以原子轉移自由基聚合合成高分子及氫鍵探討

Abstract

自1995年，原子轉移自由基聚合反應被發現之後，每年以這種技術合成的材料被發表的非常多，而這些材料也被運用在薄膜、膠合劑、潤滑劑、洗滌劑等商業用途上。因為這種聚合方法可以使用在壓克力系列、苯乙烯系列、烯烴系列等材料，且它除了有很好控制分子量的優點外，它所生產材料的分子量分佈也在1.5以下，所以目前被廣泛運用。 在高分子的物理性質研究中，相容性(Miscibility)和特殊作用力(Specific Interaction)的探討，一直是相當有趣的主題，且助於解釋許多的高分子行為。其中氫鍵作用力(Hydrogen Bonding Interaction)的探討更是本實驗室多年來研究的主要方向之一。 本論文結合了幾種用原子轉移自由基聚合方法合成的不同種類的高分子以及其氫鍵作用力的物性分析，共分成三個部分: (1) 研究嵌段共聚高分子與單聚高分子間混摻的物性。由於嵌段共聚高分子與單聚高分子間混摻相比，其物理性質應會有所差異的想法，我們用原子轉移自由基聚合方法合成聚烴乙烯甲基丙烯酸酯-聚乙烯基吡咯嵌段共聚高分子和單聚高分子，並將兩單聚高分子進行混摻。以微分式掃瞄熱卡計、紅外線光譜儀和固態核磁共振儀器觀察嵌段共聚高分子與單聚高分子間混摻對材料物性的影響。 (2) 研究線狀與星狀高分子混合物的物性。由於線狀高分子與星狀高分子相比，其物理性質應會有所差異的想法，我們用原子轉移自由基聚合方法合成線狀和星狀的聚第三丁基丙烯酸酯高分子，並將其與氧代氮代苯并環進行熱交聯。以微分式掃瞄熱卡計、紅外線光譜儀和固態核磁共振儀器觀察不同構形對材料物性的影響。 (3) 研究含多面體聚矽氧烷的高分子混合物的物性。由於把無機材料加入有機高分子裡，應會使其機械、熱、電、和有磁性的特性改變的想法，我們用原子轉移自由基聚合方法合成含多面體聚矽氧烷的壓克力高分子，並將其與酚醛樹酯進行混摻。以微分式掃瞄熱卡計、紅外線光譜儀和二維紅外線光譜儀觀察多面體聚矽氧烷對材料物性的影響。

Since it was discovered in 1995, atom transfer radical polymerization (ATRP) is a rapidly developing area. ATRP is a versatile tool to yield various materials, which are applied in many aspects, such as coatings, adhesives, lubricants, detergents, etc. with low polydispersity and controlled molecular weight. In the physical property of the polymer researches, it is of interest to study the miscibility and specific interaction. In this thesis, the experimental work was divided into three parts: (1) The studies of miscibility behavior and interactions of blends and diblock copolymers. Block copolymers composed of segments with different properties have been of considerable interest. We synthesized Poly(hydroxyethyl methacrylate)-b-Poly(vinylpyrroli- done) (PHEMA-b-PVP) by ATRP and conventional radical polymerization. The interactions in PHEMA-b-PVP diblock copolymers and PHEMA/PVP blends are observed by DSC, FT-IR and high-resolution solid-state 13C NMR spectroscopy. (2) The studies of miscibility behavior and interactions of linear and four-arm blends. Star polymers have different hydrodynamic properties and higher degrees of chain end functionality compared to linear polymers of similar composition. We synthesized the linear and four-arm Poly(tert-butyl acrylate) (PtBA) by ATRP and made them mix with benzoxazine (BZZ). Then, we heated them to yield thmosetting polymer blends. The interactions in linear and four-arm PtBA/PBZZ blends are observed by DSC, FT-IR and high-resolution solid-state 13C NMR spectroscopy. (3) The studies of the influence of specific interactions of POSS-containing polymer blends. By adding inorganic materials into organic polymers, mechanical, thermal, electrical, and magnetic properties are changed from those of pure organic polymers. We synthesized the inorganic-organic polymer hybrids involving POSS compounds by ATRP. The interactions in Poly(methyl methacrylate) (PMMA) and POSS- PMMA/phenolic blends are observed by DSC, FT-IR and 2D IR.