CN1270972A - Luminous composite of amphipathic ionic dendritic polyether-linear polyacrylic acid block copolymer and RE metal ion and its preparation - Google Patents

Luminous composite of amphipathic ionic dendritic polyether-linear polyacrylic acid block copolymer and RE metal ion and its preparation Download PDF

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CN1270972A
CN1270972A CN 00107567 CN00107567A CN1270972A CN 1270972 A CN1270972 A CN 1270972A CN 00107567 CN00107567 CN 00107567 CN 00107567 A CN00107567 A CN 00107567A CN 1270972 A CN1270972 A CN 1270972A
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polyacrylic acid
block copolymer
dendritic polyether
linear polyacrylic
amphiphilic block
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CN1136268C (en
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朱麟勇
王尔鉴
李妙贞
常志英
吴飞鹏
何勇
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Institute of Photographic Chemistry of CAS
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Abstract

The present invention relates to a luminous rare earth metal material comprising ionic dendritic polyether-linear polyacrylic acid amphilic block copolymer and rare earth metal ion in the molar ratio of 5E(-7)-5E(-4) to 2E(-5)-1.2E(-3). The luminous compound is prepared by adding at normal temperature the water solution of lanthanides metal chloride into the water solution of ionic dendritic polyether-linear polyacrylaic acid amphilic block copolymer, and remaining stationary for about 12 hr while maintaining pH at 7.5-9. It has very high luminous efficiency and may be used in light amplification, display, anti-fake, environment probe and sensor element.

Description

Ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer/rare earth ion light-emitting composite and preparation method thereof
The invention belongs to the rare earth metal field of light emitting materials, particularly belong to ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer/rare earth ion light-emitting composite and preparation method thereof.
Rare earth luminescence has the luminous efficiency height, luminescence spectrum is narrow and characteristics such as energy density height, referring to " coordination chemistry summary " magazine, and 1993 the 123rd volumes the 201st page of (Sabbatini, N.; Guardigli, M.; Lehn, J.-M., Coord.Chem.Rev. (1993), 123,201.) content.The small molecules rare earth compound has extensive studies, fluorescent material by their preparations, some has obtained at aspects such as trichromoscope, luminescent lamp, X-ray intensifying screens to use, these materials mostly are that inorganic powder or crystal are referring to " Englishize association will, dalton " magazine, 1996, the 3613rd page of (Parker, D.; William, J.A.G., J.Chem.Soc., Dalton Trans., (1996), 3613.) content.
If rare earth metal is incorporated in the polymeric matrix, be prepared into polymkeric substance/rare earth luminous matrix material, then can have raw material sources abundant, synthetic convenient, forming process is easy, in light weight and low cost and other advantages and show wide application prospect, but rare earth ion in polymer poor solubility, be difficult for to disperse, take place easily again to assemble and influence luminous efficiency.In order to improve dispersiveness, adopt the method for ligand (ligand) and rare earth metal formation complex compound in recent years, or directly utilization have the method for the Ionomer of complexing action as carrier, referring to " macromole " magazine nineteen eighty-three, the 16th volume, the 749th page of (Nagata, I.; Okamoto, Y., Macromolecules (1983), 16,749) content, simultaneously in actual applications, in order to improve the extinction ability of rare earth ion, also adopted the method for adding sensitizing agent to obtain rare earth-polymer-sensitizing agent three-component compound system, as " journal of applied " 1992, the 45th volume, the 1641st page of (Wang, L.P.; Lei, Z.Q.; Feng, H.Y.; Bao, J.T.; Wang, Y.B., J.Appl.Polym.Sci. (1992), 45,1641) report.Yet there are no the report of ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer/rare earth ion light-emitting composite.
The object of the present invention is to provide ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer/rare earth ion light-emitting composite, and the preparation method of this class light-emitting composite is provided.
Light-emitting composite of the present invention is made up of ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer and rare earth ion, and both mole ratios are 5 * 10 -7～5 * 10 -4: 2 * 10 -5～1.2 * 10 -3
Wherein the ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer is a material of main part, it is by the water soluble block copolymers (DendrPE-PAA) that hydrophobic aromatic dendritic polyether and linear ion polymer poly vinylformic acid are formed, and it has following molecular structure:
When Gi=1,
Figure A0010756700061
Or
When Gi=2,
Figure A0010756700062
Or
When Gi=3,
Gi represents the algebraically of dendritic polyether (Dendr PE) in the formula, and n represents the polymerization degree (n=10～250) of polyacrylic acid (PAA).
Rare earth ion mainly is lanthanide rare metal ion (Ln 3+), as terbium ion (Tb 3+), europium ion (Eu 3+) or dysprosium ion (Dy 3+) etc.
The preparation method of ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer of the present invention/rare earth ion light-emitting composite carries out as follows:
The first step: ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer (DendrPE-PAA) synthetic:
Synthesizing polyether dendritic-linear polyacrylic acid methyl esters segmented copolymer (Dendr.PE-PMA) at first: adopt atom transfer radical polymerization method (Atom transfer radical polymerization), is 1: 1: 2 by mole ratio with dendritic polyether halogenide, CuBr and dipyridyl (BiBy), methyl acrylate in the glass tube sealing: 10～250 amount adds above-mentioned substance successively, lead to nitrogen after 10～30 minutes, tube sealing; Temperature of reaction is controlled at 100～140 ℃, reacted 30～40 hours, be dissolved in after the cooling in the tetrahydrofuran (THF) (THF), adopt the NEUTRAL ALUMINUM post to separate then, use a large amount of methyl alcohol reprecipitations again, 60 ℃ of left and right sides vacuum-drying 24 hours obtains dendritic polyether and linear polyacrylic acid methyl esters segmented copolymer (Dendr PE-PMA).
As for the halid preparation of dendritic polyether, then adopt 7638 pages of (J.Am.Chem.Soc. (1990) 112,7638) described methods of document " JACS " nineteen ninety 112 volumes to carry out.
Secondly, synthetic ionic dendritic polyether-linear polyacrylic acid amphiphilic block copolymer (Dendr.PE-PAA): with the benzole soln that bulking value concentration is 0.003g/ml that is mixed with of the above-mentioned dendritic polyether and linear polyacrylic acid methyl esters segmented copolymer (Dendr.PE-PMA) that makes, to wherein adding the NaOH methanol solution that bulking value concentration is 0.14g/ml, the weight that makes NaOH is about 20 times of dendritic polyether-linear polyacrylic acid methyl esters segmented copolymer (Dendr.PE-PMA), reflux 2～5 hours, after the cooling reaction solution is poured in a large amount of methyl alcohol, produce precipitation, this precipitation is through centrifugation, be washed till neutrality with methyl alcohol, 60 ℃ of left and right sides vacuum-dryings 24 hours, obtain ionic dendritic polyether-linear polyacrylic acid amphiphilic block copolymer (Dendr.PE-PAA).
Second step: the preparation of ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer/rare-earth metal complex:
At normal temperatures, (DendrPE-PAA) is water-soluble with ionic dendritic polyether-linear polyacrylic acid amphiphilic block copolymer, to ionic dendritic polyether-linear polyacrylic acid amphiphilic block copolymer dissolving, add lanthanide series metal muriate (LnCl with ultrasonication again 36H 2O) aqueous solution, the volumetric molar concentration that makes DendrPE-PAA in the mixed solution is 5 * 10 -7Mol.L -1～5 * 10 -4Mol.L -1, rare earth ion Ln 3+Volumetric molar concentration be 2 * 10 -5Mol.L -1～1.2 * 10 -3Mol.L -1, and to keep pH be 7.5～9, leaves standstill about 12 hours, just obtains stable ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer/rare-earth metal complex.
Adopt different structure (Gi=0～3, n=15～250) rare-earth metal chloride of ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer and different content just can be prepared the ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer/rare earth ion light-emitting composite of various different structures and different compositions.
Purposes of the present invention: ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer of the present invention and rare earth ion light-emitting composite can be used as advanced luminescent material and are applied to all respects such as light amplification, demonstration, false proof, environment probe and sensing member.
Advantage of the present invention:
Ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer of the present invention/rare earth ion light-emitting composite adopts the ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer, have two kinds of tangible functions: the dendritic that (1) has aromatic ring structure is the three-dimensional structure polymer, its chain backbone is dendroid and distributes, and compound with regular structure has definite size and symmetry, its structural unit is exponential increasing, therefore be a kind of high-density color base aggregate, have very high light absorpting ability, can be considered " light collector ".(2) ionic two parents had both had the complexing action to rare earth ion, has self-assembly (Self-assembly) function again, under certain conditions, intermolecular association can take place, form a kind of dendroid supramolecule metal complex of novelty, this strengthens luminous antenna effect and the microenvironment effect of providing for rare earth ion.This ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer is applicable to preparation lanthanide rare metal composite, and is particularly significant to Tb, Eu, Dy with higher photoluminescence efficiency, can obtain the efficient luminescence system of different emission wavelengths.
The light-emitting composite that the present invention adopts ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer and rare earth ion to make, its specific molecule structure and intermolecular interaction, make molecule have very strong extinction ability, high energy transfer efficiency, to rare earth metal is luminous significant enhancement being arranged, is the single Tb of its luminous strength ratio 3+More than 150 times of the luminous enhancing of ionic is that conventional polyacrylic acid strengthens nearly ten times of amplitudes shown in embodiment 5 shown in embodiment 2, therefore can be used as advanced luminescent material and is applied to all respects such as light amplification, demonstration, false proof, environment probe and sensing member.
Further describe the present invention below in conjunction with embodiment:
Embodiment 1
Ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer (DendrPE-PAA)/Tb 3+The preparation of light-emitting composite
The first step: ionic dendritic polyether-linear polyacrylic acid amphiphilic block copolymer (G 3-PAA-217) synthetic:
Synthesizing polyether dendritic one linear polyacrylic acid methyl esters segmented copolymer (G at first 3-PMA-217):
1.0 mmole third generation dendritic polyether bromide (G 3-Br) (7638 pages (J.Am.Chem.Soc. (1990) 112 for synthetic method reference literature " JACS " nineteen nineties 112 volume, 7638), 1.0 mmole cuprous bromide (CuBr) and 2.0 mmoles 2,2 '-dipyridyl (BiPy) joins in the exsiccant glass tube sealing, the methyl acrylate (MA) that adds 0.10 mole again, logical N 2Tube sealing after 15 minutes, place oil bath to heat, 130 ℃ of temperature, 30 hours reaction times was dissolved in after the cooling in the tetrahydrofuran (THF) (THF), adopted the NEUTRAL ALUMINUM post to separate, obtain yellow solution, use a large amount of methyl alcohol reprecipitations again, 60 ℃ of vacuum-drying 24 hours obtains dendritic polyether-linear polyacrylic acid methyl esters segmented copolymer (G 3-PMA-101), and yield 94%, the polymerization degree (n) 101, molecular weight (Mn) is 1.0 * 10 4, molecular weight distribution (M w/ Mm) be 1.42; H 1NMR (CDCl 3) chemical shift 1.2～2.7 (br, CH and CH 2PMA), 3.75 (S, CH 2), 4.7～5.2 (d, Ph CH 2O), 6.3～6.9 (br, ArH) and 7.3～7.6 (br, PhH).
Secondly, synthetic ionic dendritic polyether-linear polyacrylic acid amphiphilic block copolymer (G 3-PAA-217):
0.3g the G that the above-mentioned the first step makes 3-PMA-101 is dissolved in (bulking value concentration is 0.003g/ml) in 100 milliliters of benzene, to wherein adding bulking value concentration is 40 milliliters of 0.14g/mlNaOH methanol solutions, the weight that makes NaOH is 18.7 times of dendritic polyether-linear polyacrylic acid methyl esters segmented copolymer (Dendr.PE-PMA), reflux 3 hours, pour into after the cooling in a large amount of methyl alcohol, produce precipitation, this precipitation is through centrifugation, be washed till neutrality with methyl alcohol, dry 24 hours of vacuum (60 ℃) obtains ionic dendritic polyether-linear polyacrylic acid amphiphilic block copolymer (G 3-PAA-101).The polymerization degree (n) 101, degree of hydrolysis are greater than 96%, and molecular weight (Mn) is 1.10 * 10 4, molecular weight distribution (M w/ Mn) be 1.42, H 1NMR (D 2O) chemical shift 1.0～2.6 (br, CH and CH 2PAA), 6.0～6.8 (br, ArH) and 7.0～7.6 (br, PhH).
Second step: ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer (DendrPE-PAA)/Tb 3+The preparation of light-emitting composite:
At normal temperatures, with ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer (G 3-PAA-101) water-soluble, with ultrasonication 10 minutes to ionic dendritic polyether-linear polyacrylic acid amphiphilic block copolymer (G 3-PAA-101) after the dissolving, add (the TbCl of 0.02 volumetric molar concentration again 36H 2O) aqueous solution makes G in the mixed solution 3-PAA-101 volumetric molar concentration is 9.02 * 10 -6Mol.L -1, Tb 3+The ionic volumetric molar concentration is 8 * 10 -4Mol.L -1, and to keep PH be 8.5, left standstill 12 hours, just obtains stable transparence ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer (G 3-PAA-101)/Tb 3+The ionoluminescence mixture.With the optical excitation of 285nm wavelength, promptly can be observed 545nm Tb 3+Luminous.
Embodiment 2
According to the method for embodiment 1, Tb 3+Ionic concn be fixed as 1.0 * 10 -3Mol/L changes G then 3The volumetric molar concentration of-PAA-101 is respectively 0 mol/L, 9.02 * 10 -7Mol/L, 4.51 * 10 -6Mol/L and 4.51 * 10 -5Mol./L is the ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer (G that obtains 3-PAA-101)/Tb 3+The 285nm optical excitation of ionoluminescence mixture, the Tb of survey 3+Luminous intensity at the 545nm place is respectively 8,48.6,140 and 1185, has shown Tb 3+The characteristic that increases sharply with polymkeric substance amphiphilic bulk concentration of luminous intensity.
Embodiment 3
According to the method for embodiment 1, fixedly G 3The concentration of-PAA-101 is 4.51 * 10 -5Mol/L changes Tb 3+Ionic concn is respectively 3.5 * 10 -5, 3.6 * 10 -4, 8.6 * 10 -4, 1.1 * 10 -3With 1.36 * 10 -3Mol/L prepares ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer (G respectively 3-PAA-101)/Tb 3+The ionoluminescence mixture, and record its luminous intensity and be respectively 67,230,780,850 and 980, Tb shown 3+Luminous intensity with Tb 3+Concentration and the characteristic that increases.
Embodiment 4
According to the method for embodiment 1, polymkeric substance two parents adopt G 3-PAA-101, concentration is 5 * 10 -4Mol/L, rare earth ion are Eu 3+, concentration adopts 1 * 10 respectively -5, 6 * 10 -5, 1.1 * 10 -4, 3.6 * 10 -4, 6.1 * 10 -4With 8.6 * 10 -4Mol/L prepares ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer (G respectively 3-PAA-101)/Tb 3+The ionoluminescence mixture, and record Eu at the 620nm place 3+Luminous intensity be respectively 32,36,38,58,82 and 96, shown Eu 3+Have and Tb 3+The similar characteristics of luminescence.
Embodiment 5
PAA, i.e. G 0, synthetic according to a conventional method;
Ionic dendritic polyether-linear polyacrylic acid amphiphilic block copolymer (G 1-PAA-75) synthetic:
1.0 mmole first-generation dendritic polyether bromide (G 1-Br) (synthetic method adopts document " JACS " nineteen nineties 112 volume, and 7638 pages (J.Am.Chem.Soc. (1990) 112,7638), 1.0 mmole cuprous bromide (CuBr) and 2.0 mmoles 2,2 '-dipyridyl (BiPy) joins in the exsiccant glass tube sealing, the methyl acrylate (MA) that adds 0.1 mole again, logical nitrogen tube sealing after 10 minutes, place oil bath to heat, 120 ℃ of temperature, 35 hours reaction times, be dissolved among the THF after the cooling, adopt the NEUTRAL ALUMINUM post to separate, obtain yellow solution, use a large amount of methyl alcohol reprecipitations again, 60 ℃ of vacuum-drying 24 hours obtains dendritic polyether-linear polyacrylic acid methyl esters segmented copolymer (G 1-PMA-75), yield 92%, polymerization degree n=75, molecular weight (Mn) 7.0 * 10 3, molecular weight distribution (M w/ Mn) 1.61, H 1NMR (CDCl 3) chemical shift 1.1～2.7 (br, CH and CH 2, PMA), 3.75 (S, CH 3), 5.03 (S, PhCH 2O), 6.5～6.7 (br, ArH) and 7.3～7.6 (br, PhH).
0.3g the above-mentioned (G that makes 1-PMA-75) be dissolved in 100 milliliters of benzene, add 40 milliliters of 0.14g/mlNaOH methanol solutions, the weight that makes NaOH is 18.7 times of dendritic polyether-linear polyacrylic acid methyl esters segmented copolymer (Dendr.PE-PMA), reflux 3 hours is poured into after the cooling in a large amount of methyl alcohol, produces precipitation, this precipitation is through centrifugation, be washed till neutrality with methyl alcohol, dry 24 hours of vacuum (60 ℃) obtains ionic dendritic polyether-linear polyacrylic acid amphiphilic block copolymer (G 1-PAA-75).Degree of hydrolysis is greater than 96%, the polymerization degree (n) 75, molecular weight (Mn) 9.0 * 10 3, molecular weight distribution (Mw/Mn) 1.61, H 1NMR (D 2O) chemical shift 0.9～2.6 (br, CH and CH 2, PAA), 6.4～6.7 (br, ArH), 7.1～7.5 (br, PhH).
Ionic dendritic polyether-polyacrylic acid amphiphilic block copolymer (G 2-PAA-85) synthetic:
1.0 mmole s-generation dendritic polyether bromide (G 2-Br) (7638 pages (J.Am.Chem.Soc. (1990) 112 for synthetic method reference literature " JACS " nineteen nineties 112 volume, 7638), 1.0 mmole cuprous bromide (CuBr) and 2.0 mmoles 2,2 '-dipyridyl (BiPy) joins in the exsiccant glass tube sealing, the methyl acrylate (MA) that adds 0.1 mole again, logical nitrogen tube sealing after 20 minutes, place oil bath to heat, 100 ℃ of temperature, 40 hours reaction times, be dissolved in after the cooling in the tetrahydrofuran (THF) (THF), adopt the NEUTRAL ALUMINUM post to separate, obtain yellow solution, use a large amount of methyl alcohol reprecipitations again, 60 ℃ of vacuum-drying 24 hours obtains dendritic polyether-linear polyacrylic acid methyl esters segmented copolymer (G 2-PMA-85), yield 88%, the polymerization degree (n) 85, molecular weight (Mn) 8.3 * 10 3, molecular weight distribution (M w/ Mn) 1.2, H 1NMR (CDCl 3), chemical shift 1.2～2.7 (br, CH and CH 2, PMA), 3.75 (S, CH 3), 4.8～5.2 (d, Ph CH 2O), 6.3～6.7 (br, ArH) and 7.3～7.6 (br, PhH).
The above-mentioned G that obtains 2-PMA-85 presses the method in second step among the embodiment 1, makes ionic dendritic polyether-linear polyacrylic acid amphiphilic block copolymer (G 2-PAA-85), the polymerization degree (n) 85, molecular weight (Mn) 8.7 * 10 3, molecular weight distribution (M w/ Mn) 1.2, degree of hydrolysis is greater than 93%, H 1NMR (D 2O), 0.9～2.6 (br, CH and CH 2, PAA) 6.0～6.8 (br, ArH) and 7.0～7.6 (br, PhH).
Fixing Tb 3+Ionic concn is 1.0 * 10 -3Mol/L, the algebraically that changes DendrPE-PAA is G 0, G 1, G 2, G 3, prepare light-emitting composite respectively according to the method in embodiment 1 second step, and record its luminous intensity and be respectively 130,220,400 and 1200, shown Tb 3+Luminous intensity rise with polymkeric substance two parent algebraically and the characteristic that obviously increases.

Claims (5)

1. ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer/rare earth ion light-emitting composite, it is characterized in that being made up of ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer and rare earth ion, both mole ratios are 5 * 10 -7～5 * 10 -4: 2 * 10 -5～1.2 * 10 -3Wherein the ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer has following molecular structure:
Figure A0010756700021
Or
Figure A0010756700022
Or
N is the polyacrylic polymerization degree, n=10～250;
Rare earth ion is the lanthanide rare metal ion.
2. ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer as claimed in claim 1/rare earth ion light-emitting composite is characterized in that described lanthanide rare metal ion is terbium ion, europium ion or dysprosium ion.
3. the preparation method of ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer as claimed in claim 1/rare earth ion light-emitting composite is characterized in that carrying out as follows:
The first step: ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer synthetic:
Synthesizing polyether dendritic-linear polyacrylic acid methyl esters segmented copolymer at first: is 1: 1: 2 by mole ratio with dendritic polyether halogenide, CuBr and dipyridyl, methyl acrylate in the glass tube sealing: 10～250 amount adds above-mentioned substance successively, lead to nitrogen after 10～30 minutes, tube sealing; Temperature of reaction is controlled at 100～140 ℃, reacts 30～40 hours, is dissolved in the tetrahydrofuran (THF) after the cooling, adopt the NEUTRAL ALUMINUM post to separate then, use a large amount of methyl alcohol reprecipitations again, 60 ℃ of left and right sides vacuum-drying 24 hours obtains dendritic polyether and linear polyacrylic acid methyl esters segmented copolymer;
Secondly, synthetic ionic dendritic polyether-linear polyacrylic acid amphiphilic block copolymer: with the benzole soln that bulking value concentration is 0.003g/ml that is mixed with of the above-mentioned dendritic polyether and linear polyacrylic acid methyl esters segmented copolymer that makes, to wherein adding the NaOH methanol solution that bulking value concentration is 0.14g/ml, the weight that makes NaOH is about 20 times of dendritic polyether-linear polyacrylic acid methyl esters segmented copolymer, reflux 2～5 hours, after the cooling reaction solution is poured in a large amount of methyl alcohol, produce precipitation, this precipitation is through centrifugation, be washed till neutrality with methyl alcohol, 60 ℃ of left and right sides vacuum-dryings 24 hours, obtain ionic dendritic polyether-linear polyacrylic acid amphiphilic block copolymer;
Second step: the preparation of ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer/rare-earth metal complex:
At normal temperatures, ionic dendritic polyether-linear polyacrylic acid amphiphilic block copolymer is water-soluble, dissolve with ultrasonication to ionic dendritic polyether-linear polyacrylic acid amphiphilic block copolymer, add the lanthanide series metal aqueous chloride solution again, making the volumetric molar concentration of mixed solution intermediate ion type dendritic polyether-linear polyacrylic acid amphiphilic block copolymer is 5 * 10 -7Mol.L -1～5 * 10 -4Mol.L -1, rare earth ion Ln 3+Volumetric molar concentration be 2 * 10 -5Mol.L -1～1.2 * 10 -3Mol.L -1, and to keep pH be 7.5～9, leaves standstill about 12 hours, just ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer/rare-earth metal complex.
4. the preparation method of ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer as claimed in claim 3/rare earth ion light-emitting composite is characterized in that described rare earth ion Ln 3+Be terbium ion, europium ion or dysprosium ion.
5. the purposes of ionic dendritic polyether and linear polyacrylic acid amphiphilic block copolymer as claimed in claim 1/rare earth ion light-emitting composite is characterized in that being applied to light amplification, demonstration, false proof, environment probe or sensing member.
CNB001075675A 2000-05-19 2000-05-19 luminous composite of amphipathic ionic dendritic polyether-linear polyacrylic acid block copolymer and RE metal ion and its preparation Expired - Fee Related CN1136268C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1309752C (en) * 2003-09-29 2007-04-11 中国科学院理化技术研究所 Polyether dendrimer hydrophobically associating acrylamide copolymer and its synthesis process
US7468413B2 (en) * 2004-01-30 2008-12-23 Khodia Inc. Rare earth aggregate formulation using di-block copolmers
CN102775981A (en) * 2012-07-17 2012-11-14 中北大学 Luminescent material of naphthoic acid functionalized polymer and rare earth complex and preparation method of luminescent material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1309752C (en) * 2003-09-29 2007-04-11 中国科学院理化技术研究所 Polyether dendrimer hydrophobically associating acrylamide copolymer and its synthesis process
US7468413B2 (en) * 2004-01-30 2008-12-23 Khodia Inc. Rare earth aggregate formulation using di-block copolmers
CN102775981A (en) * 2012-07-17 2012-11-14 中北大学 Luminescent material of naphthoic acid functionalized polymer and rare earth complex and preparation method of luminescent material
CN102775981B (en) * 2012-07-17 2014-08-06 中北大学 Luminescent material of naphthoic acid functionalized polymer and rare earth complex and preparation method of luminescent material

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