CN102875750A - Preparation method of polymer-rare earth ion luminous micelles - Google Patents
Preparation method of polymer-rare earth ion luminous micelles Download PDFInfo
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- CN102875750A CN102875750A CN2012102603362A CN201210260336A CN102875750A CN 102875750 A CN102875750 A CN 102875750A CN 2012102603362 A CN2012102603362 A CN 2012102603362A CN 201210260336 A CN201210260336 A CN 201210260336A CN 102875750 A CN102875750 A CN 102875750A
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Abstract
The invention belongs to the technical field of polymer-metal functional composite material preparation, and relates to a preparation method of polymer-rare earth ion luminous micelles. An amphipathy two-block AB type copolymer or a three-block ABA type copolymer is selected to serve as a first ligand, and molecular weight of each block and total molecular weight of a segmented copolymer are respectively determined through a testing method of nuclear magnetic resonance spectra and a gel permeation chromatography; oxide of rare earth element is contained in a beaker, excessive hydrochloric acid is added for stirring until the oxide is completely dissolved; then the beaker is placed in a water bath until liquid in the beaker is dried to obtain trivalent rare earth chloride crystals; and a polymer solution and a rare earth ion solution are mixed in proportion, organic conjugation micromolecules are added to serve as a second ligand, the polymer solution, the rare earth ion solution and the organic conjugation micromolecules are evenly mixed to be placed in a reaction vessel, and condensation backflow is carried out at a constant temperature to enable the copolymer and rare earth ions to conduct a complexing reaction to obtain the polymer-rare earth ion luminous micelles. The preparation method is simple in process, reliable in principle, strong in operability and stable in product structure.
Description
Technical field:
The invention belongs to polymer-metal functional composite material preparing technical field, the preparation method who relates to a kind of polymkeric substance-rare earth luminescence micella, rare earth ion and segmented copolymer are reacted, prepare polymkeric substance with specific morphology and performance-rare earth functional composite material by the polarity section in the cross-linked with rare earth segmented copolymer.
Background technology:
Rare earth element has more and more important application owing to its special electronic structure has very excellent light, electricity, magnetic property and catalytic performance etc. at numerous areas such as large screen display, mechanical metallurgy and petrochemical compleies.China is rare earth resources big country, and rare earth resources reserves and output are all at the forefront in the world, yet, because the protection wretched insufficiency for rare earth resources, the fundamental research of rare earth and application and development lag behind the other technologies field, cause the Rare-earth Industry chain unsound, and utility value embodies not exclusively; Development at industry technologies such as politics, economy, environment and safety lags behind the other technologies application.Therefore, strengthen the research of rare earth and use very urgently, Rare-earth Industry is changed into by simple primary products output the full-scale development of rare earth and related products is used, forms complete research and development and industrial system, the status of lifting Rare-earth Industry chain.
At present, in a series of peculiar property of rare earth element, luminescent properties has unique status and since rare earth ion itself for ultraviolet absorption a little less than, the fluorescence intensity that causes the single rare earth ion also a little less than; Cause fluorescent quenching owing to reunite in the part of rare earth ion again, all limited largely rare earth ion application in practice.A kind of effective solution with rare earth ion with have particular functional group's " part " material and carry out complexing, by " antenna effect ", obtain the complex compound that fluorescence strengthens.Because rare earth organic molecule complexes stability and processing forming are all poor, polymkeric substance-rare earth composite material has been subject to increasing attention.The preparation method of typical polymkeric substance-rare earth composite material can be divided into following two classes: (1) doping method: these class methods are directly to be doped in the rare earth small molecules in the polymeric matrix, there is not chemical b ` between the two, therefore belong to physical doping, this preparation method is simple to operate, but shortcoming is also comparatively obvious, rare earth small molecules and polymeric matrix consistency are relatively poor, cause easily being separated, simultaneously, the micromolecular inhomogeneous dispersion of rare earth very easily causes fluorescent quenching, these drawbacks limit the application of doping type polymkeric substance-rare earth composite material; (2) bonding method: by the method for coordination or polymerization, rare earth ion is connected on the polymer chain by the chemical combination key, this method can be divided into again following two kinds of paths: the one, and first coordination post polymerization namely makes first rare earth ion and monomer generation coordination reaction, then trigger monomer polymerization; The 2nd, coordination after the first polymerization, macromolecule ligand and rare earth ion that soon polymerization obtains carry out complex reaction, because the existence of coordinate bond, bonding method has overcome rare earth ion and the poor problem of macromolecule matrix consistency, while is along with the development of polymerization technique, especially RAFT is polymerized to birth and the fast development of the activity/controllable polymerization method of representative, for the preparation of bonding type polymkeric substance-rare earth functional composite material provides more alternative part.So bonding method just is used for theoretical investigation and actual production more and more, becomes the important channel of preparation polymkeric substance-rare earth functional composite material.But, because the complexing group is distributed on the whole polymer molecular chain, cause the polymkeric substance of gained-rare earth complex product to be reunited, heat not melting, also be insoluble to solvent, thereby can't process.(the chemical journal such as Jin Lan, (2006) 64:357-362), and Li Zhaoye etc. (Colloid and Polymer Science (2010) 288:1041-1046) has introduced a kind of with the method for double-hydrophilic block polymer (DHBC) with the reaction induced formation polymer micelle of rare-earth ion coordination, but according to its published report, this method only limits in the alcoholic solvent system.End is got up, and exists lower column defects in the prior art: the one, rare earth ion can not be dispersed in the polymeric matrix, and cause their part to be reunited, this is the major cause of rare earth ion concentration cancellation; The 2nd, mostly existing preparation method is to carry out in water or alcoholic solvent, and the intervention of water molecules and hydroxyl is the major incentive of polymkeric substance-rare earth composite material fluorescent quenching; The 3rd, the polymkeric substance-rare earth composite material that obtains by prior art very easily settles from solvent because of the reunion of inducing of rare earth ion to polymkeric substance, form solid sediment, heat not melting and can not be in solvent again dissolving, the follow-up processing such as can't film; The 4th, the organic solvent of the polymkeric substance-rare earth composite material that obtains by prior art beyond alcohols is (such as N, dinethylformamide, tetrahydrofuran (THF) etc.) solvability in is limited, has restricted moulding and the processing of material, thereby has limited the application in practice of such matrix material.
Summary of the invention:
The object of the invention is to overcome the defective that prior art exists, seek to design the preparation method of a kind of polymkeric substance-rare earth luminescence micella functional composite material, can farthest avoid the fluorescent quenching of rare earth ion, overcome the reunion precipitation of polymkeric substance-rare earth composite material, improve its solvability in organic solvent, satisfy material requirement in the necessary machine-shaping when the functional devices such as luminous, the opto-electronic conversion of preparation.
To achieve these goals, realization technological process of the present invention is:
(1), at first select to have two amphipathic block AB type multipolymers or three block ABA type multipolymers are the first part, determine respectively each block molecular weight separately and the total molecular weight of segmented copolymer by the testing method of NMR (Nuclear Magnetic Resonance) spectrum (NMR) and gel permeation chromatography (GPC); One or more solvent mixtures in the derivative of tetrahydrofuran (THF), DMF, methyl ethyl diketone, dioxane, benzene and benzene are as solvent, and being mixed with volumetric molar concentration is the uniform polymers soln of 0.1mol/L;
(2), the oxide compound of rare earth element is contained in the beaker, add excessive hydrochloric acid, be stirred to solid and dissolve fully; Then beaker is placed 50 ℃ of water-baths until the beaker liquid evaporation is done, obtain the trivalent rare earth muriate crystal with crystal water; Select again with step (1) in identical solvent rare earth ion is mixed with volumetric molar concentration is the uniform rare-earth ion solution of 0.1mol/L;
(3), measuring respectively polymers soln mixes with the part by weight of rare-earth ion solution according to 0.5-5:1, adding the organic conjugate small molecules with light collection effect simultaneously is Ligands, the three is mixed in the reaction vessel that is placed on reflux, under 20-80 ℃ of constant temperature condensing reflux 2-12 hour, make segmented copolymer and trivalent rare earth ions carry out coordination reaction, obtain the polymkeric substance of rare earth coordination-rare earth luminescence micella.
Two block AB type multipolymers described in the step of the present invention (1) or three block ABA type multipolymers adopt the synthetic or commercially available prod of novel active/controllable free radical polymerization process that is polymerized to representative with RAFT, one of them segments A can form with the polymerization of vinyl monomer that rare earth ion carries out coordination reaction functional group by containing, and comprises vinylformic acid, acrylamide, vinyl alcohol, vinyl pyridine, vinyl pyrrolidone, vinyl ammonia and vinyl alkane ether; Segment B is by the non-polar monomer cell formation that does not contain coordinating group, comprises vinylbenzene, ethene, tetrafluoroethylene, 1-butylene and divinyl.
Trivalent rare earth ions described in the step of the present invention (2) is the Tricationic with lanthanon of photoluminescent property, comprises cerium ion (Ce
3+), praseodymium ion (Pr
3+), neodymium ion (Nd
3+), samarium ion (Sm
3+), europium ion (Eu
3+), terbium ion (Tb
3+), dysprosium ion (Dy
3+), holmium ion (Ho
3+), erbium ion (Er
3+), thulium ion (Tm
3+) and ytterbium ion (Yb
3+).
The organic conjugate small molecules part with light collection effect described in the step of the present invention (3) adds micella with rare earth ion, obtain the polymer micelle of luminous enhancing, organic conjugate small molecules part comprises phenanthroline, beta-diketon and derivative and inorganic phosphate and derivative.
The rare earth ion that the present invention relates to can be accepted multiple ligands, and ligancy is 6-12, carries out coordination reaction by the A section on rare earth ion and the polymer chain, and different segments are connected to form crosslinked micella nuclear; Simultaneously, the nonpolar B segment that does not have coordination functional group on the polymer chain keeps solvability, stretches the shell that consists of micella to solvent phase; Micella has solvability and the fluorescence property deposited phenomenon of not reuniting in organic solvent, have dispersiveness in solid macromolecule; Micella with preparation is prepared into the solid high-efficiency luminescent composite or is distributed to spike or sensing material in the organic solvent; Micella has film forming properties, and the composite membrane that obtains through the spin coating subsequent disposal has stable mechanical property and luminescent properties.
The present invention compared with prior art, its preparation technology is simple, principle is reliable, and is workable, product structure is stable, is widely used; Crosslinked A segment makes the rare earth ion Uniform Dispersion, the micella shell that is formed by nonpolar B segment simultaneously suppresses entering of water molecules and hydroxyl, avoids the intervention such as concentration quenching that the local reunion of rare earth ion causes and water molecules and hydroxyl and the relaxation quenching phenomenon that causes; The micella shell is to the organic solvent affinity, can stably be dispersed in the solution and do not reunite, and widens the range of application of polymkeric substance-rare earth functional composite material.
Description of drawings:
Fig. 1 is the coordination structure synoptic diagram of the polymkeric substance that the present invention relates to-europium ion micella.
Fig. 2 is the transmission electron microscope photo of the polymkeric substance that the present invention relates to-europium ion micella.
Fig. 3 is the polymkeric substance that the present invention relates to-europium ion micella (solid line) and the fluorescence emission spectrogram of Europium trichloride solution (dotted line) under the 345nm exciting light.
Fig. 4 is the fluorescence emission spectrogram of rete (solid line) under the 345nm exciting light after micellar solution of the present invention (dotted line) and the spin coating.
Embodiment:
Also further describe by reference to the accompanying drawings the present invention below by embodiment.
Embodiment 1:
Present embodiment adopts first the RAFT method to synthesize the vinylbenzene of AB type-b-vinylformic acid di-block copolymer: the molar ratio according to 500:5:1 is measured respectively styrene monomer 1.612g, chain-transfer agent (trithio ester C
16H
19O
2NS
3) 0.055g and Diisopropyl azodicarboxylate initiator 0.005g, adding the 5ml dioxane is solvent, insert in the round-bottomed flask above-mentioned materials and sealing, logical nitrogen reacted 10 hours in 60 ℃ of constant temperature oil baths after about 30 minutes, and reaction after finishing splashes in about 150ml ether reaction mixture to be settled out polymkeric substance and vacuum-drying; With polystyrene and the 1.44g Acrylic Acid Monomer with the chain-transfer agent end that obtains, 0.003g the Diisopropyl azodicarboxylate initiator mixes, take the 15ml dioxane as solvent, logical nitrogen reacted 6 hours in 80 ℃ of constant temperature oil baths after 30 minutes, after finishing, reaction with reaction solution 200ml ether sedimentation, obtains vinylbenzene-b-acrylic block copolymers; Determine that with NMR (Nuclear Magnetic Resonance) spectrum and gel permeation chromatography two sections molecular weight separately of polymkeric substance are: the polystyrene section is 3640g/mol, and polyacrylic acid section 10080g/mol, polymkeric substance total molecular weight are 13720g/mol; Get above-mentioned polymkeric substance 0.5g, take the DMF of 51ml as solvent, be mixed with the polymers soln that the acrylic acid units volumetric molar concentration is 0.1mol/L; The preparation of polymkeric substance-europium ion micella is the Europium trichloride solution 5ml of measuring respectively polymers soln 15ml and 0.1mol/L according to the mol ratio of acrylic acid units/europium ion 3:1, and the phenanthroline 0.099g of adding and Europium trichloride same molar is as Ligands; Three kinds of reactants are mixed the there-necked flask that places with condensation reflux unit, and reaction is 6 hours under 40 ℃ of constant temperature oil bath environment, namely obtains the solution that europium ion cooperates polymer micelle; Determine that by transmission electron microscope photo its pattern is spheroidal (Fig. 2), show that by fluorometric investigation the micella that obtains has good fluorescence property (Fig. 3).
Embodiment 2:
Present embodiment obtains the vinylbenzene of acrylic acid units volumetric molar concentration 0.1mol/L-b-acrylic block copolymers solution according to embodiment 1; The preparation of its polymkeric substance-terbium ion micella is the terbium chloride solution 5ml of measuring respectively polymers soln 5ml and 0.1mol/L according to the mol ratio of acrylic acid units/terbium ion 1:1, and the phenanthroline 0.099g of the amount of the identical mole with terbium chloride of adding is as Ligands; Three kinds of reactants are mixed the there-necked flask that places with condensation reflux unit, and reaction is 5 hours under 50 ℃ of constant temperature oil bath environment, namely obtains the solution of terbium ion ligand polymer micella.
Embodiment 3:
The synthetic of vinylbenzene-b-that present embodiment relates to (4-vinylpridine) segmented copolymer is to measure respectively styrene monomer 1.612g according to the ratio of 500:5:1, chain-transfer agent (trithio ester C
16H
19O
2NS
3) 0.055g and Diisopropyl azodicarboxylate initiator 0.005g, adding the 5ml dioxane is solvent, insert in the round-bottomed flask above reagent and sealing, logical nitrogen reacted 10 hours in 60 ℃ of constant temperature oil baths after about 30 minutes, and reaction after finishing splashes in about 150ml ether reaction mixture to be settled out polymkeric substance and vacuum-drying; With polystyrene and the 2.200g4-vinylpyridine monomers with the chain-transfer agent end that obtains, 0.003g Diisopropyl azodicarboxylate initiator mixes, and take the 10ml dioxane as solvent, logical nitrogen reacted 6 hours in 80 ℃ of constant temperature oil baths after 30 minutes; After finishing, reaction with mixed solution 200ml ether sedimentation, obtains vinylbenzene-b-(4-vinylpridine) segmented copolymer; Determine that with NMR (Nuclear Magnetic Resonance) spectrum and gel permeation chromatography two sections molecular weight separately of polymkeric substance are: the polystyrene section is 3640g/mol, and the P4VP section is 6300g/mol, and the polymkeric substance total molecular weight is 9940g/mol; Get above-mentioned polymkeric substance 0.500g, take the tetrahydrofuran (THF) of 30ml as solvent, being mixed with vinyl pyridine unit volumetric molar concentration is the polymers soln of 0.1mol/L; The preparation of polymkeric substance-terbium ion micella is the terbium chloride solution 5ml of measuring respectively polymers soln 5ml and 0.1mol/L according to the mol ratio of vinyl pyridine unit/terbium ion 1:1, and the bipyridine 0.078g of the amount of the identical mole with terbium chloride of adding is as Ligands; Three kinds of reactants are mixed the there-necked flask that places with condensation reflux unit, and reaction is 5 hours under 50 ℃ of constant temperature oil bath environment, namely obtains the solution of terbium ion ligand polymer micella.
Embodiment 4:
Present embodiment is pressed the solution of embodiment 1 preparation polymkeric substance-europium ion micella, take glass as substrate, uses sol evenning machine that gained solution is rotated and films, rotating speed is 2000 rev/mins, 30 seconds time length, the even film layer that obtains is stable, and fluorescence property still keeps well (Fig. 4).
Claims (5)
1. the preparation method of polymkeric substance-rare earth luminescence micella is characterized in that technological process is:
(1), at first select to have two amphipathic block AB type multipolymers or three block ABA type multipolymers are the first part, determine respectively each block molecular weight separately and the total molecular weight of segmented copolymer by the testing method of NMR (Nuclear Magnetic Resonance) spectrum and gel permeation chromatography; One or more solvent mixtures in the derivative of tetrahydrofuran (THF), DMF, methyl ethyl diketone, dioxane, benzene and benzene are as solvent, and being mixed with volumetric molar concentration is the uniform polymers soln of 0.1mol/L;
(2), the oxide compound of rare earth element is contained in the beaker, add excessive hydrochloric acid, be stirred to solid and dissolve fully; Then beaker is placed 50 ℃ of water-baths until the beaker liquid evaporation is done, obtain the trivalent rare earth muriate crystal with crystal water; Select again with step (1) in identical solvent rare earth ion is mixed with volumetric molar concentration is the uniform rare-earth ion solution of 0.1mol/L;
(3), measuring respectively polymers soln mixes with the part by weight of rare-earth ion solution according to 0.5-5:1, adding the organic conjugate small molecules with light collection effect simultaneously is Ligands, the three is mixed in the reaction vessel that is placed on reflux, under 20-80 ℃ of constant temperature condensing reflux 2-12 hour, make segmented copolymer and trivalent rare earth ions carry out coordination reaction, obtain the polymkeric substance of rare earth coordination-rare earth luminescence micella.
2. the preparation method of polymkeric substance-rare earth luminescence micella according to claim 1, it is characterized in that described two block AB type multipolymers or three block ABA type multipolymers adopt the synthetic or commercially available prod of novel active/controllable free radical polymerization process that is polymerized to representative with RAFT, one of them segments A can form with the polymerization of vinyl monomer that rare earth ion carries out coordination reaction functional group by containing, and comprises vinylformic acid, acrylamide, vinyl alcohol, vinyl pyridine, vinyl pyrrolidone, vinyl ammonia and vinyl alkane ether; Segment B is by the non-polar monomer cell formation that does not contain coordinating group, comprises vinylbenzene, ethene, tetrafluoroethylene, 1-butylene and divinyl.
3. the preparation method of polymkeric substance-rare earth luminescence micella according to claim 1 is characterized in that described trivalent rare earth ions is the Tricationic with lanthanon of photoluminescent property, comprises cerium ion (Ce
3+), praseodymium ion (Pr
3+), neodymium ion (Nd
3+), samarium ion (Sm
3+), europium ion (Eu
3+), terbium ion (Tb
3+), dysprosium ion (Dy
3+), holmium ion (Ho
3+), erbium ion (Er
3+), thulium ion (Tm
3+) and ytterbium ion (Yb
3+).
4. the preparation method of polymkeric substance-rare earth luminescence micella according to claim 1, it is characterized in that described organic conjugate small molecules part with light collection effect adds micella with rare earth ion, obtain the polymer micelle of luminous enhancing, organic conjugate small molecules part comprises phenanthroline, beta-diketon and derivative and inorganic phosphate and derivative.
5. the preparation method of polymkeric substance-rare earth luminescence micella according to claim 1, it is characterized in that the rare earth ion that relates to can accept multiple ligands, ligancy is 6-12, carries out coordination reaction by the A section on rare earth ion and the polymer chain, and different segments are connected to form crosslinked micella nuclear; Simultaneously, the nonpolar B segment that does not have coordination functional group on the polymer chain keeps solvability, stretches the shell that consists of micella to solvent phase; Micella has solvability and the fluorescence property deposited phenomenon of not reuniting in organic solvent, have dispersiveness in solid macromolecule; Micella with preparation is prepared into the solid high-efficiency luminescent composite or is distributed to spike or sensing material in the organic solvent; Micella has film forming properties, and the composite membrane that obtains through the spin coating subsequent disposal has stable mechanical property and luminescent properties.
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| CN103254337A (en) * | 2013-05-07 | 2013-08-21 | 常州大学 | Beta-diketone rare earth complex and preparation method thereof |
| CN105440230A (en) * | 2016-01-06 | 2016-03-30 | 青岛大学 | Organic rare-earth solid micelle and preparation method thereof, and method for improving photoelectric conversion efficiency of solar cell |
| CN108358957A (en) * | 2018-04-19 | 2018-08-03 | 青岛大学 | A kind of preparation method of the rare earth-high molecular nanometer sphere to emit white light |
| CN109206570A (en) * | 2017-06-30 | 2019-01-15 | 翁秋梅 | A kind of compliant physical split-phase supermolecule dynamic aggregation object and its application |
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| CN111040356A (en) * | 2019-12-25 | 2020-04-21 | 青岛大学 | Three-primary-color photoluminescence device and preparation method thereof |
| CN112206724A (en) * | 2020-09-30 | 2021-01-12 | 华中科技大学 | Rare earth supermolecule gel doped with chitosan or water-soluble derivative thereof, preparation and application thereof |
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| CN103254337A (en) * | 2013-05-07 | 2013-08-21 | 常州大学 | Beta-diketone rare earth complex and preparation method thereof |
| CN105440230A (en) * | 2016-01-06 | 2016-03-30 | 青岛大学 | Organic rare-earth solid micelle and preparation method thereof, and method for improving photoelectric conversion efficiency of solar cell |
| WO2017118015A1 (en) * | 2016-01-06 | 2017-07-13 | 青岛大学 | Organic rare-earth solid micelle and preparation method therefor, and method for improving photoelectric conversion efficiency of solar cell |
| US10604699B2 (en) | 2016-01-06 | 2020-03-31 | Qingdao University | Organic rare earth solid micelle, preparation method therefor, and method for increasing photoelectric conversion efficiency of solar battery |
| CN109206570A (en) * | 2017-06-30 | 2019-01-15 | 翁秋梅 | A kind of compliant physical split-phase supermolecule dynamic aggregation object and its application |
| CN108358957A (en) * | 2018-04-19 | 2018-08-03 | 青岛大学 | A kind of preparation method of the rare earth-high molecular nanometer sphere to emit white light |
| CN110564093A (en) * | 2019-08-27 | 2019-12-13 | 北京大学 | Adjustable fluorescent ion gel with multiple stimulus responsiveness |
| CN110564093B (en) * | 2019-08-27 | 2020-07-28 | 北京大学 | Adjustable fluorescent ion gel with multiple stimulus responsiveness |
| CN111040356A (en) * | 2019-12-25 | 2020-04-21 | 青岛大学 | Three-primary-color photoluminescence device and preparation method thereof |
| CN112206724A (en) * | 2020-09-30 | 2021-01-12 | 华中科技大学 | Rare earth supermolecule gel doped with chitosan or water-soluble derivative thereof, preparation and application thereof |
| CN113136001A (en) * | 2021-04-23 | 2021-07-20 | 中国科学院长春应用化学研究所 | Preparation method of ethylene-fluorostyrene copolymer |
| CN113136001B (en) * | 2021-04-23 | 2022-05-06 | 中国科学院长春应用化学研究所 | Preparation method of ethylene-fluorostyrene copolymer |
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