【作者】 夏雪伟；

【导师】 路建美；

【作者基本信息】 苏州大学 ， 材料学， 2005， 博士

【摘要】 原子转移自由基聚合（ATRP）是新兴的活性自由基聚合中最为活跃,受到最多关注的一个分支。通过对引发剂和单体的设计,ATRP可以灵活的合成多种具有特殊结构和性能的功能性聚合物。本文以ATRP为基本合成方法,合成了端基功能化和侧链功能化的聚合物发光材料。分别将金属配合物和有机小分子发色团通过ATRP集成于聚合物体系中,克服了小分子发色团在稳定性和加工性能方面的一些缺点,在得到优异的发光性能的同时使材料具有了很好的稳定性和溶解性,并且可以很方便的成膜为材料的器件化作了准备。1.本文使用功能性引发剂,5-氯甲基-8-羟基喹啉,通过ATRP合成了分子量可控,分子量分布窄的端基功能化聚苯乙烯。并且将端基功能化聚苯乙烯作为大分子配体,通过末端的8-羟基喹啉单元与金属离子进行配位,可以得到末端含有金属配合物单元的端基功能化聚合物。Zn²⁺与聚合物末端的8-羟基喹啉的配位,增强了聚合物的荧光,在荧光发射光谱上表现为发射强度的大幅度增强。2.通过Zn²⁺和聚苯乙烯末端的8-羟基喹啉单元进行的配位合成了末端含有Zn²⁺/8-羟基喹啉配合物单元的聚苯乙烯,并用ICP测定了聚合物中的锌含量以及所含配合物的量。使用微波辐射作为辅助手段,可以在很短的时间内大幅度的推进Zn和聚苯乙烯末端的8-羟基喹啉之间的配位反应的反应进程,在微波辐射条件下反应6分钟,可以使聚合物中的锌含量达到50%,而在加热条件下反应5小时锌含量也只能达到30%。3.通过末端含有Zn²⁺/8-羟基喹啉配合物单元的聚苯乙烯和其他有机小分子配体,邻氨基苯甲酸、邻菲啰啉和8-羟基喹啉,的配位得到了以Zn²⁺为中心离子,含有大分子配体和有机小分子配体的高分子复合配合物。基于Zn（Ⅱ）的高分子复合配合物具有良好的荧光性能,并且可以通过选用不同的有机小分子配体调节高分子配合物的光物理性质。将过渡金属配合物通过配位键引入聚合物体系,可以有效的提高配合物发色团的光物理稳定性,具体表现为处于聚合物体系中的Zn（Ⅱ）配合物比相应的小分子配合物具有更长的荧光寿命。因为含有大分子配体,Zn（Ⅱ）的高分子复合配合物具有良好的溶解性和成膜性,而且在薄膜状态中也表现出良好的荧光性能。更多还原

【Abstract】 Atom transfer radical polymerization (ATRP) is the most attractive and dynamic branch of living radical polymerization. ATRP has been frequently applied to synthesize various functional polymers with specific structures and special properties. In the present thesis, ATRP was employed as a fundamental methodology for the preparation of end-group functionalized and side-chain functionalized light-emitting polymers. Chelate chromophores and low molecular weight organic chromophores were introduced into polymer system, which integrated the photophysical merits of chelates or organic chromophores into polymer and simultaneously solved the small chromophores’ problem of stability and solubility. The obtained polymers could be easily processed into stable and uniform thin films by spin-coating. The easy film forming of these polymers is practically useful for the prospective application in light emitting devices.1. In this paper, a functional initiator, 5-chloromethyl-8-hydroxyquinoline was chosen to initiate the ATRP of styrene. The obtained polystyrene contained 8-hydroxyquinoline as the end group and possessed controllable molecular weight and narrow molecular weight distribution. The obtained polymers were used as macroligand to participate in the coordination reaction with Zn~2+. The obtained polymeric complexes contained unsaturated complexof 8-hydroxyquinoline and Zn~2+ as the end group. Zn content in the polymeric complexes was determined by ICP. Introduction of Zn~2+ onto polymer’s terminal greatly enhanced the fluorescent emission intensity of the polymers.2. Microwave irradiation was employed to accelerate the reaction between Zn~2+ and polymer’s terminal 8-hydroxyquinoline. The coordination reaction was greatly enhanced by the assistance of microwave irradiation. In a very short time, a high yield of polymeric complexes could be obtained. Zn content in polymeric complexes prepared by assistance of microwave irradiation for even 6 minutes was higher than that preparedby conventional heating for 5 hours.3. The unsaturated complexes of Zn2+ and 8-hydroxyquinoline end group of polystyrene were modified by second organic ligands, 2-aminobenzoic acid, 1,10-phenthranoline and 8-hydroxyquinoline to prepared Zn(II) based mixed polymeric complexes. The mixed polymeric complexes of Zn(II) exhibited favorable fluorescent properties. The luminescent properties of mixed could be tuned by using different second ligands. Introduction of Zn(II) based mixed complexes to polymer system through coordination bond effectively ameliorated the photophysical stability of the chelate chromophores. The mixed complexes in polymer system possessed longer exciton life time than that of corresponding low molecular weight complex. The macroligands herein conferred the mixed polymeric complexes favorable solubility and ease of film forming. The mixed polymeric complexes could be easily processed into thin films and the thin films also exerted favorable fluorescent properties.4. Cmplexes of Eu3+ and Sm3+ with p-diketone, EuCl(TTA)2 ? 2H2O , SmCl(TTA)2 ?2H2O,EuCl(DBM)2 <2H2O#I Sm(DBM)2 <2H2O, were synthesized. These complexes were bonded to polymeric ligands through the coordination reaction between trivalent rare earth and the terminal 8-hydroxyquinoline. Polymers containing Eu(III) or Sm(HI) complexes as end group was strongly emissive and the intensive specific emission bands respectively ascribed to Eu3+ or Sm3+ could be observed in the fluorescent emission spectra. Due to the protection of macroligands to chromophores, the polymeric rare earth complexes were strongly emissive, although the concentrations of chromophores were very low. The application of macroligands also led to favorable solubility and easy film forming of polymeric complexes. The films of polymeric Eu(III) and Sm(III) both possessed satisfactory luminescent properties. Polymeric complexes of Eu(III) and Sm(III) both possessed specific emission bands in red light zone as well as emission bands of polystyrene in light zone, which coincided with absorbance spectra of chlorophyll. So the mixed polymeric complexes of Sm(IH) and Eu(III) could be used as light conversion agent to convert part of the UV light in sunlight to red and blule light, meeting the need of photosynthesis process.5. The coordination reactions of Eu(III) and Sm(HI) with polystyrene’s terminal 8-hydroxyquinoline unit were also accelerated by assistance of microwave irradiation. If the reaction was conducted under microwave irradiation only for 5 minutes, the obtained polymeric complexes could possessed intense specific emission bands of Eu3+or Sm3+. While it must take 3 hours or more to get the same emission intensity for polymeric complexes if the reactions were conducted by conventional heating.6. In this paper five styrenic monomers, 4-vinylstilbene (VS), 4’-N,N-dimethylamino-4-vinylstilbene (DMAVS), 4’-N,N-diethylamino -4-vinylstilbene (DEAVS), 4-(2-naphthyl)vinylstyrene (NVS) and 4-(2-anthryl)vinylstyrene (AVS) were synthesized through heterogeneous Wittig reaction between triphenyl-4-vinylbenzylphosphium chloride and five different aromatic aldehyde. The wittig reaction were catalyzed by phase transfer catalyst and conducted in biphase system. The five monomers all possessed favorable fluorescent properties. Substitution of electron donating group onto VS and the extension of conjugation length both led to red shift of emission bands, enhancement of emission intensities and fluorescent quantum yield.7. The five monomers containing conjugate chromophores as pendant side chain all could be polymerized through ATRP. The obtained homopolymers all possessed controllable molecular weight and narrow molecular weight distribution.8. The homopolymers of VS, DMAVS, DEAVS, NVS and AVS all exhibited favorable fluorescent properties. Five homopolymers all could be dissolved in common solvent and could be easily processed into thin film by spin coating. The films of the five homopolymers also exerted strong luminescent properties.更多还原