臺灣博碩士論文加值系統

由1,3-Bis[4-(4-chloroformylphenoxy)phenyl]adamantane與數種二元醇合成主鏈含有金剛烷的新型聚酯，所合成聚酯之固有黏度範圍在0.38 - 0.82 dL/g，而由GPC測得其分子量 ( Mn ) 範圍在31,000 - 92,000。這些聚酯具有良好的溶解度，可溶於o-chlorophenol、chloroform、o-dichlorobenzene、N-Methyl-2-pyrrolidone( NMP )及tetrahydrofuran( THF )等溶劑中。它們的抗張強度範圍於40.1-56.7 MPa之間，斷裂伸長率為8.5-20.2 ﹪，初始剛性模數為1.6-1.7 GPa。經由DSC分析，測得其玻璃轉移溫度(Tg)在194-284 ℃ 之間。而由TGA分析測得它們在10%重量損失時溫度，在氮氣下為468-489 ℃，在空氣下為454-493 ℃，而其在700 ℃氮氣下之燃燒殘餘率為34-48 % 。
另外也由1,4—Bis(4-carboxyphenoxy)—2-adamantylbenzene acyl chloride與數種二元醇合成新型聚酯，它們的固有黏度範圍在0.32-1.11 dL/g，這些聚酯都可塗佈成具韌性薄膜，而且這些聚酯具有良好的溶解度，可溶於o-chlorophenol、chloroform、o-dichlorobenzene、NMP、nitrobenzene及THF等溶劑中，而它們的抗張強度範圍於46.5-78.4 MPa之間，斷裂伸長率為8.7-15.7 ﹪，初始剛性模數為1.6-1.8 GPa。經由DSC分析，測得其玻璃轉移溫度(Tg)在210-288 ℃ 之間。而由TGA分析測得這些聚酯在10 %重量損失時溫度，在氮氣下為428-482 ℃，在空氣下為419-483 ℃，而其在700 ℃氮氣下之燃燒殘餘率為30-42 %。另外，也比較主鏈含金剛烷之聚脂與含金剛烷側基之聚脂的性質差異。

The new adamantane-based polyesters were synthesized by reacting of 1,3-Bis[4-(4-chloroformylphenoxy)phenyl] adamantane with various diols. The adamantane-containing polyesters had inherent viscosities of 0.38 - 0.82 dL/g and number-average molecular weights ( Mn ) of 31,000 - 92,000. All polyesters had good solubility and were soluble in o-chlorophenol, chloroform, o-dichlorobenzene, NMP and THF. Those polyesters had tensile strengths of 40.1-56.7 MPa, elongations to break of 8.5-20.2 ﹪, and initial moduli of 1.6-1.7 GPa. DSC reveal that their glass transition temperatures were found to be 194-284 ℃. The temperatures of polyesters at 10 % weight loss ranged from 468-489 ℃ in N2 atmosphere and from 454-493 ℃ in air. Their char yield ranged from 34-48 % at 700 ℃ in N2.
In addition, the new polyesters were also synthesized by reacting of 1,4—Bis(4-carboxyphenoxy)—2-adamantylbenzene acyl chloride with various diols. The polyesters with adamantane side group had inherent viscosities of 0.32-1.11 dL/g and all the films were flexible. All polyesters had good solubility and were soluble in o-chlorophenol, chloroform, o-dichlorobenzene, nitrobenzene, NMP and THF. Those polyesters had tensile strengths of 46.5-78.4 MPa, elongation to break of 8.7-15.7 ﹪, and initial moduli of 1.6-1.8 GPa. DSC reveal that their glass transition temperatures were found to be 210-288 ℃. The temperatures of polyesters at 10 % weight loss ranged from 428-482 ℃ in N2 atmosphere and from 419-483 ℃ in air. Their char yield ranged from 30-42 % at 700 ℃ in N2. In addition, a comparison of physical properties of the polyesters derived from 1,3-Bis[4-(4-chloroformylphenoxy)phenyl]adamantane with those derived from 1,4—Bis(4-carboxyphenoxy)—2-adamantylbenzene acyl chloride is also presented.

摘要................................................Ⅰ
Abstract............................................Ⅲ
目錄................................................Ⅴ
圖表索引............................................Ⅷ
第一章 緒論.........................................1
1-1 金剛烷(adamantane)的介紹........................1
1-2 聚酯的回顧......................................3
1-3 聚酯的種類......................................5
1-3-1 PET與 PBT聚酯.................................5
1-3-2 PCT聚酯.......................................6
1-3-3 全芳香族聚酯(Polyarylate).....................7
1-4 聚酯之合成方法..................................9
1-4-1 酯交換法......................................9
1-4-2 氯醯法........................................10
1-4-3高溫直接聚酯化法...............................11
1-4-4固態聚縮合法...................................12
1-5 擬進行之研究....................................13
第二章 實驗.........................................15
2-1 實驗藥品........................................15
2-2 實驗儀器........................................18
2-3 實驗程序........................................20
2-3-1 單體製備......................................20
2-3-1.1 單體的純化..................................20
2-3-1.2 製備1,3-Bis[4-(4-chloroformylphenoxy)
phenyl]adamantane (Ⅰ)..............................20
2-3-1.3 製備1,4—Bis(4-carboxyphenoxy)—2-
adamantylbenzene acyl chloride (Ⅳ)..........21
2-3-2 聚酯之合成....................................25
2-4 單體鑑定及聚合物之物性與化性分析................26
第三章 結果與討論...................................29
3-1 1,3-Bis[4-(4-chloroformylphenoxy)phenyl]
adamantane (Ⅰ)...............................29
3-1-1 單體的製備....................................29
3-1-2 聚酯的合成....................................29
3-1-3 聚酯的物性分析................................30
3-2 1,4—Bis(4-carboxyphenoxy)—2-adamantyl
benzene acyl chloride (Ⅳ)....................34
3-2-1 單體的製備....................................34
3-2-2 聚酯的合成....................................35
3-2-3 聚酯的物性分析................................36
3-3 二系類聚酯之比較................................40
第四章 結論.........................................41
參考文獻............................................42

(1) Decker, H. Z., Angew. Chem., 37, 795 ( 1924 ).
(2) Fort, R.C.; Schleyer, p.v.r., Chem. Rev., 64, 227 ( 1964 ).
(3) Baughman, G. L. J. Org. Chem., 29, 238 ( 1964 ).
(4) Novikov, S. S. ; Khardin, A. P. ; Novako, I. A. ;Radchenko, S. S. , Vysokomol. Soedin. Ser. B ,16, 155 ( 1974 ).
(5) Novikov, S. S. ; Khardin, A. P. ; Novako, I. A. ; Radchenko, S. S. , Vysokomol. Soedin. Ser. B ,18, 462 ( 1976 ).
(6) Korshak, V. V. ; Novikov, S. S. ; Vinogradov, S. V. ; Khardin, A. P. ; Vygodskii, Y. S. ; Novako, I. A. ; Orlinson, B. S. ; Radchenko, S. S. , Vysokomol. Soedin. Ser. B, 21, 248 ( 1979 ).
(7) Hsiao, S. H. ; Lee, C. T. ; Chern, Y.T., J. Polym. Sci. Polym. Chem., 37, 1619(1999).
(8) Hsiao, S. H. ; Li, C. T. , Macromolecules, 31, 7213 ( 1998 ).
(9) Chern, Y. T. ; Chung, W. H. , J. Polym. Sci. , Polym. Chem., 34, 117 ( 1996 ).
(10) 林國生，碩士論文，”製備具有1,3取代之金剛烷構造之新的聚醯胺與聚醯亞胺及其性質研究”，第18-20頁，(1998).
(11) Pixton, M. R. ; Paul, D. R. , polymer ,36, 3165 ( 1995 ).
(12) Tullos, G. L. ; Mathias, L. J. , polym. Prepr., ( Am. Chem. Sci. , Div. Polym. Chem. ) 36 ( 2 ), 316 ( 1995 ).
(13) Jensen, J. J. ; Grimsley, M. ; Mathias, L. J. , J. polym. Sci. Polym. Chem. , 34, 397 ( 1996 ).
(14) Lewis, C. M. ; Mathias, L. J. ; Wiegal, N. , polym. Prepr., ( Am. Chem. Sci. , Div. Polym. Chem. ) 36 ( 2 ) , 140 ( 1995 ).
(15) Berzelius, J. , Rapp. Ann.,26 ( 1847 ).
(16) Laurenco, A. V. , Ann. Chim. phys. ,67, 293 ( 1863 ).
(17) Davidoff, Ber. 19, 406 ( 1866 ).
(18) Kraut, K. , Justus Liebigs Ann. Chem. ,1, 150 ( 1869 ).
(19) Vorlander, Ann. ,280, 167 ( 1894 ).
(20) Whinfield, J. R. ; Dickson, J. T. , Brit. P.,578, 079 ( 1946 ).
(21) Whinfield, J. R. , Nature ,158, 930 ( 1946 ).
(22) Eastman Kodak, U. S. Pat., 2, 996, 477 ( 1961 ).
(23) Kibler, C. J. ; Bell, A. , Smith, J. G. , J. Polym. Sci. , 21, 2115 (1964 ).
(24) 黃世杰，碩士論文，”製備含金剛烷側鏈基團之新型聚醯亞胺及其性質研究”，第17-20頁，（1998）.
(25) Kotilar, A. M. , Macromol. Rev. , 16, 367 ( 1981 ).
(26) Levine, M. ; Temin, S. C. , J. Polym. Sci., 28, 179 ( 1958 ).
(27) Temin, S. C. , J. Org. Chem. , 26, 2518 ( 1961 ).
(28) Roviello, A. ; Sirigu, A. , Macromol. Khem. , 183, 895 ( 1982 ).
(29) Wick, G. ; Zeitler, H. , Macromol. Khem. , 184, 59 ( 1983 ).
(30) Heitz, W. ; Niessner, N. , Macromol. Khem. , 191, 225 ( 1990 ).
(31) Cai, R. ; Preston, J. ; Samulski, T. , Macromolecules, 25, 563 ( 1992 ).
(32) Watanabe, S. ; Kobayashi, A. ; Kakimoto, M. ; Imai. Y. , J. Polym. Sci. Polym. Chem. , 32, 909 ( 1994 ).
(33) Lenz, R. W. ; Jin, J. L. , Macromolecules, 14, 1405 ( 1981 ).
(34) Conix, A. J. , Ind. Eng. Chem., 51, 147 ( 1959 ).
(35) Nakamura, H. ; Imanishi; Sanui, K. ; Ogata, N. , Polym. J. , 11, 661 ( 1974 ).
(36) Ogata, N. ; Sanui, K. ; Vogl, O. , J. Macromol. Sci. Chem. , 16, 1145 ( 1981 ).
(37) Vinogradova, S. V. , J. Polym. Sci. , 19, 769 ( 1977 ).
(38) Morgan, P. W. , Polym. Ret. , 10 ( 1965 ).
(39) Frader, A. ; Marechal, E. , Adv. Polym. Sci. , 43, 51 ( 1982 ).
(40) Pilati, F. ; Manaresi, P., Polymer, 24, 1479 ( 1983 ).
(41) 日本公開特許公報，3-252421 ( 1991 ).
(42) 日本公開特許公報，4-72326 ( 1992 ).
(43) Liou, G. S. ; Chern, Y. T. , J. Polym. Sci. Polym. Chem., 37, 645(1999).