CN101367826A - Linking type Eu3+ organic conjunction, its copolymer red luminescent material and method of preparing the same - Google Patents
Linking type Eu3+ organic conjunction, its copolymer red luminescent material and method of preparing the same Download PDFInfo
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- CN101367826A CN101367826A CNA2008102003051A CN200810200305A CN101367826A CN 101367826 A CN101367826 A CN 101367826A CN A2008102003051 A CNA2008102003051 A CN A2008102003051A CN 200810200305 A CN200810200305 A CN 200810200305A CN 101367826 A CN101367826 A CN 101367826A
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Abstract
The present invention relates to red light-emitting bonded europium (III) polymer material and a preparation method thereof. The polymer is prepared by the radical polymerization of organic bonded europium (III) complex and polymer monomer undergo radical polymerization, which can be used in the light-emitting and display fields. The processing and filming properties of the produced light-emitting rear earth complex-polymer composite material are improved, the production cost is reduced, and the present invention has actual significance in broadening the application range of the light-emitting rear earth complex-polymer composite material. The light-emitting material is characterized by good solubility and filming property, simple preparation technique and little equipment investment. The light-emitting material can be used as anti-counterfeiting material, red fluorescent decorative material, fluorescent ink and so on.
Description
Technical field
The present invention relates to a kind of bonding type Eu
3+Organic coordination compound, its copolymer red luminescent material and preparation method thereof.
Technical background
Rare earth organic complex has unique fluorescence properties such as spectral range is wide, the fluorescence spectrum peak is narrow, fluorescence lifetime is long, the Stokes displacement is long, is widely used in luminous and the demonstration field.Make luminescent rare earth complexes-polymer composites, processing, film forming properties to improve it reduce production costs, and widen its range of application.The preparation method of rare earth polymer luminescent material is divided into two kinds: doping method and bonding method.The doping method preparation method is simple and practical, but because structural difference, and it is poor to be prone to consistency between rare earth compounding and polymeric matrix, and phenomenon such as occur being separated and fluorescence is inhomogeneous.Bonding method is bonded in rare earth compounding on polymer lateral chain or the main chain with the chemical bond mode, make stable performance, easily machine-shaping, and can be made into luminescent materials such as uniform thin film, for the rare earth polymer functional materials that obtains wide content of rare earth, high transmission rate provides possibility, but preparation technology's more complicated.
Summary of the invention
One of purpose of the present invention is to provide a kind of bonding type Eu
3+Organic coordination compound.
Two of purpose of the present invention is to provide a kind of bonding type Eu
3+The copolymer red luminescent material of organic coordination compound, it is good that this luminescent material has solvability, and film forming properties is good, luminous efficiency height, good stability, and the low characteristics of cost.
Three of purpose of the present invention is to provide the preparation method of this red fluorescence material.
For achieving the above object, reactions steps of the present invention and reaction mechanism are:
1. the organic ligand 2-allyl group-1 that has two keys, 3-diphenylpropane-1 (ADBM) synthetic:
2. the Eu that has two keys
3+Synthesizing of organic coordination compound
3. the reaction mechanism of multipolymer: by Eu with two keys
3+Organic coordination compound and polymer monomer prepare by free radicals copolymerization reaction.
According to above-mentioned reaction mechanism, the present invention adopts following technical scheme:
A kind of bonding type Eu
3+Organic coordination compound is characterized in that the structural formula of this title complex is:
A. two (2-allyl group-1,3-diphenylpropane-1) (diphenylpropane-1,3-dione(DPPO)) (1, the 10-o-phenanthroline) closes europium (III) quaternary coordination compound, i.e. Eu (ADBM)
2(DBM) (phen), be specially:
B. (2-allyl group-1,3-diphenylpropane-1) two (diphenylpropane-1,3-dione(DPPO)s) (1, the 10-o-phenanthroline) close europium (III) quaternary coordination compound, and promptly Eu (ADBM) (DBM)
2(phen), be specially:
A kind ofly prepare above-mentioned bonding type Eu
3+The method of organic coordination compound is characterized in that the concrete steps of this method are:
1. organic ligand 2-allyl group-1,3-diphenylpropane-1 ADBM's is synthetic: with the K of DBM (diphenylpropane-1,3-dione(DPPO)) and catalyst levels
2CO
3And Bu
4NBr is dissolved in the toluene, induction stirring under nitrogen protection, backflow 2-6 hour, add allyl bromide 98 then under condition of ice bath, reaction is 8-16 hour under the room temperature, and reaction finishes, remove solvent, extracted with diethyl ether, washing, remove ether, get light yellow solid, use the dehydrated alcohol recrystallization, 40 ℃ of vacuum-dryings get white needle-like crystals, be 2-allyl group-1, the 3-diphenylpropane-1; Wherein the mol ratio of DBM and allyl bromide 98 is: 1:1.1～1:1.6;
2.EuCl
3Add the ethanolic soln of gained ADBM among the step a, the ethanolic soln and 1 of DBM, the ethanolic soln of 10-o-phenanthroline in the aqueous solution; EuCl wherein
3, ADBM, DBM and 1, the mol ratio of 10-o-phenanthroline is 1:1～2:1～2:1; Regulator solution pH6-7,40-60 ℃ of reaction 8-12 hour filtered, leave standstill treat that it separates out after, washing, vacuum-drying obtains bonding type Eu
3+Organic coordination compound.
A kind of bonding type Eu
3+The copolymer red luminescent material of organic coordination compound is by above-mentioned bonding type Eu
3+Organic coordination compound and polymer monomer prepare by free radicals copolymerization reaction, it is characterized in that described polymer monomer is: vinylbenzene or methyl methacrylate; Described bonding type Eu
3+The mol ratio of organic coordination compound and polymer monomer is: 1:200～1:20000.
A kind ofly prepare above-mentioned bonding type Eu
3+The preparation method of the copolymer red luminescent material of organic coordination compound is characterized in that the concrete steps of this method are: with bonding type Eu
3+Organic coordination compound and polymer monomer vinylbenzene or methyl methacrylate are by 1:(200～20000) mol ratio be dissolved in the acetone, ultrasonic concussion is uniformly dispersed europium complex, at N
2In the atmosphere, 40～80 ℃, add initiator A IBN, reacted 10～20 hours; Reaction product ethanol redeposition; Vacuum-drying is 24 hours under 40～60 ℃ condition, gets granular disintegration, is bonding type Eu
3+The copolymer red luminescent material of organic coordination compound.
The bonding type Eu of the present invention's preparation
3+In the copolymer red luminescent material of organic coordination compound along with Eu
3+The minimizing of organic coordination compound content, the color of multipolymer shoals gradually, by light yellow to water white transparency.This material is soluble in common low boiling point solvent and N such as chloroform, acetone, methylene dichloride, and N-dimethyl formyl ammonium, the solvent that the methyl-sulphoxide isopolarity is big can also be dissolved in toluene under the condition of heating a little.And solution is placed a couple of days and muddiness do not occurred, is easy to film forming.The electron absorption stave is bright, this copolymer material does not obviously absorb at visible region, and intensive, wide uv-absorbing are all arranged at the ultraviolet region of 230～380nm, this absorption wide-band is made up of 2～3 eclipsed absorption peaks, wherein near the absorption peak 236nm is similar to the absorption peak of PMMA, corresponding to n → π of MMA segment C=O
*Transition absorbs, and is positioned near the absorption peak 264nm and the 344nm, and the absorption peak of complex ligand corresponding with it is close, can think it mainly is the ultraviolet absorption peak of beta-diketonate ligand.Fluorescence spectrum shows, along with Eu
3+The minimizing of organic coordination compound content in multipolymer, the excitation peak of multipolymer is moving to short wavelength's direction gradually, blue shift takes place, and its emission peak is identical with the emission peak of europium complex, is still 614nm.Under the exciting of UV-light, all send Eu
3+The arrowband red fluorescence of ion characteristic.Multipolymer is made solid film with spin-coating method, and its stereoscan photograph shows that europium complex is distributed to equably and is flakes among the PMMA, and material property is even, is easy to film forming, wire drawing.Can foretell that such polymer luminescent material is in luminous modification, anti-fake mark, there is application prospect in fields such as fluorescent ink.
Description of drawings
Fig. 1 is bonding type Eu
3+The structural formula of the copolymer red luminescent material of organic coordination compound.Wherein (a) is Eu (ADBM)
2(DBM) structural formula of the polymkeric substance that (phen) forms with methyl methacrylate (b) is Eu (ADBM)
2(DBM) structural formula of the polymkeric substance that (phen) forms with vinylbenzene, (c) be Eu (ADBM) (DBM)
2(phen) structural formula of the polymkeric substance that forms with methyl methacrylate, (d) be Eu (ADBM) (DBM)
2(phen) structural formula of the polymkeric substance that forms with vinylbenzene,
Fig. 2 is Eu (ADBM)
2(DBM) (phen) excitation spectrum under solid-state state and emmission spectrum (muting sensitivity, exciting slit is 3nm, the emission slit is 1.5nm).Wherein (a) is excitation spectrum; (b) be emmission spectrum.
Fig. 3 is PMMA-Eu (ADBM)
2(DBM) exciting and emmission spectrum (b1) 1:200 (highly sensitive excites and launch slit to be 3nm) (phen)).(muting sensitivity excites and launches slit to be 3nm, RF5300PC).
Fig. 4 PMMA-Eu (ADBM) 2 (DBM) is exciting and emmission spectrum under filminess (phen).(muting sensitivity excites and launches slit to be 3nm, RF5300PC).
Fig. 5 PS-Eu (ADBM) 2 (DBM) is exciting and emmission spectrum under the filminess (phen).
Fig. 6 is PMMA-Eu (ADBM)
2(DBM) (phen) SEM photo (the Eu title complex: PMMA=1:2000) of film.
Embodiment
Embodiment one: have the organic ligand 2-allyl group-1 of two keys, the synthetic method of 3-diphenylpropane-1 (ADBM) is as follows: 4.48g (0.02mol) DBM adds 11.04gK
2CO
3Powder, in the 80ml toluene solvant, 0.32gBu
4NBr makes catalyzer, induction stirring under nitrogen protection, backflow 4h; under condition of ice bath, add 1.73mL (0.02mol) allyl bromide 98 then; react 12h under the room temperature, reaction finishes, and revolves most of solvent; use extracted with diethyl ether; wash three times, revolve ether, get light yellow solid; use the dehydrated alcohol recrystallization, 40 ℃ of vacuum-dryings get white needle-like crystals.Get white needle-like crystals, productive rate 76%, 64 ℃ of mp.The structure of this compound is:
IR(KBr)/cm
-1：3451(v
OH)，3061(v
C-H)，1694，1670(v
C＝O)，1593，1579(δ
C-H，C
6H
5).
1H-NMR(CDCl
3，δ/ppm)：7.953(4H，d，
3J＝7.1Hz)，7.576(2H，t，t，
3J＝7.4Hz，
4J＝1.4Hz)，7.456(4H，t，d，
3J＝6.5Hz，
4J＝1.5Hz)，5.883(1H，m)，5.302(1H，t，
3J＝6.75Hz)，5.083(2H，q，
3J＝9.0，
4J＝1.1Hz)，2.881(2H，t，
3J＝6.6Hz)。
13C-NMR(CDCl
3，δ/ppm)：195.349，135.780，134.809，133.306，128.647，128.298，116.976，56.223，33.351。
Embodiment two: bonding type Eu
3+Organic coordination compound Eu (ADBM)
2(DBM) preparation (phen):
To 1.0mL 0.2molL
-1EuCl
3The 2-allyl group-1 that adds 0.4mmol in the ethanolic soln, 3-phenylbenzene-1, the acetone of 3-propanedione (ADBM): ethanol solution (V:V, 2:1), pH is 5～6 with 5%NaOH aqueous solution regulator solution, adds the ethanolic soln of 0.2mmol diphenylpropane-1,3-dione(DPPO) then in solution, and continuing with 5%NaOH regulator solution pH is 6～7, add 0.2mmol 1 at last, the ethanolic soln of 10-o-phenanthroline.Constant temperature water bath to 60 ℃, magnetic agitation 10h filters, leave standstill 36h after, separate out pale yellow crystals, filter crystal, with absolute ethanol washing 2 times, vacuum-drying 24h obtains Eu (ADBM) then
2(DBM) (phen) productive rate 85%.The structure of this compound is:
Ultimate analysis, EuC
63H
55O
6N
2(Eu (ADBM)
2(DBM) (Phen)), were:found (calc.): C 69.73 (69.94), N 2.61 (4.53), and H 5.23 (2.59), and C/N 26.72 (27.0).
1H-NMR (DMSO-d
6, δ/ppm): 9.07 (2H, phen), 8.46 (2H, phen), 7.97 (2H, phen), 7.76 (2H, phen), 7.62 (1H, H-C=C), 7.18 (2H, H-C=C), 6.80,6.67 (18H, phenyl ring), 6.39 (4H, C=CH
2), 5.64 (12H, phenyl ring), 3.01 (4H ,-CH
2-).
Embodiment three: bonding type Eu
3+Organic coordination compound Eu (ADBM) (DBM)
2(phen) preparation
To 1.0mL 0.2molL
-1EuCl
3The 2-allyl group-1 that adds 0.2mmol in the ethanolic soln, 3-phenylbenzene-1, the acetone of 3-propanedione (ADBM): ethanol solution (V:V, 2:1), pH is 5～6 with 5%NaOH aqueous solution regulator solution, adds the ethanolic soln of 0.4mmol diphenylpropane-1,3-dione(DPPO) then in solution, and continuing with 5%NaOH regulator solution pH is 6～7, add 0.2mmol 1 at last, the ethanolic soln of 10-o-phenanthroline.Constant temperature water bath to 60 ℃, magnetic agitation 10h filters, leave standstill 36h after, separate out pale yellow crystals, filter crystal, with absolute ethanol washing 2 times, vacuum-drying 24h obtains Eu (ADBM) (DBM) then
2(phen) productive rate 85%.The structure of this compound is:
Embodiment four: bonding type Eu
3+The preparation of the copolymer red luminescent material of organic coordination compound:
In the four-hole boiling flask that agitator, thermometer, reflux condensing tube and nitrogen conduit are housed, add europium (III) title complex Eu (ADBM) successively
2(DBM) (phen) 1mmol, methyl methacrylate 200mmol and 60ml acetone, ultrasonic concussion is uniformly dispersed europium (III) title complex.N
2In the atmosphere, under 60 ℃, add the acetone soln of initiator A IBN, constant temperature polymerization 10h, reaction product is with ethanol redeposition method purifying.Vacuum-drying 24h under 60 ℃ condition gets granular disintegration and is Eu
3+The mol ratio of organic coordination compound and methyl methacrylate is the polymer poly compound of 1:200.
Embodiment five: bonding type Eu
3+The preparation of the copolymer red luminescent material of organic coordination compound:
In the four-hole boiling flask that agitator, thermometer, reflux condensing tube and nitrogen conduit are housed, add europium (III) title complex Eu (ADBM) successively
2(DBM) (phen) 0.1mmol, methyl methacrylate 2000mmol and 60ml acetone, ultrasonic concussion is uniformly dispersed europium (III) title complex.N
2In the atmosphere, under 60 ℃, add the acetone soln of initiator A IBN, constant temperature polymerization 10h, reaction product is with ethanol redeposition method purifying.Vacuum-drying 24h under 60 ℃ condition gets water white granular disintegration and is Eu
3+The mol ratio of organic coordination compound and methyl methacrylate is the polymer poly compound of 1:20000.
Embodiment six: bonding type Eu
3+The preparation of the copolymer red luminescent material of organic coordination compound:
In the four-hole boiling flask that agitator, thermometer, reflux condensing tube and nitrogen conduit are housed, add europium (III) title complex Eu (ADBM) successively
2(DBM) (phen) 1mmol, vinylbenzene 200mmol and 60ml acetone, ultrasonic concussion is uniformly dispersed europium (III) title complex.N
2In the atmosphere, under 60 ℃, add the acetone soln of initiator A IBN, constant temperature polymerization 10h, reaction product is with ethanol redeposition method purifying.Vacuum-drying 24h under 60 ℃ condition gets granular disintegration and is Eu
3+Organic coordination compound and cinnamic mol ratio are the polymkeric substance of 1:200.
Embodiment seven: bonding type Eu
3+The preparation of the copolymer red luminescent material of organic coordination compound:
In the four-hole boiling flask that agitator, thermometer, reflux condensing tube and nitrogen conduit are housed, add europium (III) title complex Eu (ADBM) successively (DBM)
2(phen) 1mmol, methyl methacrylate 200mmol and 60ml acetone, ultrasonic concussion is uniformly dispersed europium (III) title complex.N
2In the atmosphere, under 60 ℃, add the acetone soln of initiator A IBN, constant temperature polymerization 10h, reaction product is with ethanol redeposition method purifying.Vacuum-drying 24h under 60 ℃ condition gets granular disintegration and is Eu
3+The mol ratio of organic coordination compound and methyl methacrylate is the polymkeric substance of 1:200.
Embodiment eight: bonding type Eu
3+The preparation of the copolymer red luminescent material of organic coordination compound:
In the four-hole boiling flask that agitator, thermometer, reflux condensing tube and nitrogen conduit are housed, add europium (III) title complex Eu (ADBM) successively (DBM)
2(phen) 0.1mmol, methyl methacrylate 2000mmol and 60ml acetone, ultrasonic concussion is uniformly dispersed europium (III) title complex.N
2In the atmosphere, under 60 ℃, add the acetone soln of initiator A IBN, constant temperature polymerization 10h, reaction product is with ethanol redeposition method purifying.Vacuum-drying 24h under 60 ℃ condition gets water white granular disintegration and is Eu
3+The mol ratio of organic coordination compound and methyl methacrylate is the polymer poly compound of 1:20000.
Embodiment nine: bonding type Eu
3+The preparation of the copolymer red luminescent material of organic coordination compound:
In the four-hole boiling flask that agitator, thermometer, reflux condensing tube and nitrogen conduit are housed, add europium (III) title complex Eu (ADBM) successively (DBM)
2(phen) 1mmol, vinylbenzene 200mmol and 60ml acetone, ultrasonic concussion is uniformly dispersed europium (III) title complex.N
2In the atmosphere, under 60 ℃, add the acetone soln of initiator A IBN, constant temperature polymerization 10h, reaction product is with ethanol redeposition method purifying.Vacuum-drying 24h under 60 ℃ condition gets granular disintegration and is Eu
3+Organic coordination compound and cinnamic mol ratio are the polymkeric substance of 1:200.
Claims (4)
1. bonding type Eu
3+Organic coordination compound is characterized in that the structural formula of this title complex is:
A. two (2-allyl group-1,3-diphenylpropane-1) (diphenylpropane-1,3-dione(DPPO)) (1, the 10-o-phenanthroline) closes europium (III) quaternary coordination compound, i.e. Eu (ADBM)
2(DBM) (phen), be specially:
B. (2-allyl group-1,3-diphenylpropane-1) two (diphenylpropane-1,3-dione(DPPO)s) (1, the 10-o-phenanthroline) close europium (III) quaternary coordination compound, and promptly Eu (ADBM) (DBM)
2(phen), be specially:
2. one kind prepares bonding type Eu according to claim 1
3+The method of organic coordination compound is characterized in that the concrete steps of this method are:
A. organic ligand 2-allyl group-1,3-diphenylpropane-1 ADBM's is synthetic: with the K of diphenylpropane-1,3-dione(DPPO) DBM and catalyst levels
2CO
3And Bu
4NBr is dissolved in the toluene, induction stirring under nitrogen protection, backflow 2-6 hour, add allyl bromide 98 then under condition of ice bath, reaction is 8-16 hour under the room temperature, and reaction finishes, remove solvent, extracted with diethyl ether, washing, remove ether, get light yellow solid, use the dehydrated alcohol recrystallization, 40 ℃ of vacuum-dryings get white needle-like crystals, be 2-allyl group-1, the 3-diphenylpropane-1; Wherein the mol ratio of DBM and allyl bromide 98 is: 1:1.1～1:1.6;
B. at EuCl
3Add the ethanolic soln of gained ADBM among the step a, the ethanolic soln and 1 of DBM, the ethanolic soln of 10-o-phenanthroline in the aqueous solution; EuCl wherein
3, ADBM, DBM and 1, the mol ratio of 10-o-phenanthroline is 1:1～2:1～2:1; Regulator solution pH6-7,40-60 ℃ of reaction 8-12 hour filtered, leave standstill treat that it separates out after, washing, vacuum-drying obtains bonding type Eu
3+Organic coordination compound.
3. bonding type Eu
3+The copolymer red luminescent material of organic coordination compound is by bonding type Eu according to claim 1
3+Organic coordination compound and polymer monomer prepare by free radicals copolymerization reaction, it is characterized in that described polymer monomer is: vinylbenzene or methyl methacrylate; Described bonding type Eu
3+The mol ratio of organic coordination compound and polymer monomer is: 1:200～1:20000.
4. one kind prepares bonding type Eu according to claim 3
3+The preparation method of the copolymer red luminescent material of organic coordination compound is characterized in that the concrete steps of this method are: with bonding type Eu
3+Organic coordination compound and polymer monomer vinylbenzene or methyl methacrylate are by 1:(200～20000) mol ratio be dissolved in the acetone, ultrasonic concussion is uniformly dispersed europium complex, at N
2In the atmosphere, 40 ℃～80 ℃, add initiator A IBN, reacted 10～20 hours; Reaction product ethanol redeposition; Vacuum-drying is 24 hours under 40 ℃～60 ℃ condition, gets granular disintegration, is bonding type Eu
3+The copolymer red luminescent material of organic coordination compound.
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| CN104497851A (en) * | 2015-01-17 | 2015-04-08 | 南昌航空大学 | Ultraviolet cured rare earth polymer material and preparation method thereof |
| CN105801745A (en) * | 2016-03-23 | 2016-07-27 | 太原理工大学 | Method for preparing bright-red-light-emitting iridium-europium thermometal polymer fluorescent powder |
| CN108586505A (en) * | 2018-07-03 | 2018-09-28 | 广州工程技术职业学院 | Europium complex red light material and preparation method based on two the first ligands of difference |
| CN109053777A (en) * | 2018-10-24 | 2018-12-21 | 杭州师范大学 | Luminescence generated by light rare earth compounding containing multiple polymerizable functional groups and preparation method thereof, application |
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