聚烯類均聚合體(homoplymer)及共聚合體(copolymer)如聚苯乙烯、聚丁二烯、聚異戊二烯及聚苯乙烯-聚丁二烯雙團鏈共聚合物等均為應用極廣的商業產品，其大多可用陰離子聚合製備。於均聚合體或共聚合體之陰離子聚合最後步驟中均需加入終止劑來終止反應，使用之終止劑之不同，會造成產物中含有不同種類之無機鹽類，如果產生之鹽類為氯化鋰(LiCl)，所得均聚合物之透光度皆極差，但如所產生鹽類為甲氧基鋰(LiOCH3)或氫氧化鋰(LiOH)，則產物為透明的。
本論文即為研究此微量無機鹽類對均聚合體與共聚合體透明度的影響，我們亦將不同無機鹽類，如氯化鋰(LiCl)、氯化鋅(ZnCl2)、氯化鋁(AlCl3)，加入原本透明的聚合體溶液中，觀察各無機鹽類對此溶液透明度、黏度、光散射及製備所得固體形態之影響。
基本上，氯化鋰會與聚合反應之活化劑(activator)四氫呋喃形成錯合物，此錯合物進一步被溶液中高分子團鏈所包圍進一步形成較大之凝集體(aggregate)，凝集體之大小與聚合體濃度、鹽類含量、四氫呋喃之量及所使用之溶劑都有關係，凝集體越大，光散射越強，溶液之透明度因而下降，同時也造成去除溶劑後所得固態樣品之透明度下降。因此凝集體之大小為決定最後固態樣品透明度之主要因素。

Olefinic homo- and copolymers including polystyrene, polybutadi- ene, polyisoprene and polystyrene-polybutadiene di-block coplymers are widely used commercial products and most of them can be prepared from anion polymerization. During the last step of the anionic co- and homo- polymerizations, different terminating agents were used to terminate the polymerization and to generate products containing various inorganic salts, which have profound effects on the transparency of the final polymers. For example, polymers containing lithium chloride (LiCl) are generally opaque in appearance while polymers containing lithium methoxide (Li(OCH3)) or lithium hydroxide (LiOH) are transparency.

This study concerns the effect of the inorganic salts on the polymers’ transparency. Inorganic salts such as LiCl, zinc chloride (ZnCl2), alumi- num chloride (AlCl3) were added to the polymer solution to prepare various salt/polymer solution for the study of their transparency, solution viscosity, light scattering and morphology of the solid product after solvent removal. Basically, LiCl will complex with tetrahydrofuran (THF, as activator for anionic polymerization) and the resulting complex were encompassed by the polymer coil in the solution and further aggregation occurred form particle large enough to scatter light. Size of the salt/polymer aggregates was determined by the polymer concentration, salt content, amounts of THF and the solvent applied. The large the particle size, the immense the light scattered and therefore, the reduced transparency of the salt/polymer solution and the resulting solid product after solvent removal. Particle size formed during the termination step is the key factor determining the transparency of the final solid polymers.

摘要 …………………………………………………………………… i
圖目錄 …………………………………………………………...….…ii
表目錄 …………………………………………………...………….…iii
第一章 緒論 ……………………………………………..…,……..…1
第二章 聚合體合成實驗 ………………………………………..… 34
第三章 鹽類對均聚合體(homopolymer)透明度影響之研究 …..…40
聚苯乙烯(polystyrene, PS)系統…………………..……..….40
實驗與討論 ……………………………..…………….40
聚丁二烯(polybutadiene, PB)系統……………………....….47
實驗與討論 ……………………………..…………….47
聚異戊二烯(polyisoprene, PIP)系統…………………….….49
實驗與討論 ……………………………..…………….49
結論 ……………..………………………………………….52
第四章 鹽類對單臂型嵌段共聚合體透明度影響之研究…………..103
實驗與討論 ……………………………………..…………103
結論…………………………………………………………106
第五章 總結…………………………………………………….….…113
參考文獻…………………………………………………………..…..118

1. Willmouth, F. H. in ‘‘Optical properties of polymer’’, Meeten, G. H., Editor. Elsevier Applied Science Publishers: New York-London, 1986.
2. 薛聯寶, 金關泰,陰離子聚合的理論和應用(中國友誼出版公司)
1990, p. 189.
3. Mascia, L. in ‘‘Thermoplastics: Materials Engineering’’, Elsevier Applied Science Publishers: New York-London,1982.
4. Periard, J.; Banderet. A. J. Polym. Sci. B 1970, 2, 109.
5. Morton, M. in ‘‘Block polymers’’, Plenum Press Publishers: New York- London, 1969.
6. 王興亞, 郭昌榮, 合成橡膠工業(蘭州化工研究院), 1995, 18, 279.
7. Kenkare, P. U.; Hall, C. K.; Kilpatrick, P. K. J. Colloid and Interface
Science 1996, 184, 456.
8. Han, S. K.; Royce, A. C.; Schott, H. J. Colloid and Interface Science
1984, 98, 196.
9. Angell, C. A.; Fan, H. Electrochemica Acta 1995, 40, 2397.
10. Dautzenberg, H. Macromolecules 1997, 30, 7810.
11. Dubin, P. L.; Wang, Y. L. Macromolecules 1999, 32, 7128.
12. Chu, P. P.; He, Z. P. Polymer 2001, 42, 4743.
13. Sekhon, S. S.; Deepa, S. A.; Agnihotry, S. A. Solid State Ionics 2000,
136-137, 1189.
14. Gan, Y.; Dong, D.; Hogen-Esch, T. E. Macromolecules 1995, 28, 383.
15. Ruokolainen, J.; Tanner, J.; ten Brinke, G.; Ikkala, O.; Torkkelli, M.;
Serimaa, R. Macromolecules 1995, 28, 7779.
16. Agnew, N. H. J. Polym. Sci., Polym. Chem. 1976, 14, 2819.
17. Kuil, M. E.; Mandel, M.; Smits, R. G. Macromolecules 1993, 26,
6808.
18. Mandel, M.; Kuil, M. E.; Smits, R. G. Macromolecules 1994, 27,
5599.
19. Zhu, P. W.; Napper, D. H. Colloid and Surfaces 1995, 98, 93.
20. Jorgensen, E. B.; Hvidt, S. Macromolecules 1997, 30, 2355.
21. Chu, B. Langmuir 2000, 16, 7533.
22. Moller, M. Macromolecules 2000, 33, 4791.
23. Ribbe, A. E.; Okumura, A.; Matsushige, K.; Hashimoto, T.
Macromolecules 2001, 34, 8239.
24. Douglas, E. P.; Harrison, B. S.; Zhao, H. Y. Langmuir 2001, 17, 8428.
25. Moller, M.; Spatz, J. P. Macromolecules 1996, 29, 3220.
26. Weiesner, U. Macromolecules 1997, 30, 6698.
27. Weiesner, U. Macromolecules 1999, 32, 2806.

28. Tayim, H. A.; Mahmoud, F. T. J. Oganometa. Chem. 1975, 92, 107.
29. Bronsstein, L. M.; Seregina, M. V.; Platonnova, O. A. Macromol.
Chem. Phys. 1998, 199, 1357.
30. Mirzoeva, E. S.; Bronstein, L. M.; Valetsky, P. M. Reactive Polym. 1995, 24, 243.
31. Watanabe, H.; Oishi, Y.; Kanaya, T.; Kaji, H. Macromolecules 2003, 36, 220.
32. Schmitt, B. J. Chem. Int. Ed. Eng. 1979, 18, 28.
33. Yakimnasky, A. V.; Muller, A. E.; Beylen, M. V. Macromolecules
2000, 33, 5686.
34. Oomura, K.; Furuyama, T.; Shimamura, T.; Suzuki, Y. US patent 5,434,219.
35. Morton, M. in ‘‘Anion polymerization: principles and practice’’, Academic Press, Inc.: New York, 1983.
36. Noshay, A.; McGrath, J. E. in ‘‘Block Copolymers: overview and critical survey’’, Academic Press, Inc.: New York, 1977.
37. Simha, R.; Utracki, L. A. ‘‘Block Copolymers’’, Aggarwal, S. L., Editor. Akron, OH., Plenum Press, New York- London, 1970.
38. Hsieh, H. L. in ‘‘Block and Graft Copolymers’’, Burke, J. J.; Weiss, V., Editors. Boston, MA., Syracuse University Press.: New York, 1973.