【作者】 周峻峰；

【导师】 王立；

【作者基本信息】 浙江大学 ， 高分子化学与物理， 2007， 博士

【摘要】 两亲性共聚物可以通过自组装形成不同形态的纳米级或微米级的高度有序结构，如球状、蠕虫状、棒状、囊泡状和复合状结构等，这些制得的具有特殊结构的材料在生物、医药、催化、分离及分子光电器件等领域有很好的应用前景。本文对两亲性共聚物的合成及其自组装性能方面的研究进展作一个综述；开展了两亲性共聚物的合成及其性能的研究；探讨了两亲性共聚物的合成和自组装的机理；探索了所得组装体在纳米材料制备中的应用。采用自由基聚合法合成了甲基丙烯酸十八酯和马来酸酐的无规共聚物P（SMA-co-MA），并用仲胺化合物吗啡啉化学修饰了此聚合物，制得了P（SMA-co-MPMA），用¹H-NMR、FT-IR、GPC对其进行了表征，确定了其组成和结构；研究了它们在THF／H₂O中的自组装行为，通过改变浓度、H₂O量等影响自组装的条件，制得了球形、囊泡、复合、珍珠项链状、空间网络状等多种形态的自组装体；当水含量为5.32wt％时，P（SMA-co-MA）水解产物经组装形成粒径约为300nm的复合组装体，当水含量为18.35wt％时，其经组装形成囊泡；当浓度为0.11wt％、水含量为11.1wt％时，P（SMA-co-MPMA）经组装形成珍珠项链状结构；讨论了其在不同条件下的自组装机理，并建立了可能的自组装机理模型。以BTBA为链转移剂，采用可逆加成—断链链转移（RAFT）聚合法合成了新颖的具有交替结构的嵌段共聚物P（SMA-alt-MA）-b-PSMA，用¹H-NMR、FT-IR、GPC对其进行了表征，确定了其组成和结构；研究了其在THF／H₂O中的自组装行为，通过改变浓度、H₂O量、pH值等影响自组装的条件，制得了球形、复合等多种形态的自组装体；当浓度为0.05wt％时，P（SMA-alt-MA）₅₀-b-PSMA₃₀水解产物经组装能形成粒径为150～200nm的球形结构，当浓度为0.20wt％时，其经组装形成粒径约为400nm的复合组装体；提出了其可能的自组装机理模型。采用RAFT聚合法制备了两个系列的甲基丙烯酸十八酯—N-异丙基丙烯酰胺共聚物（PSMA-b-PNIPAAm、PSMA-b-PNIPAAm-b-PSMA），用¹H-NMR、FT-IR、GPC对其进行了表征，确定了其组成和结构；研究了所得共聚物在混合溶剂中的自组装行为，通过改变溶剂种类、混合溶剂组成、嵌段比及分子量、温度等影响自组装的条件，制得了巨型复合囊泡、巨型囊泡、“珍珠项链”、球形等多种形态的自组装体；当浓度为0.1wt％、水含量为30.0wt％时，PSMA₂₉-b-PNIPAAm₂₃经组装形成粒径约为30μm的巨型复合囊泡，PSMA₁₇-b-PNIPAAm₄₀经组装形成尺寸为5-10μm的巨型囊泡，PSMA₁₇-b-PNIPAAm₃₂经组装形成粒径为800nm的球形结构；当浓度为0.1wt％、水含量为30.0wt％时，PSMA₁₀-b-PNIPAAm₆₈-PSMA₁₀经组装形成粒径约为1.0μm的“核一壳”球形结构，PSMA₁₀-b-PNIPAAm₂₆-PSMA₁₀经组装形成尺寸约为250nm的囊泡；讨论了其在不同条件下的自组装机理，建立可能的自组装机理模型。合成了甲基丙烯酸特丁酯—N-异丙基丙烯酰胺系的嵌段共聚物（PtBMA-b-PNIPAAm、P（MAA-co-PyMA）-b-PNIPAAm），用¹H-NMR、FT-IR和GPC对其进行了表征，确定了其组成和结构；研究了PtBMA-b-PNIPAAm在混合溶剂中的自组装行为，发现PtBMA-b-PNIPAAm在THF／H₂O中可以通过自组装形成球形、囊泡和三维网络结构，PtBMA-b-PNIPAAm在1，4-dioxane／H₂O中可经自组装形成囊泡和交联网络结构；研究了P（MAA-co-PyMA）-b-PNIPAAm在1，4-dioxane／H₂O中的自组装行为，用1，2-二（2-胺基乙氧基）乙烷将所得组装体的中间层MAA链段进行化学交联，制得稳定的交联温敏性荧光纳米微球。采用原子转移自由基聚合（ATRP）方法合成了三个系列的甲基丙烯酸十八酯—γ-（甲基丙烯酰氧）丙基三甲氧基硅烷的嵌段共聚物（PTMSPMA-b-PSMA-Fc-PSMA-b-PTMSPMA、PSMA-b-PTMSPMA、S-（PSMA-b-PTMSPMA）₄），用¹H-NMR和GPC对其进行了表征，确定了其组成和结构；研究了所得共聚物在混合溶剂中的自组装行为，通过改变浓度、混合溶剂组成和嵌段比及分子量等影响自组装的条件，得到了球形、囊泡和复合囊泡等形态的自组装体；当浓度为0.10wt％时，PTMSPMA₁₅-b-PSMA₃₂-Fc-PSMA₃₂-b-PTMSPMA₁₅经自组装形成复合组装体，当浓度为0.20wt％时，其经自组装形成复合囊泡；当浓度为0.10wt％时，PSMA₂₅-b-PTMSPMA₃经自组装形成复合组装体，当浓度为0.50wt％时，其经自组装形成复合囊泡；当浓度为0.05wt％、乙醇含量为10.0wt％时，S-(PSMA₁₂₈-b-PTMSPMA₅₆)₄经组装形成球，而S-(PSMA₁₂₈-b-PTMSPMA₉)₄经组装形成囊泡；将所得组装体中的三甲氧基硅烷水解和缩合，制得内部交联的有机—无机杂化纳米材料；讨论了其在不同条件下获得多种形态的有机—无机杂化纳米材料的形成机理；探索了用PSMA₂₅-b-PTMSPMA₃的组装体封装银纳米粒子，然后经溶胶—凝胶过程，制备了稳定的银纳米粒子／聚合物的“核—壳”复合纳米粒子的可能性。采用ATRP方法合成了PSMA-Crown-PSMA聚合物，用¹H-NMR、FT-IR和GPC对其进行了表征，确定了其组成和结构；研究了PSMA-Crown-PSMA在THF／H₂O中的自组装行为，通过改变分子量、H₂O量、浓度等影响自组装的条件，制得了球形、复合和中空球等多种形态的自组装体：当浓度为0.10wt％、水含量为10.0wt％时，PSMA₉-Crown-PSMA₉、PSMA₁₂-Crown-PSMA₁₂和PSMA₁₆-Crown-PSMA₁₆经自组装分别形成中空纳米球、实心纳米球和多孔单层膜；讨论它们在不同条件下的自组装机理，建立了可能的自组装机理模型；以PSMA-Crown-PSMA的自组装膜为模板，将其浸渍在AgNO₃／HF溶液中，使金属离子在冠醚基团富集，通过Ag⁺与硅原子之间的原电池氧化还原反应，使Ag⁺发生还原反应，并就地沉积形成纳米点，制得了金属纳米粒子的有序阵列。更多还原

【Abstract】 Amphiphilic polymers have received considerable attention due to their ability to self-assemble in bulk and in solution forming a range of different morphologies （e.g., spheres, rods, lamellae and large compound vesicles） through weak noncovalent interactions. These resultant aggregates have very interesting particular properties, so they have many potential applications in areas such as microreactors, microcapsules, drug delivery systems and encapsulation of various kinds of guest molecules. In this paper, progress in synthesis, self-assembly and application of amphiphilic polymers were reviewed. Many amphiphilic polymers containing mathacrylate were prepared and characterized. The self-assembly behavior of the resultant polymers in mixed solvents was investigated.Maleic anhydride-stearyl methacrylate （MA-SMA） random copolymer was synthesized via the free radical polymerization and its amide was prepared through the MA moieties being reacted with morpholine. The resultant polymers were characterized by ¹H-NMR, FT-IR and GPC It was found that the resultant polymers could form various morphologies in THF/H2O by adjusting the concentration and water content. The hydrolyzate of P（SMA-co-MA） can self-assemble into large compound micelles （LCMs） with diameter of ca. 300nm at water content of 5.32wt%, while it can form vesicles at water content of 18.35wt%; P（SMA-co-MPMA） can yield pearl-necklace aggregates at the concentration of 0.11wt% in THF/H₂O 88.9/11.1 （WAV）. The effect of the polymer-solvent interaction on these aggregations was discussed. P（MA-alt-SMA）-b-PSMA having alternating segments was prepared via the reversible-addition-fragmentation-transfer （RAFT） polymerization. The resultant polymers were characterized by ¹H-NMR, FT-IR and GPC. Various morphologies self-assembled from the hydrolyzate of P（MA-alt-SMA）-b-PSMA in THF/H₂O were obtained by varying the concentration, water content and pH value. The hydrolyzate of P（SMA-alt-MA）₅₀-b-PSMA₃₀ can self-assemble into spheres with diameter of 150～200nm at the concentration of 0.05wt%, while it can form LCMs with diameter of 400nm at the concentration of 0.20wt%.Stearyl methacrylate-N-isopropylacrylamide （SMA-NIPAAm） diblock and triblock copolymerswere synthesized via the RAFT polymerization. The resultant polymers were characterized by¹H-NMR, FT-IR and GPC. Various morphologies self-assembled from block copolymers in mixedsolvents were obtained by varying solvent, block ratio, temperature and so on. When theconcentration was maintained at 0.10wt% in THF/H₂O 70/30 （WAV）, PSMA₂₉-b-PNIPAAm₂₃ canself-assemble to giant compound vesicles with diameter of 30μm, PSMA₁₇-b-PNIPAAm₄₀ can form giant vesicles with diameter of 5-10μm, while PSMA₁₇-b-PNIPAAm₃₂ can yield spheres with diameter of 800nm. At the same condition, PSMA₁₀-b-PNIPAAm₃₈-PSMAio can form "core-shell" spheres with diameter of 1.0μm and PSMA₁₀-b-PNIPAAm₂₆-PSMA₁₀ can yield vesicles with diameter of 250nm.t-Butyl methacrylate-N-isopropylacrylamide （tBMA-NIPAAm） diblock copolymer was synthesized via the RAFT polymerization and （P（MAA-co-PyMA）-b-PNIPAAm） was prepared through the hydrolysis and esterification reactions. The resultant polymers were characterized by ¹H-NMR, FT-IR and GPC. Their self-assembly behaviors were studied in different solvents. It was found that spheres, vesicles and network can be obtained through the self-assembly of PtBMA-b-PNIPA Am/THF/H₂O system; vesicles and cross-linked network can be formed through the self-assembly of PtBMA-b-PNIPAArn/1,4-dioxane/H₂O system. The self-assemble behavior of P（MAA-co-PyMA）-b-PNIPAAm in 1,4-dioxane/H₂O was also investigated. Stable thermo-responsive fluorescent nanoballs can be prepared via the covalent cross-linking of MAA segments within the aggregates. The thermo-responsive and fluorescent properties of the nanoballs were investigated.Stearyl methacrylate-3-（trimethoxysilyl）propyl methacrylate （SMA-TMSPMA） diblock, multi-block and star block copolymers were synthesized via atom transfer radical polymerization （ATRP）. The resultant polymers were characterized by ¹H-NMR and GPC. By controlling concentration, copolymer composition and solvent composition, the different aggregates could be obtained, including spheres, vesicles, LCMs and large compound vesicles. With a base catalyst, the resultant copolymers containing R-Si（OCH₃）₃ groups were subsequently transferred into the crosslinked polysilsesquioxane by the hydrolysis and condensation reactions. This sol-gel process resulted in the formation of organic/inorganic hybrid nanomaterials. Furthermore, the aggregates of PSMA₂₅-b-PTMSPMA₃ were used to encapsulate Ag nanoparticles, stable "core-shell" inorganic/polymer nanoparticles can be prepared by the sol-gel procedure.PSMA-Crown-PSMA was synthesized via ATRP. The resultant polymers were characterized by ¹H-NMR, FT-IR and GPC. By adjusting molecular weight, water content and concentration, various morphologies could be obtained, including spheres, LCMs and hollow spheres. A metal particle array based on the self-assembled template from the polymer was prepared by the galvanic displacement reaction.更多还原