CN1431255A - Luminous nano composite material and its preparing method - Google Patents
Luminous nano composite material and its preparing method Download PDFInfo
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- CN1431255A CN1431255A CN03112784.3A CN03112784A CN1431255A CN 1431255 A CN1431255 A CN 1431255A CN 03112784 A CN03112784 A CN 03112784A CN 1431255 A CN1431255 A CN 1431255A
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 239000002114 nanocomposite Substances 0.000 title description 14
- 238000000034 method Methods 0.000 title description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 48
- 239000004927 clay Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 53
- 150000002910 rare earth metals Chemical class 0.000 claims description 38
- -1 methacryloyl amine Chemical class 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002612 dispersion medium Substances 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- 229920002379 silicone rubber Polymers 0.000 claims description 18
- 238000005341 cation exchange Methods 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 15
- 238000009775 high-speed stirring Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000260 silastic Polymers 0.000 claims description 4
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 4
- NQBWNECTZUOWID-UHFFFAOYSA-N (E)-cinnamyl (E)-cinnamate Natural products C=1C=CC=CC=1C=CC(=O)OCC=CC1=CC=CC=C1 NQBWNECTZUOWID-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- NQBWNECTZUOWID-QSYVVUFSSA-N cinnamyl cinnamate Chemical compound C=1C=CC=CC=1\C=C/C(=O)OC\C=C\C1=CC=CC=C1 NQBWNECTZUOWID-QSYVVUFSSA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 15
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000003431 cross linking reagent Substances 0.000 abstract 2
- 230000003287 optical effect Effects 0.000 abstract 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000010298 pulverizing process Methods 0.000 description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 8
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 7
- 239000003292 glue Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 3
- WLPQHPARWSMVFW-UHFFFAOYSA-N 2-dodecylbenzoic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1C(O)=O WLPQHPARWSMVFW-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- DDUVWKBTOQJWOQ-UHFFFAOYSA-N CCCCCCCCCCCCCCC(CCC[Si](OCC)(OCC)OCC)C(C)(C)Cl.N Chemical compound CCCCCCCCCCCCCCC(CCC[Si](OCC)(OCC)OCC)C(C)(C)Cl.N DDUVWKBTOQJWOQ-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000138 intercalating agent Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 230000000176 photostabilization Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DVBBRHKIBNJJTO-UHFFFAOYSA-N 2-hexadecylbenzoic acid Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1C(O)=O DVBBRHKIBNJJTO-UHFFFAOYSA-N 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- GPWWXKMSPDGDBQ-UHFFFAOYSA-N 2-octadecylbenzoic acid Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1C(O)=O GPWWXKMSPDGDBQ-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- HJHKQTDOQPBKDB-UHFFFAOYSA-N C(=O)O.C(CCCCC)C1=CC=CC=C1 Chemical compound C(=O)O.C(CCCCC)C1=CC=CC=C1 HJHKQTDOQPBKDB-UHFFFAOYSA-N 0.000 description 1
- CDQONNSVDSEKOQ-UHFFFAOYSA-N CCCCCCCCCCCCCCC(CCC[Si](OCC)(OCC)OCC)C(C)(CC)Cl.N Chemical compound CCCCCCCCCCCCCCC(CCC[Si](OCC)(OCC)OCC)C(C)(CC)Cl.N CDQONNSVDSEKOQ-UHFFFAOYSA-N 0.000 description 1
- KNVRHQGOAWMRCC-UHFFFAOYSA-N CCCCCCCCCCCCCCCC(C)(CC)Cl.N Chemical compound CCCCCCCCCCCCCCCC(C)(CC)Cl.N KNVRHQGOAWMRCC-UHFFFAOYSA-N 0.000 description 1
- YBGPBFPRWAMTKW-UHFFFAOYSA-N CCCCCCCCCCCCCCCC[N+](C)(C)C(C)(C)CCC[Si](OCC)(OCC)OCC Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C(C)(C)CCC[Si](OCC)(OCC)OCC YBGPBFPRWAMTKW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- XMQWLAKDMVCZOX-UHFFFAOYSA-N [Cl-].C[NH+](CCC[Si](OCC)(OCC)OCC)C Chemical compound [Cl-].C[NH+](CCC[Si](OCC)(OCC)OCC)C XMQWLAKDMVCZOX-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HRBYCVPFYWTROV-UHFFFAOYSA-M dimethyl-octadecyl-(3-triethoxysilylpropyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCC[Si](OCC)(OCC)OCC HRBYCVPFYWTROV-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- CCMGSHLZTIQYKA-UHFFFAOYSA-N formic acid pentylbenzene Chemical compound C(=O)O.C(CCCC)C1=CC=CC=C1 CCMGSHLZTIQYKA-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
A nano-class composite luminescent material for effectively converting the ultraviolet light to red fluorescence light is prepared from polymer (100 wt portions), clay (0.5-30), RE-organosilicon as optical converting agent (0.5-10), dispersing medium (20-400), cross-linking agent (0-10) and promoter (0-1) through the reaction between nitrate or hydrochloride of Eu or Tb, organic carboxylic acid and organosilicon surfactant for 3-6 hr, the reaction between organosilicon-type optical converting agent, clay and dispersing medium to obtain organic clay compound, dispersing in polymer, stirring, adding cross-linking agent and promoter, and moulding for 0.2-24 hr.
Description
Technical field
The present invention relates to a kind of nano luminescent matrix material and preparation method thereof, particularly one base polymer/rare earth organosilicon light-converting agent-clay nano luminescent composite and preparation method thereof.
Background technology
China is rare earth resources big country, has the whole world and can exploit 80% of rare earth reserves, and rare earth resources distribution region is wide, wide in variety, element is complete.Rare earth resources is carried out deep processing to be made the new function material of high added value and is significant.At present, the research of luminescent material is become the focus of scientific research field, especially in recent years, cross discipline and new technology, what make luminescent material syntheticly faces rare opportunities and challenges.Macromolecular compound is being brought into play important effect at rare earth fluorescence complex in the transition process of material.Contain luminescent properties and the easy machining characteristics of polymer that luminescence rare earth ionic macromolecular compound has rare earth ion concurrently, thereby cause extensive concern.Rare earth compounding is widely used in luminous and the demonstration field with its unique fluorescent characteristic, especially its " doping " development prospect of prepared functional high molecule material in polymeric matrix is more attracted people's attention.
But general rare earth compounding is difficult to reach nano level and disperses in macromolecular material, and has the photostabilization difference or problems such as luminosity factor is low, cost height, thereby meets difficulty in actual applications.
Summary of the invention
In order to overcome the problems referred to above that exist in the prior art, the invention provides one base polymer/rare earth organosilicon light-converting agent-clay nano luminescent material and preparation method thereof.
The feed composition and the weight content of nano luminescent material of the present invention are as follows:
100 parts in polymkeric substance
0.5～30 part of clay
0.5～10 part of rare earth organosilicon light-converting agent
20～400 parts in dispersion medium
0～10 part of linking agent
0～1 part of promotor.
The polymkeric substance that the present invention was suitable for is raw-silastic continuously (room temperature silicon rubber, high temperature silicon rubber, addition-type silicon rubber) or the polymkeric substance or the multipolymer that are formed by vinylformic acid, esters of acrylic acid, methacrylic acid, methyl acrylic ester, acrylamide, methacryloyl amine monomer.
The rare earth ion that the present invention was suitable for is Eu
3+, Tb
3+, provide by the nitrate or the hydrochloride of trivalent europium and terbium, adopt different rare earth ions can obtain different illumination effects.
The organic carboxyl acid that the present invention was suitable for is C
1-C
18Alkylbenzoic acid, benzaminic acid or phthalic acid or styracin or naphthoic acid.
The organic silicon surfactant that the present invention was suitable for, the chemical structure skeleton symbol is (RO)
3SiR
1N
+R
2R
3R
4X
-
In organic silicon surfactant, R is CH
3Or C
2H
5R
1For-CH
2-or-C
3H
6-; R
2Be CH
3Or C
2H
5R
3Be CH
3Or C
2H
5R
4Can be chain alkyl, as dodecyl, hexadecyl, octadecyl; Can be aliphatics vinylformic acid and ester derivative thereof also, as CH
2=CHCOOC
2H
4-or CH
2=C (CH
3) COOC
2H
4-; X is Cl, Br.
The clay that the present invention was suitable for is the inorganics that a class has laminate structure, its cationic exchange total volume is preferably 70～120meq/100g, after the effect of rare earth organosilicon light-converting agent, can make polymkeric substance be inserted into interlayer at an easy rate, and then form nano composite material.
The used dispersion medium of the present invention is water, alcohols, dimethyl formamide etc., and clay particle is disperseed this class dispersion medium and cation exchange reaction carries out.
The used linking agent of the present invention can be organoalkoxysilane, superoxide of alkyl silane, the multiple functional radical of multiple functional radical etc., as tetraethoxy, coupling agent, benzoyl peroxide.
The used promotor of the present invention can be dibutyl tin laurate, stannous octoate or need not.
Be a class novel multifunctional title complex by molecular designing synthetic rare earth organosilicon light-converting agent in this preparation methods, at first make the reaction of rare earth and organic carboxyl acid form a kind of temporary transient stable complex, select to have long-chain organosilicon surfactivity and its further reaction of specific function then, form a kind of constitutionally stable novel title complex; This type of title complex can not only increase substantially the luminous efficiency of light-converting agent, but also can be used as a kind of novel intercalator, inserts the sheet interlayer of layered silicate; Disperse phase is peeled off to nano level individual layer clay lamella, evenly be filled in the polymeric media, thereby the luminescent properties of matrix material is increased substantially.And this type of rare earth organosilicon light-converting agent itself or be scattered in the polymeric system, all can efficiently the UV-light of different-waveband be converted to the specific function of rubescent look wave band fluorescence.
Preparation method's of the present invention operation steps is as follows:
With the nitrate of trivalent europium or terbium or hydrochloride, organic carboxyl acid, organic silicon surfactant, 1: 2 in molar ratio～10: 0.2～2 20～200 ℃ of reactions 3～6 hours, obtained the stable novel rare-earth organosilicon light-converting agent of a class formation;
With 0.5～10 part of organosilicon light-converting agent and cation exchange capacity is 0.5～30 part of the clay of 70～120meq/100g, high-speed stirring in the presence of 20～400 parts dispersion medium, form uniform material, 20～200 ℃ of reactions 3～6 hours, with the product of gained through washing, dry, pulverize after, obtain functional type polyorganosilicate mixture;
0.5～30 part of above-mentioned functions type polyorganosilicate mixture is scattered in the polymkeric substance such as 100 parts of silicon rubber or acrylic or methacrylic acid, stir and add 0～10 part of linking agent after 5～10 hours, 0～1 part of promotor is poured in the mould, places 0.2～24 hour for 20～120 ℃.
The invention has the beneficial effects as follows: the rare earth organosilicon light-converting agent that the present invention adopts is the formed stable complex of rare earth-organic carboxyl acid-organic silicon surfactant, and the luminous intensity of the corresponding rare earth of its luminous strength ratio-organic carboxyl acid title complex improves 100～250%; The luminous intensity of the corresponding rare earth of the luminous strength ratio-organic carboxyl acid title complex/clay luminescent intermediates of institute of the present invention synthetic polymkeric substance/rare earth organosilicon light-converting agent-clay matrix material improves 100～250%.
The rare earth organosilicon light-converting agent title complex that the present invention adopts can not only improve the luminous efficiency of light-converting agent, but also can be used as a kind of novel intercalator, inserts the sheet interlayer of layered silicate, makes interlamellar spacing become big; Disperse phase is peeled off to nano level individual layer clay lamella, evenly be filled in the polymeric media, thereby the luminescent properties of matrix material is increased substantially.
The present invention is owing to adopted intercalation technique, well solve light-converting agent and how to have carried out nano-dispersed and problems such as the light-converting agent photostabilization is poor, luminous efficiency is low, cost height, the rare earth organosilicon light-converting agent/clay mixture of modification is easy to be dispersed in the polymeric system, forms clear films.
The rare earth organosilicon light-converting agent itself that the present invention adopts or it is scattered in the polymeric system, all can be efficiently converting the UV-light of different-waveband to light and the strongest red spectral band of effect, can be respectively that to be converted into wavelength be red fluorescence about 611nm for the UV-light of 254nm, 280nm, 320nm with wavelength.
Polymkeric substance of the present invention/rare earth organosilicon light-converting agent-clay matrix material is a kind of nano composite material, at last De matrix material not only luminescent properties increase substantially, simultaneously thermotolerance also is improved.
Embodiment
In order to be illustrated more clearly in the present invention, enumerate following examples, but these there is not any restriction to scope of the present invention.
Embodiment 1
With rare earth chloride EuCl
3, α-Nai Jiasuan, organic silicon surfactant 3-triethoxysilylpropyl dimethyl dodecyl chlorination ammonium obtained the stable novel rare-earth organosilicon light-converting agent of a class formation 20～40 ℃ of reactions 6 hours in 1: 4: 2 in molar ratio.With 0.5 part of organosilicon light-converting agent and cation exchange capacity is 0.6 part of the clay of 80meq/100g, and high-speed stirring in the presence of 20 parts dispersion medium water forms uniform material, reacts 3～4 hours at 60～80 ℃.The product of gained is functional type polyorganosilicate mixture after washing, drying, pulverizing; This polyorganosilicate composite powder is scattered in 100 parts of room temperature glue polydimethylsiloxanes with machine,massing, stirred 4 hours, add 10 parts of tetraethoxys and 1 part of stannous octoate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 20～45 ℃ 14 hours, and promptly got the silicon rubber/clay nano composite material that glows.
Embodiment 2
With rare earth chloride EuCl
3, styracin, organic silicon surfactant 3-trimethoxy silicon propyl group methylethyl cetyl chloride ammonium obtained the stable novel rare-earth organosilicon light-converting agent of a class formation 40～60 ℃ of reactions 4 hours in 1: 5: 0.2 in molar ratio.With 1 part of organosilicon light-converting agent and cation exchange capacity is 10 parts of the clays of 90meq/100g, and high-speed stirring in the presence of 100 parts dispersion medium ethanol forms uniform material, reacts 3～5 hours at 60～70 ℃.The product of gained is functional type polyorganosilicate mixture after washing, drying, pulverizing; This polyorganosilicate composite powder is scattered in 100 parts of PSIs with machine,massing, stirred 6 hours, add 5 parts of tetraethoxys and 0.4 part of dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 20～45 ℃ 14 hours, and promptly got the silicon rubber/clay nano composite material that glows.
Embodiment 3
With rare earth chloride EuCl
3, β-naphthoic acid, organic silicon surfactant 3-trimethoxy silicon propyl-dimethyl octadecyl bromination ammonium obtained the stable novel rare-earth organosilicon light-converting agent of a class formation 150～200 ℃ of reactions 3 hours in 1: 8: 2 in molar ratio.With 6 parts of organosilicon light-converting agents and cation exchange capacity is 7 parts of the clays of 80meq/100g, and high-speed stirring in the presence of 200 parts dispersion medium dimethyl formamide forms uniform material, reacts 4 hours at 80～100 ℃.The product of gained is functional type polyorganosilicate mixture after washing, drying, pulverizing; This polyorganosilicate composite powder is scattered in 100 parts of room temperature glue polydimethylsiloxanes with machine,massing, stirred 5 hours, add 5 parts of tetraethoxys and 0.3 part of dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 20～45 ℃ 14 hours, and promptly got the silicon rubber/clay nano composite material that glows.
Embodiment 4
With rare earth chloride EuCl
3, p-methylbenzoic acid, organic silicon surfactant 3-triethoxysilylpropyl dimethyl cetyl chloride ammonium obtained the stable novel rare-earth organosilicon light-converting agent of a class formation 60～80 ℃ of reactions 4 hours in 1: 6: 2 in molar ratio.With 4 parts of organosilicon light-converting agents and cation exchange capacity is 6 parts of the clays of 80meq/100g, and high-speed stirring in the presence of 300 parts dispersion medium forms uniform material, reacts 3～5 hours at 80～100 ℃.The product of gained is functional type polyorganosilicate mixture after washing, drying, pulverizing; This polyorganosilicate composite powder is scattered in 100 parts of room temperature glue polydimethylsiloxanes with machine,massing, stirred 5 hours, add 6 parts of tetraethoxys and 0.5 part of dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 20～45 ℃ 14 hours, and promptly got the silicon rubber/clay nano composite material that glows.
Embodiment 5
With rare earth chloride EuCl
3, to octadecyl phenylformic acid, organic silicon surfactant 3-triethoxysilylpropyl dimethyl cetyltrimethyl ammonium 1: 8: 2 in molar ratio 100～150 ℃ of reactions 3 hours, obtain the stable novel rare-earth organosilicon light-converting agent of a class formation.With 10 parts of organosilicon light-converting agents and cation exchange capacity is 10 parts of the clays of 100meq/100g, and high-speed stirring in the presence of 400 parts dispersion medium forms uniform material, reacts 3 hours at 70～100 ℃.Gained
Product is functional type polyorganosilicate mixture after washing, drying, pulverizing; This polyorganosilicate composite powder is scattered in 100 parts of room temperature glue polydimethylsiloxanes with machine,massing, stirred 5 hours, add 6 parts of tetraethoxys and 0.5 part of dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 20～45 ℃ 14 hours, and promptly got the silicon rubber/clay nano composite material that glows.
Embodiment 6
With rare earth chloride EuCl
3, to hexadecyl phenylformic acid, organic silicon surfactant 3-triethoxysilylpropyl dimethyl stearyl ammonium chloride 1: 8: 1 in molar ratio 80～100 ℃ of reactions 5 hours, obtain the stable novel rare-earth organosilicon light-converting agent of a class formation.With 1 part of organosilicon light-converting agent and cation exchange capacity is 30 parts of the clays of 70meq/100g, and high-speed stirring in the presence of 400 parts dispersion medium forms uniform material, reacts 4 hours at 70～100 ℃.The product of gained is functional type polyorganosilicate mixture after washing, drying, pulverizing; This polyorganosilicate composite powder is scattered in 100 parts of room temperature glue polydimethylsiloxanes with machine,massing, stirred 5 hours, add 6 parts of tetraethoxys and 0.5 part of dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 20～45 ℃ 14 hours, and promptly got the silicon rubber/clay nano composite material that glows.
Embodiment 7
With rare earth chloride EuCl
3, para-amino benzoic acid, organic silicon surfactant 3-triethoxysilylpropyl dimethyl cetyl chloride ammonium obtained the stable novel rare-earth organosilicon light-converting agent of a class formation 80～100 ℃ of reactions 4 hours in 1: 6: 2 in molar ratio.With 3 parts of organosilicon light-converting agents and cation exchange capacity is 10 parts of the clays of 120meq/100g, and high-speed stirring in the presence of 100 parts dispersion medium forms uniform material, reacts 5 hours at 70～100 ℃.The product of gained is functional type polyorganosilicate mixture after washing, drying, pulverizing; This polyorganosilicate composite powder is scattered in 100 parts of room temperature glue polydimethylsiloxanes with machine,massing, stirred 5 hours, add 6 parts of tetraethoxys and 0.5 part of dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 20～45 ℃ 14 hours, and promptly got the silicon rubber/clay nano composite material that glows.
Embodiment 8
With Eu (NO
3)
3, to amylbenzene formic acid, organic silicon surfactant 3-trimethoxy silicon propyl-dimethyl hexadecyl brometo de amonio 1: 6: 2 in molar ratio 30～60 ℃ of reactions 6 hours, obtain the stable novel rare-earth organosilicon light-converting agent of a class formation.With 5 parts of organosilicon light-converting agents and cation exchange capacity is 5 parts of the clays of 80meq/100g, and high-speed stirring in the presence of 100 parts dispersion medium forms uniform material, reacts 4 hours at 60～100 ℃.The product of gained is functional type polyorganosilicate mixture after washing, drying, pulverizing; This polyorganosilicate composite powder is scattered in 100 parts of poly-ethylene methacrylic radical siloxanes with machine,massing, stirred 5 hours, add 1 part of benzoyl peroxide, stir, pour in the mould, under 5MPa pressure,, promptly get luminous silastic/clay nanometer composite material in 125～135 ℃ of sulfurations 10～15 minutes.
Embodiment 9
With rare earth chloride TbCl
3, terephthalic acid, organic silicon surfactant 3-triethoxysilylpropyl methylethyl cetyl chloride ammonium obtained the stable novel rare-earth organosilicon light-converting agent of a class formation 80～100 ℃ of reactions 6 hours in 1: 2: 1 in molar ratio.With 3 parts of organosilicon light-converting agents and cation exchange capacity is 3 parts of the clays of 80meq/100g, and high-speed stirring in the presence of 60 parts dispersion medium forms uniform material, reacts 3～6 hours at 20～200 ℃.The product of gained is functional type polyorganosilicate mixture after washing, drying, pulverizing; This polyorganosilicate composite powder is scattered in 100 parts of polydimethylsiloxanes with machine,massing, stirred 5 hours, add 5 parts of tetraethoxys and 0.3 part of dibutyl tin laurate, stir, pour in the polytetrafluoroethyldisk disk, at least placed under 20～45 ℃ 14 hours, and promptly got luminous silicon rubber/clay nano composite material.
Embodiment 10
Basic identical with embodiment 9, just with TbCl
3Change Tb (NO into
3)
3
Embodiment 11
With rare earth chloride EuCl
3, to hexyl benzene formic acid, organic silicon surfactant 2-methylacryoyloxyethyl dimethyl 3-trimethoxy silicon propyl ammonium chloride 1: 10: 2 in molar ratio 30～60 ℃ of reactions 6 hours, obtain a class formation and stablize novel rare-earth organosilicon light-converting agent.With 2 parts of organosilicon light-converting agents and cation exchange capacity is 3 parts of the clays of 80meq/100g, and high-speed stirring in the presence of 30 parts dispersion medium forms uniform material, reacts 5 hours at 70～100 ℃.The product of gained is functional type polyorganosilicate mixture after washing, drying, pulverizing; This polyorganosilicate composite powder is scattered in 100 parts of polymethylmethacrylates with machine,massing, stirred 5 hours, pour in the polytetrafluoroethyldisk disk, placed at least 14 hours under 20～45 ℃, promptly get the silicon rubber/clay nano composite material that glows.
Embodiment 12
With rare earth chloride EuCl
3, to dodecyl phenylformic acid, organic silicon surfactant 2-methylacryoyloxyethyl dimethyl 3-triethoxysilylpropyl brometo de amonio 1: 6: 1.5 in molar ratio 20～200 ℃ of reactions 5 hours, obtain the stable novel rare-earth organosilicon light-converting agent of a class formation.With 1 part of organosilicon light-converting agent and cation exchange capacity is 0.5 part of the clay of 90meq/100g, and high-speed stirring in the presence of 10 parts dispersion medium forms uniform material, reacts 6 hours at 70～100 ℃.The product of gained is functional type polyorganosilicate mixture after washing, drying, pulverizing; This polyorganosilicate composite powder is scattered in 100 parts of polymethylmethacrylates with machine,massing, pours in the polytetrafluoroethyldisk disk, placed at least 14 hours under 20～45 ℃, promptly get the silicon rubber/clay nano composite material that glows.
Embodiment 13
With rare earth chloride EuCl
3, to dodecyl phenylformic acid, organic silicon surfactant 2-methylacryoyloxyethyl dimethyl 3-triethoxysilylpropyl ammonium chloride 1: 6: 1.5 in molar ratio 20～200 ℃ of reactions 5 hours, obtain the stable novel rare-earth organosilicon light-converting agent of a class formation.With 1 part of organosilicon light-converting agent and cation exchange capacity is 3 parts of the clays of 90meq/100g, and high-speed stirring in the presence of 20 parts dispersion medium forms uniform material, reacts 6 hours at 70～100 ℃.The product of gained is functional type polyorganosilicate mixture after washing, drying, pulverizing; This polyorganosilicate composite powder is scattered in 100 parts of polyacrylamides with machine,massing, pours in the polytetrafluoroethyldisk disk, placed at least 14 hours under 20～45 ℃, promptly get the silicon rubber/clay nano composite material that glows.
Claims (7)
1. a nano luminescent matrix material is characterized in that, its feed composition and weight content are as follows:
100 parts in polymkeric substance
0.5～30 part of clay
0.5～10 part of rare earth organosilicon light-converting agent
20～400 parts in dispersion medium
0～10 part of linking agent
0～1 part of promotor.
2. nano luminescent matrix material according to claim 1 is characterized in that described polymkeric substance is raw-silastic continuously or the polymkeric substance or the multipolymer that are formed by acrylamide, methacryloyl amine, vinylformic acid, esters of acrylic acid, methacrylic acid, methyl acrylic ester monomer.
3. nano luminescent matrix material according to claim 1 is characterized in that: described rare earth ion is Eu
3+, Tb
3+, provide by the nitrate or the hydrochloride of trivalent europium and terbium.
4. nano luminescent matrix material according to claim 1 is characterized in that: organic carboxyl acid is C
1-C
18Alkylbenzoic acid, benzaminic acid or phthalic acid or styracin or naphthoic acid.
5. nano luminescent matrix material according to claim 1 is characterized in that: organic silicon surfactant, chemical structure skeleton symbol are (RO)
3SiR
1N
+R
2R
3R
4X
-, wherein R is CH
3Or C
2H
5R
1For-CH
2-or-C
3H
6-; R
2Be CH
3Or C
2H
5R
3Be CH
3Or C
2H
5R
4Can be chain alkyl, also can be aliphatics vinylformic acid and ester derivative thereof.
6. nano luminescent matrix material according to claim 1 is characterized in that: described clay is the inorganics that a class has laminate structure, and its cationic exchange total volume is 70～120meq/100g.
7. according to the preparation method of the described nano luminescent matrix material of claim 1, follow these steps to carry out:
The nitrate of trivalent europium or terbium or hydrochloride, organic carboxyl acid, organic silicon surfactant 1: 2 in molar ratio～10: 0.2～2 20～200 ℃ of reactions 3～6 hours, are obtained constitutionally stable rare earth organosilicon light-converting agent;
With 0.5～10 part of organosilicon light-converting agent and cation exchange capacity is 0.5～30 part of the clay of 70～120meq/100g, and high-speed stirring in the presence of 20～400 parts dispersion medium forms uniform material, reacts 3～6 hours at 20～200 ℃; With the product of gained through washing, dry, pulverize, obtain the polyorganosilicate mixture;
In the polymkeric substance or multipolymer that 0.5～30 part of above-mentioned polyorganosilicate mixture is scattered in 100 parts of raw-silastic continuouslies (room temperature silicon rubber, high temperature silicon rubber, addition-type silicon rubber) or forms by acrylamide, methacryloyl amine, vinylformic acid, esters of acrylic acid, methacrylic acid, methyl acrylic ester monomer, stir and add 0～10 part of linking agent after 5～10 hours, 0～1 part of promotor, pour in the mould, place for 20～120 ℃ and promptly got product in 0.2～24 hour.
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