(3.236.175.108) 您好!臺灣時間:2021/02/28 03:24
字體大小: 字級放大   字級縮小   預設字形  
回查詢結果

詳目顯示:::

我願授權國圖
: 
twitterline
研究生:謝始榮
研究生(外文):Shih-Jung Hsieh
論文名稱:含鹵素之強誘電性液晶單體及其側鏈液晶高分子之合成與性質之探討
論文名稱(外文):Studies on the Synthesis and Properties of Halogen Containing Ferroelectric Liquid Crystals and Side Chain Liquid Crystalline Polymers
指導教授:莊祚敏薛敬和薛敬和引用關係
指導教授(外文):Tzuoh-Miin JuangGing-ho Hsiue
學位類別:碩士
校院名稱:國立交通大學
系所名稱:應用化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:1999
畢業學年度:87
語文別:中文
論文頁數:110
中文關鍵詞:強誘電性液晶雙穩定狀想可擦拭光碟自發極化值應答時間X-ray繞射介電分析
外文關鍵詞:Ferroelectric liquid crystalFLCbistable statesGoldstone mode
相關次數:
  • 被引用被引用:1
  • 點閱點閱:131
  • 評分評分:系統版面圖檔系統版面圖檔系統版面圖檔系統版面圖檔系統版面圖檔
  • 下載下載:0
  • 收藏至我的研究室書目清單書目收藏:1
液晶聚合物因有多元化之光電用途,深具研究之潛力;而液晶中的SC*相因具有強誘電性性質,而顯得格外重要。強誘電性液晶(Ferroelectric liquid crystal, FLC)具雙穩定狀想(bistable states),在電場下可控制其在穩定狀態間切換,由於切換的時間相當短(μs),比向列相液晶的切換時間快了好幾次方,因此強誘電性液晶可用於高畫質電視之顯示上;而強誘電性液晶高分子則可應用於可擦拭光碟的記錄媒體材料,可以有效的提高其應答速度。
本研究歸納實驗室數年來研究之成果,設計出以MDn12Cl為藍本,改變末端基旋光中心取代基,將氟原子及溴原子取代氯原子。因MDn12Cl液晶分子結構之液晶基堅硬度適當,末端基之部份為雙旋光中心。最重要的是,在MDn12Cl液晶單體系列中,MD112Cl擁有高自發極化值389nC/cm2,以及MD312Cl在SC*相中有數十μs 至1ms的應答時間。以鹵素原子之陰電性趨勢(F>Cl>Br)將氟原子及溴原子取代氯原子,可觀察出偶極矩的變化對液晶分子之熱運動的影響,以及對液晶分子光電特性之影響。
研究分成兩部份:
第一部份為新型液晶單體之合成、液晶相行為之探討。合成二系列之新型液晶單體MDn12F、MDn12Br,以及合成MD312Cl作為比較之基準。液晶相熱行為經由熱微差掃瞄卡計、偏光顯微鏡以及粉末x-ray繞射加以鑑定液晶相的種類與排列結構,探討不同末端旋光基對液晶相行為之影響。
結果顯示,含氟原子及溴原子之液晶單體之液晶相種類與含氯原子之液晶單體類似,其差異點在於各個液晶相溫度之分佈。
第二部份為強誘電性側鏈液晶均聚合物之合成、鑑定與介電測試。選擇第一部份所合成之液晶單體進行與聚矽氧烷之矽氫化接枝反應,。其液晶相的鑑定與分析亦以熱微差掃瞄卡計、偏光顯微鏡以及粉末X-ray繞射來分析液晶相的種類與液晶分子在聚合物中的排列結構。並介電分析討論含不同鹵素偶極之強誘電性側鏈均聚合物對液晶相行為的影響,將此結果作為液晶光電測試之參考。
結果顯示,高分子聚矽氧烷主鏈的導入,不僅擴展了整體液晶相的溫度範圍,並也擴展了Sc*相可達約100℃的範圍。並且由介電分析得知,具較強偶極之含氟強誘電性液晶側鏈均聚合物PS312F在電場之作用下,其Goldstone mode緩和強度在SC*相中隨溫度之升高而加強,且其介電緩和與損失常數均大於含氯強誘電性液晶側鏈均聚合物PS312Cl。此結果表示,若於相同機制之光電測試,也必將有相同之結果。

Liquid-crystalline polymers possess versatile optical-electric applications and therefore are potential research subjects. The Sc* phase of liquid crystals is extremely important because of its ferroelectric property. The ferroelectric liquid crystals (FLC) have bistable states and can be switched between them by controlling the electric field. The switch time is so short (μs) that it is several times order faster than the nematic liquid crystal phase, hence the FLC is applicable in high-fidelity televisions. The FLC polymers can also be adopted as a recording material in the erasable compact discs to elevate the response rate significantly.
This research concluded the results over recent years. It was to design molecules based upon MDn12Cl from which the terminal chiral center had been changed by substituting fluorine or bromine atoms for chlorine. The terminal group of MDn12Cl molecule is a two-chiral center due to the appropriate hardness of its liquid crystalline segment. Among the series of the MDn12Cl liquid crystalline monomers, MD112C has high spontaneous polarization (389 nC/cm2) and MD312Cl has fast response time between tens ofμs to 1 ms. According to the electronegativity of halogens (F>Cl>Br), effects of substitution of Cl by F and Br atoms were observed. Both the thermal movement and the electro-optical properties of liquid crystalline molecules are influenced by the change of the dipole moment.

審定書
授權書
中文摘要………………………………………………………………………i
英文摘要…………………………………………………………………..…iii
謝誌…………………………………………………………………………..iv
目錄…………………………………………………………………………...v
Scheme目錄…………………………………………………………………vii
Table目錄…………………………………………………………………..viii
Figure目錄…………………………………………………………………..ix
第一章 緒論…………………………………………….……………………….…………1
1.1 前言……………………………………………….…………………………………..1
1.2 液晶簡介………………………………………………………………….…………..3
1.3 液晶聚合物簡介………………………………………………………….………..…4
1.4 液晶相種類及其排列……………………………………………….……………..…6
1.4.1 不具光學活性液晶………………………………………………………………6
1.4.2 光學活性液晶…………….…………………………………………………….10
第二章 文獻回顧與研究動機………………………………………….………………...14
2.1強誘電性液晶………………………………………………………………………..14
2.2強誘電性液晶回顧…………………………………………………………………..14
2.3自發強誘電性液晶極化現象……………………………………………………….,19
2.4表面安定型強誘電性液晶……………………………………………………….….21
2.5強誘電性液晶的光電效應………………………………………………………..…22
2.6 強誘電性液晶高分子之介電緩和…………………………………………………..23
2.7 研究動機……………………………………………………………………………..25
第三章 實驗方法…………………………………………………………………………30
3.1 試藥…………………………………………………………….……………………30
3.2 儀器………………………………………………………………………….....……30
3.3 合成部份………………………………………………………...…………………..32
3.3.1 強誘電性液晶單體之合成………………………………………………….………32
3.3.1.1含苯甲酸甲酯間距之合成………………………………………………………..32
3.3.1.2含鹵素末端基之合成……………………………………………………………..34
3.3.1.2.1含氟強誘電性液晶單體之合成…………………………………………..…….34
3.3.1.2.2含氯強誘電性液晶單體之合成……………………………………………...…38
3.3.1.2.3含溴強誘電性液晶單體之合成…………………………..…………………….39
3.3.1.3含鹵素強誘電性液晶之合成……………………………………………….…….43
3.3.2 含鹵素強誘電性液晶側鏈均聚合物之合成…………………………….…………43
3.4 液晶相鑑定與熱性質分析………………………………………………………….49
第四章 結果與討論…………………………………………………………………...….53
4.1含鹵素強誘電性液晶單體與均聚合物之合成、鑑定……………..….…………….53
4.1.1含鹵素苯酸聯苯酯液晶基之合成…………………………………………..……..53
4.1.2含鹵素苯酸聯苯酯液晶基之鑑定…………………………………...……………..56
4.1.3含鹵素強誘電性液晶均聚合物之合成、鑑定………………………………...68
4.2含鹵素強誘電性液晶單體之液晶相鑑定與熱分析……………………………70
4.3含鹵素強誘電性液晶均聚合物之液晶相鑑定與熱分析…………………….80
4.4含鹵素強誘電性液晶單體之X-ray繞射分析…………………………………..82
4.5含鹵素強誘電性液晶均聚合物之X-ray繞射分析……………………………90
4.6含鹵素強誘電性液晶均聚合物之介電分析…………………..…………………..…94
第五章 結論……………………………………………………………………………....98
第六章 參考文獻…………………………………………………………………100

1.S. T. Kowel, L. Ye, Y. Zhang and L. M. Hayden, Opt. Eng., 26(2), 107 (1987).
2.S. Muto, T. Nagata, K. Asai, H. Ashizawa and K. Arii, Jap. J. App. Phys., 29, 1724 (1990).
3.H. G. Winfriedk and G. J. M. Krijnen, App. Phys. Lett., 55(7), 616 (1989).
4.T. Kaino and H. Kobayashi, App. Phys. Lett., 54, 1619 (1989).
5.H. Finkelmann, H. Ringsdorf and H. Windorf, Makromol. Chem., 179, 237 (1978).
6.H. Finkelmann, M. Happ, M. Portugal and H. Ringsdorf, Makromal. Chem., 179, 2541 (1978).
7.H. Finkelmann and G. Rehage, Adv. Polym. Sci., 60/61, 99 (1984).
8.V. P. Shibaev and N. A. Plate, Adv. Polym. Sci., 60/61, 173 (1984).
9.A. Cifferi, W. R. Kringbaum, R. B. Meyer, "Polymer Liquid Crystals", Academic Press, N. Y. (1982).
10.L. L. Chapoy,"Recent Advances in Liquid Crystal Polymers", Elsevier Applied Sci. London and N. Y. (1985).
11.J. Bairstow, High Technology, Oct., 44 (1986).
12.W. W. Jasobus Jr., Information Display, Mar., 14 (1985).
13.L. Vriens and B. A. J. Jascobs, Philips Tech. Rev., 41, 313 (1983/84).
14.D. J. Gravesteijn and J. Van der Veen, Philips Tech. Rev., 41, 325 (1983/84).
15.Y. Goto, N. Koshino and K. Itoh, Fujtsu Sci. & Tech. J. Sep., 412 (1984).
16.S. Ohr, Electronic Design, July, 93 (1985).
17.M. Hartmann, B.A. J. Jacobs and J. J. M. Braat, Philips Tech. Rev., 42, 37(1985).
18.H. J. Coles and R. Simon, Polymer, 26, 1801 (1985).
19.R. Simon and H. J. Coles, Polymer, 27, 811 (1986).
20.H. Finkelmann, U. Kischle and G. Rehage, Mol. Cryst. Liq. Cryst., 94, 343 (1983).
21.R. E. Goozner and H. Finkelmann, Makromol. Chem., 186, 2407 (1985).
22.G. S. Arrard and B. Williams, J. Mol. Electro., 2, 107 (1986).
23.M. Eich, J. H. Wendorff, Makromol. Chem., Rapid Commun., 8, 59 (1987).
24.G. Kaemopf, H. Loewer and M. W. Witan, Polym. Eng. & Sci., 27, 1421 (1987).
25.G. Kaemof, Polym. J., 19, 257 (1987).
26.N. A. Clark and S. T. Lagerwall, Appl. Phys. Lett., 36, 899 (1980).
27.R. B. Meyer, L. Libert, L. Strzelecki and P. Leeler, J. Phys., 36, L-69 (1975).
28.R. B. Meyer, Mol. Cryst. Liq. Cryst., 40, 33 (1977).
29.J. W. Goodby, Science, 231, 350 (1986).
30.D. M. Walba and F. Supon, J. Am. Chem. Soc., 108, 5210 (1986).
31.D. Coates, Liquid Crystals, 2, 63 (1987).
32.D. Coates, Liquid Crystals, 2, 423 (1987).
33.V. P. Shibaev, M. V. Kozlousky, L. A. Beresnev, M. L. Blinov and
N. A. Plate, Polym. Bull., 12, 299 (1984).
34.G. Decobert, F. Soyer and J. C. Dubois, Polym. Bull., 14, 179 (1985).
35.G. Decobert, J. C. Dubois, S. Esselin and C. Noel, Liquid Crystals, 1, 307 (1986).
36.J. M. Guglielminetti, G. Decobert and J. C. Dubois, Polym. Bull., 16, 411 (1986).
37.B. Hahn and V. Percec, Macromol., 20, 2961 (1987).
38.S. Wsselin, L. Boiso and C. Noel, Liquid Crystals, 2, 505(1987).
39.V. P. Shibeav, M. V. Kozlovsky and N. A. Plate, Liquid Crystals, 8, 545(1990).
40.M. Dumon, H. T. Nguyen, M. Mazuac, C. Dtrade, M. F. Achard and H. Gasparoux, Macromolecules, 23, 355(1990).
41.J. W. Gooby, et. al. "Ferroelectric Liquid Crystals", Gordon and Breach Science Publishers. (1991).
42.H. T. Nguyen, L. Navaills, P. Barois, C. Destrade and N. Isaert, Proceeding of 4th international conference on FLCs, Tokyo, O-23, 45(1993).
43R. Shao, J. Pang, N. A. Clark, J. A. Rego and D. M. Walba, Ferroelectrics, 147, 241(1993).
44.R. B.Meyer, L. Liebert, L. Strzelecki, P. J. Physique(Lett.), L-69, 36(1975).
45.T. G. Adams and R. Sinta, Mol. Cryst. Liq. Cryst., 177, 145 (1989).
46. J. H. Chen, R. C. Chang, and G. H. Hsiue, "Twisted Smectic A Phase in Some Chiral Molecules with Oligooxyethylene Spacers", Ferroelectrics, 147, 241-253, 1993.
47.J. H. Chen, R. C. Chang, G. H. Hsiue, F. W. Guu, and S. L. Wu, "Synthesis and Characterization of Four Series of Ferroelectric Liquid Crystals Containing Oligooxyethlene Spacers", Liquid Cryatals, 18, 291-301, 1994.
48.G. H. Hsiue and J. H. Chen, "Synthesis and Thermal Properties of Ferroelectric Side Chain Liquid Crystalline Polysiloxanes Based on Phenyl Ester Mesogen and Oligooxyethylene Spacers. 1. Phenyl Benzoate and Biphenyl Benzoate Mesogenic Groups", Macromolecules, 28, 4366, 1995.
49.G. H. Hsiue, G. R. Lee and J. H. Chen, "Studies of Dielectric Properties and Structures of Ferroelectric Liquid Crystals and Related Side Chain Liquid Crystal Polymers", Macromolecular Chemistry and Physics , 196, 2016, 1995.
50. J. H. Chen, G. H. Hsiue, C. P. Hwang and J. L. Wu, "Broad Liquid Crystalline Temperature Range of Ferroelectric Liquid Cryatals", Liq. Cryst., 19, 803, 1995.
51.G. H. Hsiue, C. P. Hwang and J. H. Chen, "Synthesis and Characteri-
zation of New Ferroelectric Liquid Crystals Containing (2S)-2-[6-(4-Hydroxybiphenyl-4'-carbonyloxy)-2'-naphthyl]-propionates esogenic Group and Oligo(oxyethylene) Spacers", Liq. Cryst., 20, 45, 1996.
52.J. H. Chen, G. H. Hsiue and C. P. Hwang, "Synthesis and Thermal Properties of Ferroelectric Side Chain Liquid Crystalline Polysiloxanes Based on Phenyl Ester Mesogen and Oligooxyethylene Spacers. 2. Naphthyl Biphenylcarboxylate Mesogenic Groups", Chemistry Materials, revised (1996).
53.G. H. Hsiue, J. L. Wu and J. H. Chen, "Synthesis and Characteriza-tion of New Ferroelectric Liquid Crystals Containing Phenyl Biphenyl Carboxylate Mesogenic Group and Oligooxyethylene Spacers.", Liq. Cryst., in the press (1996).
54.G. H. Hsiue, J. L. Wu, J. H. Chen and K. J. Lee, " The Molecular Modeling of Phase Transitional Behaviors of Ferroelectric Liquid Crystals", Liq. Cryst., revised (1996).
55.J. H. Chen, F. W. Guu and G. H. Hsiue, "The Electro-Optical Pro-perties of Ferroelectric Liquid Crystals with Oligooxyethylene Spacers", Macromolecular Chemistry and Physics , submitted (1996).
56.J. H. Chen, G. H. Hsiue,"The Microphase Separation of Ferroelectric Liquid Crystalline Copolymethylsiloxane", Liq. Cryst., submitted (1996).
57.J. H. Chen, G. H. Hsiue and J. L. Wu, "Synthesis and Thermal Pro-perties of Ferroelectric Side Chain Liquid Crystalline Polysiloxanes Based on Phenyl Ester Mesogen and Oligooxyethylene Spacers. 3. Phenyl Biphenyl Carboxylate Mesogenic Groups", submitted (1996).
58.J. H. Chen and G. H.Hsiue," The Synthesis and Characterization of New Ferroelectric Liquid Crystals Containing Biphenyl Biphenyl Carboxylate Mesogenic Group and Oligo(oxyethylene) Spacers", submitted (1996).
59.J. H. Chen and G. H. Hsiue, "Synthesis and Thermal Properties of Ferroelectric Side Chain Liquid Crystalline Polysiloxanes Based on Phenyl Ester Mesogen and Oligooxyethylene Spacers. 4. Bihenyl Biphenyl Carboxylate Mesogenic Groups", submitted (1996).
60.C. J. Hsieh and G. H. Hsiue, Materials Chemistry and Physics, 33, 110 (1993).
61.C. J. Hsieh, C. S. Hsu and G. H. Hsiue, J. Polym. Sci.:Part A: Polymer Chem., 8, 425 (1990).
62.H.Keller and R. Hatz, "Handbook of Liquid Crystals", 1980, chap. 2
63.W. L. McMillan, Phys. Rev., A8, 1921 (1973).
64.A. Wulf, Phys. Rev., 11A, 365 (2975)
65. P. J. Bos and K. R. Koehler, Ferroelectrics, 85, 15 (1988).
66.H. Ohrihara, A. Suzuki, Y. Isyhibashi, K. Gouhara, Y. Yamada and N. Yamamato, Jpn. J. Appl. Phys., 28, L676 (1987).
67.Y. Sato, T. Tanaka, H. Kobayashi, K. Aoki, H. Watanabe, H.Takeshita, Y. Ouchy, H. Takezoe and A. Fukuda, Jpn. J. Appl.Phys., 28, L483 (1989).
68. Y. Takanishi, Y. Ouchy, H. takezone, A. Fukuda, A. Mochizuki and M. Nakatsuka, Jpn. J. Appl. Phys., 29, L984 (1990).
69. Y. Iwasaki., K. Yoshiho, T. Uemoto and Y. Inuishi, Jap. J. Appl. Phys., 19, 2293 (1980).
70. J. Malecki, Mol. Cryst. Liq. Cryst., 1978, 44, 287.
71. M. Glogarova, J. Pavel and J. Ferroelectrcs, 1984, 55, 117.
72. A. Levstik, B.Zeks, R. Blinc and C. Filipic, J. Phys., 1979, 40, C3-303.
73. S. U. Vallerien, F. Kremer, H. Kapitza, R. Zental and W. Frank, Phys. Lett. A, 1989, 138, 219.
74. M. Ozaki, K. Yoshino, T. Sakurai, N. Mikami and R. I. Higuchi, J. Chem. Phys., 1986, 88, 3648.
75. H. Ringsdorf and R. Zental, Makromol. Chem., Rapid Commun., 1982, 183, 1245.
76. H. Kress and V. P. Shibaev, Makromol. Chem., Rapid Commun., 1984, 5, 63.
77. R. Zental, G. R. Strobl and H. Ringsdorf, Macromolecules, 1985, 18, 960.
78. F. Kremer, S. U. Vallerien, R. Zental H. Kapitza, Macromolecules, 1989, 22, 4040.
79. G. S. Attard and K. Araki, Mol. Cryst. Liq. Cry., 1986, 144, 69.
80. S. U. Vallerien, R. Zental, F Kremer, H. Kapitza and E. W. Fischer, Macromol. Chem., Rapid Commun., 1989, 10, 333.
81.T. Sakurai, N. Mikame, R. Higuchi, M. Honma, M. Ozaki and K. Yoshino,Ferroelectrics, 85, 469-478 (1988).
82.T. Sakurai, N. Mikame, R. Higuchi, M. Honma, M. Ozaki and K. Yoshino,J. Chem. Soc. Commun., 978 (1986).
83.C. Bahr and G. Heppke, Mol. Cryst. Liq. Cryst., L4, 31 (1986).
84.K. Yoshino, M. Ozaki, S. Kishio,T. Sakurai, N. Mikami and M. Honma, Mol.Cryst.Liq.Cryst., 144, 87 (1987).
85. S. Kishio, M. Ozaki, K. Yoshino, T. Sakurai, N. Mikami and R. Higuchi, Japan. J. Appl. Phys., 26(4), 513-516 (1987).
86. T. Sierra, J. L. Serrano, M. B. Ros, A. Ezeurra and J. ZuBia, J. Am. Chem. Soc., 1992, 114, 7645-7651.
87. V. Percec and H. Oda., Macromolecules, 1994, 27, 12-25.

QRCODE
 
 
 
 
 
                                                                                                                                                                                                                                                                                                                                                                                                               
第一頁 上一頁 下一頁 最後一頁 top
系統版面圖檔 系統版面圖檔