以1,4-二氯甲氧基丁烷(BCMB)为氯甲基化试剂,使聚砜(PSF)氯甲基化(CM),形成氯甲基化聚砜(CMPSF),然后用6-羟基-2-萘甲酸(HNA)使CMPSF的氯甲基与HNA的酚羟基之间发生亲核取代反应,将萘甲酸(NA)配基键合在聚砜侧链,制得了功能化改性的聚砜NAPSF.采用红外光谱和核磁共振氢谱对其结构进行了表征.考察了主要因素对CMPSF与HNA之间亲核取代反应的影响规律,分析了反应机理,优化了反应条件.结果表明,CMPSF与HNA之间取代反应的速率与亲核试剂HNA的浓度无关,遵循SN1的反应机理；使用极性较强的溶剂二甲亚砜,有利于亲核取代反应的进行；在适宜条件下,CMPSF的氯甲基转化率可达96％,NA的键合量为1.68 mmol/g.将NAPSF与Eu(Ⅲ)离子配位,制得了聚合物-稀土配合物NAPSF-Eu(Ⅲ),它不仅发射出Eu3+离子的特征荧光,而且对Eu3+离子的荧光发射显示出很强的敏化作用.萘甲酸功能化的大分子配基NAPSF对Eu3+离子的敏化作用,远强于苯甲酸(BA)功能化的大分子配基BAPSF对Eu3+离子的敏化作用.
参考文献
| [1] | Setua S,Menon D,Asok A,et al.Folate Receptor Targeted,Rare-earth Oxide Nanocrystals for Bi-modal Fluorescence and Magnetic Imaging of Cancer Cells[J].Biomaterials,2010,31(4):714-729. |
| [2] | Li D G,Zhu J,Cheng Z P,et al.A Combination of Raft and "Click" Chemistry Techniques to Synthesize Polymeric Europium Complexes with Selective Fluorescence Emission[J].React Funct Polym,2009,69(4):240-245. |
| [3] | Shuumugam R,Tew G N.Dialing in Color with Rare Earth Metals:Facile Photoluminescent Production of True White Light[J].Polym Adv Technol,2007,18(11):940-945. |
| [4] | Liu D,Wang Z G,Yu H,et al.Fluorescence Properties of Novel Rare Earth Complexes Using Carboxyl-containing Polyaryletherketones as Macromolecular Ligands[J].Eur Polym J,2009,45 (8):2260-2268. |
| [5] | Liu D,Wang Z G.Novel Polyaryletherketones Bearing Pendant Carboxyl Groups and Their Rare Earth Complexes,Part Ⅰ:Synthesis and Characterization[J].Polym J,2008,49(23):4960-4967. |
| [6] | Suo Q L,Lu F,Shi J W,et al.Studies on Synthesis and Fluorescent Property of Rare Earth Complexes RE(ABMF)2AA and Copolymers RE(ABMF) 2AA-co-MMA[J].Polym J,2009,27(1):28-32. |
| [7] | Yan C H,Yu C J,Hu H H,et al.Preparation and Properties of RE3 + Doped Luminescent Co-polymer by Solution Copolymerization[J].Polym J,2009,27(5):761-766. |
| [8] | Wen S P,Zhang X P,Hu S,et al.Fluorescence and Judd-ofelt Analysis of Rare Earth Complexes with Maleic Anhydride and Acrylic Acid[J].J Rare Earths,2008,26(6):787-791. |
| [9] | Gao B J,Li F,Z R X,et al.Preparation of Aromatic Carboxylic Acid-functionalized Polysulfone and Preliminary Exploration of Florescence Emission Character of Formed Polymer-rare Earth Complexes[J].Synth Met,2012,162(5/6):503-510. |
| [10] | Maji S,Viswanathan K S.Ligand-sensitized Fluorescence of Eu3+ Using Naphthalene Carboxylic Acids as Ligands[J].J Lumin,2008,128 (8):1255-1261. |
| [11] | Hilder M,Junk P C,Kynast U H,et al.Spectroscopic Properties of Lanthanoid Benzene Carboxylates in the Solid State:Part 1[J].J Photochem Photobiol A:Chem,2009,202 (1):10-20. |
| [12] | Du R K,Gao B J,Li Y B,et al.Preparation and Structure/Property Relationship of Polysulfone Anion-exchange Membranes[J].Acta Polym Sin,2010,1(7):121-128 (in Chinese).杜瑞奎,高保娇,李延斌,等.聚砜阴离子交换膜的制备及结构与性能研究[J].高分子学报,2010,1(7):121-128. |
| [13] | Xi P,Gu X H,Chen C F,et al.Synthesis,Characterization and Luminescent Properties of New Highly Luminescent Organic Ligand and Complexes of Trivalent Rare Earth[J].Spectrochim Acta Part A,2007,66(3):667-671. |
| [14] | Guo L,Wu S Z,Zeng F,et al.Synthesis and Fluorescence Property of Terbium Complex with Novel Schiff-base Macromolecular Ligand[J].Eur Polym J,2006,42 (7):1670-1675. |
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