【作者】 文小伟；

【导师】 路建美；

【作者基本信息】 苏州大学 ， 应用化学， 2007， 硕士

【摘要】 1，合成了一种新型的喹啉衍生物类单体2，7，7-三甲基-3-乙氧羰基-4-（4-丙烯酰胺苯基）-5-氧代-1，4，5，6，7，8-六氢喹啉（TEOHQ），并以2-溴代异丁酸乙酯（EBiB）为引发剂，氯化亚铜（CuCl）／五甲基二乙烯基三胺（PMDETA）为催化剂，环己酮为溶剂通过原子转移自由基聚合（ATRP）的方法制备TEOHQ与苯乙烯的共聚物。元素分析，GPC，¹H-NMR以及荧光发射光谱用来表征共聚物。数均分子量随转化率的线性增加及相对较窄的分子量分布证明了聚合反应的可控性。讨论了温度、单体投料比以及引发剂浓度对共聚反应的影响。详细考察了单体及其共聚物的荧光性能，并利用Mayo-Lewis公式测定了两种单体的竞聚率。2，合成了另一种新型的喹啉衍生物类单体2-[4-（2，7，7-三甲基-3-乙氧羰基-5-氧代-1，4，5，6，7，8-六氢喹啉）苯氧基]甲基丙烯酸乙酯（HQPEMA），并以2-（4-氯甲基苯基）苯并噁唑（CMPB）为引发剂，CuCl／PMDETA为催化剂，环己酮为溶剂通过ATRP法制备聚合物。GPC，¹H-NMR以及荧光发射光谱用来表征聚合物。研究结果表明：HQPEMA的ATRP聚合体系呈现很好的活性聚合特征。考察引发剂浓度及催化剂浓度对聚合反应的影响。通过对单体和聚合物荧光性能的研究发现既有供电子生色团又存在吸电子c-c双键的单体HQPEMA发生荧光“结构自淬灭”现象。此外，聚合物溶液的荧光性能具有浓度淬灭效应以及溶剂化效应。聚合物成膜后的最大荧光发射峰与其DMF溶液相比出现50nm的红移现象。3，利用普通自由基聚合得到含喹啉衍生物链段的共聚物poly（TEOHQ-co-St），运用荧光发射光谱研究了poly（TEOHQ-co-St）溶液对Al³⁺、Zn²⁺、Ni²⁺、Cu²⁺、Co²⁺、Fe³⁺、Mg²⁺的认知能力。Al³⁺、Zn²⁺、Ni²⁺、Cu²⁺、Co²⁺掺入使共聚物溶液荧光发射强度出现一定程度的淬灭，而较低浓度的Fe³⁺掺入则会使荧光强度出现完全淬灭，说明poly（TEOHQ-co-St）对Fe³⁺有非常好的选择性和灵敏性。然而，Mg²⁺的掺入不但不会使共聚物溶液的荧光发射强度如其它金属阳离子一样发生淬灭，反而会增强荧光发射强度。4，利用普通自由基聚合的方法聚合喹啉衍生物类单体HOPEMA得到聚合物poly（HQPEMA），运用荧光发射光谱研究了poly（HQPEMA）溶液对金属阳离子(Zn²⁺、Cu²⁺、Ni²⁺、Al³⁺、Mg²⁺、Fe³⁺、Co²⁺、Sn²⁺及Mn²⁺)的选择性，在所研究的金属阳离子中只有Fe³⁺的掺入能够使聚合物溶液的荧光强度出现较大程度的淬灭，说明poly（HQPEMA）对Fe³⁺有很好的选择性。讨论了不同溶剂对金属阳离子掺入后聚合物溶液荧光发射光谱的影响。更多还原

【Abstract】 1, A novel quinoline derivative monomer 2,7,7-trimethyl-3-ethoxycarbonyl-4-（4-acrylamidephenyl）-5-oxo-1,4,5,6,7,8-hexhydricquinoline（TEOHQ） was synthesized. Thecopolymers were prepared by atom transfer radical copolymerization of TEOHQ withStyrene（St） using Ethyl 2-bromoisobutyrate（EBiB） as initiator, CuCl/ N,N,N’,N",N"-pentamethyldiethylenetriamine （PMDETA） as catalyst and Cyclohexanone assolvent. Element analysis, GPC, ¹H-NMR and Fluorescent emission spectroscopy wereused to characterize copolymers. The linear increase of number average molecularweight（Mn） versus total conversion and the relatively narrow molecular weightdistribution （Mw/Mn） confirmed the copolymerization was controllable. The effects oftemperature、feed ratio of monomers and the concentrations of initiator on thecopolymerization were discussed. In addition, we investigated the fluorescent propertyof the monomer and its copolymer with styrene. Moreover, the reactivity ratio of theTEOHQ and St was also measured with the method of Mayo-Lewis.2, A novel functional monomer incorporating quinoline derivative moiety as the sidegroup was synthesized and polymerized utilizing atom transfer radicalpolymerization（ATRP） technique, which was conducted by using2-（4-chloromethylphenyl）benzoxazole（CMPB） as initiator, CuCl/PMDETA as catalystand Cyclohexanone as solvent. GPC, ¹H-NMR and Fluorescent emission spectroscopywere used to characterize polymers. The linear increase of number average molecularweight（Mn） versus conversion and the relatively narrow molecular weightdistribution（Mw/Mn） confirmed the polymerization was controllable. Factors such as the concentrations of initiator and catalyst, which can affect the ATRP system, werediscussed in the paper. In addition, the fluorescence "structural self-quenching effect"of the monomer HQPEMA which bearing electron-donating chromophore group andelectron-accepting carbon-carbon double bond was observed. We also found thefluorescence properties of the newly obtained polymers depended on both the polymersolution’s concentration and the solvents. Meanwhile, the fluorescence emissionproperty of the polymer film was investigated and the result showed that the emissionpeak maxima of the polymer film shifted 50nm towards high wavelength with respectto the polymer in DMF solution.3, The copolymer poly（YEOHQ-co-St） which containing quinoline derivative chainsegment was synthesized by the conventional radical polymerization. The recognitionabilities ofpoly（TEOHQ-co-St） to Al³⁺、Zn²⁺、Ni²⁺、Cu²⁺、Co²⁺、Fe³⁺and Mg²⁺ werestudied by means of the fluorescence spectroscopy. The fluorescence emission intensityof copolymer solution quenched definitely when the addition or Al³⁺、Zn²⁺、Ni²⁺、Cu²⁺and Co²⁺, while adding the very low concentration of Fe³⁺, the fluorescence intensityquenched completely, this result showed the high selectivity and sensitivity ofpoly（TEOHQ-co-St） towards Fe³⁺. In addition, the fluorescence intensity enhancedother than quenched when the addition of Mg²⁺ to the copolymer solution.4, The polymer poly（HQPEMA） was synthesized by polymerizing the monomerincorporating quinoline derivative moiety utilizing conventional radicalpolymerization. The selectivities of poly（HQPEMA） to metal cations(Zn²⁺、Cu²⁺、Ni²⁺、Al³⁺、Mg²⁺、Fe³⁺、Co²⁺、Sn²⁺ and Mn²⁺) were studied by means of fluorescencespectroscopy. Among these metal cations, the Fe³⁺ was an unique cation to quenchobviously the fluorescence emission intensity and confirmed the good selectivity ofpoly（HQPEMA） towards Fe³⁺. Moreover, the effects of the different solvents on thefluorescence emission spectrum of polymer solutions containing metal cations were discussed.更多还原