新型具高折射率之芳香族聚醯亞胺/二氧化鈦混成 奈米複合光學材料之合成性質與研究

Novel Aromatic Polyimide-Nanocrystalline-Titania Hybrid Optical Films with High Refractive Index

林柏翰(Po-Han Lin)

指導教授 ： 劉貴生

國立臺灣大學/工學院/高分子科學與工程學研究所/碩士(2009年)

https://doi.org/10.6342/NTU.2009.00909

摘要

芳香族聚醯亞胺是眾所皆之的高熱安定性及高折射率材料，因此在學術研究及光電元件的應用上十分廣泛，但是其應用性受限於低溶解度及難熔性。導入羥基於聚醯亞胺結構中是一個重要的方法，不僅可以有效地提升溶解度，並且提供了有機及無機材料鍵結的反應位置。由於有機/無機混成材料較其單一材料具有機械性質、熱性質、及光學性質上的提昇效果，因此近年來已逐漸受到重視及研究。本論文的研究目標為設計與合成出新穎的高分子/二氧化鈦混成材料並探討其在光學膜上的應用，進而製作出色淡、透明性、高折射率光學膜。
在第二章中，首先合成兩種新型含羥基的二胺單體2,3-bis(4-amino-3-hydroxyphenoxy)naphthalene 及2,7-bis(4-amino-3-hydroxyphenoxy)naphthalene，並聚合出兩系列新穎的可溶性聚醯亞胺。具有羥基的聚醯亞胺與四丁基鈦可進一步藉由控制有機/無機莫耳比例成功地製備有機/無機混成光學材料。此光學薄膜(100-500 nm)的折射率可由二氧化鈦含量自由地調控(n介於1.67-1.99)。更進一步，我們成功合成出二氧化鈦含量達50 %的光學厚膜，此光學厚膜(20-30 μm)的折射率及二氧化鈦含量皆高過於至今的所有文獻。此系統的光學厚膜亦具有高撓曲性、高機械強度、出色的熱性質、低熱膨脹係數、高折射率，及可見光區的高穿透度。
在第三章中，導入六氟基團於具有羥基的聚醯亞胺中，更有效地增加了材料的溶解度。一系列的高折射率及高光學透明性的聚醯亞胺-二氧化鈦混成光學材料也成功地合成，其光學薄膜(100-1000 nm)的折射率可由二氧化鈦含量自由地調控(1.61-1.99)。此有機/無機光學厚膜(20-30 μm)亦具有高撓曲性、高機械強度、出色的熱性質、低熱膨脹係數、高折射率，及可見光區的高穿透度。

關鍵字

聚醯亞胺 ； 二氧化鈦 ； 混成 ； 高折射率 ； 光學薄膜

並列摘要

Aromatic polyimides are well known as excellent heat-resistant and high refractive index materials which have been widely investigated and applied for optoelectronic devices. However, their applicability has been limited because of the normally insolubility and infusibility in the fully imidized form. The incorporation of hydroxyl groups on the backbones of the polyimides was an important strategy to ensure the solubility and provided the reactive sites for organic-inorganic bonding. Composites that consist of polymer–inorganic hybrid materials have recently attracted considerable interests due to their enhanced mechanical, thermal, optical properties compared to the corresponding individual inorganic or polymer component. The research goals of this thesis were design and synthesis of novel polymer/titania hybrid materials and investigated their applications in optical films. Furthermore, the lower colorness, high optical transparency, and high refractive index optical films could also be prepared.
Chapter 2 included two series of novel soluble polyimides with hydroxy-substituted which were synthesized from the new diamines, 2,3-bis(4-amino-3-hydroxyphenoxy)naphthalene and 2,7-bis(4-amino-3-hydroxyphenoxy)naphthalene, with various commercial tetracarboxylic dianhydrides, respectively. High refractive index polyimide–titania hybrid optical films were successfully prepared from the soluble hydroxy-substituted polyimides and titanium butoxide by controlling the organic/inorganic molar ratio. The tunable refractive index (1.67-1.99) of hybrid thin films (100-500 nm) could be obtained by controlling titania content. Moreover, the thick titania hybrid films could also be achieved even with the relatively high titania content as high as 50 wt%. To the best of our knowledge, the refractive index and titania content are the highest to date among the polymer–titania hybrid optical films (20-30 µm in thickness). All these obtained hybrid thick films revealed excellent thermal properties with low CTE, good mechanical properties and flexibility, high refractive index, and good optical transparency in the visible region.
Chapter 3 showed the effective approach of improving the solubility of aromatic polyimides by incorporation of the hexafluoroisopropylidene (6F) and hydroxyl groups into polymer backbone. High refractive index and optical transparency polyimide–titania hybrid optical films were also successfully prepared. The refractive index (1.61-1.99) of hybrid thin films (100 nm-1000 nm) could be obtained by tuning titania content, and the hybrid thick films (20-30 µm) also exhibited enhanced mechanical properties and good flexibility, excellent thermal properties with lower CTE, high refractive index, and good optical transparency in the visible region.

並列關鍵字

polyimide ； titania ； hybrid ； high refractive index ； optical films

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