【作者】 傅祺；

【导师】 施文芳；

【作者基本信息】 中国科学技术大学 ， 高分子化学与物理， 2009， 博士

【摘要】 超支化聚合物具有高度支化的分子拓扑结构,独特的物理化学性能以及易于合成及修饰的特点,目前已经成为高分子科学研究的重要领域。然而具有光敏性能的超支化大分子的研究才处于起步阶段。本文通过对超支化聚酯进行端基修饰得到多种具有光敏性能的聚合物,并对其在光交联/解聚与光响应方面的性能进行了相关研究。此外,还利用“thiol-ene”体系的光敏性能合成了聚（硫醚-酯）系列的超支化多元醇。1.超支化聚酯端基修饰及其“thiol-ene”体系光聚合性能研究通过对Boltorn^?系列超支化聚酯多元醇进行巯基封端,从而得到超支化多巯基大分子TAH40;还通端基修饰得到了基于Boltorn^?H20的超支化多烯丙基醚低聚物AEH20,以及基于Boltorn^?P1000的超支化多官能团降冰片烯低聚物NCP1000。将上述产物与多官能团单体分别组合形成二元“thiol-ene”光聚合体系,并对其UV光聚合反应性能进行了相关研究。2.多巯基超支化聚酯的制备及其“thiol-acrylate”体系无引发剂光聚合性能研究对超支化聚酯Boltorn^?H20与P1000进行巯基乙酸酯化封端合成多巯基超支聚酯TAH20与TAP1000,使其与不同官能度的丙烯酸酯单体组成无引发剂的二元“thiol-acrylate”光固化体系,采用Photo-DSC研究了其光聚合反应行为。研究发现,该体系在无引发剂存在下亦表现出很高的光敏性能,在较高巯基浓度下,在室温及空气环境中UV辐照即可迅速交联。3.4-甲基香豆素端基超支化聚合物的合成及其可逆光响应行为研究利用“thiol-ene”反应,对超支化聚酯Boltorn^?H40进行修饰,获得了具有光响应性能的端基为4-甲基香豆素基团的超支化聚合物MCTH40。通过¹HNMR、FT-IR光谱与GPC方法对产物进行了结构表征。对产物可逆的光致交联(UVA,λ_max=365 nm)以及光致解聚(UVC,λ_max=254 nm)行为采用紫外-可见吸收光谱与荧光光谱的测定分析进行了研究。通过RAFT聚合方法,合成了线形香豆素类聚合物PVBMC,对具有不同拓扑结构的功能聚合物MCTH40与PVBMC的可逆光响应行为进行了比较研究。4.7-羟基香豆素端基超支化聚酯的合成及其可逆光响应与pH响应性能研究首先合成含有7-羟基香豆素基团的丙烯酸酯类单体（EGCA）,通过“thiol-ene”加成反应对巯基改性的超支化聚酯进行封端修饰,得到香豆素端基的超支化聚酯。采用¹HNMR、FT-IR和GPC方法对其结构进行了分析表征;对HCTH40的可逆光致交联/解聚行为以及pH响应性能进行了相关研究。5.“巯基-双建反应合成超支化聚（硫醚-酯）多元醇及其结构表征利用高效的“thiol-ene”加成反应,先以双羟甲基丙酸对苯乙烯苄酯（BMPVB）与多元巯基单体合成了结构较规整的聚（硫醚-酯）多元醇PTE[OH]-A1/B1,再通过巯基封端修饰,再“thiol-ene”UV辐照加成反应,合成了具有较高官能度与分子量的聚（硫醚-酯）多元醇PTE[OH]-A2/B2与A3/B3。通过¹HNMR、FT-IR和GPC方法对产物结构进行了表征。更多还原

【Abstract】 Hyperbranched polymers have been an important field for research and applications of polymer science in resent years.They own highly branched molecular structures,perform special physical and chemical properties,and can be easily synthesized,relatively.Because of their large number of surface functional group,they are also facile for chemical modification.Moreover,photosensitive hyperbranched polymer also becomes the focus of polymer scientists.In this doctoral dissertation different terminal functionalized hyperbranched polyester were synthesized and applied in photo crosslinking and photo responsive systems. Furthermore,a series of hyperbranched poly（thiol ether-ester） polyol with relatively high degree of branching were synthesized through UV induced "thiol-ene" reaction.1.Terminal functionalized hyperbranched polymers and their photopolymerization behaviors in "thiol-ene" UV curing systemsHyperbranched polyester polythiol,TAH40,was prepared by thiol modification of Boltron^? H40.And multi-ene hyperbranched polyester oligmers, including allyl ether terminal functionalized AEH20 and norbornene end-capped NCP1000,were also synthesized and characterized by ¹H NMR spectral analysis. The UV-induced photopolymerization behavior of binary thiol-ene system was real-time monitored with Photo-DSC in air.The UV photo reactivity of obtained thiol-ene systems was also evaluated.2.Thiol functionalized hyperbranched polyesters and their application in photoinitiator-free "thiol-acrylate" photopolymerization systemHyperbranched polythiol polyester TAH20 and TAP1000 were synthesized by surface modification of Boltron^? H20 and P1000 and characterized by ¹H NMR spectral analysis.And obtained polythiol were used in photoinitiator-free "thiol-acrylate" systems with different multi-functional acrylate monomers.The UV induced photopolymerization of "thiol-acrylate" systems was evaluated by Photo-DSC method.The "thiol-acrylate" system performed very high photosensitivity and cured very fast under UV irradiation without addition of photoinitiator in air atmosphere.3.4-Methyleoumarin terminally funetionalized hyperbranehed polester and its reversible photo responsive propertiesHyperbranched polymer with 4-methylcoumarin terminal group（MCTH40） was prepared via thiol-ene addition reaction of thiol-modified hyperbranched polyester TAH40 and a vinyl monomer（7-（4-vinyl-benzyloxyl）-4-methylcoumarin,VBMC）, and characterized with ¹H NMR and FT-IR spectroscopy.Its reversible photo-crosslinking/photo-cleavage behavior was evaluated based on the UV-Vis and FL spectroscopic analysis,and compared with the linear polymer,PVBMC.4.7-hydroxycoumarin terminally funetionalized hyperbranehed polyester and its reversible photo and pH responsive propertiesThe 7-hydroxycoumarin terminal functionalized hyperbranched polyester, HCTH40,was prepared via thiol-ene addition between TAH40 and an acrylate 7-hydroxycoumarin monomer,EGCA.The product was characterized with ¹H NMR and FT-IR spectroscopy.Its reversible photo responsive behavior and the pH-dependent fluorescence emitting property were investigated by UV-Vis, fluorescence spectral and GPC analysis.The results indicated that the HCTH40 performed relatively steady photo reversibility and pH responsive behavior. 5.Syntheis of hyperbranched poly（thiol ether-ester） polyol through "thiol-ene" addition methodHyperbranched poly（thiol ether-ester） polyols（PTE[OH]） were synthesized by combined thiol terminal functionalization and "thiol-ene" addition reaction. PTE[OH]-A1 and B1 were synthesized by "thiol-ene" between two multi-functional thiol monomers and a new vinyl benzyl ester（BMPVB）,respectively.Furthermore, PTE[OH]-A2,B2,A3,and B3,were synthesized by successive reactions of thiol glycolic acetate esterification and "thiol-ene" photo addition.The products were characterized with ¹H NMR,FT-IR and GPC methods.And the analysis results reflected that obtained hyperbranched poly（thiol ether-ester） polyol owned high degree of branching.更多还原