CN104193860A - Method for synthesizing polyhedron oligomerization silsesquioxane macromolecule composite luminescent material containing rare earth - Google Patents
Method for synthesizing polyhedron oligomerization silsesquioxane macromolecule composite luminescent material containing rare earth Download PDFInfo
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Abstract
The invention discloses a method for synthesizing a polyhedron oligomerization silsesquioxane macromolecule composite luminescent material containing rare earth. The method comprises the following steps: firstly, coordinating organic ligand modified polyhedron oligomerization silsesquioxane of a cage-shaped structure with a first ligand rare earth ion by using a sol-gel method according to the coordination chemistry principle, subsequently introducing polymethyl methacrylate as a second ligand which can be coordinated with the rare earth ion, and coordinating, thereby obtaining the polyhedron oligomerization silsesquioxane macromolecule composite luminescent material which is good in fluorescence property and thermal stability, contains rare earth and is of the cage-shaped structure. The synthesis method is gentle in experiment condition, the whole preparation system is easy to establish and simple and convenient to operate, the conditions are easy to control, and a product is stable in quality.
Description
Technical field
The invention belongs to RE polymer composite preparing technical field, be specifically related to a kind of synthetic method of the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth.
Background technology
Rare earth organic complex makes it send the characteristic fluorescence of rare earth ion by uv-absorbing and the intramolecular energy transfer of organic ligand, but the photo and thermal stability of rare earth organic complex itself is poor, due to quencher non-radiative multipole phonon decays as the stretching vibration of oh group brings around such as solvation waters, can reduce its emissive porwer, this has just limited its use range and effect greatly.Therefore, rare earth organic complex is doped in and in specific inorganic matrix, forms composite organic-inorganic material and can improve preferably this situation, and shown good application prospect in fields such as chemistry, biological, medicine and materials.
In recent years, polyhedral oligomeric silsesquioxane (hereinafter to be referred as POSS) is as the structural unit of compound with regular structure, can assemble the matrix material of the different special construction of preparation, and with the POSS of active function groups the possibility that POSS has brought polymerization and connected other materials that exists for due to active function groups, therefore can utilize POSS for presoma, by further chemical reaction, connect specific material and carry out modification.Utilize the coordination of organic ligand in rare earth ion and POSS base presoma, form chemically crosslinked, the POSS based composites that its organic ligand is changed to surname carries out structural characterization, thermal performance test and photoluminescence performance research.Infrared spectroscopic study result shows, rare-earth salts and POSS base presoma, by coordinate bond, interaction has occurred.Heat is analyzed and researched and is shown, rare earth/POSS based composites is compared thermostability with pure rare earth title complex and is improved.Fluorescence spectrum shows, this matrix material thing has the characteristic fluorescence performance of rare earth ion, is that a class has rare earth high polymer functional materials special construction and application potential.These provide important evidence for developing POSS modified RE polymer composite.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth, first will utilize coordination chemistry principle that the polyhedral oligomeric silsesquioxane of the cage structure through organic ligand modification is passed through to method and the first ligand rare earth ion coordination of collosol and gel, and then introduce and can as Ligands, carry out coordination with the polymethylmethacrylate (hereinafter to be referred as PMMA) of rare-earth ion coordination, finally obtain having the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material of the cage structure containing rare earth of good fluorescence property and thermostability.
A synthetic method that contains the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material of rare earth, is characterized in that specifically comprising the steps:
(1), the configuration of rare earth nitrate ethanolic soln
Rare earth nitrate is dissolved in ethanol, obtains rare earth nitrate ethanolic soln, its concentration is preferably 1mmol/L;
Described rare earth nitrate is Tb (NO
3)
3or Eu (NO
3)
3;
(2), the preparation of the polyhedral oligomeric silsesquioxane presoma of the cage structure of organic ligand modification
The polyhedral oligomeric silsesquioxane of cage structure is dissolved in organic solvent, then add silane coupling agent, then under nitrogen atmosphere, controlling temperature is 65 ℃ and reacts 3h, then add organic ligand, continue reaction 6h, the reaction solution rotary evaporation of gained, obtains the polyhedral oligomeric silsesquioxane presoma that yellow oily liquid is the cage structure of organic ligand modification;
Described organic solvent is N-N-dimethyl formamide or tetrahydrofuran (THF), and its consumption is in polyhedral oligomeric silsesquioxane: the ratio that organic solvent is 1mol:15-20ml is calculated;
The polyhedral oligomeric silsesquioxane of described cage structure is the mono amino polyhedral oligomeric silsesquioxane of cage structure or the sulfydryl polyhedral oligomeric silsesquioxane of cage structure;
Described silane coupling agent is 4,4-methylene-bis (phenylcarbimide) or the silica-based propyl isocyanate of triethoxy;
Described organic ligand is methyl ethyl diketone or Whitfield's ointment;
The polyhedral oligomeric silsesquioxane of above-mentioned cage structure used: silane coupling agent: the amount of organic ligand, calculate in molar ratio, i.e. the polyhedral oligomeric silsesquioxane of cage structure: silane coupling agent: organic ligand is 1:2:1;
(3), the coordination of the first ligand rare earth ion
The polyhedral oligomeric silsesquioxane presoma of the cage structure of prepared organic ligand modification in step (2) is dissolved in N-N-solvent dimethylformamide, then with the speed of 2-8ml/min, add the rare earth nitrate ethanolic soln of step (1) gained, be preferably 5ml/min, then add concentration of volume percent be 37% hydrochloric acid or add tetraethoxy simultaneously and hydrochloric acid that concentration of volume percent is 37% with facilitation of hydrolysis, then under agitation condition, react 6h, the reaction solution of the binary matrix material that obtains containing rare earth ion;
The amount of above-mentioned rare earth nitrate ethanolic soln used, in rare earth nitrate: the ratio that the mol ratio of the polyhedral oligomeric silsesquioxane presoma of the cage structure of organic ligand modification is 1:3 is calculated;
The consumption of the hydrochloric acid that above-mentioned N-N-dimethyl formamide, tetraethoxy and concentration of volume percent used are 37%, in N-N-dimethyl formamide: tetraethoxy: the ratio that the hydrochloric acid that concentration of volume percent is 37% is 15-20ml:0-2ml:0.2ml is calculated;
(4), the coordination of Ligands polymethylmethacrylate
In the reaction solution of the binary matrix material that contains rare earth ion of step (3) gained, add polymethyl methacrylate, then control temperature and be 65 ℃ and react 12h, suction filtration, with ethanol repetitive scrubbing, obtain solid sample powder, after vacuum-drying, finally obtain the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth at 80 ℃;
The add-on of above-mentioned polymethyl methacrylate, in the binary matrix material that contains rare earth ion: the ratio that the mol ratio of polymethyl methacrylate is 1:1 is calculated.
Beneficial effect of the present invention
The synthetic method of a kind of polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth of the present invention, by covalent linkage, organic and inorganic component is fitted together, thereby overcome the shortcoming of small molecules luminescent material mechanicalness and stability deficiency, improved the luminescent properties of pure rare earth organic complex, finally the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material fluorescence lifetime containing rare earth of gained is long, luminous quantum efficiency is high and have higher thermostability.
Further, the synthetic method of a kind of polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth of the present invention, its synthesis technique is simple, and whole preparation system easily builds, and easy and simple to handle, condition is easily controlled, and product processing facilitates simple and direct.
Further, the synthetic method of a kind of polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth of the present invention, reaction conditions is gentle, and without using any additive etc., therefore, this synthetic method has the feature of economy, cost cheapness.
Accompanying drawing explanation
The mono amino polyhedral oligomeric silsesquioxane presoma of the cage structure of the organic ligand modification of Fig. 1, embodiment 1 step (2) gained is the infrared spectrogram of ACAC-POSS;
The polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb of Fig. 2, embodiment 1 gained is Tb (ACAC-POSS)
3pMMA and pure methyl ethyl diketone terbium are Tb (ACAC)
3thermogravimetric curve;
The binary matrix material that contains rare earth Tb ion of Fig. 3, embodiment 1 step (3) gained is Tb (ACAC-POSS)
3and the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb of the final gained of step (4) is Tb (ACAC-POSS)
3the exciting light spectrogram of PMMA;
The binary matrix material that contains rare earth Tb ion of Fig. 4, embodiment 1 step (3) gained is Tb (ACAC-POSS)
3and the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb of the final gained of step (4) is Tb (ACAC-POSS)
3the utilizing emitted light spectrogram of PMMA.
Embodiment
Below by embodiment, also the present invention is further described by reference to the accompanying drawings, but protection scope of the present invention is not limited to these embodiment.
Utilize structure, thermostability, the luminescent properties of the inventive method products therefrom can adopt respectively infrared absorption spectrum (FT-IR), thermogravimetric analysis (TGA), fluorescence spectrum (PL) etc. to characterize.
Raw material used in various embodiments of the present invention, is commercially available.
embodiment 1
A synthetic method that contains the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material of rare earth, is characterized in that specifically comprising the steps:
(1), the configuration of rare earth Terbium trinitrate ethanolic soln
1.87g terbium sesquioxide is put into beaker, add 20ml concentrated nitric acid and 5ml hydrogen peroxide, to the whole dissolvings of terbium sesquioxide, be then heated to 60 ℃ and react 1h, after the reaction solution evaporate to dryness of gained, obtain solid nitric acid terbium;
The amount of terbium sesquioxide, nitric acid and hydrogen peroxide that above-mentioned reaction is used, in terbium sesquioxide: concentrated nitric acid: the ratio that hydrogen peroxide is 1g:10.7ml:2.7ml is calculated;
The solid nitric acid terbium of gained is dissolved in dehydrated alcohol, and obtaining concentration is 1mmol/L rare earth Terbium trinitrate ethanolic soln;
(2), the preparation of the mono amino polyhedral oligomeric silsesquioxane presoma of the cage structure of organic ligand modification
By 0.874g(1mmol) the mono amino polyhedral oligomeric silsesquioxane (POSS) of cage structure is dissolved in 20ml tetrahydrofuran solvent, then add 0.22g(1mmol) silane coupling agent, then back flow reaction 3h under nitrogen atmosphere, then add 0.05g(0.5mmol) organic ligand methyl ethyl diketone (ACAC), continue reaction 6h, the reaction solution rotary evaporation of gained, obtaining the mono amino polyhedral oligomeric silsesquioxane presoma that yellow oily liquid is the cage structure of organic ligand modification is ACAC-POSS;
The mono amino polyhedral oligomeric silsesquioxane of above-mentioned cage structure used: silane coupling agent: the amount of organic ligand methyl ethyl diketone is calculated in molar ratio, is the mono amino polyhedral oligomeric silsesquioxane of cage structure: silane coupling agent: organic ligand methyl ethyl diketone is 1:2:1;
Described silane coupling agent is 4,4-methylene-bis (phenylcarbimide);
(3), the coordination of the first ligand rare earth ion
By 1.14(0.5mmol) the mono amino polyhedral oligomeric silsesquioxane presoma of the cage structure of the organic ligand modification of gained is that ACAC-POSS is dissolved in N-N-dimethyl formamide (DMF) solvent of 20ml in step (2), then controlling drop rate is that 2ml/min dropwise adds 3.3ml(0.33mmol) concentration of step (1) gained is 1mmol/L Terbium trinitrate ethanolic soln, dropwise, the aqueous hydrochloric acid that the concentration of volume percent that adds 0.5ml is 37% carrys out facilitation of hydrolysis, then under agitation condition, react 6h, the binary matrix material that obtains containing rare earth Tb ion is Tb (ACAC-POSS)
3reaction solution,
The amount of above-mentioned Terbium trinitrate ethanolic soln used, in Terbium trinitrate: the ratio that the mol ratio of the mono amino polyhedral oligomeric silsesquioxane presoma of the cage structure of organic ligand modification is 1:3 is calculated;
(4), the coordination of Ligands polymethyl methacrylate
To 1.20g(1mmol) the binary matrix material that contains rare earth Tb ion of step (3) gained is Tb (ACAC-POSS)
3reaction solution in add 0.1g(0.5mmol) polymethyl methacrylate (be called for short PMMA), then control temperature and be 65 ℃ and react 12h, the reaction solution of gained removes desolventizing through rotary evaporation, filter, washing, the dry polyhedral oligomeric silsesquioxane based high molecular composite luminescent material finally obtaining containing rare earth Tb is Tb (ACAC-POSS)
3pMMA;
The add-on of above-mentioned polymethyl methacrylate is Tb (ACAC-POSS) by the binary matrix material that contains rare earth terbium ion
3: the ratio that the mol ratio of polymethyl methacrylate is 1:1 is calculated.
Adopt SPECTRUM 100 type infrared absorption spectrometers (U.S. Perkin Elmer) to measure the structure of the mono amino polyhedral oligomeric silsesquioxane precursor A CAC-POSS of the cage structure of the organic ligand modification of above-mentioned steps (2) gained, the infrared spectra of gained as shown in Figure 1, as can be seen from Figure 1 the characteristic peak of the mono amino polyhedral oligomeric silsesquioxane of organic ligand methyl ethyl diketone and cage structure all can manifest, and has shown that thus the mono amino polyhedral oligomeric silsesquioxane of cage structure is by the successful modification of organic ligand methyl ethyl diketone;
Adopt Pyris 1 TGA thermal-analysis instrumentation (U.S. Perkin Elmer 10 K/min, N
2) to the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb of above-mentioned gained, be Tb (ACAC-POSS)
3the thermal characteristics of PMMA is measured, with pure methyl ethyl diketone terbium be Tb (ACAC)
3contrast, the thermogravimetric curve figure of gained as shown in Figure 2, the Tb in Fig. 2 (ACAC-POSS)
3pMMA represents that the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb is Tb (ACAC-POSS)
3pMMA, Tb (ACAC)
3represent that pure methyl ethyl diketone terbium is Tb title complex (ACAC)
3, as can be seen from Figure 2 the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb is Tb (ACAC-POSS)
3pMMA is Tb (ACAC) than pure methyl ethyl diketone terbium
3temperature of initial decomposition want high, decomposition curve is also more slow, has shown that thus the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb is Tb (ACAC-POSS)
3pMMA is Tb (ACAC) than pure methyl ethyl diketone terbium
3thermostability to get well;
Adopting RF-5301 type steady-state fluorescence spectrograph (Japanese Shimadzu company) is Tb (ACAC-POSS) to the binary matrix material that contains rare earth Tb ion in the reaction solution of above-mentioned steps (3) gained
3and the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb of the final gained of step (4) is Tb (ACAC-POSS)
3the excitation spectrum of PMMA is measured, the exciting light spectrogram of gained as shown in Figure 3, the Tb in figure (ACAC-POSS)
3represent that the binary matrix material that contains rare earth Tb ion is Tb (ACAC-POSS)
3, Tb (ACAC-POSS)
3the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material that PMMA is expressed as containing rare earth Tb is Tb (ACAC-POSS)
3pMMA, as can be seen from Figure 3 the binary matrix material that contains rare earth Tb ion of step (3) gained is Tb (ACAC-POSS)
3and the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb of the final gained of step (4) is Tb (ACAC-POSS)
3the maximum excitation wavelength of PMMA is all positioned near 353nm, has shown that thus the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb of final gained is Tb (ACAC-POSS)
3pMMA meets the characteristic emission of Tb ion.
Adopting RF-5301 type steady-state fluorescence spectrograph (Japanese Shimadzu company) is Tb (ACAC-POSS) to the binary matrix material that contains rare earth Tb ion in the reaction solution of above-mentioned steps (3) gained
3and the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb of the final gained of step (4) is Tb (ACAC-POSS)
3the emmission spectrum of PMMA is measured, the utilizing emitted light spectrogram of gained as shown in Figure 4, the Tb in figure (ACAC-POSS)
3represent that the binary matrix material that contains rare earth Tb ion is Tb (ACAC-POSS)
3, Tb (ACAC-POSS)
3the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material that PMMA is expressed as containing rare earth Tb is Tb (ACAC-POSS)
3pMMA, as can be seen from Figure 4 the binary matrix material that contains rare earth Tb ion of step (3) gained is Tb (ACAC-POSS)
3and the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb of the final gained of step (4) is Tb (ACAC-POSS)
3all there is the characteristic emission cutting edge of a knife or a sword of Tb ion in PMMA, and the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb of the final gained of step (4) is Tb (ACAC-POSS)
3the luminous intensity of PMMA is higher, has shown that thus the introducing of polymethylmethacrylate is Tb (ACAC-POSS) to the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb of final gained
3pMMA luminous has promoter action.
embodiment 2
A synthetic method that contains the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material of rare earth, specifically comprises the steps:
(1), the configuration of rare earth nitrate terbium ethanolic soln, with embodiment 1
(2), the preparation of the mono amino polyhedral oligomeric silsesquioxane presoma of the cage structure of organic ligand modification
By 0.874g(1mmol) the mono amino polyhedral oligomeric silsesquioxane (POSS) of cage structure is dissolved into the N of 15ml, in dinethylformamide (DMF) solvent, then adding 20ml concentration is the silane coupling agent (0.2g of 10mg/ml, tetrahydrofuran solution 1mmol), then under nitrogen atmosphere, controlling temperature is 65 ℃ of reaction 3h, then add 0.05g(0.5mmol) organic ligand methyl ethyl diketone (ACAC), continue reaction 6h, the reaction solution rotary evaporation of gained, obtaining the mono amino polyhedral oligomeric silsesquioxane presoma that yellow oily liquid is the cage structure of organic ligand modification is ACAC-POSS,
The mono amino polyhedral oligomeric silsesquioxane of above-mentioned cage structure used: silane coupling agent: the amount of organic ligand methyl ethyl diketone is calculated in molar ratio, is the mono amino polyhedral oligomeric silsesquioxane of cage structure: silane coupling agent: organic ligand methyl ethyl diketone is 1:2:1;
Described silane coupling agent is TEPIC;
(3), the coordination of the first ligand rare earth ion
By 1.074g(1mmol) the mono amino polyhedral oligomeric silsesquioxane presoma of the cage structure of the organic ligand modification of gained is that ACAC-POSS is dissolved in N-N-dimethyl formamide (DMF) solvent of 15ml in step (2), then controlling drop rate is that 2ml/min dropwise adds 3.3ml(0.3mmol) concentration of step (1) gained is 1mmol/L rare earth Terbium trinitrate ethanolic soln, dropwise, then add successively the aqueous hydrochloric acid that the tetraethoxy (TEOS) of 0.2ml and the concentration of volume percent of 0.2ml are 37% to carry out facilitation of hydrolysis, then under agitation condition, react 6h, the binary matrix material that obtains containing rare earth Tb ion is Tb (ACAC-POSS)
3reaction solution,
The amount of above-mentioned Terbium trinitrate ethanolic soln used, in Terbium trinitrate: the ratio that the mol ratio of the mono amino polyhedral oligomeric silsesquioxane presoma of the cage structure of organic ligand modification is 1:3 is calculated;
(4), the coordination of Ligands polymethyl methacrylate
To 1.14g(1mmol) the binary matrix material that contains rare earth Tb ion of step (3) gained is Tb (ACAC-POSS)
3reaction solution in add 0.1g(0.5mmol) polymethyl methacrylate, then control temperature and be 65 ℃ and react 12h, the reaction solution of gained is through suction filtration, dry at 80 ℃ after dehydrated alcohol repetitive scrubbing, the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material finally obtaining containing rare earth Tb is Tb (ACAC-POSS)
3pMMA;
The add-on of above-mentioned polymethyl methacrylate, in the binary matrix material that contains rare earth Tb ion: the ratio that the mol ratio of polymethyl methacrylate is 1:1 is calculated.
Adopt the structure that SPECTRUM 100 type infrared absorption spectrometers (U.S. Perkin Elmer) are ACAC-POSS to the mono amino polyhedral oligomeric silsesquioxane presoma of the cage structure of the organic ligand modification of above-mentioned steps (2) gained to measure, the characteristic peak of the mono amino polyhedral oligomeric silsesquioxane of result organic ligand methyl ethyl diketone and cage structure all can manifest, and has shown that thus the mono amino polyhedral oligomeric silsesquioxane of cage structure is by the successful modification of organic ligand methyl ethyl diketone;
Adopt Pyris 1 TGA thermal-analysis instrumentation (U.S. Perkin Elmer 10 K/min, N
2) to the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb of above-mentioned gained, be Tb (ACAC-POSS)
3the thermal characteristics of PMMA is measured, and with pure methyl ethyl diketone terbium, is Tb (ACAC)
3for contrast, result shows that the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb is Tb (ACAC-POSS)
3pMMA is Tb (ACAC) than pure methyl ethyl diketone terbium
3temperature of initial decomposition want high, decomposition curve is also more slow, has shown that thus the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb is Tb (ACAC-POSS)
3pMMA is Tb (ACAC) than pure methyl ethyl diketone terbium
3thermostability to get well;
Adopting Shimadzu RF-5301 type steady-state fluorescence spectrograph is Tb (ACAC-POSS) to the binary matrix material that contains rare earth Tb ion in the reaction solution of above-mentioned steps (3) gained
3and the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb of the final gained of step (4) is Tb (ACAC-POSS)
3the luminescent properties of PMMA is measured, and result shows that the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Tb is Tb (ACAC-POSS)
3the intensity at the ternary characteristic emission peak of PMMA is all Tb (ACAC-POSS) than the binary matrix material that contains rare earth Tb ion
3the intensity of binary feature emission peak want high, shown that thus the introducing of polymetylmethacrylate is Tb (ACAC-POSS) to the binary matrix material that contains rare earth Tb ion
3there is sensibilized.
embodiment 3
A synthetic method that contains the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material of rare earth, specifically comprises the steps:
(1), rare earth Eu (NO
3)
3the configuration of ethanolic soln
1.75g europium sesquioxide is put into beaker, add 10ml nitric acid, to the whole dissolvings of europium sesquioxide, be then heated to 60 ℃ and react 1h, after the processing of the reaction solution of gained through stirring evaporate to dryness, obtain solid nitric acid europium;
Above-mentioned reaction europium sesquioxide used, the amount of nitric acid, in europium sesquioxide: nitric acid: the ratio that hydrogen peroxide is 1g:10ml is calculated;
The solid nitric acid europium of gained is dissolved in dehydrated alcohol, and obtaining concentration is the rare earth Eu (NO3) of 0.1 mol/L
3ethanolic soln;
(2), the preparation of the sulfydryl polyhedral oligomeric silsesquioxane presoma of the cage structure of organic ligand modification
By 0.891g(1mmol) the sulfydryl polyhedral oligomeric silsesquioxane (POSS) of cage structure is dissolved into the N of 15ml, in dinethylformamide (DMF) solvent, then add 10ml(0.1g, the tetrahydrofuran solution of the silane coupling agent that 1mmol) concentration is 10mg/ml, then under nitrogen atmosphere, controlling temperature is 65 ℃ of reaction 3h, then add 0.05g(0.5mmol) organic ligand methyl ethyl diketone (ACAC), continue reaction 6h, the reaction solution rotary evaporation of gained, obtaining the sulfydryl polyhedral oligomeric silsesquioxane presoma that yellow oily liquid is the cage structure of organic ligand modification is ACAC-POSS,
The sulfydryl polyhedral oligomeric silsesquioxane of above-mentioned cage structure used: silane coupling agent: the amount of organic ligand methyl ethyl diketone is calculated in molar ratio, is the sulfydryl polyhedral oligomeric silsesquioxane of cage structure: silane coupling agent: organic ligand methyl ethyl diketone is 1:2:1;
Described silane coupling agent is the silica-based propyl isocyanate of triethoxy;
(3), the coordination of the first ligand rare earth ion
By 1.291g(1mmol) the sulfydryl polyhedral oligomeric silsesquioxane precursor A CAC-POSS of the cage structure of prepared organic ligand modification is dissolved in 15mlN-N-solvent dimethylformamide in step (2), the speed of then controlling drop rate and be 2ml/min dropwise adds 3.3mL(0.33mmol) concentration of step (1) the gained rare earth Eu (NO that is 0.1mol/L
3)
3ethanolic soln, dropwise, so add successively the aqueous hydrochloric acid that the tetraethoxy (TEOS) of 2ml and the concentration of volume percent of 0.2ml are 37% to carry out facilitation of hydrolysis, then under agitation condition, react 6h, the binary matrix material that obtains containing rare earth Eu ion is Eu (ACAC-POSS)
3reaction solution;
Above-mentioned rare earth Eu (NO used
3)
3the amount of ethanolic soln, by Eu (NO
3)
3: the ratio that the mol ratio of the sulfydryl polyhedral oligomeric silsesquioxane presoma of the cage structure of organic ligand modification is 1:3 is calculated;
(4), the coordination of Ligands polymethyl methacrylate
To 1.31g(1mmol) the binary matrix material Eu (ACAC-POSS) that contains rare earth Eu ion of step (3) gained
3reaction solution in add 0.2g(1mmol) polymethyl methacrylate, then control temperature and be 65 ℃ and react 12h, the reaction solution of gained is through suction filtration, dry at 80 ℃ after dehydrated alcohol repetitive scrubbing, the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material finally obtaining containing rare earth Eu is Eu (ACAC-POSS)
3pMMA;
The add-on of above-mentioned polymethyl methacrylate, in the binary matrix material that contains rare earth Eu ion: the ratio that the mol ratio of polymethyl methacrylate is 1:1 is calculated.
Adopt the structure that SPECTRUM 100 type infrared absorption spectrometers (U.S. Perkin Elmer) are ACAC-POSS to the sulfydryl polyhedral oligomeric silsesquioxane presoma of the cage structure of the organic ligand modification of above-mentioned steps (2) gained to measure, the characteristic peak of the sulfydryl polyhedral oligomeric silsesquioxane of result organic ligand methyl ethyl diketone and cage structure all can manifest, and has shown that thus cage structure polyhedral oligomeric silsesquioxane is by the successful modification of organic ligand methyl ethyl diketone;
Adopt Pyris 1 TGA thermal-analysis instrumentation (U.S. Perkin Elmer 10 K/min, N
2) to the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Eu of above-mentioned gained, be Eu (ACAC-POSS)
3the thermostability of PMMA is measured, and with pure methyl ethyl diketone europium complex, is Eu (ACAC)
3in contrast, result shows that the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Eu is Eu (ACAC-POSS)
3pMMA is Eu (ACAC) than pure methyl ethyl diketone europium
3temperature of initial decomposition want high, decomposition curve is also more slow, has shown that thus the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Eu is Eu (ACAC-POSS)
3pMMA is Eu (ACAC) than pure methyl ethyl diketone europium
3thermostability to get well;
Adopting Shimadzu RF-5301 type steady-state fluorescence spectrograph is Eu (ACAC-POSS) to the binary matrix material that contains rare earth Eu ion in the reaction solution of above-mentioned steps (3) gained
3and the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Eu of the final gained of step (4) is Eu (ACAC-POSS)
3the luminescent properties of PMMA is measured, and result shows that the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Eu of the final gained of step (4) is Eu (ACAC-POSS)
3the intensity at the ternary characteristic emission peak of PMMA is all Eu (ACAC-POSS) than the binary matrix material that contains rare earth Eu ion of step (3) gained
3the intensity of binary feature emission peak want high, shown that thus the introducing of polymethylmethacrylate is Eu (ACAC-POSS) to the binary matrix material that contains rare earth Eu ion
3there is sensibilized.
embodiment 4
A synthetic method that contains the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material of rare earth, specifically comprises the steps:
(1), rare earth Eu (NO
3)
3the configuration of ethanolic soln
1.75g europium sesquioxide is put into beaker, add 10ml nitric acid, to the whole dissolvings of europium sesquioxide, be then heated to 60 ℃ and react 1h, after the processing of the reaction solution of gained through stirring evaporate to dryness, obtain solid nitric acid europium;
Above-mentioned reaction europium sesquioxide used, the amount of nitric acid, in europium sesquioxide: nitric acid: the ratio that hydrogen peroxide is 1g:10ml is calculated;
The solid nitric acid europium of gained is dissolved in dehydrated alcohol, and obtaining concentration is the rare earth Eu (NO of 0.1mol/L
3)
3ethanolic soln;
(2), the preparation of the mono amino polyhedral oligomeric silsesquioxane presoma of the cage structure of organic ligand modification
By 0.874g(1mmol) the mono amino polyhedral oligomeric silsesquioxane of cage structure is dissolved into the N of 15ml, in dinethylformamide solvent, then add 20ml(0.2g, the tetrahydrofuran solution of the silane coupling agent that 0.2mmol) concentration is 10mg/ml, then under nitrogen atmosphere, controlling temperature is 65 ℃ of reaction 3h, then the Whitfield's ointment that adds 1mmol, continue reaction 6h, the reaction solution rotary evaporation of gained, obtaining the cage structure polyhedral oligomeric silsesquioxane presoma that yellow oily liquid is organic ligand modification is Sal-POSS;
The mono amino polyhedral oligomeric silsesquioxane of above-mentioned cage structure used: silane coupling agent: the salicylic amount of organic ligand is calculated in molar ratio, is the mono amino polyhedral oligomeric silsesquioxane of cage structure: silane coupling agent: organic ligand Whitfield's ointment is 1:2:1;
Described silane coupling agent is the silica-based propyl isocyanate of triethoxy;
(3), the coordination of the first ligand rare earth ion
By 1.074g(1mmol) the mono amino polyhedral oligomeric silsesquioxane presoma Sal-POSS of the cage structure of prepared organic ligand modification is dissolved in the N-N-solvent dimethylformamide of 15ml in step (2), then controlling drop rate is that 2ml/min dropwise adds 3.3mL(0.33mmol) concentration of step (1) the gained rare earth Eu (NO that is 0.1mol/L
3)
3ethanolic soln, dropwises, and adding 0.2ml concentration of volume percent is that 37% aqueous hydrochloric acid carrys out facilitation of hydrolysis, then under agitation condition, reacts 6h, and the binary matrix material that obtains containing rare earth Eu ion is Eu (Sal-POSS)
3reaction solution;
Above-mentioned rare earth Eu (NO used
3)
3the amount of ethanolic soln, by Eu (NO
3)
3: the ratio that the mol ratio of the cage structure polyhedral oligomeric silsesquioxane presoma of organic ligand modification is 1:3 is calculated;
(4), the coordination of Ligands polymethyl methacrylate
To 1.14g(1mmol) the binary matrix material Eu (Sal-POSS) that contains rare earth Eu ion of step (3) gained
3reaction solution in add 0.2g(1mmol) polymethyl methacrylate, then control temperature and be 65 ℃ and react 12h, the reaction solution of gained is through suction filtration, after dry at 80 ℃ after dehydrated alcohol repetitive scrubbing, the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material finally obtaining containing rare earth Eu is Eu (Sal-POSS)
3pMMA;
The add-on of above-mentioned polymethyl methacrylate, in the binary matrix material that contains rare earth Eu ion: the ratio that the mol ratio of polymethyl methacrylate is 1:1 is calculated.
Adopt the structure that SPECTRUM 100 type infrared absorption spectrometers (U.S. Perkin Elmer) spectrometer is Sal-POSS to the mono amino polyhedral oligomeric silsesquioxane presoma of the cage structure of the organic ligand modification of above-mentioned steps (2) gained to measure, the characteristic peak of the mono amino polyhedral oligomeric silsesquioxane of result organic ligand Whitfield's ointment and cage structure all can manifest, and has shown that thus the mono amino polyhedral oligomeric silsesquioxane of cage structure is by the successful modification of organic ligand Whitfield's ointment;
Adopt Pyris 1 TGA thermal-analysis instrumentation (U.S. Perkin Elmer 10 K/min, N
2) to the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Eu of above-mentioned gained, be Eu (Sal-POSS)
3the thermostability of PMMA is measured, and with pure Whitfield's ointment europium complex, is Eu (sal)
3for contrast, result shows that the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Eu is Eu (Sal-POSS)
3pMMA is Eu (sal) than pure Whitfield's ointment europium
3temperature of initial decomposition want high, decomposition curve is also more slow, has shown that thus the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Eu is Eu (Sal-POSS)
3pMMA is Eu (sal) than pure Whitfield's ointment europium
3thermostability to get well;
Adopting Shimadzu RF-5301 type steady-state fluorescence spectrograph is Eu (Sal-POSS) to the binary matrix material that contains rare earth Eu ion in the reaction solution of step (3) gained
3and the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Eu of the final gained of step (4) is Eu (Sal-POSS)
3the luminescent properties of PMMA is measured, and result shows that the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth Eu of the final gained of step (4) is Eu (Sal-POSS)
3the binary matrix material that the intensity at the ternary characteristic emission peak of PMMA all contains rare earth Eu ion than step (3) is Eu (Sal-POSS)
3the intensity of binary feature emission peak want high, shown that thus the introducing of Ligands polymetylmethacrylate is Eu (Sal-POSS) to the binary matrix material that contains rare earth Eu ion
3there is sensibilized.
In sum, the synthetic method of a kind of polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth of the present invention, the material of gained has good photo and thermal stability and the novel easy easy control of synthetic method route.
The above-mentioned description to embodiment is can understand and apply the invention for the ease of those skilled in the art.Person skilled in the art obviously can easily make various improvement to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement of making for the present invention and modification all should be within protection scope of the present invention.
Claims (4)
1. contain a synthetic method for the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material of rare earth, it is characterized in that specifically comprising the steps:
(1), the configuration of rare earth nitrate ethanolic soln
Rare earth nitrate is dissolved in ethanol, obtains rare earth nitrate ethanolic soln;
Described rare earth nitrate is Tb (NO
3)
3or Eu (NO
3)
3;
(2), the preparation of the polyhedral oligomeric silsesquioxane presoma of the cage structure of organic ligand modification
The polyhedral oligomeric silsesquioxane of cage structure is dissolved in organic solvent, then add silane coupling agent, then under nitrogen atmosphere, controlling temperature is 65 ℃ and reacts 3h, then add organic ligand, continue reaction 6h, the reaction solution rotary evaporation of gained, obtains the polyhedral oligomeric silsesquioxane presoma that yellow oily liquid is the cage structure of organic ligand modification;
The polyhedral oligomeric silsesquioxane of described cage structure is the mono amino polyhedral oligomeric silsesquioxane of cage structure or the sulfydryl polyhedral oligomeric silsesquioxane of cage structure;
Described silane coupling agent is 4,4-methylene-bis (phenylcarbimide) or the silica-based propyl isocyanate of triethoxy;
Described organic ligand is methyl ethyl diketone or Whitfield's ointment;
The polyhedral oligomeric silsesquioxane of above-mentioned cage structure used: silane coupling agent: the amount of organic ligand, calculate in molar ratio, i.e. the polyhedral oligomeric silsesquioxane of cage structure: silane coupling agent: organic ligand is 1:2:1;
(3), the coordination of the first ligand rare earth ion
The polyhedral oligomeric silsesquioxane presoma of the cage structure of prepared organic ligand modification in step (2) is dissolved in N-N-solvent dimethylformamide, then the rare earth nitrate ethanolic soln that adds step (1) gained, then add concentration of volume percent be 37% hydrochloric acid or add tetraethoxy simultaneously and hydrochloric acid that concentration of volume percent is 37% with facilitation of hydrolysis, then under agitation condition, react 6h, the reaction solution of the binary matrix material that obtains containing rare earth ion;
The amount of above-mentioned rare earth nitrate ethanolic soln used, in rare earth nitrate: the ratio that the mol ratio of the polyhedral oligomeric silsesquioxane presoma of the cage structure of organic ligand modification is 1:3 is calculated;
(4), the coordination of Ligands polymethyl methacrylate
In the reaction solution of the binary matrix material that contains rare earth ion of step (3) gained, add polymethyl methacrylate, then control temperature and be 65 ℃ and react 12h, suction filtration, with ethanol repetitive scrubbing, obtain solid sample powder, after vacuum-drying, finally obtain the polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth at 80 ℃;
The add-on of above-mentioned polymethyl methacrylate, in the binary matrix material that contains rare earth ion: the ratio that the mol ratio of polymethyl methacrylate is 1:1 is calculated.
2. the synthetic method of a kind of polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth as claimed in claim 1, is characterized in that:
In step (1), the concentration of the rare earth nitrate ethanolic soln of gained is 1mol/L;
Organic solvent described in step (2) is N-N-dimethyl formamide or tetrahydrofuran (THF), and its consumption is in the polyhedral oligomeric silsesquioxane of cage structure: the ratio that organic solvent is 1mol:15-20ml is calculated;
The consumption of the hydrochloric acid that in step (3), N-N-dimethyl formamide, tetraethoxy and concentration of volume percent used is 37%, in N-N-dimethyl formamide: tetraethoxy: the ratio that the hydrochloric acid that concentration of volume percent is 37% is 15-20ml:0-2ml:0.2ml is calculated.
3. the synthetic method of a kind of polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth as claimed in claim 1, is characterized in that in step (3), adding the speed of rare earth nitrate ethanolic soln is 2-8ml/min.
4. the synthetic method of a kind of polyhedral oligomeric silsesquioxane based high molecular composite luminescent material containing rare earth as claimed in claim 3, is characterized in that in step (3), adding the speed of rare earth nitrate ethanolic soln is 5ml/min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105969335A (en) * | 2016-05-12 | 2016-09-28 | 上海理工大学 | Preparation method of POSS (Polyhedral Oligomeric Silsesquioxane)-based/rare earth ion liquid fluorescent soft material |
| CN106467706A (en) * | 2016-09-21 | 2017-03-01 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of environmentally friendly organic inorganic hybridization preservative protective film |
| CN109370571A (en) * | 2018-11-16 | 2019-02-22 | 上海理工大学 | A kind of POSS base poly ion liquid/rare-earth luminescent material and preparation method thereof |
| CN116462974A (en) * | 2023-04-29 | 2023-07-21 | 先锋导电材料工业（苏州）有限公司 | Heat-conducting silica gel sheet and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220266A (en) * | 2008-01-24 | 2008-07-16 | 同济大学 | Process for producing beta-diketone functionalization rare earth mesoporous hybridisation luminescent material |
| CN101429430A (en) * | 2008-12-11 | 2009-05-13 | 同济大学 | Process for producing sulfhydryl functionalized rare earth-macromolecule composite luminescent material |
| CN102942921A (en) * | 2012-11-30 | 2013-02-27 | 上海理工大学 | Preparation method of polymer functional rare-earth/organic/inorganic mesoporous fluorescent material |
| CN103012464A (en) * | 2013-01-11 | 2013-04-03 | 河北工业大学 | Novel cage type low polysilsesquioxane and rare earth light-emitting material thereof |
-
2014
- 2014-08-15 CN CN201410403041.5A patent/CN104193860B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220266A (en) * | 2008-01-24 | 2008-07-16 | 同济大学 | Process for producing beta-diketone functionalization rare earth mesoporous hybridisation luminescent material |
| CN101429430A (en) * | 2008-12-11 | 2009-05-13 | 同济大学 | Process for producing sulfhydryl functionalized rare earth-macromolecule composite luminescent material |
| CN102942921A (en) * | 2012-11-30 | 2013-02-27 | 上海理工大学 | Preparation method of polymer functional rare-earth/organic/inorganic mesoporous fluorescent material |
| CN103012464A (en) * | 2013-01-11 | 2013-04-03 | 河北工业大学 | Novel cage type low polysilsesquioxane and rare earth light-emitting material thereof |
Non-Patent Citations (2)
| Title |
|---|
| BINGYAN，XIAO-FEI QIAO: "Rare-earth/Inorganic/Organic Polymeric Hybrid Materials:Molecular Assembly,Regular Microstructure and Photoluminescence"", 《J.PHYS.CHEM.B》 * |
| KAI SHENG ET AL.: ""Near-white light luminescent material from Eu(III) complexes encapsulated in silica/PMMA matrices"", 《J MATER SCI:MATER ELECTRON》 * |
Cited By (7)
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|---|---|---|---|---|
| CN105969335A (en) * | 2016-05-12 | 2016-09-28 | 上海理工大学 | Preparation method of POSS (Polyhedral Oligomeric Silsesquioxane)-based/rare earth ion liquid fluorescent soft material |
| CN105969335B (en) * | 2016-05-12 | 2019-01-15 | 上海理工大学 | A kind of preparation method of POSS base/rare earth ion liquid fluorescence soft material |
| CN106467706A (en) * | 2016-09-21 | 2017-03-01 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of environmentally friendly organic inorganic hybridization preservative protective film |
| CN109370571A (en) * | 2018-11-16 | 2019-02-22 | 上海理工大学 | A kind of POSS base poly ion liquid/rare-earth luminescent material and preparation method thereof |
| CN109370571B (en) * | 2018-11-16 | 2022-04-05 | 上海理工大学 | POSS-based polyion liquid/rare earth fluorescent material and preparation method thereof |
| CN116462974A (en) * | 2023-04-29 | 2023-07-21 | 先锋导电材料工业（苏州）有限公司 | Heat-conducting silica gel sheet and preparation method thereof |
| CN116462974B (en) * | 2023-04-29 | 2023-09-29 | 先锋导电材料工业（苏州）有限公司 | Heat-conducting silica gel sheet and preparation method thereof |
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