随着可控聚合与自组装技术的的发展，大分子自组装已经成为制备纳米材料的重要手段。通过调控聚合物的化学组成与结构设计，可以得到具有不同结构与用途的纳米材料。然而，相比于广泛研究的嵌段共聚物自组装，均聚物自组装的发展处于明显的滞后状态。尚存在如下未解决的科学问题：1)缺乏合适的构筑单元；2)组装机理尚不清楚；3)均聚物组装体结构难以解析；4)应用领域尚待开拓。 针对上述科学问题，本论文中设计并合成了三类两亲性均聚物。具体如下： 1)构筑了侧链型偶氮苯均聚物，深入探究了该聚合物自组装形成开口尺寸可控的纳米碗的机理，并证实了非共价键的协同作用在均聚物自组装中的重要作用；2)设计并合成了聚酰胺酸均聚物，通过分子内亚胺化反应诱导的结晶自组装制备了多级复杂结构，丰富了均聚物自组装体的形貌，并证实了均聚物也可以经历结晶成核-生长的过程进行自组装；3)利用不同的表征方法，对均聚物囊泡的结构进行了深入解析，并辅助数学建模对其进行验证；4)将功能性端基引入到均聚物中，丰富了两亲性均聚物的设计策略，在此基础上探究了均聚物自组装体在催化、水处理与储能领域的潜在应用。 首先，我们研究了非共价键及其协同作用对于均聚物自组装行为的影响，制备了开口尺寸可控的纳米碗。利用可逆加成-断裂链转移(RAFT)聚合合成了多种侧链型偶氮苯均聚物，通过化学设计，将氢键与π-π作用供体引入到均聚物侧链中。均聚物间的非共价键作用如氢键、π-π作用等会对组装过程中的分子链运动起到重要影响，从而决定组装体的形貌。当偶氮苯均聚物(PAzoMA)分子间仅有π-π作用时，组装形成均聚物复合胶束；而当均聚物(PHAzoMA)同时具有分子间／内氢键与π-π作用时，两种非共价键作用的协同会诱导均聚物形成纳米碗。随着分子量的继续增加，纳米碗的开口尺寸不断变大，并呈现出线性关系。追踪纳米碗的形成过程，我们准确监测了纳米碗的形成过程，并对其形成机理进行了详细阐述。通过设计不同结构的均聚物进行验证，成功将该纳米碗制备策略进行了推广。 其次，针对活性聚合难以放大的缺点，简化聚合物的制备步骤，改善反应条件。本文中利用逐步聚合，将肼与均苯四甲酸二酐聚合得到聚酰胺酸(PAA)均聚物。通过亚胺化反应，可以使均聚物主链中发生环化反应，显著提高均聚物分子链的刚性与规整性，通过结晶驱动均聚物进行自组装。发生亚胺化反应后生成P(AA-stat-I)，此时利用溶剂交换法可诱导P(AA-stat-I)进行结晶自组装，得到均一分布的纳米束。随着均聚物浓度的增加，纳米束会进行多级自组装并最终形成花瓣状组装体。同时，增加PAA在DMF中的浓度可诱导P(AA-star-I)在DMF中进行结晶自组装。随着浓度的增加，P(AA-star-I)自组装形成梭形纳米片并进行多级自组装，最终形成沙漏型超结构。该方法制备简便，准备大规模制备的潜力。随后，我们详细研究了结晶驱动对于均聚物自组装的影响，并利用沙漏型超结构作为前驱体制备了具有多级孔结构的沙漏形氮掺杂碳材料。 再次，针对均聚物囊泡结构难以解析的问题。本文中利用结构明晰的两亲性聚酰胺酸(PAA)均聚物作为构筑单元，制备了均聚物囊泡。逐步聚合反应在室温进行，无需催化剂与惰性气体保护，具备大规模制备的潜力。得到均聚物囊泡后，我们通过不同的样品制备方法，利用TEM与光散射技术对均聚物囊泡的双亲膜结构进行解析，明确了均聚物囊泡膜中亲疏水组分共存的本质。随后，探究了PAA囊泡在能源存储领域的应用。将上述均聚物囊泡在惰性气氛中煅烧，可得到结构完整的氮掺杂空心纳米碳球，该碳球在电化学储能中表现出非常优异的性能。 最后，针对均聚物自组装体难以进行多功能化设计的缺点，本节中利用偶氮苯封端的链转移剂(Azo-DDMAT)将功能性基团引入到均聚物中，得到两亲性均聚物(Azo-PEEA)。均聚物可通过疏水作用与π-π相互作用进行自组装，形成有微相分离结构的多室胶束与聚合物囊泡。基于偶氮苯基团与多环芳烃的π-π相互作用，该囊泡可以在短时间内高效吸附水中的多环芳烃。此外，还可利用聚合物中的氮原子与氯金酸根离子之间的相互作用，制备等离子体囊泡。该等离子囊泡显示出优异的催化性能与具有温度响应性的光学性能。升高温度，等离子体囊泡的局部表面等离子体共振(LSPR)吸收峰产生红移并表现出优异的表面增强拉曼散射(SERS)性能。 关键词：均聚物，自组装，囊泡，能源存储，水处理

 With the development of living polymerization techniques and the breakthroughs in the filed of self-assembly, macromolecular self-assembly has been a widely used method to fabricate nanomaterials with diverse morphologies, which can be manipulated by regulating the chemical composition and structure of the polymers, etc. However, compared to the widely studied block copolymer self-assembly, the development of homopolymer self-assembly is very limited and hysteretic due to the following unsolved scientific problems: 1) lack of proper building blocks; 2) the self-assembly mechanism of homopolymers is still unclear; 3) the structure of homopolymer assemblies is difficult to analyze and 4) the applications of homopolymer assemblies are very limited. In order to resolve the above scientific problems, three types of amphiphilic homopolymers were designed and synthesized in this dissertation, which enriched the building blocks of homopolymers for self-assembly. The details are as follows: 1) The homopolymers with side chain azobenzne moieties were designed and synthesized to self-assemble into nanobowls with uniform size. The mechanism of the formation of the nanobowls with controlled openings and interior holes was explored. Besides, the important role of the synergy of non-covalent interactions such as hydrogen bonds and π-π interactions in the formation of nanobowls was also confirmed. 2) The poly(amic acid) homopolymer was designed and synthesized by stepwise polymerization under ambient temperature, which can self-assemble into high ordered structures derived from the imidization reaction-induced hierarchical self-assembly, enriching the morphorlogies of the nanostructures self-assembled from homopolymers. More importantly, we confirmed the importance of crystallization of homopolymers in the formation of complicated nanostructures by self-assembly. 3) Using different characterization methods, the amphiphilic membrane structure of the homopolymer vesicles is deeply analyzed, and the mathematical modeling is also established to verify the membrane structure and calculate the membrane thickness. 4) The azobenzene end group was introduced to the homopolymer chian by using chain transfer agent to enrich the design stragegy of amphiphilic homopolymers, exploring the potential applications of homopolymer nanostructures in the fields of catalysis, water treatment and energy storage. Firstly, we studied the influence of non-covalent bonds and their synergistic effects on the self-assembly behavior of homopolymers, and prepared nano-bowls with controlled opening sizes. A variety of side chain azobenzene homopolymers with hydrogen bonds and π-π interaction donors were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Non-covalent bonds between homopolymers such as hydrogen bonding and π-π interaction had a critical influence on the macromolecular chain mobility during assembly, thus determining the morphology of the assemblies. When the azobenzene homopolymer (PAzoMA) only provids π-π interactions, it forms homopolymer compound micelles (HCMs). However, nanobowls are formed by PHAzoMA homopolymer because of the formation of hydrogen bonding and π-π interaction, the synergy of which significantly reduces the chain mobility during self-assembly. As the molecular weight increases, the opening size of the nanobowls continues to increase and exhibits a linear relationship. Tracking the formation process of the nanobowl, we investigated the formation process of the nanobowl and proposed its formation mechanism. The preparation strategy of nanobowl was successfully extended to other homopolymers with different structures. Secondly, we used stepwise polymerization technique to massively fabricate amphiphilic homopolymers for self-assembly at mild conditons, since it needs the protection of inert atmosphere and is difficult to prepare polymers on a large scale by living polymerizations. PAA homopolymer was synthesized by the stepwise polymerization of hydrazine and pyromellitic dianhydride at ambient temperature. When heated in DMF, the PAA underwent imidization reaction to form poly(amic acid-stat-imide) (P(AA-stat-I)), which significantly increases the rigidity and regularity of the molecular chains. With the addition of water, P(AA-stat-I) self-assembles into nanobundles with uniform size driven by crystallization. As the concentration of P(AA-stat-I) increases, the nanobundles undergo hierarchical self-assembly and the flower-like structure is formed eventually. Upon further increasing the concentration of PAA, the crystallization-induced self-assembly of P(AA-stat-I) occurs in DMF. At low concentration, spindle-shaped nanosheets are formed, which then undergoes hierarchical self-assembly to form hourglass-shaped superstructures at the concentration of 150 ㎎/mL. It is worth noting that the hourglass-shaped superstructure can be prepared in large quantity by the “one-pot” crystallization-induced self-assembly of PAA. Subsequently, we studied the effect of crystallization on the self-assembly of homopolymers in detail, and prepared hourglass-shaped nitrogen-doped carbon material with multi-stage pore structure by using the hourglass-shaped superstructure as a precursor. Thirdly, considering the problem in investigating the structure of homopolymer assemblies, homopolymer vesicles are prepared using an amphiphilic polyamic acid (PAA) as building blocks, whose structure is well-studied. The stepwise polymerization was carried out at room temperature without catalyst and the protection of inert gas. The amphiphilic membrane structure of homopolymer vesicles was investigated by TEM analysis with different sample preparation methods and light scattering. The coexistence of both hydrophilic and hydrophobic components in the homopolymer vesicle membrane was also clarified. Subsequently, the applications of PAA vesicles in energy storage were studied. The nitrogen-doped hollow carbon spheres (N-HCSs) were prepared using PAA vesicles as precursor, which exhibits excellent performance in electrochemical energy storage. Finally, an amphiphilic homopolymer (Azo-PEEA) with azobenzene functional group was prepared by RAFT polymerization with an azobenzene-teminated chain transfer agent (Azo-DDMAT). During the self-assembly process, milticompartment micelles with microphase seperations and vesicles can be obtained due to the hydrophobic and π-π interactions. Based on the π-π interaction of the azobenzene groups and the polycyclic aromatic hydrocarbons (PAHs), the PAHs can be efficiently removed in waste water by the vesicle in short time. Moreover, chloroauric acid ions can be enriched on the membrane of the vesicles and reduced in situ to form plasmonic vesciels, which exhibited excellent catalytic capability and temperature determined optical properties. When the temperature rose, the gold nanoparticles on the membrane of plasmonic vesicles come closer, creating local “hot spots” in the gap between adjacent gold nanoparticles, leading to the red shift of the local surface plasmon resonance (LSPR) peaks and better surface-enhanced Raman scattering (SERS) property. Key Words: amphiphilic homopolymer, self-assembly, polymer vesicle, energy storage, water remediation