CN106243355B - Ligand functionalized polymer-rare-earth complexes luminous material of amino phenolic bidentate schiff bases and preparation method thereof - Google Patents
Ligand functionalized polymer-rare-earth complexes luminous material of amino phenolic bidentate schiff bases and preparation method thereof Download PDFInfo
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- CN106243355B CN106243355B CN201610535431.7A CN201610535431A CN106243355B CN 106243355 B CN106243355 B CN 106243355B CN 201610535431 A CN201610535431 A CN 201610535431A CN 106243355 B CN106243355 B CN 106243355B
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Abstract
The invention belongs to macromolecule-rare-earth compound luminescent material fields, and in particular to a kind of ligand functionalized polymer-rare-earth complexes luminous material of amino phenolic bidentate schiff bases and preparation method thereof.The preparation method will have coordination to rare earth ion and introduce polymer pendant groups with the amino phenolic bidentate schiff bases aglucon for being sensitized difunctional effect, then with rare-earth ion coordination, the ligand functionalized polymer of amino phenolic bidentate schiff bases-rare earth complex luminescent material is obtained.Again by the complex respectively with smaller ligand Phen or 2,2 '-bipyridyls, which supplement, to be coordinated, and the ligand functionalized polymer of amino phenolic bidentate schiff bases-rare earth ternary complexes luminescent material is obtained.This method is easy to accomplish, solves the problems such as rare earth compounding dispersion is uneven, polymer substrate performance is poor in the prior art, opened up a new way to prepare novel high polymer-rare earth luminescent material.
Description
Technical field
The invention belongs to macromolecule-rare-earth compound luminescent material technical fields, and in particular 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 technique
In electroluminescent material field, the macromolecule-rare earth compounding for emitting fluorescence is a kind of high performance material.Such material
Material is both with the excellent luminescent properties of small molecule rare earth compounding, for example, luminous intensity is high, transmitting band narrow (monochromaticjty is good), glimmering
The light service life is long and Stokes shift is big；Excellent performance also numerous with high polymer simultaneously, for example, excellent mechanical property
Energy, good physical and chemical stability, homogeneous speciality, speciality especially easily processed into type.These characteristics are advantageous to
The practical application of such material, in the high-tech areas such as luminescence generated by light and electroluminescent and solar energy conversion, macromolecule-rare earth
Complex luminescent material suffers from very wide, potential application prospect.However, up to the present, it is more successfully such
Material report is very few, and to meet the needs of scientific technological advance, macromolecule-rare-earth complexes luminous material needs are ground energetically
Study carefully and develops.
Preparing macromolecule-rare-earth complexes luminous material, there are mainly two types of approach: (1) first synthesis contains rare earth compounding knot
Then the monomer of structure makes function monomer that polymerization reaction occur；(2) try that the side chain of polymer macromolecule is made to contain aglucon, make this
A little aglucons and rare earth ion are directly coordinated and obtain product.But the synthesis of the monomer of the structure containing rare earth compounding is more difficult, and position
Inhibition effect makes polymerization reaction be difficult to carry out, and products therefrom molecular weight is not high, therefore in comparison, the second way is to prepare high score
Son-rare-earth complexes luminous material effective way.But to successfully obtain such functional material, need to carry out meticulous point
Son designs and by effective macromolecular reaction approach, and the side group of macromolecular chain can just be made really to become effective aglucon.Gao Bao
It is tender to wait the aglucon (benzene that try by macromolecular reaction to rare earth ion with coordination chelating and sensitized luminescence dual function
Formic acid, naphthoic acid etc.) it is bonded in polymer lateral chain, then it is coordinated function macromolecular and Eu (III) and Tb (III) ion chelating,
Be prepared for the good macromolecule-rare-earth complexes luminous material of multiple 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 bases
Compound is the important aglucon of one kind of metal ion, in molecule in addition to imines N atom, is also tended to containing other with atom, i.e., it
Can be multiple tooth aglucon, stable chelate can be formed with rare earth ion by chelating ligands；More importantly Schiff alkalizes
Rare earth ion can be effectively sensitized by strong light absorption-intramolecular energy containing conjugation aromatic ring mostly in adduct molecule
Fluorescent emission, so that complex is launched hyperfluorescence, therefore, schiff's base type macromolecule-rare-earth complexes luminous material have ten
Divide good development prospect.
Summary of the invention
There is the problems such as dispersion is uneven, polymer substrate performance is poor for rare earth compounding in the prior art in the present invention, mention
For: (1) a kind of novel amino phenolic bidentate schiff bases ligand functionalized polymer-rare-earth complexes luminous material enhances hair
Optical property；(2) a kind of preparation of the ligand functionalized polymer-rare-earth complexes luminous material of novel amino phenolic bidentate schiff bases
Method.
The modified polysulfone PSF-AL of functionalized polymer used in the present invention-side chain bonding acetaldehyde (AL) group can be by
It is prepared according to method described in document [Zhang Dandan, Cha Xianyu, Gao Baojiao, applied chemistry, 2016,33 (1): 53-62].
The present invention adopts the following technical scheme that realization:
A kind of ligand functionalized polymer-rare-earth complexes luminous material of amino phenolic bidentate schiff bases, by amino phenolic
The side group that bidentate schiff bases aglucon introduces polymer obtains amino phenolic bidentate schiff bases aglucon function then with rare-earth ion coordination
It can fluidized polymer-rare earth complex luminescent material；Again by the ligand functionalized polymer-rare earth of amino phenolic bidentate schiff bases
Respectively with smaller ligand Phen or 2,2 '-bipyridyls supplement to be coordinated two-element match luminescent material, and it is double to obtain amino phenolic
The ligand functionalized polymer of tooth schiff bases-rare earth ternary complexes luminescent material.
The polymer is polysulfones (PSF) or polystyrene (PS), resulting amino phenolic bidentate schiff bases aglucon function
Energy fluidized polymer-rare earth complex luminescent material structure is as shown in the formula (I), resulting amino phenolic bidentate schiff bases aglucon
Functionalized polymer-rare earth ternary complexes luminescent material structure is as shown in the formula (II),
Formula (I) formula (II),
M in formula3+For rare earth ion.
The preparation method of the ligand functionalized polymer-rare-earth complexes luminous material of amino phenolic bidentate schiff bases,
Include the following steps:
0.40-0.50 g polymer is added in 50 mL solvents and sufficiently dissolves, adds 0.85-0.95 by the first step
G is warming up to 60-80 DEG C, N to chloromethylbenzene formaldehyde and 0.14-0.16 mL catalyst2Isothermal reaction 10-12 h under atmosphere, instead
Go out polymer with ethanol precipitation after answering, polymer dilute hydrochloric acid, ethyl alcohol and distilled water alternately wash, and are dried under vacuum to perseverance
Weight is polymer-modified to get side chain bonding benzaldehyde (BA) aglucon；
Second step, by bonding benzaldehyde (BA) aglucon polymer-modified of side chain made from the 0.40-0.50g first step or
Directly adopt the polymer-modified (according to document [Zhang Dandan, Cha Xianyu, height of 0.40-0.50g side chain bonding acetaldehyde (AL) group
Protect tender, applied chemistry, 2016,33 (1): 53-62] described in method preparation) 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 is gone out with ethanol precipitation poly- after reaction
Object is closed, polymer ethyl alcohol and distilled water alternately wash, is dried under vacuum to constant weight to get side chain and is bonded with amino phenolic bidentate seat
The functionalized polymer of husband's alkali aglucon；
Third step, the functionalized polymer that the side chain of 0.30-0.50g is bonded with amino phenolic bidentate schiff bases aglucon are molten
In 50 mL solvents, pH=7 ~ 8 are adjusted with NaOH solution, add a certain amount of rare earth crystal, is warming up to 55-65 DEG C, perseverance
Temperature reaction 8-10h goes out polymer with ethanol precipitation after reaction, and polymer washing is dry, obtains amino phenolic bidentate schiff bases
Ligand functionalized polymer-rare earth complex luminescent material；
The functionalized polymer that 0.30-0.50g side chain is bonded with amino phenolic bidentate schiff bases aglucon is dissolved in by the 4th step
In 50 mL solvents, a certain amount of rare earth crystal is added, is warming up to 55-65 DEG C, isothermal reaction 4-6 h adds small molecule
Ligand, constant temperature the reaction was continued 8-10 h go out polymer with ethanol precipitation after reaction, and polymer washing is dry to get amino
The ligand functionalized polymer of phenolic bidentate schiff bases-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 third step and the 4th step is terbium trichloride crystal (TbCl3·6H2O) or europium chloride is brilliant
Body (EuCl3·6H2O)；The ratio between amount of substance of schiff bases aglucon and rare earth ion in functionalized polymer is 3:1.
Smaller ligand described in 4th step is Phen (Phen) or bipy 2,2' bipyridyl (Bipy)；Functional poly
The ratio between the amount of substance of schiff bases aglucon and rare earth ion closed in object is 3:1；The amount of substance of smaller ligand and rare earth ion it
Than for 1:1.
First, second and third and four solvent described in step be dimethyl sulfoxide (DMSO), dimethyl acetamide (DMAC) or two
Any one in methylformamide (DMF).
Ligand functionalized polymer-the rare-earth complexes luminous material of amino phenolic bidentate schiff bases to illustrate the invention,
It is further described below in conjunction with attached drawing:
Fig. 1 is modified polysulfone PSF-AL, the functionalization polysulfones PSF-AO as made from PSF-AL, complex PSF- (AO)3-
Tb (III) and PSF- (AO)3-Tb(Ⅲ)-(Phen)1Infrared spectroscopy.In the spectrogram of Fig. 1 modified polysulfone PSF-AL, except display
Outside whole characteristic absorptions of polysulfones, in 1675 cm-1For the characteristic absorption peak of aldehyde radical, 2726 cm-1Place is C-H key on aldehyde radical
Stretching vibration absworption peak；In 1730 cm-1For the stretching vibration absworption peak of C=O key on ester group.Functionalization polysulfones PSF-AO's
In spectrogram, 1675 cm-1With 2726 cm-1The aldehyde radical characteristic absorption at place obviously weakens or disappears, illustrates the aldehyde radical of PSF-AL
Almost all converts；Meanwhile in 1662 cm-1The stretching vibration that C=N key occurs in place absorbs, in 3456 cm-1Locate
The stretching vibration of existing phenolic hydroxyl group shows that polysulfones side chain has been bonded o-aminophenol, forms the functional poly of bidentate schiff bases aglucon
Sulfone PSF-AO.
At two-element match PSF- (AO)3In the spectrogram of-Tb (III), occurs new weak absorbing peak in complex and be located at
415cm-1With 526 cm-1ν should be belonged toTb-NAnd νTb-OStretching vibration peak, schiff bases imines C=N key with stretching vibration absorb
Peak is from 1662 original cm-1Red shift is to 1658 cm-1, illustrate the O-H and Tb of ligand schiff bases imines C=N key and phenol3+
Coordination forms chela ring, makes on ring electron cloud to Tb3+Transfer, causes original C=N bond energy by the resonance knot of C ═ N-Tb key
Structure weakens, therefore νC=NThe displacement of frequency low frequency.Bonded ligand AO indicated above is sent out in the form of bidentate aglucon with Tb (III) ion
Chelating coordination has been given birth to, binary macromolecule-rare earth compounding PSF- (AO) is formd3- Tb (III), while in 3254 cm-1Feature
Peak becomes wider, shows the presence for having water of coordination.
At ternary complex PSF- (AO)3-Tb(Ⅲ)-(Phen)1Spectrogram in, also there is new weak absorbing peak and be located at
419 cm-1With 528 cm-1ν should be belonged toTb-NAnd νTb-OStretching vibration peak, and the stretching vibration of schiff bases imines C=N key absorbs
Peak is from 1662 original cm-1Red shift is to 1655 cm-1, this is because addition (its of complex molecule small molecular aglucon Phen
The characteristic absorption peak of imines C=N key is also in 1650 cm-1Near), complex ligancy increases, and energy reduces, and makes schiff bases 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 N atom of N atom on alkali imines C=N key, the O atom on phenol ring and Phen is coordinated with Tb (III) ion
Effect, forms ternary macromolecule-rare earth compounding PSF- (AO)3-Tb(Ⅲ)-(Phen)1。
Fig. 2 gives the infrared spectroscopy of polysulfones PSF, benzaldehyde modified polysulfones PSF-BA and functionalization polysulfones PSF-BAOP.
In the spectrogram of benzaldehyde modified polysulfones PSF-BA, in addition to whole characteristic absorptions of display polysulfones, 1679 cm-1 There is aldehyde in place
The characteristic absorption of base C=O key；2735 cm-1There is c h bond stretching vibration absworption peak on aldehyde radical in place.In functionalization polysulfones PSF-
In the spectrogram of BAOP, 1679 cm-1With 2735 cm-1The aldehyde radical characteristic absorption at place disappears substantially, at the same time, in 1643cm-1There is schiff bases group Central Asia amine-CH=N key stretching vibration absorption in place, and in 3452 cm-1There is phenolic hydroxyl group in place
Stretching vibration sufficiently shows that benzaldehyde modified polysulfones PSF-BA has had occurred Schiff base with o-aminophenol and reacted, and is formed
The functionalization polysulfones PSF-BAOP of bidentate schiff bases aglucon.
In addition the ligand functionalized polymer-rare-earth complexes luminous material of amino phenolic bidentate schiff bases to illustrate the invention
The characteristics of luminescence, the luminescent properties of the material are studied using fluorescence emission spectrum, by the amino phenolic bidentate schiff bases of preparation
Ligand functionalized polymer-rare-earth complexes luminous material is configured to DMF solution, surveys its fluorescence emission spectrum.And respectively by two
First complex and ternary complex are dissolved in chloroform, prolong stream film forming in culture dish, are placed in the baking oven that temperature is 40 DEG C, are removed
The film (thickness of film is about 60 μm) of two-element match and ternary complex is made in solvent, drying and forming-film respectively, measures film
Fluorescence emission spectrum.
Fig. 3 is to measure rare earth luminescent material TbCl using 350nm as excitation wavelength3, ligand 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, more strong fluorescence also occurs for prepared functionalization polysulfones PSF-AO itself (by being total to for bonded ligand AO
Produced by the big pi bond system of yoke), two-element match PSF- (AO) is formed with Tb (III) ion coordination3After-Tb (III), itself
Fluorescent emission greatly weakens, and the location and shape of the fluorescent emission bands of a spectrum of the two-element match are identical as Tb (III) ion, table
Bright complex launches the characteristic fluorescence of Tb (III) ion, and fluorescent emission intensity ratio TbCl3 About 10 times are improved by force；Form three
First complex PSF- (AO)3-Tb(Ⅲ)-(Phen)1Afterwards, complex launches the characteristic fluorescence of Tb (III) ion, and fluorescent emission
Intensity ratio TbCl3 Intensity improves about 18 times, and the fluorescent emission Weaken degree of ligand itself is bigger, or even almost without showing
The dynamics of intramolecular energy is bigger.
Fig. 4 is the two-element match PSF- (AO) for prolonging stream membrane formation process preparation3- Tb (III) and ternary complex PSF- (AO)3-
Tb(Ⅲ)-(Phen)1Solid film fluorescence emission spectrum.It is shown in figure, two-element match PSF- (AO)3- Tb (III) with
Ternary complex PSF- (AO)3-Tb(Ⅲ)-(Phen)1Solid film equally launch the characteristic fluorescence of Tb (III) ion, and
And there is higher fluorescent emission intensity, that is, stronger sensibilization is presented.
Fig. 5 is to measure rare earth luminescent material EuCl using 335nm as excitation wavelength3, ligand 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, more strong fluorescence also occurs for prepared functionalization polysulfones PSF-BAOP itself (by bonded ligand
Produced by the big pi bond system of the conjugation of BAOP), two-element match PSF- (BAOP) is formed with Eu (III) ion coordination3-Eu(III)
Afterwards, the fluorescent emission of itself greatly weakens, and the location and shape of the fluorescent emission bands of a spectrum of the two-element match and Eu (III)
Ion is identical, shows that complex launches the characteristic fluorescence of Eu (III) ion, and fluorescent emission intensity ratio EuCl3 It improves about by force
13 times；It is formed ternary complex PSF- (BAOP)3-Eu(Ⅲ)-(Phen)1Afterwards, complex launch Eu (III) ion feature it is glimmering
Light, and fluorescent emission intensity ratio EuCl3 About 25 times are improved by force, the fluorescent emission Weaken degree of ligand itself is bigger, Nai Zhiji
Do not have, shows that the dynamics of intramolecular energy is bigger.
Fig. 6 is the two-element match PSF- (BAOP) for prolonging stream membrane formation process preparation3- Eu (III) and ternary complex PSF-
(BAOP)3-Eu(Ⅲ)-(Phen)1Solid film fluorescence emission spectrum.It is shown in figure, two-element match PSF-
(BAOP)3- Eu (III) and ternary complex PSF- (BAOP)3-Eu(Ⅲ)-(Phen)1Solid film equally launch Eu (III)
The characteristic fluorescence of ion, and there is higher fluorescent emission intensity, that is, stronger sensibilization is presented.
Fig. 7 is to measure rare earth luminescent material EuCl using 335nm as excitation wavelength3, ligand 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, more strong fluorescence also occurs for prepared functional polystyrene PS-BAOP itself, with Eu (III)
Ion coordination forms two-element match PS- (BAOP)3After-Eu (III), the fluorescent emission of itself greatly weakens, and the binary
The location and shape of the fluorescent emission bands of a spectrum of complex are identical as Eu (III) ion, show that complex launches Eu (III) ion
Characteristic fluorescence, and fluorescent emission intensity ratio EuCl3 About 9.5 times are improved by force；It is formed ternary complex PS- (BAOP)3-Eu
(Ⅲ)-(Bipy)1Afterwards, complex launches the characteristic fluorescence of Eu (III) ion, and fluorescent emission intensity ratio EuCl3 It improves by force
About 21 times, the fluorescent emission Weaken degree of ligand itself is bigger, or even almost without showing the dynamics of intramolecular energy more
Greatly.
Fig. 8 is the two-element match PS- (BAOP) for prolonging stream membrane formation process preparation3- Eu (III) and ternary complex PS-
(BAOP)3-Eu(Ⅲ)-(Bipy)1Solid film fluorescence emission spectrum.It is shown in figure, two-element match PS- (BAOP)3-
Eu (III) and ternary complex PS- (BAOP)3-Eu(Ⅲ)-(Bipy)1Solid film equally launch the spy of Eu (III) ion
Fluorescence is levied, and there is higher fluorescent emission intensity, that is, stronger sensibilization is presented.
Fig. 9 is to measure rare earth luminescent material EuCl using 335nm as excitation wavelength3, ligand 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, more strong fluorescence also occurs for prepared functionalization polysulfones PSF-BAMP itself (by bonded ligand
Produced by the big pi bond system of the conjugation of BAMP), two-element match PSF- (BAMP) is formed with Eu (III) ion coordination3-Eu(III)
Afterwards, the fluorescent emission of itself greatly weakens, and the location and shape of the fluorescent emission bands of a spectrum of the two-element match and Eu (III)
Ion is identical, shows that complex launches the characteristic fluorescence of Eu (III) ion, and fluorescent emission intensity ratio EuCl3 It improves about by force
15 times；It is formed ternary complex PSF- (BAMP)3-Eu(Ⅲ)-(Phen)1Afterwards, complex launch Eu (III) ion feature it is glimmering
Light, and fluorescent emission intensity ratio EuCl3 About 32 times are improved by force, the fluorescent emission Weaken degree of ligand itself is bigger, Nai Zhiji
Do not have, shows that the dynamics of intramolecular energy is bigger.
Figure 10 is the two-element match PSF- (BAMP) for prolonging stream membrane formation process preparation3- Eu (III) and ternary complex PSF-
(BAMP)3-Eu(Ⅲ)-(Phen)1Solid film fluorescence emission spectrum.It is shown in figure, two-element match PSF-
(BAMP)3- Eu (III) and ternary complex PSF- (BAMP)3-Eu(Ⅲ)-(Phen)1Solid film equally launch Eu (III)
The characteristic fluorescence of ion, and there is higher fluorescent emission intensity, that is, stronger sensibilization is presented.
Compared with prior art, the present invention its remarkable advantage: (1) preparation method will to rare earth ion have coordination with it is quick
The amino phenolic schiff bases aglucon for changing difunctional effect introduces polymer lateral chain, which can not only form between rare earth ion
Stable macromolecule-rare earth compounding, and there is biggish conjugate rigid plane, polymer can be strengthened significantly with basal orientation rare earth
The Transfer of energy of ion enhances luminescent properties；(2) the ligand functionalized polymerization of amino phenolic bidentate schiff bases of the invention
Object-rare-earth complexes luminous material also introduces smaller ligand in addition to the amino phenolic schiff bases aglucon of polymer lateral chain, this
The collaboration coordination sensibilization of a little smaller ligands improves the luminescent properties of the material further；(3) this hair
It is bright to obtain a kind of novel bonding type functionalized polymer-rare earth luminescent material, and open the new way for preparing the luminescent material
Diameter.
Detailed description of the invention
Fig. 1 is modified polysulfone PSF-AL, the functionalization polysulfones PSF-AO as made from PSF-AL, complex PSF- (AO)3-
Tb (III) and PSF- (AO)3-Tb(Ⅲ)-(Phen)1Infrared spectrogram；
Fig. 2 is the infrared spectrogram of polysulfones PSF, benzaldehyde modified polysulfones PSF-BA and functionalization polysulfones PSF-BAOP；
Fig. 3 is the rare earth luminescent material TbCl using 350nm as excitation wavelength3, ligand PSF-AO, two-element match PSF-
(AO)3- Tb (III) and ternary complex PSF- (AO)3-Tb(Ⅲ)-(Phen)1Fluorescence emission spectrogram of compound in DMF solution；
Fig. 4 is the two-element match PSF- (AO) for prolonging stream membrane formation process preparation3- Tb (III) and ternary complex PSF- (AO)3-
Tb(Ⅲ)-(Phen)1Solid film fluorescence emission spectrogram of compound；
Fig. 5 is the rare earth luminescent material EuCl using 335nm as excitation wavelength3, ligand 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 the two-element match PSF- (BAOP) for prolonging stream membrane formation process preparation3- Eu (III) and ternary complex PSF-
(BAOP)3-Eu(Ⅲ)-(Phen)1Solid film fluorescence emission spectrogram of compound；
Fig. 7 is the rare earth luminescent material EuCl using 335nm as excitation wavelength3, ligand 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 the two-element match PS- (BAOP) for prolonging stream membrane formation process preparation3- Eu (III) and ternary complex PS-
(BAOP)3-Eu(Ⅲ)-(Bipy)1Solid film fluorescence emission spectrogram of compound；
Fig. 9 is the rare earth luminescent material EuCl using 335nm as excitation wavelength3, ligand 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 the two-element match PSF- (BAMP) for prolonging stream membrane formation process preparation3- Eu (III) and ternary complex PSF-
(BAMP)3-Eu(Ⅲ)-(Phen)1Solid film fluorescence emission spectrogram of compound.
Specific embodiment
A kind of ligand functionalized polymer-rare-earth complexes luminous material of amino phenolic bidentate schiff bases, by amino phenolic
The side group that bidentate schiff bases aglucon introduces polymer obtains amino phenolic bidentate schiff bases aglucon function then with rare-earth ion coordination
It can fluidized polymer-rare earth complex luminescent material；Again by the ligand functionalized polymer-rare earth of amino phenolic bidentate schiff bases
Respectively with smaller ligand Phen or 2,2 '-bipyridyls supplement to be coordinated two-element match luminescent material, and it is double to obtain amino phenolic
The ligand functionalized polymer of tooth schiff bases-rare earth ternary complexes luminescent material.
The polymer is polysulfones (PSF) or polystyrene (PS), resulting amino phenolic bidentate schiff bases aglucon function
Energy fluidized polymer-rare earth complex luminescent material structure is as shown in the formula (I), resulting amino phenolic bidentate schiff bases aglucon
Functionalized polymer-rare earth ternary complexes luminescent material structure is as shown in the formula (II),
Formula (I) formula (II),
M in formula3+For rare earth ion.
The preparation method of the ligand functionalized polymer-rare-earth complexes luminous material of amino phenolic bidentate schiff bases,
Include the following steps:
0.40-0.50 g polymer is added in 50 mL solvents and sufficiently dissolves, adds 0.85-0.95 by the first step
G is warming up to 60-80 DEG C, N to chloromethylbenzene formaldehyde and 0.14-0.16 mL catalyst2Isothermal reaction 10-12 h under atmosphere, instead
Go out polymer with ethanol precipitation after answering, polymer dilute hydrochloric acid, ethyl alcohol and distilled water alternately wash, and are dried under vacuum to perseverance
Weight is polymer-modified to get side chain bonding benzaldehyde (BA) aglucon；
Second step, by bonding benzaldehyde (BA) aglucon polymer-modified of side chain made from the 0.40-0.50g first step or
Directly adopt the polymer-modified (according to document [Zhang Dandan, Cha Xianyu, height of 0.40-0.50g side chain bonding acetaldehyde (AL) group
Protect tender, applied chemistry, 2016,33 (1): 53-62] described in method preparation) 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 is gone out with ethanol precipitation poly- after reaction
Object is closed, polymer ethyl alcohol and distilled water alternately wash, is dried under vacuum to constant weight to get side chain and is bonded with amino phenolic bidentate seat
The functionalized polymer of husband's alkali aglucon；
Third step, the functionalized polymer that the side chain of 0.30-0.50g is bonded with amino phenolic bidentate schiff bases aglucon are molten
In 50 mL solvents, pH=7 ~ 8 are adjusted with NaOH solution, add a certain amount of rare earth crystal, is warming up to 55-65 DEG C, perseverance
Temperature reaction 8-10h goes out polymer with ethanol precipitation after reaction, and polymer washing is dry, obtains amino phenolic bidentate schiff bases
Ligand functionalized polymer-rare earth complex luminescent material；
The functionalized polymer that 0.30-0.50g side chain is bonded with amino phenolic bidentate schiff bases aglucon is dissolved in by the 4th step
In 50 mL solvents, a certain amount of rare earth crystal is added, is warming up to 55-65 DEG C, isothermal reaction 4-6 h adds small molecule
Ligand, constant temperature the reaction was continued 8-10 h go out polymer with ethanol precipitation after reaction, and polymer washing is dry to get amino
The ligand functionalized polymer of phenolic bidentate schiff bases-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 third step and the 4th step is terbium trichloride crystal (TbCl3·6H2O) or europium chloride is brilliant
Body (EuCl3·6H2O)；The ratio between amount of substance of schiff bases aglucon and rare earth ion in functionalized polymer is 3:1.
Smaller ligand described in 4th step is Phen (Phen) or bipy 2,2' bipyridyl (Bipy)；Functional poly
The ratio between the amount of substance of schiff bases aglucon and rare earth ion closed in object is 3:1；The amount of substance of smaller ligand and rare earth ion it
Than for 1:1.
The second, solvent described in the step of two, three and four is dimethyl sulfoxide (DMSO), dimethyl acetamide (DMAC) or two
Any one in methylformamide (DMF).
Embodiment 1: in four-hole boiling flask, being added 0.4g modified polysulfone PSF-AL and 50 mL DMAC, after completely dissolution, then
0.18g OAP is added, is warming up to 70 DEG C, N2Isothermal reaction 9h under atmosphere goes out polymer with ethanol precipitation after reaction, polymerization
Object ethyl alcohol and distilled water alternately wash, and are dried under vacuum to constant weight to get side chain and are bonded with amino phenolic bidentate schiff bases 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, with NaOH solution adjust pH=7 ~ 8, then plus
Enter 0.043g terbium trichloride crystal, be warming up to 65 DEG C, isothermal reaction 10h goes out polymer with ethanol precipitation after reaction, polymerization
Object washing, it is dry, obtain the ligand functionalized polymer of amino phenolic bidentate schiff bases-rare earth complex luminescent material PSF-
(AO)3-Tb(III)。
0.35 g functionalized polymer PSF-AO is dissolved in 50 mL DMAC, 0.05 g terbium trichloride crystal is added,
65 DEG C, 4 h of isothermal reaction are warming up to, adds 0.03 g smaller ligand Phen, the reaction was continued 10 h, the reaction of 65 DEG C of constant temperature
After with ethanol precipitation go out polymer, polymer washing is dry to get the ligand functionalized polymerization of amino phenolic bidentate schiff bases
Object-rare earth ternary complexes luminescent material PSF- (AO)3-Tb(Ⅲ)-(Phen)1。
Embodiment 2: in four-hole boiling flask, 50 mLDMAC and 0.44 g PSF is added, dissolves PSF sufficiently, adds
0.92 g is to chloromethylbenzene formaldehyde and 0.15 mL anhydrous stannic chloride, and constant temperature is in 70 DEG C, in N2Carry out 12 is stirred to react under atmosphere
h.Go out polymer with ethanol precipitation after reaction, polymer dilute hydrochloric acid, ethyl alcohol and distilled water are alternately washed, is dried under vacuum to
Constant weight is bonded the modified polysulfone PSF-BA of benzaldehyde (BA) aglucon to get side chain.Benzaldehyde bonded amount is 1.78mmol/g.
Again in four-hole boiling flask, 0.5g modified polysulfone PSF-BA and 50 mL DMAC is added and adds after completely dissolution
0.19 g OAP, is warming up to 65 DEG C, N2Isothermal reaction 8h under atmosphere goes out polymer, polymer with ethanol precipitation after reaction
It is alternately washed with ethyl alcohol and distilled water, is dried under vacuum to constant weight to get side chain and is bonded with amino phenolic bidentate schiff bases aglucon
The bonded amount of functionalized polymer PSF-BAOP, aglucon BAOP are divided into 1.35mmol/g.
The functionalized polymer PSF-BAOP of 0.30 g is dissolved in 50 mL DMAC, adjusts pH=7 ~ 8 with NaOH solution,
0.043g europium chloride crystal is added, is warming up to 55 DEG C, isothermal reaction 8h goes out polymer with ethanol precipitation after reaction,
Polymer washing, it is dry, obtain the ligand functionalized polymer of amino phenolic bidentate schiff bases-rare earth complex luminescent material
PSF-(BAOP)3-Eu(III)。
0.30 g functionalized polymer PSF-BAOP is dissolved in 50 mL DMAC, it is brilliant to add 0.043g europium chloride
Body is warming up to 55 DEG C, isothermal reaction 5h, adds 0.027 g smaller ligand Phen, 55 DEG C of constant temperature the reaction was continued 8 h, instead
Go out polymer with ethanol precipitation after answering, polymer washing is dry ligand functionalized poly- to get amino phenolic bidentate schiff bases
Close object-rare earth ternary complexes luminescent material PSF- (BAOP)3-Eu(III)-(Phen)1。
Embodiment 3: in four-hole boiling flask, 50 mLDMSO and 0.4 g PS is added, dissolves PS sufficiently, adds 0.95
G is to chloromethylbenzene formaldehyde and the anhydrous titanium tetrachloride of 0.16 mL, and constant temperature is in 80 DEG C, in N2It is stirred to react under atmosphere and carries out 10 h.Instead
Go out polymer with ethanol precipitation after answering, polymer dilute hydrochloric acid, ethyl alcohol and distilled water alternately wash, and are dried under vacuum to perseverance
For weight to get the modified polystyrene PS-BA of side chain bonding benzaldehyde (BA) aglucon, benzaldehyde bonded amount is 1.57mmol/g.
Again in four-hole boiling flask, 0.4g modified polystyrene PS-BA and 50 mL DMSO is added, after completely dissolution, then plus
Enter 0.16 g OAP, is warming up to 70 DEG C, N2Isothermal reaction 10h under atmosphere goes out polymer with ethanol precipitation after reaction, polymerization
Object ethyl alcohol and distilled water alternately wash, and are dried under vacuum to constant weight to get side chain and are bonded with amino phenolic bidentate schiff bases 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, adjusts pH=7 ~ 8 with NaOH solution, then
0.07g europium chloride crystal is added, is warming up to 60 DEG C, isothermal reaction 9h goes out polymer with ethanol precipitation after reaction, polymerization
Object washing, it is dry, obtain the ligand functionalized polymer of amino phenolic bidentate schiff bases-rare earth complex luminescent material PS-
(BAOP)3-Eu(III)。
0.50 g functionalized polymer PS-BAOP is dissolved in 50 mL DMSO, 0.07g europium chloride crystal is added,
60 DEG C, isothermal reaction 6h are warming up to, adds 0.04 g smaller ligand Bipy, 60 DEG C of constant temperature the reaction was continued 9 h, reaction terminates
Go out polymer with ethanol precipitation afterwards, polymer washing is dry to get the ligand functionalized polymer-of amino phenolic bidentate schiff bases
Rare earth ternary complexes luminescent material PS- (BAOP)3-Eu(III)-(Bipy)1。
Embodiment 4: in four-hole boiling flask, 50 mLDMAC and 0.5 g PSF is added, dissolves PSF sufficiently, adds
0.85 g is to chloromethylbenzene formaldehyde and 0.14 mL aluminum trichloride (anhydrous), and constant temperature is in 60 DEG C, in N2Progress is stirred to react under atmosphere
11h.Go out polymer with ethanol precipitation after reaction, polymer dilute hydrochloric acid, ethyl alcohol and distilled water alternately wash, vacuum drying
To constant weight to get 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, 0.45g modified polysulfone PSF-BA and 50 mL DMAC is added and adds after completely dissolution
0.18g MAP is warming up to 60 DEG C, N2Isothermal reaction 8h under atmosphere, goes out polymer with ethanol precipitation after reaction, and polymer is used
Ethyl alcohol and distilled water alternately wash, and are dried under vacuum to the function that constant weight is bonded with amino phenolic bidentate schiff bases aglucon to get side chain
Energy fluidized polymer PSF-BAMP, the bonded amount of aglucon BAMP are divided into 1.30mmol/g.
The functionalized polymer PSF-BAMP of 0.40g is dissolved in 50 mL DMAC, adjusts pH=7 ~ 8 with NaOH solution, then
0.06g europium chloride crystal is added, is warming up to 65 DEG C, isothermal reaction 10h goes out polymer with ethanol precipitation after reaction, gathers
Object washing is closed, it is dry, obtain the ligand functionalized polymer of amino phenolic bidentate schiff bases-rare earth complex luminescent material PSF-
(BAMP)3-Eu(III)。
0.40 g functionalized polymer PSF-BAMP is dissolved in 50 mL DMAC, 0.06g europium chloride crystal is added,
65 DEG C, isothermal reaction 6h are warming up to, adds 0.035 g smaller ligand Phen, 65 DEG C of constant temperature the reaction was continued 8 h, reaction knot
Shu Houyong ethanol precipitation goes out polymer, and polymer washing is dry to get the ligand functionalized polymerization of amino phenolic bidentate schiff bases
Object-rare earth ternary complexes luminescent material PSF- (BAMP)3-Eu(III)-(Phen)1。
Claims (8)
1. a kind of ligand functionalized polymer-rare-earth complexes luminous material of amino phenolic bidentate schiff bases, it is characterised in that: will
The side group that amino phenolic bidentate schiff bases aglucon introduces polymer obtains amino phenolic bidentate Schiff then with rare-earth ion coordination
The ligand functionalized polymer of alkali-rare earth complex luminescent material；It is again that amino phenolic bidentate schiff bases is ligand functionalized poly-
Object-rare earth complex luminescent material is closed respectively with smaller ligand Phen or 2, and 2 '-bipyridyls, which supplement, to be coordinated, and ammonia is obtained
The ligand functionalized polymer of base phenolic bidentate schiff bases-rare earth ternary complexes luminescent material；The polymer is polysulfones PSF
Or polystyrene PS.
2. a kind of ligand functionalized polymer of amino phenolic bidentate schiff bases according to claim 1-rare earth compounding hair
Luminescent material, it is characterised in that: the resulting ligand functionalized polymer-rare earth complex of amino phenolic bidentate schiff bases shines
Material includes structure shown in Formulas I, the resulting ligand functionalized polymer of amino phenolic bidentate schiff bases-rare earth ternary complexes hair
Luminescent material includes structure shown in Formula II,
Formulas I Formula II,
M in formula3+For rare earth ion.
3. a kind of ligand functionalized polymer-rare earth compounding of amino phenolic bidentate schiff bases as described in claim 1 shines
The preparation method of material, characterized by the following steps:
0.40-0.50 g polymer is added in 50 mL solvents and sufficiently dissolves, adds 0.85-0.95 g couple by the first step
Chloromethylbenzene formaldehyde and 0.14-0.16 mL catalyst, are warming up to 60-80 DEG C, N2Isothermal reaction 10-12 h under atmosphere, reaction knot
Shu Houyong ethanol precipitation goes out polymer, and polymer dilute hydrochloric acid, ethyl alcohol and distilled water alternately wash, and is dried under vacuum to constant weight, i.e.,
Obtain the polymer-modified of side chain bonding benzaldehyde BA aglucon；
Side chain made from the 0.40-0.50g first step is bonded the polymer-modified of benzaldehyde BA aglucon or directly adopted by second step
It is dissolved in 50 mL solvents with 0.40-0.50g side chain bonding the polymer-modified of acetaldehyde AL group, adds 0.16-0.19 g
Amino-phenol, be warming up to 60-70 DEG C, N2Isothermal reaction 8-10h under atmosphere, goes out polymer with ethanol precipitation after reaction,
Polymer ethyl alcohol and distilled water alternately wash, and are dried under vacuum to constant weight to get side chain and are bonded with amino phenolic bidentate schiff bases
The functionalized polymer of aglucon；
The functionalized polymer that the side chain of 0.30-0.50g is bonded with amino phenolic bidentate schiff bases aglucon is dissolved in 50 by third step
In mL solvent, pH=7 ~ 8 are adjusted with NaOH solution, a certain amount of rare earth crystal is added, is warming up to 55-65 DEG C, isothermal reaction
8-10h goes out polymer with ethanol precipitation after reaction, and polymer washing is dry, obtains amino phenolic bidentate schiff bases aglucon function
It can fluidized polymer-rare earth complex luminescent material；
The functionalized polymer that 0.30-0.50g side chain is bonded with amino phenolic bidentate schiff bases aglucon is dissolved in 50 by the 4th step
In mL solvent, a certain amount of rare earth crystal is added, is warming up to 55-65 DEG C, isothermal reaction 4-6 h adds small molecule and matches
Body, constant temperature the reaction was continued 8-10 h go out polymer with ethanol precipitation after reaction, and polymer washing is dry to get amino phenols
The ligand functionalized polymer of type bidentate schiff bases-rare earth ternary complexes luminescent material.
The material 4. the ligand functionalized polymer-rare earth compounding of amino phenolic bidentate schiff bases according to claim 3 shines
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. the ligand functionalized polymer-rare earth compounding of amino phenolic bidentate schiff bases according to claim 3 or 4 shines
The preparation method of material, it is characterised in that: amino-phenol described in second step is o-aminophenol OAP or m-aminophenol
MAP。
The material 6. the ligand functionalized polymer-rare earth compounding of amino phenolic bidentate schiff bases according to claim 5 shines
The preparation method of material, it is characterised in that: rare earth crystal described in third step and the 4th step is terbium trichloride crystal TbCl3·
6H2O or europium chloride crystal EuCl3·6H2O；The amount of the substance of schiff bases aglucon and rare earth ion in functionalized polymer it
Than for 3:1.
The material 7. the ligand functionalized polymer-rare earth compounding of amino phenolic bidentate schiff bases according to claim 6 shines
The preparation method of material, it is characterised in that: smaller ligand described in the 4th step is Phen Phen or 2,2 '-bipyridyls
Bipy；The ratio between amount of substance of smaller ligand and rare earth ion is 1:1.
The material 8. the ligand functionalized polymer-rare earth compounding of amino phenolic bidentate schiff bases according to claim 7 shines
The preparation method of material, it is characterised in that: first, second and third and four solvent described in step be dimethyl sulfoxide DMSO, dimethyl second
Any one in amide DMAC or dimethylformamide DMF.
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