新型含龐大懸掛基團剛硬型聚(啶-醯亞胺)之合成與物性研究

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研究生：	張鳳全 Feng-Chyuan Chang
論文名稱：	新型含龐大懸掛基團剛硬型聚(啶-醯亞胺)之合成與物性研究 Synthesis and Characterization of Novel Rigid-Rod Poly(pyridine-imide) with Bulky Pendent Group
指導教授：	廖德章 Der-Jang Liaw
口試委員:	李魁然 Kueir-Rarn Lee 李文福 Wen-Fu Lee 汪昆立 Kun-Li Wang 許應舉 Ying-Gev Hsu
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2006
畢業學年度：	94
語文別：	英文
論文頁數：	61
中文關鍵詞：	聚醯亞胺、龐大懸掛基團、齊齊巴賓反應
外文關鍵詞：	polyimide, pyridine, bulky pendent group, chichibabin reaction
相關次數：	點閱：324 下載：1
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利用齊齊巴賓反應(Chichibabin reaction)合成兩種具有啶雜環基團與龐大懸掛基團的新型二胺單體，此新型二胺單體接著與4,4’-六氟異亞丙基二酐(6FDA)單體在N-甲基-2-咯酮溶劑中進行聚縮合反應製備新型聚(啶-醯亞胺)聚合物，利用此兩種新型二胺單體所製備的聚(啶-醯亞胺)聚合物在室溫或加熱下可溶於四氫喃、N-甲基-2-咯酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、γ-丁內酯、啶、二甲基亞石風與環己酮，聚(啶-醯亞胺)聚合物在450 ℃下相當穩定且於空氣下的10%重量損失溫度高於520℃。這些聚合物可利用溶劑N,N-二甲基乙醯胺鑄成強韌、可撓曲的薄膜，其抗張強渡高於90 MPa，抗張模數高於1.8 GPa。紫外線可見光吸收光譜顯示這些聚(啶-醯亞胺)聚合物的吸收範圍在200-400 nm，利用酸進行質子化後可發出強烈的螢光。

Two new diamines containing pyridine heterocyclic group and bulky pendent substituent units was synthesized by chichibabin reaction and used in a preparation of poly(pyridine-imide)s by direct polycondensation with 4,4'-hexafluoroisopropylidenediphathalic anhydride (6FDA) in N-methyl-2-pyrrolidinone (NMP). The poly(pyridine-imide)s derived from two diamines with bulky pendent substituent were soluble in solvents including tetrahydrofuran(THF), N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), γ-butyrolactone, pyridine, dimethylsulfoxide (DMSO) and cyclohexanone at room temperature or upon heating. These poly(pyridine-imide)s were fairly stable up to a temperature above 450 ℃ and lost 10% weight temperature higher than 520 ℃ in air. The poly(pyridine-imide)s could be cast into film from DMAc solution and was thermally converted into tough and flexible polyimide film. The poly(pyridine-imide)s film had a tensile strength above 90 MPa and a tensile modulus higher the 1.8 GPa. The poly(pyridine-imide)s showed a pair of reversible oxidation redox couples around -1.2 V vs Ag/AgCl in DMF solution. The optical properties exhibited the UV-vis absorption bands at the region of 200－400 nm and possessed strong fluorescent after protonated with acid.

中文摘要-----------------------------------------------------------------------------  I
英文摘要-----------------------------------------------------------------------------  II
誌謝----------------------------------------------------------------------------------  III
目錄----------------------------------------------------------------------------------  IV
圖表索引----------------------------------------------------------------------------  VI
INTRODUCTION-------------------------------------------------------------------  1
Chapter 1
Novel Poly(pyridine-imide) with Pendent Naphthalene Group: Synthesis, Thermal, optical, Electrochemical and Protonation Characterization

1.1	 ABSTRACT--------------------------------------------------------------------  4
1.2	 MATERIALS-------------------------------------------------------------------  5
1.3	 MEASUREMENTS-----------------------------------------------------------  6
1.4	 EXPERIMENTAL-------------------------------------------------------------  8
1.4.1	Monomer synthrsis---------------------------------------------------  8
1.4.2	Polymerization－preparation of poly(pyridine-imide)
(PPyI-1)--------------------------------------------------------------  10
1.5 RESULTS AND DISCUSSION---------------------------------------------  12
1.5.1 Synthesis of monomer------------------------------------------------  12
1.5.2 Synthesis of polymer--------------------------------------------------  13
1.5.3 Properties 0f polymer-------------------------------------------------  14

Chapter 2
Novel Poly(pyridine-imide) with Pendent Pyrene Group: Synthesis, Thermal, optical, Electrochemical and Protonation Characterization

2.1	 ABSTRACT------------------------------------------------------------------  22
2.2	 MATERIALS-----------------------------------------------------------------  23
2.3	 MEASUREMENTS---------------------------------------------------------  24
2.4	 EXPERIMENTAL-----------------------------------------------------------  26
2.4.1	Monomer synthrsis-------------------------------------------------  26
2.4.2	Polymerization－preparation of poly(pyridine-imide)
(PPyI-2) -------------------------------------------------------------  28
2.6 RESULTS AND DISCUSSION---------------------------------------------  30
2.6.1 Synthesis of monomer------------------------------------------------  30
2.6.2 Synthesis of polymer--------------------------------------------------  30
2.6.3 Properties of polymer-------------------------------------------------  31
CONCLUSIONS-------------------------------------------------------------------  39
REFERENCE-----------------------------------------------------------------------  40

附  錄 1----------------------------------------------------------------------------  43
附  錄 2----------------------------------------------------------------------------  52
作者簡介----------------------------------------------------------------------------  53

圖表索引

Scheme 1.1	Synthesis of new monomer 4-(2-Naphthyl)-2,6-bis(4-aminophenyl)
pyridine (NBAPP)---------------------------------------------------------------  9
Scheme 1.2	Preparation of poly(pyridine-imide) PPyI-1--------------------------------  11
Scheme 2.1	Synthesis of new monomer 4-(1-Pyrene)- 2,6-bis(4-aminophenyl)
pyridine (PBAPP)------------------------------------------------------------  27
Scheme 2.2	Preparation of poly(pyridine-imide) PPyI-2--------------------------------  29

Figure 1.1	The chemical structure of NBNPP-------------------------------------------  12
Figure 1.2	TGA curves of PPyI-1 in nitrogen and air atmosphere at a heating rate
of 10 ℃．min-1-----------------------------------------------------------------  15
Figure 1.3	UV-vis spectra of PPy-1 in THF solution, solid and protonatd with
HCl and MSA.------------------------------------------------------------------  17
Figure 1.4.	Absorption spectra of poly(pyridine-imide) PPyI-1 with MSA as
a function of concentration----------------------------------------------------  18
Figure 1.5	Emission spectra of poly(pyridine-imide) PPyI-1 protonation
with HCl-------------------------------------------------------------------------  19
Figure 1.6	Cyclic voltammogram of polymer PPyI-1 in DMF with Bu4NClO4
(0.1 M) as the supporting electrolyte-----------------------------------------  20
Figure 2.1	TGA curves of PPyI-2 in nitrogen and air atmosphere at a heating
rate of 10 ℃．min-1-------------------------------------------------------------  32
Figure 2.2	UV-vis absorption and fluorescence emission spectra of PPyI-2 in
dilute THF solution (Figure 2a and 2b), solid film (Figure 2c
and 2d)---------------------------------------------------------------------------  34
Figure 2.3	UV-vis absorption spectra of PPyI-2 protonated with HCl
------------------------------------------------------------------------------------  35
Figure 2.4.	UV-vis absorption spectra of PPyI-2 protonated with MSA
------------------------------------------------------------------------------------  35
Figure 2.5	Emission spectra of PPyI-2 protonated with HCl -------------------------  37
Figure 2.6	Cyclic voltammogram of polymer PPyI-2 in DMF with Bu4NClO4
(0.1 M) as the supporting electrolyte------------------------------------------  38

                                

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