In this thesis, we propose a method to control the size and morphology of block polymer phase behaviors, and to prepare new polymer structures by varying the amount and types of selective additives. Systems containing selective additives such as a corresponding homopolymer, selective solvent, molecules with intermolecular interactions and non-solvents are proposed, and were used to investigate the effect of additives on polymerization-induced nanostructuring. The phase behavior of the block polymer materials was modulated by adding polylactide homopolymer (PLA-OH) and acetonitrile (MeCN) to a reaction mixture of styrene (S), divinylbenzene (DVB), polylactide macro-chain transfer agent (PLA-CTA). As a result, micro- and macrophase separation and self-assembly processes during polymerization were controlled, resulting in block polymer materials with controlled sizes and various morphologies. Also, by adding tannic acid, which forms intermolecular interactions with the PLA block, to a solution containing polystyrene-b-polylactide (PS-b-PLA), we studied how the chirality match between the polymer and additive molecules affected self-assembly behavior. Finally, we proposed a method of preparing a hierarchical structure, by inducing independent micro- and macro phase separation. A high internal phase emulsion (HIPE) was prepared by adding water as a non-solvent to a reaction mixture containing S, DVB and PLA-CTA, and then the water-oil interface was stabilized by the addition of a surfactant. By proceeding sequentially with the PIMS process and hyper-cross-linking, a hierarchically porous polymer with micro-, meso- and macroporous structures was successfully prepared.
본 학위 논문에서는 styrene (S), divinylbenzene (DVB), polylactide macro chain transfer agent (PLA-CTA) 를 포함하는 반응 혼합물에 PLA 미세도메인에 선택적으로 참가하는 PLA 단일고분자(PLA-OH)와 아세토니트릴(MeCN)을 첨가제로 이용하여 중합이 유도되는 과정에서 일어나는 미세, 거대상분리와 자기조립을 조절하여 형성되는 겹연속 구조의 크기와 형성되는 구조의 형상을 조절하는 방법을 제시하였다. 또한 PLA 와 선택적으로 상호작용할 수 있는 키랄성 분자인 탄닌산을 polystyrene-b-polylactide (PS-b-PLA) 에 첨가함으로써 분자 비대칭성의 분자간 상호작용에 대한 영향을 유도되는 자기조립 현상의 변화를 통해 조사하였다. 마지막으로 S, DVB 그리고 PLA-CTA 반응 혼합물에 비용매인 물을 첨가하고 계면을 안정화하여 고 내상 에멀전을 이용한 계층적다공성 고분자의 합성 방법을 제시하였다.
