CN102212361A - Aromatic or aliphatic formic acid-rare earth complex molecular hybrid luminescent material and preparation method thereof - Google Patents
Aromatic or aliphatic formic acid-rare earth complex molecular hybrid luminescent material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an aromatic or aliphatic formic acid-rare earth complex molecular hybrid luminescent material and a preparation method thereof. The structure of the material is shown in the general formula (1), wherein R1 represents hydrogen atom or C1-10 alkyl; R2 represents aryl, aromatic ester, aromatic amine, aromatic imide, arylether, C1-10 alkyl, ether, amino, aliphatic amide, imide or ester group; M represents B, P, Si, Ti or Al; RE represents rare-earth metal such as Eu, Tb and Sm; and A represents the second ligand phenanthroline (phen) and bipyridine (bpy). The preparation method comprises the following steps: firstly, using the aromatic or aliphatic carboxylic acid monomer with alkene or cycloalkene type double bond and the organosilane monomer with mercapto group to perform alkene-mercapto addition and obtain an organosilane modified aromatic or aliphatic carboxylic acid product; and secondly, reacting with acid rare ions and the second ligand N,N ligand to generate the rare earth complex with the organosilane modified hydrolysable and condensable functional group, and using coupling agent and adopting the sol-gel method to prepare the rare earth hybrid luminescent material under the combined action of catalyst and initiator. The general formula (1) is as below.
Description
Technical field
The present invention relates to a kind of luminescent material, relate to a kind of fragrance or fatty formic acid rare earth compounding molecular hybrid luminescent materials and preparation method thereof of containing specifically.
Background technology
Along with science and technology development, the rare earth material of single character can not satisfy the needs that people live and produce, and Development of Materials trend is to have complementary functions in recent years, performance optimization.Can prepare the hybrid material of excellent performance by two or more function hydridization, performance complement and optimization.With respect to polymkeric substance, advantage such as inorganic materials has good light, heat and chemical heat stability, hardness is big and mechanical property is good.The rare earth compounding luminous intensity is big, monochromaticity good, and its internal quantum efficiency can reach 100%; But certain shortcoming is arranged also: relatively poor as light stability and thermostability.Therefore if with polymkeric substance and the compound synthetic hydridization matrix of inorganic materials, the stability of material will be improved greatly, resulting like this hybrid luminescent material has had both the advantage of organic and inorganic material, and the practicability that promotes rare-earth hybridized material is further developed.Though hybrid material is the compound of two or more materials, because the stronger reactive force of two alternate existence or formed interpenetrating(polymer)networks, the size of microcell is usually at Nano grade, sometimes or even the hydridization of molecular level, so works very well.In addition the character of hybrid material also be not only simply adding of being formed and, and usually show many other excellent properties.
Sol-gel method is because its building-up process is simple, and service temperature is suitable, is subjected to paying close attention to widely.Utilize sol-gel method that rare earth compounding is introduced in the various matrix, prepare inorganic/organic hybrid luminescent material, the gained material has concurrently organic and advantage inorganic materials, has good luminescent properties simultaneously again.In building-up process,, can carry out structure regulating, performance optimization to final material, thereby obtain high efficient luminous material by changing kind and the ratio and the preparation condition of presoma.Different according to reactive force between hybrid material middle-weight rare earths title complex and the matrix, can be divided into the first kind hybrid material (two is alternate with combinations such as weak bond such as hydrogen bonds) and the second class hybrid material (two-phase ask with strong bond such as covalent linkage etc. in conjunction with).In first kind hybrid material,, be difficult to suppress the active centre and be rare earth ion and produce bunch because there is more weak reactive force between the component, and the component skewness, hotchpotch is easily by elimination.The characteristics of the second class hybrid material are to have very strong reactive force between organic constituent and the inorganic component, and generally the form with covalent linkage links to each other.This class material is fixed with good effect for the luminescence center ionic, and component can be on molecular level uniform distribution, can avoid the reunion in active centre effectively.
We adopt the method for alkene mercapto addition, have synthesized fragrance or fatty formic acid compounds that a class has machine silane, and this compound mainly plays two effects, form matrix as its hydrolytie polycondensation of presoma, and it again with rare-earth ion coordination.Hydrolytie polycondensation forms network structure, has suppressed the polymerization of rare earth ion and by elimination, also shows one of very strong luminous reason even this also is a rare earth ion when low doping concentration very, and the network structure that forms makes to be separated and controls to nano-scale.We have at first synthesized fragrance or the aliphatic carboxylic acid monomer that contains alkene class or ring alkene double bond, again at free radical thermal initiation or light-initiated fragrance or the fatty formic acid compounds that generates organosilane down with the organosilane monomer generation alkene mercapto addition reaction that contains sulfydryl, with rare-earth ion coordination, perhaps add second part phenanthroline or the dipyridyl, the organosilane presoma hydrolytic condensation that has lower and upper rare earth compounding after stating coordination again at coupling agent has made with what the Si-C covalent linkage connected and has had a very strong luminous rare-earth hybridized material.The fragrance or the fatty formic acid compounds of institute's synthetic organosilane have two effects, as organosilane, can be as the presoma of sol gel reaction, and the presoma of this organic decoration forms network structure through hydrolysis condensation reaction; Because it has benzoic derivative, again can with rare-earth ion coordination, and come the sensitization rare earth luminescence by so-called antenna effect, also rare earth compounding is grafted in the mesoporous matrix.
On the angle of coordination chemistry, rare earth ion tends to the polygamy position, carboxyl is organic negative ion, satisfy charge balance as first part, and the adding of the second part phenanthroline or dipyridyl can be satisfied ligancy, can also reduce the polarity of title complex, improve volatile performance, improve the conductivity of rare earth compounding.The second suitable part can improve the carrier transport of coordination compound.Experimental result shows passes through the grafting of Si-C covalent linkage to the skeleton of hybrid material with organic ligand, can overcome the shortcoming that the traditional preparation process method is brought effectively.Doping content is improved, and the gained material homogeneity is better, and under bigger doping content, the quencher phenomenon does not take place.
Summary of the invention
Technical problem: the purpose of this invention is to provide a kind of fragrance or fatty formic acid rare earth compounding molecular hybrid luminescent materials and preparation method thereof, the molecular hybrid luminescent materials that this material is a kind of doping height, good film-forming property, luminous efficiency is high, possesses satisfactory stability, prepare easy, be convenient to the large-area display device of processing and preparing, and cost is lower.Preparation method of the present invention under gentle relatively reaction conditions, takes the method co-production rare earth class molecular hybrid luminescent materials of addition of alkene mercapto and collosol and gel, the productive rate height, and reactions steps is simple.
Technical scheme: fragrance or aliphatic carboxylic acid monomer that the present invention at first will contain alkene class or ring alkene double bond carry out the addition of alkene mercapto with the organosilane monomer that contains sulfydryl, obtain fragrance or aliphatic carboxylic acid product that organosilane is modified; Then with the rare earth ion and the second part N, the effect of N part generates the rare earth compounding contain organic hydride modified hydrolyzable condensation functional group, in the presence of coupling agent, under the acting in conjunction of catalyzer and initiator, sol-gel obtains rare-earth hybridized luminescent material.Rare-earth hybridized luminescent material provided by the invention can contain the rare earth compounding of organic hydride modified hydrolyzable condensation functional group and the ratio of coupling agent by change, and then the content of change rare earth compounding in hybrid material, wherein, the weight content of rare earth compounding is the 1-30% of the weight of hybrid material.About the fluorescence quantum efficiency 30%-75% of the hybrid luminescent materials that the present invention obtains.This luminescent material is good, the good film-forming property of good stability, solvability, long service life, luminous efficiency height not only, be convenient to the large-area display device of processing and preparing, and driving voltage is low, and cost is lower, and is significant to the flat panel display device that develops superior performance of future generation.
Fragrance provided by the invention or fatty formic acid rare earth compounding molecular hybrid luminescent materials are expressed as following general formula (1) compound:
General formula (1)
R wherein
1Expression hydrogen atom or contain the alkyl of 1～10 carbon atom, R
2Be aromatic base, aromatic ester, fragrant acid amides, fragrant imide, aryl oxide, the alkyl that contains 1～10 carbon atom, ether, amino, fats acid amides, imide or ester group; M represents B, P, Si, Ti or Al, and the RE of general formula (1) represents the metal-rare-earth metal, as: europium, terbium, samarium; A represents the second part N, and the N part can be phenanthroline and dipyridyl.
The preparation method of fragrance provided by the invention or fatty formic acid rare earth compounding molecular hybrid luminescent materials may further comprise the steps:
General formula (2)
General formula (3)
General formula (4) HS-R
1-SiX
3
(1). the organosilane monomer that contains sulfydryl of the fragrance that contains alkene class or ring alkene double bond of general formula (2) expression or aliphatic carboxylic acid monomer, general formula (4) expression is dissolved in the organic solvent, 0～100 ℃ is carried out the addition reaction of alkene mercapto in the presence of initiator, according to alkene mercapto addition mechanism
Obtain fragrance or aliphatic carboxylic acid product with the modification of general formula (3) expression organosilicon;
(2). with fragrance or the aliphatic carboxylic acid product monomer that the expression organosilicon of general formula (3) expression is modified, N, N part A, coupling agent is dissolved in organic solvent, and 30～100 ℃ are carried out the polymeric gel reaction in the presence of catalyzer, and drying obtains product;
R in its formula of (3) and the general formula (4)
1Expression hydrogen atom or contain the alkyl of 1～10 carbon atom, X is the group of can be hydrolyzed reaction and generation-OH; R in general formula (2) and the general formula (3)
2Be aromatic base, aromatic ester, fragrant acid amides, fragrant imide, aryl oxide, the alkyl that contains 1～10 carbon atom, ether, amino, fats acid amides, imide or ester group.
The consumption of step (1) reactant is, by the mole umber, with 1 part of the fragrance that contains alkene double bond of general formula (2) expression or aliphatic carboxylic acid monomer, with 1～10 part of the sulfydryl siloxanyl monomers of representing with formula (4), with 0.01～10 part of initiator, add 5～500 parts of non-polar organic solvents, 0～100 ℃ is carried out the addition reaction of alkene mercapto under logical nitrogen, the anhydrous condition, according to alkene mercapto addition mechanism, obtain fragrance or the aliphatic carboxylic acid product modified with general formula (3) expression organosilicon; The consumption of step (2) reactant is by the mole umber, with 1 part in the inorganic salt of rare earth, 3～10 parts of fragrance that the expression organosilicon of general formula (3) expression is modified or aliphatic carboxylic acid product monomers, the second part N, 1～10 part of N part A, 0～100 part of coupling agent, 1～100 part of catalyzer adds 5～500 parts of organic solvents, and 30～100 ℃ are carried out the polymeric gel reaction, 20～80 ℃ of dryings, obtain product then; R in its formula of (3) and the general formula (4)
1Expression hydrogen atom or contain the alkyl of 1～10 carbon atom, the middle R of general formula (2) and general formula (3)
2Be aromatic base, aromatic ester, fragrant acid amides, fragrant imide, aryl oxide, the alkyl that contains 1～10 carbon atom, ether, amino, fats acid amides, imide or ester group, X is the group of can be hydrolyzed reaction and generation-OH.
Be that described X is alkoxyl group, acyloxy or halogen.
The inorganic salt of described rare earth are the nitrate or the halide salts of rare earth; Described coupling agent is silane coupling agent, titanate coupling agent, aluminate coupling agent, bimetal coupling agent, phosphate coupling agent, boric acid ester coupler or chromium complex; Described catalyzer is one or more the mixture in water, mineral acid, mineral alkali, organic acid, the organic bases; Described initiator is azo class, peralcohol or benzil ketals; Described non-polar organic solvent is methylene dichloride, chloroform, tetrahydrofuran (THF), 1,2-ethylene dichloride, toluene or dimethylbenzene; Described organic solvent is ethanol, tetrahydrofuran (THF), acetone, acetonitrile, dimethyl sulfoxide (DMSO), N, the mixture of one or more in the adjacent acyl triamine of dinethylformamide or hexamethyl; The polymeric gel reaction times is 1～20 hour, and be 7～42 days time of drying.
Described silane coupling agent is a tetramethoxy-silicane, tetraethoxysilane, the acyloxy silane class, the ketoximinosilanes class, the aminosilane class, amide group silicane or different propenyloxy group class, described titanate coupling agent is a titanium isopropylate, tetrabutyl titanate or tetra-sodium type monoalkoxytitanates class, described bimetal coupling agent is aluminium titanium composite coupler or zirconium Al-system coupling agent, described catalyzer is a hydrogenchloride, nitric acid, sulfuric acid, sodium hydroxide, acetic acid, to biphenol, hexamethylenetetramine or quadrol or dibutyl tin laurate, described azo-initiator is a Diisopropyl azodicarboxylate, and described peralcohol initiator is a benzoyl peroxide.
Beneficial effect: of the present inventionly contain fragrance or fatty formic acid rare earth compounding molecular hybrid luminescent materials can be used as the electroluminescent flat panel display device.
Because the present invention is being incorporated into fragrance or fatty formic acid rare earth compounding unit on the organosilicon that can form inorganic network in the mode of covalent bonds under the condition of gentleness, in the transparency that has kept material and mechanical property, the ratio fragrant or fatty formic acid rare earth compounding monomer and coupling agent that contains the crosslinkable condensation by adjusting can obtain containing the higher molecular hybrid material of rare earth compounding content, can strengthen luminous efficient and stability.Make this luminescent material both have the rare earth compounding good luminescent characteristic, have concurrently organic again and excellent properties inorganic materials.By the solvent washing experiment, lithography experiments has confirmed the intermolecular crosslinking structure that formed; Infrared spectra,
1Signs such as H-NMR, heat analysis, ultimate analysis, prove the existence of this material middle-weight rare earths title complex and determined the relative content of inorganic component, and organic segment and the inorganic alternate covalent linkage that exists really, (stretching vibration peak of Si-O-Si is at 1085cm for this result and infrared spectrum analysis
-1Near) unanimity as a result; In addition, further characterized the structure and the form of material, found that material is the system of a homogeneous, do not occurred being separated by scanning electron microscope.By testing the room temperature fluorescence extinction curve of rare-earth hybridized luminescent material, confirm that the rare earth compounding hybrid material all is the one-level decay, have only a kind of luminescence center, further illustrate rare earth compounding in material, distributes very homogeneous, not gathering.Characterize by the thermal characteristics of heat analysis to material, testimonial material has excellent thermal characteristics (thermolysis is stabilized in about 400 ℃); Photoelectric properties to these materials are tested, ultra-violet absorption spectrum (Eu (NCM-Si)
3Near 280nm, Eu (NCM-Si)
3Phen is at 317nm, Eu (NCM-Si)
3Bpy is at the 309nm place, Tb (NCM-Si)
3Near 281nm, Tb (NCM-Si)
3Phen is at 314nm, Tb (NCM-Si)
3Bpy is at the 306nm place), emmission spectrum (Eu (NCM-Si)
3, Eu (NCM-Si)
3Phen, Eu (NCM-Si)
3The feature emission peak 580nm of europium, 593nm, 617nm have appearred in bpy; Tb (NCM-Si)
3, Tb (NCM-Si)
3Phen, Tb (NCM-Si)
3The emission of terbium feature has appearred in bpy
5D
4-
7F
j(j=3,4,5,6) transition, respectively at 622nm, 584nm, 544nm, 493nm), PL efficient is 35%～75%, proved that described rare earth compounding hybrid material has identical glow peak with corresponding small molecules rare earth compounding, the segment of the hydrolyzable condensation of introducing and different substituting groups do not influence the change of emission wavelength; The luminescent material that is used to make electroluminescent device with the method and the described monomer availability excellence of sol-gel is described.
Luminescent material good stability of the present invention, doping height, good film-forming property, luminous efficiency height, synthesis technique are simple, with low cost, for the consumption that reduces natural resources, alleviate raw-material short situation, the flat panel display device that develops superior performance of future generation is significant.
Description of drawings
Fig. 1 is the part luminescent material (Eu (NCM-Si) that the present invention relates to
3, Eu (NCM-Si)
3Phen, Eu (NCM-Si)
3Bpy, Tb (NCM-Si)
3, Tb (NCM-Si)
3Phen, Tb (NCM-Si)
3The concrete molecular structural formula of bpy.
Fig. 2 is the luminescent material that the contains europium complex (Eu (NCM-Si) that the present invention relates to
3, Eu (NCM-Si)
3Phen, Eu (NCM-Si)
3The uv-visible absorption spectroscopy figure of bpy.
Fig. 3 is the luminescent material Tb (NCM-Si) that contains terbium coordination compound that the present invention relates to
3, Tb (NCM-Si)
3Phen, Tb (NCM-Si)
3The uv-visible absorption spectroscopy figure of bpy.
Fig. 4 is the luminescent material that the contains europium complex (Eu (NCM-Si) that the present invention relates to
3, Eu (NCM-Si)
3Phen, Eu (NCM-Si)
3The emmission spectrum figure of bpy.
Fig. 5 is the luminescent material Tb (NCM-Si) that contains terbium coordination compound that the present invention relates to
3, Tb (NCM-Si)
3Phen, Tb (NCM-Si)
3The emmission spectrum figure of bpy.
Fig. 6 is the rare-earth hybridized luminescent material (Eu (NCM-Si) that the present invention relates to
3The room temperature fluorescence extinction curve.
Embodiment
The structure that contains the rare-earth hybridized luminescent material of fatty formic acid or fragrant formic acid is represented by general formula (1):
General formula (1)
R wherein
1Expression hydrogen atom or contain the alkyl of 1～10 carbon atom, R
2Be aromatic base, aromatic ester, fragrant acid amides, fragrant imide, aryl oxide, the alkyl that contains 1～10 carbon atom, ether, amino, fats acid amides, imide or ester group; M represents B, P, Si, Ti or Al; The RE of general formula (1) represents the metal-rare-earth metal, as: europium, terbium, samarium etc.; A represents the second part N, and the N part can be phenanthroline and dipyridyl etc.
The preparation method of fragrance of the present invention or the rare-earth hybridized luminescent material of fatty formic acid class may further comprise the steps:
General formula (2)
General formula (3)
General formula (4) HS-R
1-SiX
3
(1). with the fragrance or the aliphatic carboxylic acid monomer that contain alkene class or ring alkene double bond of general formula (2) expression, the organosilane monomer that contains sulfydryl of general formula (4) expression is dissolved in the organic solvent, 0～100 ℃ is carried out the addition reaction of alkene mercapto in the presence of initiator, according to alkene mercapto addition mechanism
Obtain fragrance or aliphatic carboxylic acid product with the modification of general formula (3) expression organosilicon;
(2). with fragrance or the aliphatic carboxylic acid product monomer that the expression organosilicon of general formula (3) expression is modified, N, N part A, coupling agent is dissolved in organic solvent, and 30～100 ℃ are carried out the polymeric gel reaction in the presence of catalyzer, and drying obtains product.
R in its formula of (3) and the general formula (4)
1Expression hydrogen atom or contain the alkyl of 1～10 carbon atom, X is the group of can be hydrolyzed reaction and generation-OH; R in general formula (2) and the general formula (3)
2Be aromatic base, aromatic ester, fragrant acid amides, fragrant imide, aryl oxide, the alkyl that contains 1～10 carbon atom, ether, amino, fats acid amides, imide or ester group.
Fragrance of the present invention or fatty formic acid rare earth compounding molecular hybrid luminescent materials preparation method's optimum condition is: the consumption of step (1) reactant is by the mole umber, with 1 part of the fragrance that contains alkene double bond of general formula (2) expression or aliphatic carboxylic acid monomer, with 1～10 part of the sulfydryl siloxanyl monomers of representing with general formula (4), join 5～500 parts of non-polar organic solvents with 0.01～10 part of initiator, 0～100 ℃ is carried out fragrance or the aliphatic carboxylic acid product that the addition reaction of alkene mercapto obtains representing with general formula (3) the organosilicon modification under logical nitrogen, the anhydrous condition; The consumption of step (2) reactant is by the mole umber, with 1 part in the inorganic salt of rare earth, 3～5 parts of fragrance that the expression organosilicon of general formula (3) expression is modified or aliphatic carboxylic acid product monomers, the second part N, 1～3 part of N part A, 0～100 part of coupling agent, 1～100 part of catalyzer adds 5～500 parts of organic solvents, and 30～100 ℃ are carried out the polymeric gel reaction, 20～80 ℃ of dryings, obtain product then.R in its formula of (3) and the general formula (4)
1Expression hydrogen atom or contain the alkyl of 1～10 carbon atom, the middle R of general formula (2) and general formula (3)
2Be aromatic base, aromatic ester, fragrant acid amides, fragrant imide, aryl oxide, the alkyl that contains 1～10 carbon atom, ether, amino, fats acid amides, imide or ester group, X is the group of can be hydrolyzed reaction and generation-OH.Described preparation method is the method for addition of alkene mercapto and sol-gel, and described radical initiator is for azo-initiator and peroxide initiator commonly used, as benzoyl peroxide (BPO), Diisopropyl azodicarboxylate (AIBN) etc.; Described non-polar organic solvent is methylene dichloride, chloroform, tetrahydrofuran (THF), 1,2-ethylene dichloride, toluene, dimethylbenzene etc.; Described organic solvent is ethanol, tetrahydrofuran (THF), acetone, acetonitrile, dimethyl sulfoxide (DMSO), N, the mixture of one or more in the adjacent acyl triamine of dinethylformamide or hexamethyl; The inorganic salt of described rare earth can be nitrate, halide salt of rare earth etc.; Described coupling agent is silane coupling agent such as tetramethoxy-silicane, tetraethoxysilane, acyloxy silane class, ketoximinosilanes class, aminosilane class, amide group silicane, different propenyloxy group class etc., titanate coupling agent such as titanium isopropylate, tetrabutyl titanate, tetra-sodium type monoalkoxytitanates class etc., aluminate coupling agent, bimetal coupling agent such as aluminium titanium composite coupler, zirconium Al-system coupling agent etc., phosphate coupling agent, boric acid ester coupler, chromium complex etc.; Described catalyzer is one or more the mixture in water, mineral acid, mineral alkali, organic acid, the organic bases; Described mineral acid can be hydrogenchloride, nitric acid, sulfuric acid, described mineral alkali can be a sodium hydroxide etc., described organic acid can be an acetic acid, described organic bases can be to biphenol, hexamethylenetetramine, quadrol or dibutyl tin laurate etc., described azo-initiator is a Diisopropyl azodicarboxylate, and described peralcohol initiator is a benzoyl peroxide.The polymeric gel reaction times is 1～20 hour, and be 7～42 days time of drying.
Following examples are to further specify of the present invention, are not limitations of the present invention.
Embodiment 1:
In three-necked bottle, add maleic anhydride 10.3g (105mmol), the ethyl acetate that adds 200mL (2242mmol), stirring makes it dissolving, slowly add 13.7g (100mmol) para-amino benzoic acid in batches, continue reaction 3h under the room temperature, a large amount of faint yellow solids occurs, be to such an extent that intermediate product is equipped with N-to carboxyl phenyl maleimide amino acid, filtration, drying.Carboxyl phenyl maleimide amino acid is joined the N-of reaction gained in the 500mL three-necked bottle that has magnetic agitation and reflux, add 2.0g (24mmol) anhydrous sodium acetate, the diacetyl oxide of 50mL (529mmol), system is warmed up to 70 ℃ of reaction 4h, reaction product is poured in a large amount of distilled water and placed and spend the night, a large amount of rice white precipitations appears, filter to collect and repeatedly with distilled water wash, in 40 ℃ of dryings of vacuum drying oven, obtain pure N-(4-carboxyl phenyl) maleimide (CPM) about three times with methanol-water (6/1) recrystallization, yield 90%, fusing point 238-240 ℃.
1H-NMR(CDCl
3)：8.20-8.18(2H，Ph-H)，7.55-7.63(2H，Ph-H)，6.89(2H，s，-CH＝CH-).IR(KBr，cm-1)：3150(-OH)，2980(-CH)，2300(COOH)，1770，1700(C＝O)，1633(C＝C)，1385(-CH)，1600，1508(aromatic)。
Embodiment 2:
At N
2Under the protection of atmosphere; in reaction flask, add 3-sulfydryl propyl trimethoxy silicane 2.1560g (11mmol); N-(4-carboxyl phenyl) maleimide 2.17g (10mmol); add initiator Diisopropyl azodicarboxylate 0.0328g (0.2mmol); all be dissolved in 30mL (370mmol) tetrahydrofuran (THF); stirring makes it dissolving and mixes; vacuumize 1～2min; charge into nitrogen; vacuumize again; two to three times so repeatedly, 0.5h is at room temperature carried out in reaction, at last reaction flask is placed 70 ℃ of reactions of oil bath constant temperature 8h.Termination reaction obtains the tetrahydrofuran solution of NCM-Si, and filtrate is poured into a large amount of normal hexane reprecipitations, obtains white precipitate, and with cold normal hexane washing repeatedly, drying obtains product NCM-Si under the vacuum.NCM-Si：
1H-NMR(DMSO)：8.06-8.03(2H，Ph-H)，7.44-7.35(2H，Ph-H)，4.25(1H，-CH(C＝O)-S)，3.45(9H，s，-OCH
3)，2.66(2H，-CH
2(C＝O)-C)，2.49-2.43(S-CH
2-C)，1.74-1.58(C-CH2-C)，0.67(2H，-CH
2-Si)。
Embodiment 3:
At N
2Protection takes by weighing 1.126g (3.333mmol) Eu (NO of metering down
3)
36H
2O, with 20mL (260mmol) N, the dinethylformamide dissolving, and regulate the pH value about 6-7, slowly be added drop-wise in the tetrahydrofuran solution of NCM-Si (get 4.13g (10mmol) NCM-Si, be dissolved in 30mL (370mmol) tetrahydrofuran (THF)), after at room temperature reacting 24h, obtain the tetrahydrofuran solution of the benzoic acids rare earth compounding that the organo-siloxane of crosslinkable condensation modifies, add 1.12mL (5mmol) tetraethoxy TEOS while stirring, 0.9mL (50mmol) H
2O splashes into the generation that a dilute hydrochloric acid promotes hydrolysis then in system.After the hydrolysis, the pH value that adds suitable vulkacit H regulation system in system maintains 6-7, filters with the nanofiltration membrane of 0.45 μ m then, and the mixing solutions that magnetic agitation obtains makes it to become a homogeneous system.Mixing solutions at first removes low boiling point solvent under reduced pressure, and room temperature was placed 3 days, places 2 days down for 50 ℃, and 100 ℃ were heated after fixing 2 days, were not contained the rare-earth hybridized luminescent material Eu (NCM-Si) of second part
3
Embodiment 4:
At N
2Protection takes by weighing 0.575g (1.67mmol) Tb (NO of metering down
3)
36H
2O, with 10mL (130mmol) N, the dinethylformamide dissolving, and regulate the pH value about 6-7, slowly be added drop-wise in the tetrahydrofuran solution of NCM-Si (get 2.08g (5mmol) NCM-Si, be dissolved in 20mL (247mmol) tetrahydrofuran (THF)), after at room temperature reacting 48h, obtain the tetrahydrofuran solution of the benzoic acids rare earth compounding that the organo-siloxane of crosslinkable condensation modifies, add 0.56mL (2.5mmol) tetraethoxy TEOS while stirring, 0.45mL (25mmol) H
2O splashes into the generation that a dilute hydrochloric acid promotes hydrolysis then in system.After the hydrolysis, the pH value that adds suitable vulkacit H regulation system in system maintains 6-7, filters with the nanofiltration membrane of 0.45 μ m then, and the mixing solutions that magnetic agitation obtains makes it to become a homogeneous system.Mixing solutions at first removes low boiling point solvent under reduced pressure, and room temperature was placed 3 days, places 2 days down for 60 ℃, and 120 ℃ were heated after fixing 2 days, were not contained the rare-earth hybridized luminescent material Tb (NCM-Si) of second part
3
Embodiment 5:
At N
2Protection takes by weighing 0.676g (2.0mmol) Eu (NO of metering down
3)
36H
2O, with 15mL (195mmol) N, the dinethylformamide dissolving, and regulate the pH value about 6-7, slowly be added drop-wise in the tetrahydrofuran solution that contains NCM-Si and phenanthroline and (get 2.48g (6.0mmol) NCM-Si and 0.360g (2.0mmol) phenanthroline, be dissolved in 25mL (308mmol) tetrahydrofuran (THF)), after at room temperature reacting 24h, obtain the tetrahydrofuran solution of the benzoic acids rare earth compounding that the organo-siloxane of crosslinkable condensation modifies, add 0.78ml (3.5mmol) tetraethoxy TEOS while stirring, 0.9mL (50mmol) H
2O splashes into the generation that a dilute hydrochloric acid promotes hydrolysis then in system.After the hydrolysis, the pH value that adds suitable vulkacit H regulation system in system maintains 6-7, filters with the nanofiltration membrane of 0.45 μ m then, and the mixing solutions that magnetic agitation obtains makes it to become a homogeneous system.Mixing solutions at first removes low boiling point solvent under reduced pressure, and room temperature was placed 3 days, places 2 days down for 60 ℃, and 100 ℃ were heated after fixing 2 days, obtained containing the rare-earth hybridized luminescent material Eu (NCM-Si) of the second part phenanthroline
3Phen.
Embodiment 6:
At N
2Protection takes by weighing 0.844 (2.5mmol) Eu (NO of metering down
3)
36H
2O, with 20mL (260mmol) N, the dinethylformamide dissolving, and regulate the pH value about 6-7, slowly be added drop-wise to and contain NCM-Si and 2,2 '-(get 3.10g (7.5mmol) NCM-Si and 0.39g (2.5mmol) 2 in the tetrahydrofuran solution of dipyridyl, 2 '-dipyridyl, be dissolved in 30mL (370mmol) tetrahydrofuran (THF)), after at room temperature reacting 24h, obtain the tetrahydrofuran solution of the benzoic acids rare earth compounding that the organo-siloxane of crosslinkable condensation modifies, add 1.12ml (5.0mmol) tetraethoxy TEOS while stirring, 1.1mL (61mmol) H
2O splashes into the generation that a dilute hydrochloric acid promotes hydrolysis then in system.After the hydrolysis, the pH value that adds suitable vulkacit H regulation system in system maintains 6-7, filters with the nanofiltration membrane of 0.45 μ m then, and the mixing solutions that magnetic agitation obtains makes it to become a homogeneous system.Mixing solutions at first removes low boiling point solvent under reduced pressure, and room temperature was placed 3 days, placed 2 days down for 70 ℃, 100 ℃ of heating after fixing 2 days, obtain containing second part 2,2 '-the rare-earth hybridized luminescent material Eu (NCM-Si) of dipyridyl
3Bpy.
Embodiment 7:
At N
2Protection takes by weighing 0.997g (2.2mmol) Tb (NO of metering down
3)
36H
2O, with 15mL (195mmol) N, the dinethylformamide dissolving, and regulate the pH value about 6-7, slowly be added drop-wise in the tetrahydrofuran solution that contains NCM-Si and phenanthroline and (get 2.73g (6.6mmol) NCM-Si and 0.396g (2.2mmol) phenanthroline, be dissolved in 25mL (309mmol) tetrahydrofuran (THF)), after at room temperature reacting 48h, obtain the tetrahydrofuran solution of the benzoic acids rare earth compounding that the organo-siloxane of crosslinkable condensation modifies, add 0.90mL (4.0mmol) tetraethoxy TEOS while stirring, 0.63mL (35mmol) H
2O splashes into the generation that a dilute hydrochloric acid promotes hydrolysis then in system.After the hydrolysis, the pH value that adds suitable vulkacit H regulation system in system maintains 6-7, filters with the nanofiltration membrane of 0.45 μ m then, and the mixing solutions that magnetic agitation obtains makes it to become a homogeneous system.Mixing solutions at first removes low boiling point solvent under reduced pressure, and room temperature was placed 3 days, places 2 days down for 70 ℃, and 110 ℃ were heated after fixing 2 days, obtained containing the rare-earth hybridized luminescent material Tb (NCM-Si) of the second part phenanthroline
3Phen.
Embodiment 8:
At N
2Protection takes by weighing 0.680g (1.5mmol) Tb (NO of metering down
3)
36H
2O, with 10mL (130mmol) N, the dinethylformamide dissolving, and regulate the pH value about 6-7, slowly be added drop-wise to and contain NCM-Si and 2,2 '-(get 1.86g (4.5mmol) NCM-Si and 0.234g (1.5mmol) 2 in the tetrahydrofuran solution of dipyridyl, 2 '-dipyridyl, be dissolved in 20mL (247mmol) tetrahydrofuran (THF)), after at room temperature reacting 48h, obtain the tetrahydrofuran solution of the benzoic acids rare earth compounding that the organo-siloxane of crosslinkable condensation modifies, add 0.60mL (2.67mmol) tetraethoxy TEOS while stirring, 0.45mL (25mmol) H
2O splashes into the generation that a dilute hydrochloric acid promotes hydrolysis then in system.After the hydrolysis, the pH value that adds suitable vulkacit H regulation system in system maintains 6-7, filters with the nanofiltration membrane of 0.45 μ m then, and the mixing solutions that magnetic agitation obtains makes it to become a homogeneous system.Mixing solutions at first removes low boiling point solvent under reduced pressure, and room temperature was placed 3 days, placed 2 days down for 60 ℃, 100 ℃ of heating after fixing 2 days, obtain containing second part 2,2 '-the rare-earth hybridized luminescent material Tb (NCM-Si) of dipyridyl
3Bpy.
Claims (6)
1. fragrance or fatty formic acid rare earth compounding molecular hybrid luminescent materials is characterized in that this luminescent material is expressed as following general formula (1) compound:
General formula (1)
R wherein
1Expression hydrogen atom or contain the alkyl of 1～10 carbon atom, R
2Be aromatic base, aromatic ester, fragrant acid amides, fragrant imide, aryl oxide, the alkyl that contains 1～10 carbon atom, ether, amino, fats acid amides, imide or ester group; M represents B, P, Si, Ti or Al, and the RE of general formula (1) represents the metal-rare-earth metal, as: europium, terbium, samarium; A represents the second part N, and the N part can be phenanthroline and dipyridyl.
2. the fragrance or the preparation method of fatty formic acid rare earth compounding molecular hybrid luminescent materials according to claim 1 is characterized in that this method may further comprise the steps:
General formula (2)
General formula (3)
General formula (4) HS-R
1-SiX
3
1). the organosilane monomer that contains sulfydryl of the fragrance that contains alkene class or ring alkene double bond of general formula (2) expression or aliphatic carboxylic acid monomer, general formula (4) expression is dissolved in the organic solvent, 0～100 ℃ is carried out the addition reaction of alkene mercapto in the presence of initiator, according to alkene mercapto addition mechanism
Obtain fragrance or aliphatic carboxylic acid product with the modification of general formula (3) expression organosilicon;
2). with fragrance or the aliphatic carboxylic acid product monomer that the expression organosilicon of general formula (3) expression is modified, N, N part A, coupling agent is dissolved in organic solvent, and 30～100 ℃ are carried out the polymeric gel reaction in the presence of catalyzer, and drying obtains product;
R in its formula of (3) and the general formula (4)
1Expression hydrogen atom or contain the alkyl of 1～10 carbon atom, X is the group of can be hydrolyzed reaction and generation-OH; R in general formula (2) and the general formula (3)
2Be aromatic base, aromatic ester, fragrant acid amides, fragrant imide, aryl oxide, the alkyl that contains 1～10 carbon atom, ether, amino, fats acid amides, imide or ester group.
3. according to the preparation method of described fragrance of claim 2 or fatty formic acid rare earth compounding molecular hybrid luminescent materials, it is characterized in that: the consumption of step (1) reactant is, by the mole umber, with 1 part of the fragrance that contains alkene double bond of general formula (2) expression or aliphatic carboxylic acid monomer, with 1～10 part of the sulfydryl siloxanyl monomers of representing with formula (4), with 0.01～10 part of initiator, add 5～500 parts of non-polar organic solvents, logical nitrogen, 0～100 ℃ is carried out the addition reaction of alkene mercapto under the anhydrous condition, according to alkene mercapto addition mechanism, obtain fragrance or the aliphatic carboxylic acid product modified with general formula (3) expression organosilicon; The consumption of step (2) reactant is by the mole umber, with 1 part in the inorganic salt of rare earth, 3～10 parts of fragrance that the expression organosilicon of general formula (3) expression is modified or aliphatic carboxylic acid product monomers, the second part N, 1～10 part of N part A, 0～100 part of coupling agent, 1～100 part of catalyzer adds 5～500 parts of organic solvents, and 30～100 ℃ are carried out the polymeric gel reaction, 20～80 ℃ of dryings, obtain product then; R in its formula of (3) and the general formula (4)
1Expression hydrogen atom or contain the alkyl of 1～10 carbon atom, the middle R of general formula (2) and general formula (3)
2Be aromatic base, aromatic ester, fragrant acid amides, fragrant imide, aryl oxide, the alkyl that contains 1～10 carbon atom, ether, amino, fats acid amides, imide or ester group, X is the group of can be hydrolyzed reaction and generation-OH.
4. according to the preparation method of claim 2 or 3 described fragrance or fatty formic acid rare earth compounding molecular hybrid luminescent materials, it is characterized in that described X is alkoxyl group, acyloxy or halogen.
5. according to the preparation method of claim 2 or 3 described fragrance or fatty formic acid rare earth compounding molecular hybrid luminescent materials, the inorganic salt that it is characterized in that described rare earth are nitrate or halide salts of rare earth; Described coupling agent is silane coupling agent, titanate coupling agent, aluminate coupling agent, bimetal coupling agent, phosphate coupling agent, boric acid ester coupler or chromium complex; Described catalyzer is one or more the mixture in water, mineral acid, mineral alkali, organic acid, the organic bases; Described initiator is azo class, peralcohol or benzil ketals; Described non-polar organic solvent is methylene dichloride, chloroform, tetrahydrofuran (THF), 1,2-ethylene dichloride, toluene or dimethylbenzene; Described organic solvent is ethanol, tetrahydrofuran (THF), acetone, acetonitrile, dimethyl sulfoxide (DMSO), N, the mixture of one or more in the adjacent acyl triamine of dinethylformamide or hexamethyl; The polymeric gel reaction times is 1～20 hour, and be 7～42 days time of drying.
6. according to claim 2, the preparation method of 3 or 5 described fragrance or fatty formic acid rare earth compounding molecular hybrid luminescent materials, it is characterized in that described silane coupling agent is a tetramethoxy-silicane, tetraethoxysilane, the acyloxy silane class, the ketoximinosilanes class, the aminosilane class, amide group silicane or different propenyloxy group class, described titanate coupling agent is a titanium isopropylate, tetrabutyl titanate or tetra-sodium type monoalkoxytitanates class, described bimetal coupling agent is aluminium titanium composite coupler or zirconium Al-system coupling agent, described catalyzer is a hydrogenchloride, nitric acid, sulfuric acid, sodium hydroxide, acetic acid, to biphenol, hexamethylenetetramine or quadrol or dibutyl tin laurate, described azo-initiator is a Diisopropyl azodicarboxylate, and described peralcohol initiator is a benzoyl peroxide.
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Cited By (5)
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| CN104194776A (en) * | 2014-09-09 | 2014-12-10 | 吉林大学 | Functionalized rare-earth complex organic/inorganic hybrid luminescent material and preparation method thereof |
| CN106748993A (en) * | 2016-11-29 | 2017-05-31 | 周口师范学院 | A kind of hybrid luminescent materials based on Michael addition reactions and preparation method thereof |
| CN107012527A (en) * | 2017-04-01 | 2017-08-04 | 北京金辰西维科安全印务有限公司 | A kind of ageing-resistant fluorescent composition of rare earth and application thereof |
| CN112645975A (en) * | 2020-11-04 | 2021-04-13 | 重庆顺泽生物技术研究院有限公司 | Silicon-phenanthroline derivatives, preparation and use thereof |
| CN112876896A (en) * | 2021-01-26 | 2021-06-01 | 苏州中来光伏新材股份有限公司 | Rare earth metal organic complex coated zinc oxide titanium nano sol and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104194776A (en) * | 2014-09-09 | 2014-12-10 | 吉林大学 | Functionalized rare-earth complex organic/inorganic hybrid luminescent material and preparation method thereof |
| CN106748993A (en) * | 2016-11-29 | 2017-05-31 | 周口师范学院 | A kind of hybrid luminescent materials based on Michael addition reactions and preparation method thereof |
| CN106748993B (en) * | 2016-11-29 | 2020-03-20 | 周口师范学院 | Hybrid luminescent material based on Michael addition reaction and preparation method thereof |
| CN107012527A (en) * | 2017-04-01 | 2017-08-04 | 北京金辰西维科安全印务有限公司 | A kind of ageing-resistant fluorescent composition of rare earth and application thereof |
| CN112645975A (en) * | 2020-11-04 | 2021-04-13 | 重庆顺泽生物技术研究院有限公司 | Silicon-phenanthroline derivatives, preparation and use thereof |
| CN112876896A (en) * | 2021-01-26 | 2021-06-01 | 苏州中来光伏新材股份有限公司 | Rare earth metal organic complex coated zinc oxide titanium nano sol and preparation method thereof |
| CN112876896B (en) * | 2021-01-26 | 2022-05-17 | 苏州中来光伏新材股份有限公司 | Rare earth metal organic complex coated zinc oxide titanium nano sol and preparation method thereof |
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