CN1313565C - Rare earth/polymer composite luminous material and its preparation method - Google Patents
Rare earth/polymer composite luminous material and its preparation method Download PDFInfo
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- CN1313565C CN1313565C CNB2004100706073A CN200410070607A CN1313565C CN 1313565 C CN1313565 C CN 1313565C CN B2004100706073 A CNB2004100706073 A CN B2004100706073A CN 200410070607 A CN200410070607 A CN 200410070607A CN 1313565 C CN1313565 C CN 1313565C
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 153
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 117
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 30
- 229920000642 polymer Polymers 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title abstract description 34
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 60
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- -1 rare earth ions Chemical class 0.000 claims abstract description 38
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 150000002978 peroxides Chemical class 0.000 claims abstract description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000011159 matrix material Substances 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 150000001451 organic peroxides Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 229920002521 macromolecule Polymers 0.000 abstract description 25
- 150000001875 compounds Chemical class 0.000 abstract description 15
- 239000013110 organic ligand Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 31
- 229920013649 Paracril Polymers 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 239000004594 Masterbatch (MB) Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 206010070834 Sensitisation Diseases 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 3
- 206010047700 Vomiting Diseases 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- TXBBUSUXYMIVOS-UHFFFAOYSA-N thenoyltrifluoroacetone Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CS1 TXBBUSUXYMIVOS-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 230000008673 vomiting Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Images
Abstract
The present invention relates to a rare earth/macromolecule composite luminous material and a preparation method thereof. An organic ligand and a cooperation reagent which can be well matched with rare earth ions, and acrylic acid which can increase reaction activity in situ are mainly used for reacting and preparing RE (TTA) 2 (AA) phen which can transmit Sm<3+> or Eu<3+> characteristic fluorescence. Then, the RE (TTA) 2 (AA) phen is filled into nitrile rubber which comprises strong polar group-CN, and meanwhile, peroxide is added into the nitrile rubber, the reaction in situ can be generated in crosslink, and consequently, the rare earth organic coordination compound/macromolecule composite luminous material is prepared. The composite material can sensitize the luminescence of the rare earth ions, can compensate the defect of small absorption coefficient of the rare earth ions in an ultraviolet area and a visible light area, and can increase the luminous intensity of the rare earth ions.
Description
Technical field
The present invention relates to a kind of rare earth/macromolecule composite luminescent material and preparation method thereof.Matrix material and the preparation method who obtains with rare earth organic complex and macromolecule matrix material reaction in particularly.
Background technology
Rare earth element is a kind of ideal luminescent material because of the structure of its 4f electronic shell has the characteristics of luminescence, studies show that the luminous efficiency of rare earth ion own is low, but rare earth can constitute rare earth organic complex with the organic ligand with high specific absorbance.Because organic ligand is stronger in the absorption of ultraviolet, visible region, and can be transferred to central ion emission light to excited energy by radiationless transition effectively, thereby the sensitization rare earth ion is luminous, remedy rare earth ion in ultraviolet, defective that visible region uptake factor ε is very little, thereby improved the luminous intensity of rare earth ion.The organic ligand that research has at present related to mainly contains: beta-diketon class, aromatic cycle compound, heterogeneous ring compound etc.
]
1963, Wolff and Pressley studied Eu (TTA)
3(TTA: thenyltrifluoroacetone) fluorescence in polymethylmethacrylate and laser property, started rare earth high polymer research frontier
]Entered since the eighties, the researchist has prepared rare earth/macromolecule composite luminescent material with methods such as rare earth and polymer blending, rare earth organic complex monomer polymerizations.But because the blending method mainly is to realize by mechanical blending, melt blending, solvent or solvent dissolving, and most of rare earth compounds especially rare earth inorganics and resin affinity are little, rare earth compound is difficult to be evenly dispersed in the resin, this not only makes the transparent deformation of material poor, the strength of materials is reduced, and therefore this simple doping way can not get the high transparent rare earth high polymer material of high rare-earth content.Thereby limited their application greatly.Polymerization be with the rare earth ion Direct Bonding on macromolecular chain, therefore, it is little to have overcome doping type rare earth high polymer middle-weight rare earths compound and resin affinity to a certain extent, shortcomings such as the material transparency and poor mechanical property, for the rare earth high polymer functional materials that obtains wide content of rare earth high transmission rate provides the possibility approach, at present mainly by following three approach: reactive functional groups such as reactions such as carboxyl, hydroxyl on (1) rare earth ion and the macromolecular chain; (2) contain ligand on rare earth ion and the chain, these dentates mainly contain beta-diketon base, carboxyl, sulfonic group, pyridyl, porphyryl, crown ether base and cave ether etc.; (3) contain monomer homopolymerization or copolymerization, the polycondensation etc. of rare earth metal.But polymerization is subjected to the restriction of processing condition own, and the content of rare earth of its system also can't improve too much, can occur " quencher " phenomenon when content of rare earth is too high.Prepare rare earth/polyamide compoiste material as JP8-73735 is disclosed with polymerization, the content of rare-earth salts is controlled at below 20%.Research shows that also polymer architecture has a significant impact the rare earth luminescence performance, and this has also just illustrated by different synthetic methods can obtain the rare earth of different luminescent properties from aggressiveness.Therefore, the rare earth high polymer material that rare earth compounding and polymer are carried out compoundly prepare high rare-earth content, high transmission rate, has stabilized illumination performance and other premium propertiess becomes the target that people pursue.
The Chinese patent (patent No. 01136311.8) " preparation method of rare earth/polymer composite " that is obtained by the applicant has proposed with macromolecule matrix material and rare earth organic salt, superoxide and auxiliary agent reaction in obtain the method for rare earth/polymer composite, this method reaches nano level with rare earth and disperses in macromolecule matrix, and form special ultra micro composite structure, this structure is to the light of rare earth,, performances such as magnetic produce special influence, aspect the light characteristic of performance rare earth, because matrix material particular configuration of matrix material in solid-state of this method preparation is fixed, making dissociates reduces to minimum, luminescent properties is better, still can be made into transparent material under higher rare earth concentration, this makes rare earth/polymer composite in luminous field vast application prospect be arranged.Yet because the luminous efficiency of rare earth ion itself is low, this patented method adopts rare earth organic salt and macromolecule matrix material in-situ polymerization, still fail to remedy rare earth ion in ultraviolet, defective that the visible region uptake factor is little, therefore do not have the luminous intensity of the most effective raising rare earth ion.
Summary of the invention
The present invention is for solving rare earth ion in ultraviolet, defective that the visible region uptake factor is little, effectively improve the luminous intensity of rare earth ion, a kind of rare earth/macromolecule composite luminescent material and in-situ reaction preparation method thereof are provided, contain in this material and can effectively absorb outside energy and can pass to its luminous rare earth organic complex of rare earth ion sensitization, make material have high fluorescent; This in-situ reaction preparation method makes rare earth organic complex reach nano level in macromolecule matrix and disperses, and can increase substantially the rare earth consumption and " quencher " do not take place, and technology is simple.
Rare earth/macromolecule composite luminescent material that the present invention proposes, comprise rare earth organic complex and can carry out crosslinked macromolecule matrix material by enough organo-peroxides, rare earth organic complex is the synthetics of rare earth (RE)/thenoyltrifluoroacetone (HTTA)/vinylformic acid (HAA)/neighbour luxuriant and rich with fragrance sound of vomiting quinoline (phen), and its molecular formula is RE (TTA)
2(AA) phen, wherein RE is rare earth metal samarium Sm or rare earth metal europium Eu, 1～40 part of rare earth organic complex content, 100 parts of macromolecule matrix materials.
Above-mentioned macromolecular material matrix is a paracril.
Thenoyltrifluoroacetone in the rare earth organic complex of the present invention (HTTA) can effectively absorb outside energy and transmission ofenergy can be given the rare earth ion sensitization that it is luminous, and adjacent luxuriant and rich with fragrance sound of vomiting quinoline (phen) then can act synergistically with HTTA; Vinylformic acid (HAA) is for having the organic carboxyl acid of two keys, and it adds in position can provide the functional group that can react man-hour, makes reaction in be achieved.Rare earth ion in such title complex can with the polar group generation coordination in the rubber that contains strong polar group, thereby can be effectively outside energy be shifted to rare earth ion by polar group (as-CN group), improve its luminous efficiency.
The macromolecular material that the present invention uses is paracril (NBR), because paracril has strong polar-CN group, can and rare earth ion between produce coordination, thereby effectively outside energy is shifted to rare earth ion by-CN group, improve its luminous efficiency.
The macromolecule matrix material that the present invention uses is not limited to paracril, can select for use different macromolecular materials to do body material according to the difference of purposes.
The invention allows for the preparation method of rare earth/macromolecule composite luminescent material, macromolecule matrix material and rare earth organic complex are made with the peroxide crosslinking reaction in, it is characterized in that: synthesizing rare-earth organic coordination compound at first, the hydrochloric acid reaction of rare earth oxide europium sesquioxide or Samarium trioxide and 40%～70% is converted into rare earth chloride, again with the thenoyltrifluoroacetone of this chloride soln and certain mol proportion, vinylformic acid (HAA) and adjacent luxuriant and rich with fragrance sound of vomiting quinoline (phen) mix, in water-bath after the reacting by heating, pH value to 5～6 with 1: 1 ammonia soln regulator solution, normal temperature leaves standstill, filter, it is RE (TTA) that the vacuum drying oven oven dry obtains molecular formula
2(AA) synthetics of phen; With 1～40 part of synthetic rare earth organic complex, 100 parts of macromolecule matrix materials and superoxide and auxiliary agent reaction under processing temperature are prepared composite luminescent material.
The superoxide that above-mentioned reaction in uses is normally used kind, as: two 2,5, DCP etc.Reaction in condition and existing reaction in technology are similar, do not have particular requirement.
Effect of the present invention: selected energy and Sm
3+Or Eu
3+Ion form the beta-diketon class part and the collaborative reagent of matched well and contain two bond energys enough increase reactive behavior the vinylformic acid prepared in reaction can launch Sm
3+Or Eu
3+The organic coordination compound RE (TTA) of ion characteristic fluorescence
2(AA) phen (RE=Sm or Eu).Shift effectively by intramolecular energy excited energy is transferred to central ion from the form of organic ligand by nonradiative transition, thereby sensitization rare earth ion luminous, remedy rare earth ion in ultraviolet, defective that the visible region uptake factor is little, improved the luminous intensity of rare earth ion.
Preparation method of the present invention prepares luminescent composite with synthetic rare earth organic complex and macromolecule matrix material reaction in.Make rare earth organic complex reach nano level in macromolecule matrix and disperse, can increase substantially the rare earth consumption, and its luminous intensity is higher, and " quencher " do not take place, technology is simple.
The present invention can make elasticity or stiff film, sheet material, sheet material etc. according to the difference of using needs.Material can be used for various light conversion field, as the visible light that UV-light changed into specific wavelength with as the necessary light source of plant-growth; Or white light is converted into the monochromatic optical wave of specific wavelength, and make various luminous energy controlling elementss or the like, provide wide space for manually making light.
Description of drawings:
Fig. 1 is Eu (TTA)
3The fluorescent emission spectrogram of phen rare earth organic complex;
Fig. 1 is Eu (TTA)
3The fluorescent emission spectrogram of phen rare earth organic complex;
Fig. 2 is Sm (TTA)
3The fluorescent emission spectrogram of phen rare earth organic complex;
Fig. 3 is Eu (TTA)
3The fluorescent emission spectrogram of phen/NBR compound system rubber unvulcanizate;
Fig. 4 is Sm (TTA)
3The fluorescent emission spectrogram of phen/NBR compound system rubber unvulcanizate;
Fig. 5 is Eu (TTA)
3The fluorescent emission spectrogram of phen/NBR compound system cross-linked rubber;
Fig. 6 is Sm (TTA)
3The fluorescent emission spectrogram of phen/NBR compound system cross-linked rubber;
Embodiment:
The used macromolecule matrix material of the present invention is not limited to paracril, during enforcement, when used macromolecule matrix material is rubber, can use rubber tooling commonly used such as mill, Banbury mixer etc., and processing temperature normal temperature gets final product.In the Composite Preparation process, all adopt the rubber master batch method, promptly earlier rubber and Synergist S-421 95 blend commonly used are made rubber master batch, on aforesaid device, mix then, baking carries out the reaction in moulding and can make this matrix material with rare earth organic complex.
When used macromolecular material is thermoplasticity or thermoplastic elastomer, can on common equipments such as hot-rolling mill, Banbury mixer, twin screw extruder, process, processing temperature is controlled in 100～120 ℃ of scopes, and working method has two kinds of direct blending method and rubber master batch methods.Directly the blending method be exactly under the processing temperature condition with thermoplastic molten, adding Synergist S-421 95 (as antioxidant, tenderizer, other processing aids etc.) adds rare earth organic complex again.The rubber master batch method is applicable to the more situation that gets of Synergist S-421 95 consumption, this method is earlier with thermoplastic molten, add Synergist S-421 95 (as antioxidant, tenderizer, other processing aids etc.) make rubber master batch, and then carry out blend with rare earth organic complex, utilize mold pressing, roll, extrude, inject to such an extent that method is carried out the reaction in moulding and made matrix material.
Below in conjunction with embodiment the present invention is described further.
Embodiment 1: earlier the hydrochloric acid reaction with rare-earth oxidation shirt and 1: 1 is converted into rare earth chloride SmCl
3, again with this chloride soln and TTA, HAA and phen 1: 2: 1 in molar ratio: 1 mixes, 60 ℃ of reactions after 2 hours down, to 5-6, normal temperature leaves standstill with the pH value of 1: 1 ammonia soln regulator solution, filters, product spends the night in 80 ℃ of vacuum drying ovens, prepares (Sm (TTA)
2(AA) phen), 100 parts of paracrils (NBR) are with rare earth organic complex (Sm (TTA)
2(AA) matrix material of 2 parts of compositions phen).
Reaction in is implemented and Composite Preparation: mill running under the normal temperature, and add 100gNBR and make its bag roller, add rare earth organic complex (Sm (TTA)
2(AA) 2g mixing phen) is eaten powder and is finished that to add 3g two 2,5, plays ten triangle bags, evenly descends sheet, be positioned over again in 10cm * 6cm * 2cm mould, and the exhaust of pressurizeing, pressure is 100kg/cm
2, suppress (reaction in took place in this stage) after 15 minutes, mould is taken out the taking-up sample.
Embodiment 2: 100 parts of paracrils (NBR), and with the rare earth organic complex (Sm (TTA) of embodiment 1 preparation
2(AA) matrix material of 5 parts of compositions phen).Reaction in is implemented and Composite Preparation: mill running under the normal temperature, and add 100gNBR and make its bag roller, add rare earth organic complex (Sm (TTA)
2(AA) 5g mixing phen) is eaten powder and is finished that to add 3g two 2,5, plays ten triangle bags, and following sheet is even, is positioned in 10cm * 6cm * 2cm mould again, the exhaust of pressurizeing, and pressure is 100kg/cm
2, suppress (reaction in took place in this stage) after 15 minutes, mould is taken out the taking-up sample.
Embodiment 3: 100 parts of paracrils (NBR), and with the rare earth organic complex (Sm (TTA) of embodiment 1 preparation
2(AA) matrix material of 8 parts of compositions phen).Reaction in is implemented and Composite Preparation: mill running under the normal temperature, and add 100gNBR and make its bag roller, add rare earth organic complex (Sm (TTA)
2(AA) 8g mixing phen) is eaten powder and is finished that to add 3g two 2,5, plays ten triangle bags, and following sheet is even, is positioned in 10cm * 6cm * 2cm mould again, the exhaust of pressurizeing, and pressure is 100kg/cm
2, suppress (reaction in took place in this stage) after 15 minutes, mould is taken out the taking-up sample.
Embodiment 4: 100 parts of paracrils (NBR), and with the rare earth organic complex (Sm (TTA) of embodiment 1 preparation
2(AA) matrix material of 10 parts of compositions phen).Reaction in is implemented and Composite Preparation: mill running under the normal temperature, and add the 100gNBR rubber master batch and make its bag roller, add rare earth organic complex (Sm (TTA)
2(AA) 10g mixing phen) is eaten powder and is finished that to add 3g two 2,5, plays ten triangle bags, and following sheet is even, is positioned in 10cm * 6cm * 2cm mould again, the exhaust of pressurizeing, and pressure is 100kg/cm
2, suppress (reaction in took place in this stage) after 15 minutes, mould is taken out the taking-up sample.
Embodiment 5: 100 parts of paracrils (NBR), and with the rare earth organic complex (Sm (TTA) of embodiment 1 preparation
2(AA) matrix material of 15 parts of compositions phen).Reaction in is implemented and Composite Preparation: mill running under the normal temperature, and add the 100gNBR rubber master batch and make its bag roller, add rare earth organic complex (Sm (TTA)
2(AA) 5g mixing phen) adds remaining rare earth organic complex (Sm (TTA) again
2(AA) 10g phen) eats powder and finishes that to add 3g two 2,5, plays ten triangle bags, and following sheet is even, is positioned in 10cm * 6cm * 2cm mould again, the exhaust of pressurizeing, and pressure is 100kg/cm
2, suppress (reaction in took place in this stage) after 15 minutes, mould is taken out the taking-up sample.
Embodiment 6: 100 parts of paracrils (NBR), and with the rare earth organic complex (Sm (TTA) of embodiment 1 preparation
2(AA) matrix material of 38 parts of compositions phen).Reaction in is implemented and Composite Preparation: mill running under the normal temperature, and add the 100gNBR rubber master batch and make its bag roller, add rare earth organic complex (Sm (TTA)
2(AA) 10g mixing phen) adds remaining rare earth organic complex (Sm (TTA) again
2(AA) 28g phen) eats powder and finishes that to add 3g two 2,5, plays ten triangle bags, and following sheet is even, is positioned in 10cm * 6cm * 2cm mould again, the exhaust of pressurizeing, and pressure is 100kg/cm
2, suppress (reaction in took place in this stage) after 15 minutes, mould is taken out the taking-up sample.
Embodiment 7: earlier the hydrochloric acid reaction with rare-earth oxidation europium and 1: 1 is converted into rare earth chloride EuCl
3, again with this chloride soln and TTA, HAA and phen 1: 2: 1 in molar ratio: 1 mixes, 60 ℃ of reactions after 2 hours down, to 5-6, normal temperature leaves standstill with the pH value of 1: 1 ammonia soln regulator solution, filters, product spends the night in 80 ℃ of vacuum drying ovens, prepares (Eu (TTA)
2(AA) phen).100 parts of paracrils (NBR) are with rare earth organic complex (Eu (TTA)
2(AA) matrix material of 3 parts of compositions phen).Reaction in is implemented and Composite Preparation: mill running under the normal temperature, and add the 100gNBR rubber master batch and make its bag roller, add rare earth organic complex (Eu (TTA)
2(AA) 3g mixing phen) is eaten powder and is finished that to add 3g two 2,5, plays ten triangle bags, and following sheet is even, is positioned in 10cm * 6cm * 2cm mould again, the exhaust of pressurizeing, and pressure is 100kg/cm
2, suppress (reaction in took place in this stage) after 15 minutes, mould is taken out the taking-up sample.
Embodiment 8: 100 parts of paracrils (NBR), and with the rare earth organic complex (Eu (TTA) of embodiment 7 preparations
2(AA) matrix material of 6 parts of compositions phen).Reaction in is implemented and Composite Preparation: mill running under the normal temperature, and add the 100gNBR rubber master batch and make its bag roller, add rare earth organic complex (Eu (TTA)
2(AA) 6g mixing phen) is eaten powder and is finished that to add 3g two 2,5, plays ten triangle bags, and following sheet is even, is positioned in 10cm * 6cm * 2cm mould again, the exhaust of pressurizeing, and pressure is 100kg/cm
2, suppress (reaction in took place in this stage) after 15 minutes, mould is taken out the taking-up sample.
Embodiment 9: 100 parts of paracrils (NBR), and with the rare earth organic complex (Eu (TTA) of embodiment 7 preparations
2(AA) matrix material of 9 parts of compositions phen).Reaction in is implemented and Composite Preparation: mill running under the normal temperature, and add the 100gNBR rubber master batch and make its bag roller, add rare earth organic complex (Eu (TTA)
2(AA) 9g mixing phen) is eaten powder and is finished that to add 3g two 2,5, plays ten triangle bags, and following sheet is even, is positioned in 10cm * 6cm * 2cm mould again, the exhaust of pressurizeing, and pressure is 100kg/cm
2, suppress (reaction in took place in this stage) after 15 minutes, mould is taken out the taking-up sample.
Embodiment 10: 100 parts of paracrils (NBR), and with the rare earth organic complex (Eu (TTA) of embodiment 7 preparations
2(AA) matrix material of 15 parts of compositions phen).Reaction in is implemented and Composite Preparation: mill running under the normal temperature, and add the 100gNBR rubber master batch and make its bag roller, add rare earth organic complex (Eu (TTA)
2(AA) 5g mixing phen) adds remaining rare earth organic complex (Eu (TTA) again
2(AA) phen) 10g eats powder and finishes that to add 3g two 2,5, plays ten triangle bags, and following sheet is even, is positioned in 10cm * 6cm * 2cm mould again, the exhaust of pressurizeing, and pressure is 100kg/cm
2, suppress (reaction in took place in this stage) after 15 minutes, mould is taken out the taking-up sample.
Embodiment 11: 100 parts of paracrils (NBR), and with the rare earth organic complex (Eu (TTA) of embodiment 7 preparations
2(AA) matrix material of 20 parts of compositions phen).Reaction in is implemented and Composite Preparation: mill running under the normal temperature, and add the 100gNBR rubber master batch and make its bag roller, add rare earth organic complex (Eu (TTA)
2(AA) 10g mixing phen) adds remaining rare earth organic complex (Eu (TTA) again
2(AA) phen) 10g eats powder and finishes that to add 3g two 2,5, plays ten triangle bags, and following sheet is even, is positioned in 10cm * 6cm * 2cm mould again, the exhaust of pressurizeing, and pressure is 100kg/cm
2, suppress (reaction in took place in this stage) after 15 minutes, mould is taken out the taking-up sample.
Embodiment 12: 100 parts of paracrils (NBR), and with the rare earth organic complex (Eu (TTA) of embodiment 7 preparations
2(AA) matrix material of 40 parts of compositions phen).Reaction in is implemented and Composite Preparation: mill running under the normal temperature, and add the 100gNBR rubber master batch and make its bag roller, add rare earth organic complex (Eu (TTA)
2(AA) 10g mixing phen) adds remaining rare earth organic complex (Eu (TTA) again
2(AA) phen) 30g eats powder and finishes that to add 3g two 2,5, plays ten triangle bags, and following sheet is even, is positioned in 10cm * 6cm * 2cm mould again, the exhaust of pressurizeing, and pressure is 100kg/cm
2, suppress (reaction in took place in this stage) after 15 minutes, mould is taken out the taking-up sample.
For the explanation reaction in generation we use scanning electronic microscope (SEM) and the prepared rare earth organic complex (Eu (TTA) of projection electron microscope (TEM)
2(AA) phen, Sm (TTA)
2(AA) pattern phen), rare earth organic complex (Eu (TTA)
2(AA) phen, Sm (TTA)
2(AA) phen) these three kinds of states of pattern that unreacted pattern and rare earth organic complex carry out in macromolecule matrix after the reaction in macromolecule matrix are observed.The variation of the rare earth organic complex size of particles that arrives by contrast SEM and tem observation, under the heat of primary macroparticle (10 microns) by mechanical shearing, the effect of power physical mechanical by refinement, size of particles is (below 1 a micron) in rubber unvulcanizate, again by being reduce (the reaching nano level) of size in the rare earth organic complex particle revulcanization glue that micron order distributes in the rubber unvulcanizate, confirmed the generation of reaction in, and refinement and the homodisperse of filler in macromolecule matrix played good effect.
In order to illustrate that prepared matrix material possesses good luminous property, we are to the organic coordination compound (Eu (TTA) of different rare earth elements
2(AA) phen, Sm (TTA)
2(AA) phen) and the fluorescence property of corresponding NBR based composites (sulfuration, sulfuration) test respectively.Test result such as Fig. 1 be to shown in Figure 6, and the fluorescence intensity that shows matrix material strengthens with the increase of rare earth compounding content, does not have " quenching of fluorescence " phenomenon Eu wherein shown in Figure 5 (TTA) takes place
3The fluorescence pattern of phen/NBR compound system cross-linked rubber and Eu (TTA) shown in Figure 3
31 to 6 curve is respectively the luminous intensity curve of rare earth part content when being 3 parts, 5 parts, 9 parts, 15 parts, 20,40 parts in the fluorescence pattern of phen/NBR compound system rubber unvulcanizate; Sm shown in Figure 6 (TTA)
3The fluorescence pattern of phen/NBR compound system cross-linked rubber and Sm (TTA) shown in Figure 4
31 to 6 curve is respectively the luminous intensity curve of rare earth part content when being 2 parts, 5 parts, 8 parts, 10 parts, 15,38 parts in the fluorescence pattern of phen/NBR compound system rubber unvulcanizate; From scheming as seen, when content of rare earth is increased to a certain degree, the fluorescence intensity of cross-linked rubber even be higher than the fluorescence intensity of the pure organic coordination compound that is added.And the fluorescence intensity of rubber unvulcanizate when cross-linked rubber is higher than identical content of rare earth illustrates that New Photoinduced rare earth of the present invention/macromolecular LED matrix material has excellent luminescent properties, has broad application prospects.
Claims (3)
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| CN102964639A (en) * | 2011-08-31 | 2013-03-13 | 赛轮股份有限公司 | Tire fluorescent sidewall rubber and preparation method |
| CN102604391A (en) * | 2012-02-16 | 2012-07-25 | 上海交通大学 | Preparation method of silicone rubber composite material with fluorescence |
| CN104152065B (en) * | 2014-08-06 | 2016-01-27 | 宁波华丰包装有限公司 | A kind of have the EVA packaging adhesive film turning photoeffect |
| CN115197440B (en) * | 2022-08-12 | 2024-02-13 | 复旦大学 | Customizable plant fluorescence model and preparation method thereof |
| CN115433405A (en) * | 2022-08-26 | 2022-12-06 | 江苏博云塑业股份有限公司 | Anti-aging light conversion material, anti-aging light conversion film and preparation method thereof |
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