CN101173168A - Method for producing rare earth luminous organic/inorganic hybridisation composite material - Google Patents
Method for producing rare earth luminous organic/inorganic hybridisation composite material Download PDFInfo
- Publication number
- CN101173168A CN101173168A CNA2007101134018A CN200710113401A CN101173168A CN 101173168 A CN101173168 A CN 101173168A CN A2007101134018 A CNA2007101134018 A CN A2007101134018A CN 200710113401 A CN200710113401 A CN 200710113401A CN 101173168 A CN101173168 A CN 101173168A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- preparation
- solvent
- organic
- inorganic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preparation method of a rare-earth luminescent organic or inorganic hybrid composite material, belonging to the technical field of the preparation of rare-earth luminescent composite materials with transparency organic-inorganic copolymer network. the preparation method comprises the following steps: at first, an organic-inorganic copolymer is synthesized; a silane coupling agent and a monomer are polymerized in an organic solvent; another solvent is added to precipitate a product; then the product and the inorganic component that can be polymerized are hydrolyzed and condensed under acidic catalytic condition, and a rare-earth luminescent active center and a polymer plasticizer are added at the later reaction phase; the sol is poured into a mold, and the final material is acquired after gelation and drying. The invention has the advantages that: the process steps of the method are easy to operate; the acquired material has good luminous performance, transparency, film forming ability, mechanical intensity and chemical stability, and the application result is ideal.
Description
Technical field:
The invention belongs to hybrid Composite Preparation technical field, relate to a kind of preparation method of rare earth luminous hybrid matrix material, the gained material has good luminous property, mechanical property, stability and transparent.
Background technology:
Along with science and technology development, the material of single character can not satisfy people's needs.Function by two or more materials is compound, performance complement and optimization, can prepare the matrix material of excellent performance, and hybrid Composite Preparation technology is arisen at the historic moment.Because the stronger reactive force of two alternate existence or formed interpenetrating(polymer)networks, the size of microcell is usually at nano level, sometimes or even the molecular water sane level, so the transparency of material is high, the compound of the two also provides condition for the luminescent properties that improves rare earth compounding.According to the power of reactive force between the hybrid composite material two-phase, hybrid composite material can be divided into I type hybrid composite material and II type hybrid composite material: the more weak reactive force of I type hybrid composite material two alternate existence, as: hydrogen bond, Van der Waals force; The reactive force that II type hybrid composite material two is alternate is stronger, and generally the form with covalent linkage links to each other.
At present, preparation for first kind hybrid luminescent materials has 3 kinds of methods, method one is to add synthetic in advance good rare earth organic complex in the sol-gel precursor solution of preparation hydridization matrix, and in the process of gel conversion, rare earth compounding is wrapped in the micropore of matrix at colloidal sol; Method two is earlier synthetic certain substrate material, then substrate material be impregnated in the solution of rare earth compounding and obtains luminous hybrid material; Method three is an original position synthesizing rare-earth title complex in substrate formed process.But the more weak reactive force of existence in the first kind hybrid material of above-mentioned three kinds of methods preparation because between the component, be difficult to suppress the active centre and be rare earth ion and produce bunch, and the component skewness, hotchpotch is easily by elimination, simultaneously, also relative complex is a little for these technologies of preparing itself.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, thereby can avoid the reunion in active centre effectively.In recent years, the research of this class material has caused material supply section scholar's extensive interest.Employings such as Okamoto have prepared several series luminescence rare earth polymer complex with rare earth ion and the method that contains the polymer reaction of coordinating group, and employed polymkeric substance has 3 classes: 1) contain carboxyl or sulfonic polymkeric substance; 2) contain the polymkeric substance of beta-diketon structure; 3) polystyrene that is partly replaced by the carboxylic aroyl.But this mode prepares rare earth high polymer, can not obtain the higher luminescent material of fluorescence intensity.Increase along with content of rare earth, " concentration quenching " phenomenon can appear in these polymkeric substance, and this is that synthetic title complex middle-weight rare earths ion coordination number is not being met by this way because the rare-earth ion coordination number is higher, ion aggregation just taking place form ion cluster, causes quenching of fluorescence.Another kind method is to carry out polymerization with small molecules rare earth compounding monomer.Elder generation's synthesizing rare-earth polymerisable monomer, homopolymerization or copolymerization make organometallic polymer and are the rare-earth complex copolymerized macromolecule then.The fluorescent material middle-weight rare earths ion distribution that makes in this way evenly, still can keep fluorescence intensity to increase linear increment when not cluster, thereby rare earth metal content is higher with content of rare earth, concentration quenching under high doping do not occur, and can make the good material of transparency.The research of this respect and application are all many.Grandson at first synthesizes the small molecules ternary complex Eu that contains vinylformic acid (AA) according to brave the grade
3+(TTA) (AA), prepare the rare earth high polymer title complex with methyl methacrylate copolymer then.But this method more complicated, the monomeric productivity ratio of synthesized micromolecule rare earth compounding is lower, is difficult to realize suitability for industrialized production.Recently, small molecules parts such as phenanthroline that also useful organosilane is modified and dipyridyl, in the presence of rare earth ion, made inorganic/organic hybrid matrix material by hydrolytie polycondensation TEOS and above-mentioned organosilane presoma, utilize silane coupling agent that organic and inorganic part are coupled together simultaneously in addition, in the sol gel reaction process, introduce rare earth ion, these two kinds of compounds of institute's synthetic have two effects, as the organosilicon acid esters, can be as the presoma of sol gel reaction, the presoma of this organic decoration forms network structure through hydrolysis condensation reaction; Because it has the organic heterocyclic part, 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.But, sum up present technological method, all exist the technology relative complex, various controlled poor, Material Physics, the chemical property of preparation are not ideal enough.
Summary of the invention:
The objective of the invention is to overcome the shortcoming that prior art exists, seek to propose a kind of preparation method of transparent rare earth luminous hybrid matrix material newly, make the stronger reactive force of two alternate formation or form interpenetrating(polymer)networks, the size of microcell is usually at nano level, sometimes or even the molecular water sane level, has high transparency to guarantee material.
To achieve these goals, the technical solution adopted in the present invention adopts the synthetic hybrid matrix material of cryosol----gel method original position, comprises polymerization, hydrolysis, polycondensation, mixing, press mold and ageing drying process step; Earlier silane coupling agent and the polymer monomer with good filming and transparency are carried out polymerization in organic solvent; Make again that product and inorganic silicate are hydrolyzed, polycondensation, and add polymeric plasticizer (or not adding) and rare earth luminous active centre in the reaction later stage; Make product through press mold and ageing drying more at last, its concrete preparation process is as follows:
(1), the polymerization under logical nitrogen and magnetic agitation condition with silane coupling agent and polymer monomer, the benzene series solvent is made solvent, thermal initiation type initiator is made initiator, 20-90 ℃ the reaction 1-10 hour; Reaction soln poured into product precipitation is separated out;
(2), with resulting polymers heterocyclic dissolution with solvents, inorganic silicate is made solvent with alcoholic solvent, use acid-catalyzed hydrolysis respectively, ultrasonic concussion is carried out reaction fast;
(3), above-mentioned prehydrolysis solution is mixed, add the alcoholic solution of the adjacent phenanthroline of rare earth ion salt and small molecules part, add glycols polymkeric substance (as polyoxyethylene glycol) as softening agent (or not adding);
(4), colloidal sol is poured in the mould, put into 20-90 ℃ of baking oven ageing, drying, product.
Silane coupling agent of the present invention is the silicic acid lipoid substance, comprises tetraethyl orthosilicate ester, the positive silicon ester of tetramethyl-; The organic polymer monomer comprises methacrylic ester; Inorganic component contains the compound of silicate class of organic unsaturated double-bond, comprises propyl methacrylate; Organic solvent is benzene series solvent and derivative thereof, comprises toluene; Thermal initiator comprises Diisopropyl azodicarboxylate, benzoyl peroxide and normal hexane; The heterocyclic solvent comprises tetrahydrofuran (THF); The acid of catalytic hydrolysis comprises aqueous hydrochloric acid; Softening agent is the glycols polymkeric substance, comprises polyoxyethylene glycol; Alcoholic solvent comprises ethanol; Rare earth ion salt comprises samarium, europium, terbium, dysprosium, praseodymium, neodymium and holmium trivalent haloid; Inorganic silicate comprises tetraethoxy.
The present invention has fully utilized the long higher characteristics of lifetime of excited state, purity of color of rare earth element; Organism can be with the rare earth ion that passes to of Energy Efficient as part, and has good film-forming properties; Inorganic matrix has good light, thermostability and chemical stability and mechanical strength; Adopt the synthetic hybrid matrix material of low-temperature sol-gel method original position, two-phase is combined closely with chemical bond, and the introducing of the very convenient rare earth ion of collosol state, make gained material uniform mixing on reduced size, have the transparency; Ultra-sonic dispersion can promote the ionic collision, and reaction is carried out fast.
Embodiment:
Further describe content of the present invention below in conjunction with embodiment.
Embodiment 1:
Earlier in the 100ml there-necked flask, add 30ml toluene, 10.8ml methyl methacrylate, 6ml silane coupling agent NQ-57,1.0g Diisopropyl azodicarboxylate, logical nitrogen protection, 65 ℃ of magnetic agitation 3 hours; With normal hexane 300ml the product precipitation is separated out; The 1.5g polymer dissolution in the 8ml tetrahydrofuran (THF), will be added 2ml ethanol, and adds the aqueous hydrochloric acid of an amount of pH=2 respectively in the 2.55ml tetraethoxy, put into ultrasonic cleaning machine reaction 10 minutes, mix; Add the ethanolic soln 0.1ml of terbium and the ethanolic soln 0.1ml of adjacent phenanthroline, add polyoxyethylene glycol (200) 0.6ml; Colloidal sol is poured in the mould, put into 20-90 ℃ of baking oven ageing, dry 2 days, it was stand-by to make the hybrid composite material product.
Embodiment 2:
According to embodiment 1 described preparation method, when other condition was identical, the consumption of methyl methacrylate changed 16.2ml into.
Embodiment 3:
According to embodiment 1 described preparation method, 75 ℃ of magnetic agitation 2 hours do not add the polyoxyethylene glycol softening agent, and other condition is constant.
Embodiment 4:
According to embodiment 1 described preparation method, polyoxyethylene glycol (200) consumption is 2.3ml, tetraethoxy consumption 1.3ml, and other is constant.
Embodiment 5:
Press embodiment 1 described preparation method, earlier in the 100ml there-necked flask, add 30ml toluene, 16.2ml methyl methacrylate, 6ml silane coupling agent NQ-57,1.0g Diisopropyl azodicarboxylate, logical nitrogen protection, 65 ℃ of magnetic agitation 3 hours; With normal hexane 300ml the product precipitation is separated out; The 0.77g polymer dissolution in the 5ml tetrahydrofuran (THF), will be added 2ml ethanol, and adds the aqueous hydrochloric acid of an amount of pH=2 respectively in the 2.55ml tetraethoxy, put into ultrasonic cleaning machine reaction 10 minutes, mix; Add the ethanolic soln 0.1ml of terbium and the ethanolic soln 0.1ml of adjacent phenanthroline, add Macrogol 200 1.2ml; Colloidal sol is poured in the mould, put into 20-90 ℃ of baking oven ageing, dry 2 days, it was stand-by to make the hybrid composite material product.
Experiment records the prepared product of present embodiment and reaches goal of the invention and effect.
Claims (4)
1. the preparation method of a rare earth luminous hybrid matrix material is characterized in that adopting cryosol----gel method original position to synthesize the hybrid matrix material, comprises polymerization, hydrolysis, mixing, press mold and ageing drying process step.
2. according to the preparation method of claim 1 described rare earth luminous hybrid matrix material, it is characterized in that polymerization under logical nitrogen and magnetic agitation condition with silane coupling agent and polymer monomer, the benzene series solvent is made solvent, thermal initiation type initiator is made initiator, and 20-90 ℃ was reacted 1-10 hour; Reaction soln poured into product precipitation is separated out; With resulting polymers heterocyclic dissolution with solvents, inorganic silicate is made solvent with alcoholic solvent, use acid-catalyzed hydrolysis respectively, ultrasonic concussion is carried out reaction fast.
3. according to the preparation method of claim 1 described rare earth luminous hybrid matrix material, it is characterized in that prehydrolysis solution is mixed, the alcoholic solution that adds the adjacent phenanthroline of rare earth ion salt and small molecules part adds or does not add the glycols polymkeric substance as softening agent; Colloidal sol is poured in the mould, put into 20-90 ℃ of baking oven ageing, drying gets product.
4. the preparation method of rare earth luminous hybrid matrix material according to claim 1 is characterized in that silane coupling agent is the silicic acid lipoid substance, comprises tetraethyl orthosilicate ester, the positive silicon ester of tetramethyl-; The organic polymer monomer comprises methacrylic ester; Inorganic component contains the compound of silicate class of organic unsaturated double-bond, comprises propyl methacrylate; Organic solvent is benzene series solvent and derivative thereof, comprises toluene; Thermal initiator comprises Diisopropyl azodicarboxylate, benzoyl peroxide and normal hexane; The heterocyclic solvent comprises tetrahydrofuran (THF); The acid of catalytic hydrolysis comprises aqueous hydrochloric acid; Softening agent is the glycols polymkeric substance, comprises polyoxyethylene glycol; Alcoholic solvent comprises ethanol; Rare earth ion salt comprises samarium, europium, terbium, dysprosium, praseodymium, neodymium and holmium trivalent haloid; Inorganic silicate comprises tetraethoxy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101134018A CN101173168A (en) | 2007-09-30 | 2007-09-30 | Method for producing rare earth luminous organic/inorganic hybridisation composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101134018A CN101173168A (en) | 2007-09-30 | 2007-09-30 | Method for producing rare earth luminous organic/inorganic hybridisation composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101173168A true CN101173168A (en) | 2008-05-07 |
Family
ID=39421927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101134018A Pending CN101173168A (en) | 2007-09-30 | 2007-09-30 | Method for producing rare earth luminous organic/inorganic hybridisation composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101173168A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319661A (en) * | 2016-08-27 | 2017-01-11 | 青岛大学 | Method for preparing macromolecule-micro-nano luminescent composite fiber |
-
2007
- 2007-09-30 CN CNA2007101134018A patent/CN101173168A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319661A (en) * | 2016-08-27 | 2017-01-11 | 青岛大学 | Method for preparing macromolecule-micro-nano luminescent composite fiber |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103626933B (en) | A kind of polysilsesquioxane-polyacrylic ester-nanosized SiO_2 composite emulsion and preparation method thereof and application | |
| CN101899128A (en) | Hollow nano silica microsphere modified polyacrylate nuclear shell structure composite emulsion and thin film | |
| Chen et al. | EVA film doped with β-diketones macromolecular lanthanide complexes: preparation, characterization and application | |
| CN101067079B (en) | Nanometer hybridized phosphor in core-shell structure and its preparation process | |
| CN101255273B (en) | Method for preparing luminescent rear earth-polyethylene glycol polymer composites | |
| CN102002358B (en) | Method for preparing polymethylacrylic acid functionalized rare-earth polymer composite luminescent material | |
| CN101935457A (en) | Method for manufacturing high-refractive index TiO2/organic silicon hybrid coating | |
| CN101173168A (en) | Method for producing rare earth luminous organic/inorganic hybridisation composite material | |
| CN1200046C (en) | Luminous nano composite material and its preparing method | |
| CN102212361A (en) | Aromatic or aliphatic formic acid-rare earth complex molecular hybrid luminescent material and preparation method thereof | |
| CN1291991C (en) | Preparation method of multihydroxy sesqui siloxane | |
| CN101429430A (en) | Process for producing sulfhydryl functionalized rare earth-macromolecule composite luminescent material | |
| CN101381463B (en) | Polymer with backbone chain having silicon-aromatic bispropargyl ether structure and preparation method thereof | |
| CN103740358B (en) | Rare earth organic-inorganic hybrid luminescent material and preparation method thereof | |
| CN116102685A (en) | Template agent for anti-reflection and anti-reflection coating liquid with small particle size and high stability and application thereof | |
| CN1169849C (en) | Process for synthesizing non-solvent nm-class high-polymer/rare-earth compound hybridized luminous material | |
| CN102618275B (en) | Method for preparing rare-earth organic and inorganic zinc oxide semiconductor nanopore composite luminescent material based on hydroxyl functionalization | |
| CN106633567A (en) | Method for preparing rare earth luminescent composite materials | |
| CN102220127B (en) | Carboxyl group and sulfhydryl group double-functionalization-based preparation method of rare earth organic and inorganic semiconductor illumination gelatin | |
| CN100567389C (en) | A kind of preparation method of multicolor luminescence rare earth-polyvinylpyrrolidonemacromolecule macromolecule composite material | |
| CN110964157B (en) | Block copolymer brush polymer based on polystyrene-poly (dimethylaminoethyl methacrylate) and preparation method thereof | |
| CN109370571B (en) | POSS-based polyion liquid/rare earth fluorescent material and preparation method thereof | |
| CN101735799B (en) | Preparation method of organic/inorganic/polymeric composite luminescent material of sulfoxide functionalization rare earth | |
| CN102002359B (en) | Method for preparing beta-diketone functional rare-earth organic luminous gel based on silicon-boron composite network | |
| CN100448905C (en) | High-polymer molecular hybrid luminescent materials containing 8-hydroxyquinoline metal complex and production thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080507 |