Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3245
標題: 經連續自我反覆反應製備超分支聚醯亞胺材料及其非線性光學特性之研究
Sequential Self-Repetitive Reaction Toward Full Polyimides Featuring Hyperbranched Structures With Stable Optical Nonlinearity.
作者: 黃嬿玲
Huang, Yan-Ling
關鍵字: 非線性光學
NLO
超分枝狀
連續自我反覆反應
Hyperbranched
SSRR
出版社: 化學工程學系所
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摘要: 二次非線性光學高分子在光學元件的實際的應用上,需改善發色團基的極化效率及提升材料熱穩定性。本研究以新式的連續自我反覆反應(Sequential Self-Repetitive Reaction ; SSRR)製備了兩系列高熱穩定性之超分枝狀聚醯亞胺高分子,藉由超分枝狀特有的三維與多孔性結構來將其中的發色團基相互區隔,使系統在含有高發色團基濃度時能夠減少聚集且維持良好的極化率,提高其非線性光學特性。 本研究以雙異氰酸鹽 (4,4’-methylene diphenylisocyanate;MDI) 單體作為起始原料來製備高分子,以催化劑環磷化物(DMPO),將異氫酸鹽全數二量化形成poly-carbodiimide(poly-CDI),並添加含有雙羧酸官能基之發色團基(DNDI)及含有三羧酸官能基之單體(TA),進行連續自我反覆反應後,製備超分枝狀聚醯亞胺高分子(HBPI-DNDI42, HBPI-DNDI22, HBPI-DNDI23)。為了的增加材料的熱穩定性與光電性質,本研究亦利用相同的製程製備了另一系列含有發色團基(DACDI) 的超分枝狀聚醯亞胺高分子(HBPI-DACDI42, HBPI-DACDI22, HBPI-DACDI23)。此外,為了能明瞭的探討超分枝結構在材料中的效應,本研究以雙羧酸BA單體取代三羧酸TA單體製備了相對應的線性聚醯亞胺高分子材料(LPI-DNDI, LPI-DACDI )作為比較探討。 所製備之超分枝狀聚醯亞胺高分子材料均展現良好的有機可溶性且成膜性佳,而各系列材料的玻璃轉移溫度約在144-212 oC,光電數值約在14-37 pm/V (830 nm)。相較於線性高分子材料,兩系列(DNDI及DACDI )超分枝狀聚醯亞胺高分子均展現較好的熱穩定性及較高的電光係數。於導入不同發色團基的部分,DNDI系列之材料其電光係數值較DACDI的電光係數值高而DACDI系列的材料則具有較好的熱性質。此外,材料在120 oC操作溫度下有優越的長時間熱穩定性,而超分枝狀材料也因其三維立體結構的多孔特性使其擁有相對較低的光學損失值。
For practical applicability, Second-order nonlinear optical (NLO) polymers must exhibit large EO coefficients (r33) with good temporal stability when their devices are operated at elevated temperatures. To achieve these features, we introduced the concept of the three-dimensional spatial separation of the chromophores endowing the polymers with favorable site-isolation effects and developed two series of thermally stable nonlinear optical hyperbranched polyimides via a sequential self-repetitive reaction process. The polyimides were synthesized by the reaction of 4,4’-methylenediphenyl isocyanate (MDI),chromophore 2,4-diamino-4’- (4-nitrophenyl-diazenyl)-azobenzene derivative containing diimde-di(ester-acid)(DNDI), and 1,1,1-tris (4-carboxy-3- methoxycarbonylphenoxy)ethane (TA). Polycarbodiimide (poly-CDI) was first synthesized from MDI. Two acid-ester compounds (DNDI and TA) was then reacted with poly-CDI to form poly(N-acylurea). After the curing process, N-acylurea moiety was converted to ester-amide structure via SSRR and further subjected to a ring-closure reaction to form DNDI containing hyperbranched NLO polyimides (HBPI-DNDI42, HBPI-DNDI22, and HBPI-DNDI23). In order to further enhance the thermal stability and EO coefficient, the other chromophre, bis(4-aminophenyl(4-(4-nitrophenyl) -diazenyl)-phenyl)amine derivative containing diimde-di(ester-acid) (DACDI) was also incorporated into the the polyimide to form DACDI containing hyperbranched NLO polyimides (HBPI-DACDI42, HBPI-DACDI22, and HBPI-DNDI23). In addition, two linear polyimides (LPI-DNDI and LPI-DACDI) were synthesized via the same reaction process for the sake of comparison. The resulting NLO hyperbranched polymers exhibited excellent organosolubility with Tgs of 144-212 oC, which is favorable for the fabrication of high quality optical thin films with electro-optical coefficients, r33 of 14-37 pm/V (830 nm). Compare with linear polyimides, both two series hyperbranched polymers possessed the higher stability and larger EO coefficients. This result revealed that the site isolation effect derived from the hyperbranched structures enhanced the NLO properties of polyimides. Excellent long term stability at 120oC was obtained for two series of hyperbranched NLO polyimides Moreover, the uniform void distribution of hyperbranched structure resulted in lower optical losses relative to that of the corresponding linear polyimide.
URI: http://hdl.handle.net/11455/3245
其他識別: U0005-2108201213362200
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