs the strongest fluorescence (by bonded ligand
The conjugation big π key system of BAOP is produced), form two-element match PSF-(BAOP) with Eu (III) ion coordination3-Eu(III)
After, the fluorescent emission of itself greatly weakens, and the position of the fluorescent emission bands of a spectrum of this two-element match and shape and Eu (III)
Ion is identical, shows that coordination compound launches the characteristic fluorescence of Eu (III) ion, and fluorescent emission intensity compares EuCl3 Improve by force about
13 times；Form ternary complex PSF-(BAOP)3-Eu(Ⅲ)-(Phen)1After, the feature that coordination compound launches Eu (III) ion is glimmering
Light, and fluorescent emission intensity compares EuCl3 Improve by force about 25 times, it is bigger that the fluorescent emission of part itself weakens degree, Nai Zhiji
Do not have, show that the dynamics of intramolecular energy is bigger.
Fig. 6 is to prolong two-element match PSF-(BAOP) prepared by stream membrane formation process3-Eu (III) and ternary complex PSF-
(BAOP)3-Eu(Ⅲ)-(Phen)1The fluorescence emission spectrum of solid film.Figure shows, two-element match PSF-
(BAOP)3-Eu (III) and ternary complex PSF-(BAOP)3-Eu(Ⅲ)-(Phen)1Solid film launch Eu (III) equally
The characteristic fluorescence of ion, and there is higher fluorescent emission intensity, i.e. present higher sensibilization.
Fig. 7 is with 335nm as excitation wavelength, measures rare earth luminescent material EuCl3, part PS-BAOP, two-element match
PS-(BAOP)3-Eu (III) and ternary complex PS-(BAOP)3-Eu(Ⅲ)-(Bipy)1Fluorescence emission in DMF solution
Spectrogram.As seen from the figure, itself also there is the strongest fluorescence in prepared functional polystyrene PS-BAOP, with Eu (III)
Ion coordination forms two-element match PS-(BAOP)3After-Eu (III), the fluorescent emission of itself greatly weakens, and this binary
The position of the fluorescent emission bands of a spectrum of coordination compound is identical with Eu (III) ion with shape, shows that coordination compound launches Eu (III) ion
Characteristic fluorescence, and fluorescent emission intensity compares EuCl3 Improve by force about 9.5 times；Form ternary complex PS-(BAOP)3-Eu
(Ⅲ)-(Bipy)1After, coordination compound launches the characteristic fluorescence of Eu (III) ion, and fluorescent emission intensity compares EuCl3 Improve by force
About 21 times, it is bigger that the fluorescent emission of part itself weakens degree, or even almost without, show the dynamics of intramolecular energy more
Greatly.
Fig. 8 is to prolong two-element match PS-(BAOP) prepared by stream membrane formation process3-Eu (III) and ternary complex PS-
(BAOP)3-Eu(Ⅲ)-(Bipy)1The fluorescence emission spectrum of solid film.Figure shows, two-element match PS-(BAOP)3-
Eu (III) and ternary complex PS-(BAOP)3-Eu(Ⅲ)-(Bipy)1Solid film launch the spy of Eu (III) ion equally
Levy fluorescence, and there is higher fluorescent emission intensity, i.e. present higher sensibilization.
Fig. 9 is with 335nm as excitation wavelength, measures rare earth luminescent material EuCl3, part PSF-BAMP, two-element match
PSF-(BAMP)3-Eu (III) and ternary complex PSF-(BAMP)3-Eu(Ⅲ)-(Phen)1Fluorescent emission in DMF solution
Spectrogram.As seen from the figure, prepared functionalization polysulfones PSF-BAMP itself also occurs the strongest fluorescence (by bonded ligand
The conjugation big π key system of BAMP is produced), form two-element match PSF-(BAMP) with Eu (III) ion coordination3-Eu(III)
After, the fluorescent emission of itself greatly weakens, and the position of the fluorescent emission bands of a spectrum of this two-element match and shape and Eu (III)
Ion is identical, shows that coordination compound launches the characteristic fluorescence of Eu (III) ion, and fluorescent emission intensity compares EuCl3 Improve by force about
15 times；Form ternary complex PSF-(BAMP)3-Eu(Ⅲ)-(Phen)1After, the feature that coordination compound launches Eu (III) ion is glimmering
Light, and fluorescent emission intensity compares EuCl3 Improve by force about 32 times, it is bigger that the fluorescent emission of part itself weakens degree, Nai Zhiji
Do not have, show that the dynamics of intramolecular energy is bigger.
Figure 10 is to prolong two-element match PSF-(BAMP) prepared by stream membrane formation process3-Eu (III) and ternary complex PSF-
(BAMP)3-Eu(Ⅲ)-(Phen)1The fluorescence emission spectrum of solid film.Figure shows, two-element match PSF-
(BAMP)3-Eu (III) and ternary complex PSF-(BAMP)3-Eu(Ⅲ)-(Phen)1Solid film launch Eu (III) equally
The characteristic fluorescence of ion, and there is higher fluorescent emission intensity, i.e. present higher sensibilization.
The present invention compared with prior art, its remarkable advantage: (1) this preparation method rare earth ion will be had coordination with quick
Change difunctional effect amino phenolic Schiff's base aglucon introduce polymer lateral chain, this aglucon can not only and rare earth ion between formed
Stable macromolecule-rare earth compounding, and there is bigger conjugate rigid plane, can significantly strengthen polymer aglucon to rare earth
The Transfer of energy of ion, strengthens luminescent properties；(2) the amino phenolic ligand functionalized polymerization of bidentate Schiff's base of the present invention
Thing-rare-earth complexes luminous material, except the amino phenolic Schiff's base aglucon of polymer lateral chain, also introduces smaller ligand, this
The collaborative coordination sensibilization of a little smaller ligand makes the luminescent properties of this material further be improved；(3) this
The bright one novel key mould assembly functionalized polymer-rare earth luminescent material that obtains, and open the new way preparing this luminescent material
Footpath.
Accompanying drawing explanation
Functionalization polysulfones PSF-AO, the coordination compound PSF-(AO) that Fig. 1 is modified polysulfone PSF-AL, prepared by PSF-AL3-
Tb (III) and PSF-(AO)3-Tb(Ⅲ)-(Phen)1Infrared spectrogram；
Fig. 2 is polysulfones PSF, benzaldehyde modified polysulfones PSF-BA and the infrared spectrogram of functionalization polysulfones PSF-BAOP；
Fig. 3 is with 350nm as excitation wavelength, rare earth luminescent material TbCl3, part PSF-AO, two-element match PSF-(AO)3-
Tb (III) and ternary complex PSF-(AO)3-Tb(Ⅲ)-(Phen)1Fluorescence emission spectrogram in DMF solution；
Fig. 4 is to prolong two-element match PSF-(AO) prepared by stream membrane formation process3-Tb (III) and ternary complex PSF-(AO)3-Tb
(Ⅲ)-(Phen)1The fluorescence emission spectrogram of solid film；
Fig. 5 is with 335nm as excitation wavelength, rare earth luminescent material EuCl3, part PSF-BAOP, two-element match PSF-
(BAOP)3-Eu (III) and ternary complex PSF-(BAOP)3-Eu(Ⅲ)-(Phen)1Fluorescence emission spectrum in DMF solution
Figure；
Fig. 6 is to prolong two-element match PSF-(BAOP) prepared by stream membrane formation process3-Eu (III) and ternary complex PSF-(BAOP)3-
Eu(Ⅲ)-(Phen)1The fluorescence emission spectrogram of solid film；
Fig. 7 is with 335nm as excitation wavelength, rare earth luminescent material EuCl3, part PS-BAOP, two-element match PS-
(BAOP)3-Eu (III) and ternary complex PS-(BAOP)3-Eu(Ⅲ)-(Bipy)1Fluorescence emission spectrum in DMF solution
Figure；
Fig. 8 is to prolong two-element match PS-(BAOP) prepared by stream membrane formation process3-Eu (III) and ternary complex PS-(BAOP)3-Eu
(Ⅲ)-(Bipy)1The fluorescence emission spectrogram of solid film；
Fig. 9 is with 335nm as excitation wavelength, rare earth luminescent material EuCl3, part PSF-BAMP, two-element match PSF-
(BAMP)3-Eu (III) and ternary complex PSF-(BAMP)3-Eu(Ⅲ)-(Phen)1Fluorescence emission spectrum in DMF solution
Figure；
Figure 10 is to prolong two-element match PSF-(BAMP) prepared by stream membrane formation process3-Eu (III) and ternary complex PSF-
(BAMP)3-Eu(Ⅲ)-(Phen)1The fluorescence emission spectrogram of solid film.
Detailed description of the invention
A kind of amino ligand functionalized polymer-rare-earth complexes luminous material of phenolic bidentate Schiff's base, by amino phenolic
Bidentate Schiff's base aglucon introduces the side base of polymer, then with rare-earth ion coordination, obtains amino phenolic bidentate Schiff's base aglucon merit
Can fluidized polymer-rare earth complex luminescent material；Again by the amino ligand functionalized polymer-rare earth of phenolic bidentate Schiff's base
Two-element match luminescent material respectively with smaller ligand Phen or 2,2-bipyridyl supplements coordination, obtains amino phenolic double
The ligand functionalized polymer of tooth Schiff's base-rare earth ternary complexes luminescent material.
Described polymer is polysulfones (PSF) or polystyrene (PS), the amino phenolic bidentate Schiff's base aglucon merit of gained
Can fluidized polymer-rare earth complex luminescent material structure as shown in the formula (I), the amino phenolic bidentate Schiff's base aglucon of gained
Functionalized polymer-rare earth ternary complexes luminescent material structure as shown in the formula (II),
Formula (I) formula (II),
M in formula3+For rare earth ion.
The preparation method of the described amino ligand functionalized polymer-rare-earth complexes luminous material of phenolic bidentate Schiff's base,
Comprise the steps:
The first step, joins 0.40-0.50 g polymer in 50 mL solvents and fully dissolves, add 0.85-0.95 g couple
Chloromethylbenzene formaldehyde and 0.14-0.16 mL catalyst, be warming up to 60-80 DEG C, N2Isothermal reaction 10-12 h under atmosphere, reaction knot
Shu Houyong ethanol is settled out polymer, the alternately washing of polymer dilute hydrochloric acid, ethanol and distilled water, is dried under vacuum to constant weight, i.e.
Obtain the polymer-modified of side chain bonding benzaldehyde (BA) aglucon；
Second step, the side chain 0.40-0.50g first step prepared is bonded the polymer-modified or direct of benzaldehyde (BA) aglucon
Use 0.40-0.50g side chain bonding acetaldehyde (AL) group polymer-modified (according to document [Zhang Dandan, looks into aobvious space, Gao Baojiao,
Applied chemistry, 2016,33 (1): 53-62] described in prepared by method) it is dissolved in 50 mL solvents, add 0.16-0.19 g
Amino-phenol, be warming up to 60-70 DEG C, N2Isothermal reaction 8-10h under atmosphere, reaction is settled out polymer with ethanol after terminating,
The alternately washing of polymer ethanol and distilled water, is dried under vacuum to constant weight, obtains side chain and be bonded with amino phenolic bidentate Schiff's base
The functionalized polymer of aglucon；
3rd step, the functionalized polymer that the side chain of 0.30-0.50g is bonded with amino phenolic bidentate Schiff's base aglucon is dissolved in 50
In mL solvent, regulate pH=7 ~ 8 by NaOH solution, add a certain amount of rare earth crystal, be warming up to 55-65 DEG C, isothermal reaction
8-10h, reaction is settled out polymer with ethanol after terminating, and polymer is washed, and is dried, obtains amino phenolic bidentate Schiff's base aglucon merit
Can fluidized polymer-rare earth complex luminescent material；
4th step, the functionalized polymer that 0.30-0.50g side chain is bonded with amino phenolic bidentate Schiff's base aglucon is dissolved in 50
In mL solvent, add a certain amount of rare earth crystal, be warming up to 55-65 DEG C, isothermal reaction 4-6 h, add little molecule and join
Body, constant temperature continues reaction 8-10 h, and reaction is settled out polymer with ethanol after terminating, and polymer is washed, and is dried, obtains amino phenols
The ligand functionalized polymer of type bidentate Schiff's base-rare earth ternary complexes luminescent material.
Catalyst described in the first step is anhydrous stannic chloride, aluminum trichloride (anhydrous) or anhydrous titanium tetrachloride.
Amino-phenol described in second step is o-aminophenol (OAP) or m-aminophenol (MAP).
Rare earth crystal described in 3rd step and the 4th step is terbium trichloride crystal (TbCl3·6H2Or europium chloride is brilliant O)
Body (EuCl3·6H2O)；Schiff's base aglucon in functionalized polymer is 3:1 with the thing mass ratio of rare earth ion.
Smaller ligand described in 4th step is Phen (Phen) or 2,2-bipyridyl (Bipy)；Functional poly
Schiff's base aglucon in compound is 3:1 with the thing mass ratio of rare earth ion；The material amount of smaller ligand and rare earth ion it
Ratio is 1:1.
The second, the solvent described in two, three and four steps is dimethyl sulfoxide (DMSO), dimethyl acetylamide (DMAC) or two
Any one in methylformamide (DMF).
Embodiment 1: in four-hole boiling flask, adds 0.4g modified polysulfone PSF-AL and 50 mL DMAC, after fully dissolving, then
Add 0.18g OAP, be warming up to 70 DEG C, N2Isothermal reaction 9h under atmosphere, reaction is settled out polymer with ethanol after terminating, polymerization
The alternately washing of thing ethanol and distilled water, is dried under vacuum to constant weight, obtains side chain and be bonded with amino phenolic bidentate Schiff's base aglucon
Functionalized polymer PSF-AO, the bonded amount of aglucon AO is 1.15mmol/g.
The functionalized polymer PSF-AO of 0.3 g is dissolved in 50 mL DMAC, regulates pH=7 ~ 8 by NaOH solution, then add
Entering 0.043g terbium trichloride crystal, be warming up to 65 DEG C, isothermal reaction 10h, reaction is settled out polymer with ethanol after terminating, polymerization
Thing is washed, and is dried, obtains the amino ligand functionalized polymer of phenolic bidentate Schiff's base-rare earth complex luminescent material PSF-
(AO)3-Tb(III)。
0.35 g functionalized polymer PSF-AO is dissolved in 50 mL DMAC, adds 0.05 g terbium trichloride crystal,
It is warming up to 65 DEG C, isothermal reaction 4 h, add 0.03 g smaller ligand Phen, 65 DEG C of constant temperature continue reaction 10 h, reaction
Being settled out polymer with ethanol after end, polymer is washed, and is dried, obtains the amino phenolic ligand functionalized polymerization of bidentate Schiff's base
Thing-rare earth ternary complexes luminescent material PSF-(AO)3-Tb(Ⅲ)-(Phen)1。
Embodiment 2: in four-hole boiling flask, adds 50 mLDMAC and 0.44 g PSF, makes PSF fully dissolve, add
0.92 g is to chloromethylbenzene formaldehyde and 0.15 mL anhydrous stannic chloride, and constant temperature is in 70 DEG C, at N2Stir reaction under atmosphere and carry out 12
h.Reaction is settled out polymer with ethanol after terminating, the alternately washing of polymer dilute hydrochloric acid, ethanol and distilled water, is dried under vacuum to
Constant weight, obtains the modified polysulfone PSF-BA of side chain bonding benzaldehyde (BA) aglucon.Benzaldehyde bonded amount is 1.78mmol/g.
Again in four-hole boiling flask, add 0.5g modified polysulfone PSF-BA and 50 mL DMAC, after fully dissolving, add
0.19 g OAP, is warming up to 65 DEG C, N2Isothermal reaction 8h under atmosphere, reaction is settled out polymer, polymer with ethanol after terminating
With ethanol and distilled water alternately washing, it is dried under vacuum to constant weight, obtains side chain and be bonded with amino phenolic bidentate Schiff's base aglucon
Functionalized polymer PSF-BAOP, the bonded amount of aglucon BAOP is divided into 1.35mmol/g.
The functionalized polymer PSF-BAOP of 0.30 g is dissolved in 50 mL DMAC, regulates pH=7 ~ 8 by NaOH solution,
Add 0.043g europium chloride crystal, be warming up to 55 DEG C, isothermal reaction 8h, reaction is settled out polymer with ethanol after terminating,
Polymer is washed, and is dried, obtains the amino ligand functionalized polymer of phenolic bidentate Schiff's base-rare earth complex luminescent material
PSF-(BAOP)3-Eu(III)。
0.30 g functionalized polymer PSF-BAOP is dissolved in 50 mL DMAC, adds 0.043g europium chloride brilliant
Body, is warming up to 55 DEG C, isothermal reaction 5h, adds 0.027 g smaller ligand Phen, and 55 DEG C of constant temperature continue reaction 8 h, instead
Being settled out polymer with ethanol after should terminating, polymer is washed, and is dried, and obtains amino phenolic bidentate Schiff's base ligand functionalized poly-
Compound-rare earth ternary complexes luminescent material PSF-(BAOP)3-Eu(III)-(Phen)1。
Embodiment 3: in four-hole boiling flask, adds 50 mLDMSO and 0.4 g PS, makes PS fully dissolve, add 0.95
G is to chloromethylbenzene formaldehyde and the anhydrous titanium tetrachloride of 0.16 mL, and constant temperature is in 80 DEG C, at N2Stir reaction under atmosphere and carry out 10 h.Instead
It is settled out polymer with ethanol after should terminating, the alternately washing of polymer dilute hydrochloric acid, ethanol and distilled water, it is dried under vacuum to perseverance
Weight, obtains the MPS PS-BA of side chain bonding benzaldehyde (BA) aglucon, and benzaldehyde bonded amount is 1.57mmol/g.
Again in four-hole boiling flask, add 0.4g MPS PS-BA and 50 mL DMSO, after fully dissolving, then add
Enter 0.16 g OAP, be warming up to 70 DEG C, N2Isothermal reaction 10h under atmosphere, reaction is settled out polymer with ethanol after terminating, polymerization
The alternately washing of thing ethanol and distilled water, is dried under vacuum to constant weight, obtains side chain and be bonded with amino phenolic bidentate Schiff's base aglucon
Functionalized polymer PS-BAOP, the bonded amount of aglucon BAOP is divided into 1.28mmol/g.
The functionalized polymer PS-BAOP of 0.50g is dissolved in 50 mL DMSO, regulates pH=7 ~ 8 by NaOH solution, then
Adding 0.07g europium chloride crystal, be warming up to 60 DEG C, isothermal reaction 9h, reaction is settled out polymer with ethanol after terminating, polymerization
Thing is washed, and is dried, obtains the amino ligand functionalized polymer of phenolic bidentate Schiff's base-rare earth complex luminescent material PS-
(BAOP)3-Eu(III)。
0.50 g functionalized polymer PS-BAOP is dissolved in 50 mL DMSO, adds 0.07g europium chloride crystal,
It is warming up to 60 DEG C, isothermal reaction 6h, add 0.04 g smaller ligand Bipy, 60 DEG C of constant temperature continue reaction 9 h, and reaction terminates
Being settled out polymer with ethanol afterwards, polymer is washed, and is dried, obtain the amino phenolic ligand functionalized polymer of bidentate Schiff's base-
Rare earth ternary complexes luminescent material PS-(BAOP)3-Eu(III)-(Bipy)1。
Embodiment 4: in four-hole boiling flask, adds 50 mLDMAC and 0.5 g PSF, makes PSF fully dissolve, add
0.85 g is to chloromethylbenzene formaldehyde and 0.14 mL aluminum trichloride (anhydrous), and constant temperature is in 60 DEG C, at N2Stir reaction under atmosphere to carry out
11h.Reaction is settled out polymer with ethanol after terminating, the alternately washing of polymer dilute hydrochloric acid, ethanol and distilled water, vacuum drying
To constant weight, obtaining the modified polysulfone PSF-BA of side chain bonding benzaldehyde (BA) aglucon, benzaldehyde bonded amount is 1.36mmol/g.
Again in four-hole boiling flask, add 0.45g modified polysulfone PSF-BA and 50 mL DMAC, after fully dissolving, add
0.18g MAP, is warming up to 60 DEG C, N2Isothermal reaction 8h under atmosphere, reaction is settled out polymer with ethanol after terminating, and polymer is used
The alternately washing of ethanol and distilled water, is dried under vacuum to constant weight, obtains side chain and be bonded with the merit of amino phenolic bidentate Schiff's base aglucon
Energy fluidized polymer PSF-BAMP, the bonded amount of aglucon BAMP is divided into 1.30mmol/g.
The functionalized polymer PSF-BAMP of 0.40g is dissolved in 50 mL DMAC, regulates pH=7 ~ 8 by NaOH solution, then
Adding 0.06g europium chloride crystal, be warming up to 65 DEG C, isothermal reaction 10h, reaction is settled out polymer with ethanol after terminating, poly-
Compound is washed, and is dried, obtains the amino ligand functionalized polymer of phenolic bidentate Schiff's base-rare earth complex luminescent material PSF-
(BAMP)3-Eu(III)。
0.40 g functionalized polymer PSF-BAMP is dissolved in 50 mL DMAC, adds 0.06g europium chloride crystal,
It is warming up to 65 DEG C, isothermal reaction 6h, add 0.035 g smaller ligand Phen, 65 DEG C of constant temperature continue reaction 8 h, reaction knot
Shu Houyong ethanol is settled out polymer, and polymer is washed, and is dried, obtains the amino phenolic ligand functionalized polymerization of bidentate Schiff's base
Thing-rare earth ternary complexes luminescent material PSF-(BAMP)3-Eu(III)-(Phen)1。
Claims (8)
1. the amino ligand functionalized polymer-rare-earth complexes luminous material of phenolic bidentate Schiff's base, it is characterised in that: will
Amino phenolic bidentate Schiff's base aglucon introduces the side base of polymer, then with rare-earth ion coordination, obtains amino phenolic bidentate Schiff
The ligand functionalized polymer of alkali-rare earth complex luminescent material；Again by ligand functionalized for amino phenolic bidentate Schiff's base poly-
Compound-rare earth complex luminescent material respectively with smaller ligand Phen or 2,2-bipyridyl supplement coordination, obtain ammonia
The ligand functionalized polymer of base phenolic bidentate Schiff's base-rare earth ternary complexes luminescent material.
The amino ligand functionalized polymer of phenolic bidentate Schiff's base-rare earth compounding luminescence material the most according to claim 1
Material, it is characterised in that: described polymer is polysulfones (PSF) or polystyrene (PS), the amino phenolic bidentate Schiff's base of gained
Ligand functionalized polymer-rare earth complex luminescent material structure as shown in the formula (I), the amino phenolic bidentate Schiff of gained
The ligand functionalized polymer of alkali-rare earth ternary complexes luminescent material structure as shown in the formula (II),
Formula (I) formula (II),
M in formula3+For rare earth ion.
3. the amino ligand functionalized polymer of phenolic bidentate Schiff's base as claimed in claim 1-rare earth compounding is luminous
The preparation method of material, it is characterised in that: comprise the steps:
The first step, joins 0.40-0.50 g polymer in 50 mL solvents and fully dissolves, add 0.85-0.95 g couple
Chloromethylbenzene formaldehyde and 0.14-0.16 mL catalyst, be warming up to 60-80 DEG C, N2Isothermal reaction 10-12 h under atmosphere, reaction knot
Shu Houyong ethanol is settled out polymer, the alternately washing of polymer dilute hydrochloric acid, ethanol and distilled water, is dried under vacuum to constant weight, i.e.
Obtain the polymer-modified of side chain bonding benzaldehyde (BA) aglucon；
Second step, the side chain 0.40-0.50g first step prepared is bonded the polymer-modified or direct of benzaldehyde (BA) aglucon
Use 0.40-0.50g side chain bonding the polymer-modified of acetaldehyde (AL) group to be dissolved in 50 mL solvents, add 0.16-
The amino-phenol of 0.19 g, is warming up to 60-70 DEG C, N2Isothermal reaction 8-10h under atmosphere, reaction is settled out poly-with ethanol after terminating
The alternately washing of compound, polymer ethanol and distilled water, is dried under vacuum to constant weight, obtains side chain and be bonded with amino phenolic bidentate seat
The functionalized polymer of husband's alkali aglucon；
3rd step, the functionalized polymer that the side chain of 0.30-0.50g is bonded with amino phenolic bidentate Schiff's base aglucon is dissolved in 50
In mL solvent, regulate pH=7 ~ 8 by NaOH solution, add a certain amount of rare earth crystal, be warming up to 55-65 DEG C, isothermal reaction
8-10h, reaction is settled out polymer with ethanol after terminating, and polymer is washed, and is dried, obtains amino phenolic bidentate Schiff's base aglucon merit
Can fluidized polymer-rare earth complex luminescent material；
4th step, the functionalized polymer that 0.30-0.50g side chain is bonded with amino phenolic bidentate Schiff's base aglucon is dissolved in 50
In mL solvent, add a certain amount of rare earth crystal, be warming up to 55-65 DEG C, isothermal reaction 4-6 h, add little molecule and join
Body, constant temperature continues reaction 8-10 h, and reaction is settled out polymer with ethanol after terminating, and polymer is washed, and is dried, obtains amino phenols
The ligand functionalized polymer of type bidentate Schiff's base-rare earth ternary complexes luminescent material.
The amino ligand functionalized polymer of phenolic bidentate Schiff's base-rare earth compounding luminescence material the most according to claim 3
The preparation method of material, it is characterised in that: catalyst described in the first step is anhydrous stannic chloride, aluminum trichloride (anhydrous) or anhydrous four
Titanium chloride.
5. luminous according to the amino ligand functionalized polymer of phenolic bidentate Schiff's base described in claim 3 or 4-rare earth compounding
The preparation method of material, it is characterised in that: the amino-phenol described in second step is o-aminophenol (OAP) or m-aminophenol
(MAP)。
The amino ligand functionalized polymer of phenolic bidentate Schiff's base-rare earth compounding luminescence material the most according to claim 5
The preparation method of material, it is characterised in that: the rare earth crystal described in the 3rd step and the 4th step is terbium trichloride crystal (TbCl3·
6H2Or europium chloride crystal (EuCl O)3·6H2O)；Schiff's base aglucon in functionalized polymer and the material amount of rare earth ion
Ratio be 3:1.
The amino ligand functionalized polymer of phenolic bidentate Schiff's base-rare earth compounding luminescence material the most according to claim 6
The preparation method of material, it is characterised in that: the smaller ligand described in the 4th step is Phen (Phen) or 2,2-bipyridyl
(Bipy)；Smaller ligand is 1:1 with the thing mass ratio of rare earth ion.
The amino ligand functionalized polymer of phenolic bidentate Schiff's base-rare earth compounding luminescence material the most according to claim 7
The preparation method of material, it is characterised in that: first, second and third and four solvent described in step is dimethyl sulfoxide (DMSO), dimethyl
Any one in acetamide (DMAC) or dimethylformamide (DMF).
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| CN107083237A (en) * | 2017-05-06 | 2017-08-22 | 中北大学 | A kind of ligand functionalized polymer rare earth complex luminescent material of Phen |
| CN110643047A (en) * | 2019-09-09 | 2020-01-03 | 东华大学 | Europium rare earth complex modified porous polymer and preparation and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107083237A (en) * | 2017-05-06 | 2017-08-22 | 中北大学 | A kind of ligand functionalized polymer rare earth complex luminescent material of Phen |
| CN110643047A (en) * | 2019-09-09 | 2020-01-03 | 东华大学 | Europium rare earth complex modified porous polymer and preparation and application thereof |
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