【作者】 王成超；

【导师】 朱秀林； 张伟；

【作者基本信息】 苏州大学 ， 高分子化学与物理， 2010， 硕士

【摘要】 本论文通过可逆加成断裂链转移(Reversible Additional-Fragmentation Chain Transfer, RAFT)聚合法,合成了三种不同类型的聚合物,利用聚合物侧链或者端基含有的8-羟基喹啉可配位基团与铝离子进行配位,分别制备了三种高分子化的8-羟基喹啉铝(Alq3)金属配合物。同时对三种不同的Alq3功能化聚合物进行了紫外和荧光性能的考察。本论文的主要研究内容如下:(1)合成了含有8-羟基喹啉基团的烯类单体2-((8-hydroxyquinoline-5-yl)methoxy)ethyl methacrylate (HQHEMA),分别和苯乙烯(styrene, St)以及甲基丙烯酸甲酯(methyl methacrylate, MMA)进行了共聚。共聚反应采用二硫代萘甲酸异丁腈酯(2-cyanoprop-2-yl dithionaphthalenoate, CPDN)为RAFT试剂,偶氮二异丁腈(2,2’-Azobisisobutyronitrile, AIBN)为引发剂。聚合过程呈现“活性”/可控特征。利用聚合物侧链带有的8-羟基喹啉基团,和异丙醇铝以及醋酸锌进行了配位反应,制备了高分子化的含8-羟基喹啉铝/锌基团的聚合物。得到的聚合物在一般有机溶剂里具有较好的溶解性。通过GPC, 1H NMR, UV-vis和荧光光谱对得到的聚合物进行了表征。(2)合成了甲基丙烯酸酯类的偶氮单体,甲基丙烯酸-6-(4′-甲氧基-4″-氧-偶氮苯)己酯(6-[4-(4-methoxyphenylazo)phenoxy]hexylmethactylate, MMAZO)。以CPDN作为RAFT试剂,AIBN作为引发剂的条件下进行了MMAZO和HQHEMA的共聚合,得到了含有不同比例偶氮苯基团的共聚物。通过配位化学反应合成了侧链既含有偶氮苯基团,同时又含有8-羟基喹啉铝基团的聚合物。紫外吸收标准曲线法和电感耦合等离子体原子发射光谱法(ICP-ACS)表征了配位后聚合物中金属铝离子的含量。利用偶氮苯基团在紫外光照条件下的顺-反异构化的特性,考察了配位后的聚合物在不同紫外光照时间条件下的紫外和荧光性能。(3)合成带有8-羟基喹啉基团的黄原酸酯(O-ethyl S-(8-hydroxyquinolin-5-yl)methyl carbonodithioate,HQ-MADIX),并以HQ-MADIX为RAFT试剂调控了醋酸乙烯酯(vinyl acetate, VAc)的聚合。聚合过程呈现“活性”/可控的特征。利用聚合物端基8-羟基喹啉基团的可配位性,制备合成了末端含有8-羟基喹啉铝基团的聚醋酸乙烯酯。考察了配位后的聚合物在溶液状态和膜状态下的紫外和荧光性能。更多还原

【Abstract】 In this thesis, three different Alq3-Functionalized polymers were synthesized via RAFT (co)polymerization technique. The optical properties were also investigated.The main work in this thesis is summarized as following:(1) (2-((8-hydroxyquinoline-5-yl) methoxy) ethyl methacrylate, HQHEMA) was successfully synthesized. The copolymerizations of HQHEMA with styrene (St) or methyl methacrylate (MMA) were carried out in the presence of 2-cyanoprop-2-yl dithionaphthalenoate (CPDN), respectively. The polymerization behaviors showed the typical‘living’natures by the first-order polymerization kinetics, the linear dependence of molecular weights of the polymers on the monomer conversions with the relatively narrow molecular weight distributions (PDI), and the successful chain extension experiments. The soluble polymers having tris(8-hydroxyquinoline)aluminum (Alq3) and bis(8-hydroxyquinoline) znic(II) (Znq2) units were obtained via complexation reaction between the polymers and aluminium isopropoxide or zinc acetate in the presence of monomeric 8-hydroxyquinoline, respectively, which had strong fluorescent emission at 520 nm. The obtained polymers were characterized by GPC, 1H NMR, UV-vis and fluorescent spectra.(2) Monomer containing azobenzene unit, (6-[4-(4-methoxyphenylazo) phenoxy] hexylmethacrylate (MMAZO), was synthesized and copolymerized with HQHEMA using CPDN as the RAFT agent and AIBN as the initiator. The obtained polymers were coordinated with aluminium isopropoxide in the presence of monomeric 8-hydroxyquinoline and the Alq3-functionalized polymers were obtained. The concentration of the Al3+ was tested by UV-vis standard curve and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The fluorescent intensity of the polymer increased with UV-vis irradiation time.(3) A novel RAFT agent containing 8-hydroxyquinoline unit, O-ethyl S-(8-hydroxyquinolin-5-yl)methyl carbonodithioate (HQ-MADIX), was successfully synthesized and employed to mediate the polymerization of vinyl acetate (VAc). The polymerization behaviors showed the typical‘living’natures. The 8-hydroxyquinoline unit was successfully introduced into the end of the polymer chain. The end-capped Alq3-functionalized polymer was synthesized via coordination reaction with aluminium isopropoxide in the presence of monomeric 8-hydroxyquinoline in THF. The UV-vis and fluorescent spectra indicated that the polymer showed the similar optical properties of Alq3 both in the solution and thin film state.更多还原