有機/無機混成及超雙疏材料的研究

Abstract

有機/無機混成及超雙疏材料的研究 學生：沈永清 指導教授：張豐志教授 國立交通大學應用化學所 摘要

本論文中以開發有機/無機混成材料及利用有機/無機混成材料開發新型的超雙疏高分子為研究主體，內容分為四大主題:

1. 多面體聚矽氧烷之表面改質與奈米複合材料性質研究 我們經由styrene, 4-acetoxystyrene及acetohydrazide製備了一系列新型含八酚官能基之OS-POSS, OP-POSS及 OA-POSS多面體聚矽氧烷(Polyhedral Oligomeric Silsesquioxane)。這些含八酚官能基多面體聚矽氧烷具備有機官能基表面改質及低的玻璃轉化溫度，使其與高分子間相容性增加而得以製備有機-無機奈米複合材料，我們將這些八酚官能基多面體聚矽氧烷與polystyrene、 poly(4-acetoxystyrene)及 poly(4-vinylpyridine) 製備相容性良好之有機-無機奈米複合材料。

2. 低表面能之Polyacrylate/Polybenzoxazine網狀互穿體特性研究 利用快速光聚合硬化的三官能基壓克力單體(TMPTA)形成交聯體，及可熱硬化之N-methyl bisbenzoxazine (BA-m)單體，製備Polyacrylate/polybenzoxazine (PA/PBZZ) 網狀互穿體。本研究中，我們發現 Polybenzoxazine 氫鍵可與壓克力的carbonyl groups形成交互作用增進兩者的相容性，並且可以獲得不含氟亦不含矽氧烷，較鐵氟龍更低表面能的高分子材料。

3. 新型超雙疏含氟之矽奈米粒子合成 利用sol-gel反應合成含氟之矽奈米粒子有機無機混成材料，使表面同時具有粗糙微結構及疏水官能基，所製備出之材料對水及二碘甲烷接觸角分別為167.5° 及 158.6°，因此是一個超低表面能超雙疏材料。此外，對於大豆油(soybean oil)、decahysronaphthalene、diesel fuel及xylene的接觸角也分別達到146.6°、142.5°、140.4°及140.5°，具有相當好的超疏水及超疏油之超雙疏性。

4. 不含氟之Methyltriethoxysilane/Tetraethoxysilane超雙疏之矽奈米粒子研究 以往疏水/疏油性材料都是利用含氟之化合物，本研究則透過sol-gel反應合成，利用methyltriethoxysilane (MTES)的甲基疏水官能基與tetraethoxysilane (TEOS) 創造物理的微結構粗糙表面，不含氟之化合物，所製備出之奈米粒子有機無機混成材料，對水及二碘甲烷接觸角分別為149.8° 及 133.1°，並且達到比氟化合物更低之1.38 mJ/m2超低表面能，因此成功製備出一個不含氟超低表面能之超雙疏材料。

The Study of Organic/Inorganic Hybrid and Superamphiphobic Materials Student：Yuung-Ching Sheen Advisor：Dr. Feng-Chih Chang Institute of Applied of chemistry National Chiao Tung University

Abstract

In this study, we focus on four major subjects which based on super low surface free energy organic/inorganic hybrid materials:

1. Synthesis and Characterization of Amorphous Octakis-Functionalized Polyhedral Oligomeric Silsesquioxanes for Polymer Nanocomposites We have synthesized the polyhedral oligomeric silsesquioxanes (POSS) derivatives OS-POSS and OA-POSS through the hydrosilylation of styrene and 4-acetoxystyrene, respectively, with octakis(dimethylsiloxy)silsesquioxane (Q8M8H). We then prepared OP-POSS through acetoxyl hydrazinolysis of OA-POSS with hydrazine monohydrate. We blended octakis-functionalized POSS OS-POSS, OA-POSS, and OP-POSS with polystyrene, poly(4-acetoxystyrene), and poly(4-vinylpyridine), respectively, and investigated the effects of the resulting intermolecular aromatic hydrophobic, dipole-dipole, and hydrogen-bonding interactions, respectively. In which the POSS–polymer intermolecular interactions were of similar strength to the POSS–POSS interactions.

2. Low Surface Free Energy of Interpenetrating Polyacrylate and Polybenzoxazine Networks Polyacrylate/ polybenzoxazine (PA/PBZZ) full-interpenetrating networks (f-IPNs) were prepared by rapid photopolymerization of triacrylate monomers (TMPTA) and thermal polymerization of N-methyl bisbenzoxazine (BA-m). For PA/BA-m Semi-interpenetrating (s-IPNs), BA-m monomers can be frozen and dispersed in the UV-cured PA network by rapid photopolymerization within 5 min. After thermal polymerization, the phenol units of ring-opened PBZZ segments can form the hydrogen bonding interface with carbonyl groups in the improvement of the compatibility between PBZZ domains and PA networks. The low-surface-free-energy (27.4 mJ/cm2) PA/PBZZ f-IPNs can be obtained for waterproof coating materials.

3. New approach to Fabricate an Extremely Super-amphiphobic Surface Based on Fluorinated Silica nanoparticles A simple approach has been developed to fabricate an extremely super-amphiphobic coating material based on fluorinated silica nanoparticles resulting contact angles of water and diiodomethane at 167.5° and 158.6°, respectively. The contact angle of diiodomethane at 158.6° is substantially higher than the highest literature reported value we know of at 110°. In addition, this developed film also possesses extremely high contact angles with other organic liquids such as soybean oil(146.6°), decahysronaphthalene(142.5°), diesel fuel(140.4°) and xylene(140.5°). This developed super-amphiphobic organic-inorganic hybrid film possesses unique liquid repellency for both water and organic liquids that can be used as functional coatings on numerous substrates by a simple coating process.

4. Non-Fluorinated Superamphiphobic Surfaces Through Sol–Gel Processing of Methyltriethoxysilane and Tetraethoxysilane We developed an extremely superamphiphobic coating material by the tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES) sol–gel derived materials. TEOS and MTES derived moieties were designed for a physical roughness and hydrophobic surface characteristic, respectively. As the MTES composition increased to 25 mole% (T5M3), the coated surface had the contact angles of 149.8° and 133.1° for water and CH2I2, respectively. It revealed that the T5M3-coated surface exhibited both super-hydrophobicity and super-oleophobicity, i.e., superamphiphobicity. Also, it had a relatively low surface energy (1.38 mJ/m2) considerably lower than that of the F-silane coated surface with 39.3 mJ/m2. The present study suggests that superamphiphobic surface could be achieved by non-fluorinated sol-gel derived silica materials.