劉貴生Liou, Guey-Sheng臺灣大學:高分子科學與工程學研究所林柏翰Lin, Po-HanPo-HanLin2010-05-122018-06-292010-05-122018-06-292009U0001-1208200909293500http://ntur.lib.ntu.edu.tw//handle/246246/183156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。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。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.hapter 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.hapter 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.TABLE OF CONTENTSBSTRACT (in English)………………………………….…………….. iBSTRACT (in Chinese)……………………………………….…….....iiiABLE OF CONTENTS………………………………………….…….. ivIST OF TABLES………………………...…………………….……… ixIST OF FIGURES…………………………………………………….. xiHAPTER 1………………………………………………………….......1HAPTER 2…………………………………………………………….44HAPTER 3……………………………………..………………….....109HAPTER 1eneral Introduction.1 HIGH PERFORMANCE POLYMERS……………………………........................2.1.1 Preparation of Aromatic Polyimides ...............................................................4.1.2 Modification of Aromatic Polyimides.............................................................6.1.3 Modification of PI by Incorporation of Hydroxyl Group................................9.1.4 Modification of PI by Incorporation of Naphthalene....................................10.2 HIGH REFRACTIVE INDEX MATERIALS........................................................11.3 FUNCTIONAL HYBRID ORGANIC-INORGANIC NANOCOMPOSITES......16.3.1 Background of Sol-gel Chemistry..................................................................20.3.2 Titania Based Hybrid Nanocomposites..........................................................24.3.3 Hydrothermal Crystallization…………………………..................................25.3.4 Titania-Polyimide Hybrids………………………….......................................27.4 OPTICAL AFFECT OF HYBRID NANOCOMPOSITES......................................33.5 RESEACH MOTIVATION……………………………….......................................34EFERENCES AND NOTES.......................................................................................35HAPTER 2acile Preparation for Nanocrystalline-Titania Hybrids From Hydroxy-Containing Polyimide: Novel Flexible PI-TiO2 Optical Films with High Refractive Index, Good Optical Transparency, and Excellent Thermally Dimensional StabilityBSTRACT OF CHAPTER 2.......................................................................................45.1 INTRODUCTION....................................................................................................46.2 EXPERIMENTAL SECTION...................................................................................49 2.2.1 Materials...........................................................................................................49 2.2.2 Monomer Synthesis.........................................................................................49 2,3-bis(3-benzyloxy-4-nitrophenoxyl)naphthalene (2,3-2)............................49 2,3-bis(4-amino-3-hydroxyphenoxy)naphthalene (2,3-3)…..........................50 2,7-bis(3-benzyloxy-4-nitrophenoxyl)naphthalene (2,7-2)............................51 2,7-bis(4-amino-3-hydroxyphenoxy)naphthalene (2,7-3)..............................51 2.2.3 Polymer Synthesis...........................................................................................57 2.2.4 Preparation of the Films..................................................................................59 2.2.5 Preparation of Polyimide-Titania Hybrid Films.............................................59 2.2.6 Preparation of Titania Films (TP100)……………….....................................65 2.2.7 Measurements.....................................................................................................65.3 RESULTS AND DISCUSSION..................................................................................67 2.3.1 Monomer Synthesis........................................................................................67 2.3.2 Polymer Synthesis...........................................................................................68 2.3.3 Polymer Properties............................................................................................73asic Characterization..................................................................................73ptical Properties.........................................................................................76 2.3.4 Hybrid Properties..............................................................................................79tructural characterizations…………...........................................................79hermal Properties…...................................................................................81orphology Analyses...................................................................................89ptical Properties.........................................................................................97ultilayer antireflection coatings...............................................................104.4 SUMMARY............................................................................................................106EFERENCES AND NOTES.....................................................................................107HAPTER 3ew Approaching for Organic-Inorganic Hybrids Based on Hydroxy-Containing 6F-Polyimide: Novel Flexible PI-TiO2 Optical Films with High Optical Transparency, Tunable Refractive Index, and Excellent Thermal StabilityBSTRACT OF CHAPTER 3....................................................................................110.1 INTRODUCTION.................................................................................................111.2 EXPERIMENTAL SECTION...............................................................................114 3.2.1 Materials..........................................................................................................114.2.2 Polymer Synthesis...........................................................................................114 3.2.3 Preparation of Polyimide-Titania Hybrid Films...........................................114 2.2.6 Preparation of Titania Films (TP100)………………...................................118 2.2.7 Measurements...................................................................................................118.3 RESULTS AND DISCUSSION...............................................................................120 3.3.1 Polymer Synthesis........................................................................................... 120 3.3.2 Polymer Properties........................................................................................122asic Characteristion..................................................................................122 3.3.3 Hybrid Properties............................................................................................124tructural characterizations……….............................................................124hermal Properties….................................................................................124orphology Analyses..................................................................................131ptical Properties.......................................................................................137ultilayer antireflection coatings...............................................................144.4 SUMMARY............................................................................................................146EFERENCES AND NOTES.....................................................................................147 LIST OF TABLESHAPTER 1.1 Some Typical Aromatic High Performance Polymers............................................3.2 Commercially Available Aromatic Polyimides.......................................................5.3 Some Soluble Aromatic Polyimides.......................................................................8.4 Refractive Index and Absorption Coefficients at Three Different Wavelengths in The Visible Range for Some Inorganic Materials................................................14.5 Components, Synthesis Method and RI of Some Metal Oxide–Polymer Nanocomposites with High RI……......................................................................15.6 Properties of Conventional Organic and Inorganic Components.........................19.7 Electronegativity (χ), Coordination Number (N), and Degree of Unsaturation (N - Z) of Some Metals (Z=4)…………………........................................................20HAPTER 2.1 Reaction Composition and Properties of The 2,3-PHIc Hybrid Films...............62.2 Reaction Composition and Properties of The 2,7-PHIc Hybrid Films...............63.3 Inherent Viscosities and Elemental Analysis of Polyimides................................69.4 Inherent Viscosities and GPC Data of Polyimides..............................................72.5 Solubility of Polyimides......................................................................................74.6 Thermal Properties of Polyimides.......................................................................75.7 Thermal Properties of 2,3-PHIc Hybrid Materials.............................................83.8 Color Coordinates and Cutoff Wavelength (λo) from UV-Vis Spectra of 2,3-PHIc Hybrid Materials ……………………………...…...………………103HAPTER 3.1 Reaction Composition and Properties of the 6FPI Hybrid Films......................116.2 Inherent Viscosity and GPC Data of Polyimide.................................................120.3 Solubility of Polyimide........................................................................................123.4 Thermal Properties of 6FPI Hybrid Materials...................................................126.5 Color Coordinates and Cutoff Wavelength (λo) from UV-Vis Spectra of 6FPI Hybrid Materials……………………………………………………………….........143IST OF FIGURESHAPTER 1.1 The different types pf hybrid materials...................................................................17.2 Selected interactions typically applied in hybrid materials and their relative strength………………………………......................................................................18.3 Schematics of size control in in situ composite synthesis....................................18.4 Polymerization behavior of aqueous silica...........................................................22.5 The images and the crystal structures of anatase, rutile and brookite..................24.6 Reaction scheme for hydrothermal crystallization of anatase...............................26.7 Thickness and refractive index of the sol-gel titania film at different annealing temperatures, green dots are thickness, and purple triangles are refractive index at 632.8 nm……………………………………………………………………...26.8 Left: Reaction scheme for the preparation of the aminoalkoxysilane capped PMDA–titania films; right: refractive index, extinction coefficeint versus titania fraction.................................................................................................................29.9 The synthetic procedure used to produce TiO2/BTDA–DMMDA......................30.10 Left: flow chart of the procedures to prepare the PI/TiO2 hybrid films;right: TEM photographs and selected-area electron diffraction(SAED) patterns…………...31.11 Left: Chemical structures of monomers and polymers; right: steps involved in the synthesis of polymer-trapped titania nanoclusters……………………………...31.12 Semi-alicyclic sulfur-containing PAA and silica-modified anatase TiO2…........32.13 (a) Reaction scheme for the preparation of the carboxylic acid end groups PI–titania films; (b) refractive index (c) UV-Vis-NIR absorption spectra….…...32.14 Scheme of light scattering loss for traditional composites and nanocomposites.............................................................................................................33HAPTER 2.1 (a) 1H NMR and (b) 13C NMR spectra of compound 2.3-2 in DMSO-d6...........53.2 (a) 1H NMR and (b) 13C NMR spectra of compound 2.3-3 in DMSO-d6...........54.3 (a) 1H NMR and (b) 13C NMR spectra of compound 2.7-2 in DMSO-d6...........55.4 (a) 1H NMR and (b) 13C NMR spectra of compound 2.7-3 in DMSO-d6...........56.5 The photo of high refractive index, flexible, and good transparent polyimide (2,3-PHIc)-nanocrystalline-titania (2,3TP50) hybrid optical films (thickness=20~30 μm)………………………………………………………….64.6 The photo of high refractive index, flexible, and good transparent polyimide (2,7-PHIc)-nanocrystalline-titania (2,7TP50) hybrid optical films (thickness=20~30 μm)...........................................................................................64.7 The FTIR spectrum of (a) 2,3-PI (without OH) (b) 2,3-PHIc..............................70.8 The FTIR spectrum of 2,7-PHIc.........................................................................71.9 Transmittance UV-visible spectra of 2,3-PHI (thickness:1-3 μm)………….....77.10 Variation of the refractive index of 2,3-PHI........................................................78.11 Variation of the refractive index of 2,7-PHI………………………...…..….….78.12 FTIR spectra of the studied films (a) 2,3-PHIc (b) 2,3TP50……......…..……..79.13 FTIR spectra of the studied films (a) 2,3-PHIc (b) 2,3TP50……......…..……..80.14 TGA thermograms of 2,3-PHIc hybrid materials in N2......................................84.15 TGA thermograms of 2,3-PHIc hybrid materials in air………............................84.16 TGA thermograms of 2,7-PHIc hybrid materials in N2......................................85.17 TGA thermograms of 2,7-PHIc hybrid materials in air………............................85.18 DSC curves of the 2,3-PHIc hybrid at a heating rate of 10 oC/min under a nitrogen flow………………………………………...........................................86.19 TMA curve of 2,3TP10 with a heating rate of 10 oC/min……………….…......87.20 (a) Storage modulus and (b) Tan delta curves of 2,3-PHIc hybrid materials......88.21 SEM image of the 2,3-PHIc hybrid materials (a)2,3TP50 (coat on glass) (b)2,3TP70 (coat on glass) (c)2,3TP50 (film) (d) 2,3-PI (without OH)&TiO2(30%).................................................................................................90.22 SEM image of the 2,7-PHIc hybrid films coated on glass (a) 2,7TP50(film, thickness20~30 μm) (b) 2,7TP70(coat on glass, thickness100~500 nm)............92.23 AFM of the 2,3TP50 hybrid films coated on glass (a) phase images (b) height images; 2,3TP70 hybrid films coated on glass (c) phase images (d) height images..................................................................................................................93.24 AFM of the 2,7TP50 hybrid films coated on glass (a) phase images (b) height images; 2,7TP70 hybrid films coated on glass (c) phase images (d) height images..................................................................................................................94.25 TEM images of the 2,3-PHIc hybrid materials (a) 2,3TP50 and (b) 2,3TP70...95.26 XRD patterns of the 2,3-PHIc and 2,3TP10-2,3TP70 hybrid materials……....96.27 Variation of the refractive index of the 2,3-PHIc hybrid materials 2,3TP0-TP100,with wavelength.The insert figure shows the variation of refractive index with titania content....................................................................99.28 Variation of the refractive index of the 2,7-PHIc hybrid materials 2,7TP0-TP100,with wavelength.The insert figure shows the variation of refractive index with titania content..................................................................100.29 Transmittance UV-visible spectra of 2,3-PHIc and 2,7-PHIc (thickness: 1-3 μm)…………………………………………………………………...……….101.30 Transmittance UV-visible spectra of 2,3-PHIc hybrid materials (thickness: 0.1-0.5 μm)…………………………………………………………………... 102.31 Transmittance UV-visible spectra of 2,3-PHIc hybrid materials (thickness: 20-30 μm)………...………………………………………………….………..102.32 Variation of the reflectance with wavelength: (a) optical glass and (b) the three-layer anti-reflection coating. The insert figure shows the structure of the three-layer anti-reflection coating. ……………………………….…………..105HAPTER 3.1 The photo of high transparent, flexible, and refractive index polyimide (6FPI)-nanocrystalline-titania (6TP50) hybrid optical films (thickness:20~30 μm).......................................................................................................................117.2 FTIR spectra of the studied films (a) 6FPI (b) 6TP50.......................................121.3 TGA thermograms of 6FPI hybrid materials in N2............................................127.4 TGA thermograms of 6FPI hybrid materials in air........................................ ...128.5 TMA curve of 6TP30 with a heating rate of 10 oC/min.................................... 129.6 (a) Storage modulus and (b) Tan delta curves of 6FPI hybrid materials...........130.7 SEM image of the 6FPI hybrid materials (a) 6TP50 (film) (b) 6TP70 (coat on glass).....................................................................................................................133.8 AFM of the 6TP50 hybrid films coated on glass (a) phase images (b) height images; 6TP70 hybrid films coated on glass (c) phase images (d) height images.................................................................................................................134.9 TEM images of the 6FPI hybrid materials (a) 6TP50 and (b) 6TP70..............135.10 XRD patterns of the 6FPI and 6TP10-6TP70 hybrid materials........................136.11 Variation of the refractive index of the 6FPI hybrid materials 6TP0-TP100, with wavelength.The insert figure shows the variation of refractive index with titania content............................................................................................................ ...139.12 Variation of the extinction coefficients of the polyimide-titania hybrid films in the range of 300 –800 nm……………………………………………….... ......140.13 Transmittance UV-visible spectra of 6FPI hybrid materials (thickness: 0.1-1.0 μm)..................................................................................................................... 141.14 Transmittance UV-visible spectra of 6FPI hybrid materials (thickness: 20-30 μm)………………………………………………………………….................142.15 Variation of the reflectance with wavelength: (a) optical glass and (b) the three-layer anti-reflection coating. The insert figure shows the structure of the three-layer anti-reflection coating......................................................................145application/pdf7970034 bytesapplication/pdfen-US聚醯亞胺二氧化鈦混成高折射率光學薄膜polyimidetitaniahybridhigh refractive indexoptical filmsthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/183156/1/ntu-98-R96549006-1.pdf