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 PDFInfo
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- 229920002125 Sokalan® Polymers 0.000 title claims abstract description 73
- 239000004584 polyacrylic acid Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims description 15
- 229920001400 block copolymer Polymers 0.000 title claims description 7
- 229910021645 metal ion Inorganic materials 0.000 title claims description 3
- 239000002131 composite material Substances 0.000 title description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 58
- 229920000570 polyether Polymers 0.000 claims abstract description 58
- 229920000469 amphiphilic block copolymer Polymers 0.000 claims abstract description 53
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 43
- -1 rare-earth metal ions Chemical class 0.000 claims abstract description 37
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 13
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 230000003321 amplification Effects 0.000 claims abstract description 4
- 238000003199 nucleic acid amplification method Methods 0.000 claims abstract description 4
- 239000000523 sample Substances 0.000 claims abstract description 4
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims 4
- 239000000412 dendrimer Substances 0.000 claims 1
- 229920000736 dendritic polymer Polymers 0.000 claims 1
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 150000002602 lanthanoids Chemical class 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 10
- 150000004702 methyl esters Chemical class 0.000 description 10
- 238000007789 sealing Methods 0.000 description 8
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000001226 reprecipitation Methods 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 241000555268 Dendroides Species 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000002525 ultrasonication Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
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- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polyethers (AREA)
Abstract
本发明属于稀土金属发光材料领域,它由离子型聚醚树枝体－线性聚丙烯酸两亲嵌段共聚物和稀土金属离子组成,两者的摩尔数比为5×10－7～5×10－4:2×10－5～1.2×10－3。在常温下,按以上配比将镧系金属氯化物水溶液加入至离子型聚醚树枝体－线性聚丙烯酸两亲嵌段共聚物水溶液中,保持pH为7.5～9,静置12小时左右,便得离子型聚醚树枝体－线性聚丙烯酸两亲嵌段共聚物/稀土金属复合物。它具有很高的发光效率,能应用于光放大、显示、防伪、环境探针和传感元件。The invention belongs to the field of rare-earth metal luminescent materials. It is composed of ionic polyether dendron-linear polyacrylic acid amphiphilic block copolymer and rare-earth metal ions, and the molar ratio of the two is 5×10 -7 to 5×10 - 4 : 2× 10-5 to 1.2× 10-3 . At room temperature, add the lanthanide metal chloride aqueous solution to the ionic polyether dendrimer-linear polyacrylic acid amphiphilic block copolymer aqueous solution according to the above ratio, keep the pH at 7.5-9, and let it stand for about 12 hours. The ionic polyether dendron-linear polyacrylic acid amphiphilic block copolymer/rare earth metal complex was obtained. It has high luminous efficiency and can be used in light amplification, display, anti-counterfeiting, environmental probes and sensing elements.
Description
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,
Or
When Gi=2,
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)
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Cited By (3)
| 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 hydrophobic association acrylamide copolymer and synthesis method thereof |
| 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 |
-
2000
- 2000-05-19 CN CNB001075675A patent/CN1136268C/en not_active Expired - Fee Related
Cited By (4)
| 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 hydrophobic association acrylamide copolymer and synthesis method thereof |
| 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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