我們成功地製備了兩種不同分子量大小，具有高磺酸化程度及分子量分布集 中的團鍊共聚高分子電解質。此兩種高分子電解質具有相同的鍊段長度及相似的 磺酸化程度；以不同濃度溶在水溶液中時會形成不同型態的微包結構。苯胺單體 在與團鍊共聚高分子電解質經由在水溶液中進行乳化共聚合反應後，可獲得 PAni/block polyelectrolyte 複合物。經由 TEM 觀察複合物的微結構，發現高分子電 解質濃度和反應時間長短會決定此複合物的微結構，此外團鍊共聚高分子電解質 的分子量也是重要的參數。大分子量的團鍊共聚高分子電解質在水溶液中形成穩 定的固定尺寸的微包並隨著濃度變化有不同的聚集結構，由此高分子獲得的PAni 複合物的結構則以微包形成的串珠為基礎，尺寸隨反應時間增加而變大，應為聚 苯胺持續聚合所造成。當團鍊共聚高分子電解質的濃度增加時，PAni 複合物會有 較高密度的聚集，且PAni 在較短的反應時間內即聚合完全，反應時間增加只增加 PAni 複合物的聚集程度；每當高分子濃度增加一倍，導電度會急遽上升 3~4 個級 數；此外，在導電度的實驗中亦發現只需要相當少量的苯胺單體便可得到具有良 好的導電度的PAni 複合物。相對的，小分子量的團鍊共聚高分子電解質在不同濃 度的水溶液中形成的微包型態及尺寸較不固定，與苯胺單體進行共聚合反應的行 為也比較複雜。大致上的趨勢是：複合物的尺寸會隨反應時間增加而變大，高分 子濃度的增加也會造成比較大尺寸的聚集物；但所得PAni 複合物的導電度並不 高，需做二次摻雜才能使導電度提高，且較無明顯且一致的變化趨勢。導電度可 能受到PAni 複合物的生長機制、摻雜的程度及微結構的影響，需做進一步的探討 及研究。
未來展望
此研究中所設計的高分子電解質及與PAni 產生的複合物具有多種微結構，尤 其是PAni/polyelectrolyte 複合物藉由改變高分子電解質水溶液濃度而有複雜不易 解釋之現象產生，特別是小分子量的高分子電解質。而小分子量高分子電解質在 水溶液中所呈現的結構就已經複雜許多，這可能是導致PAni/polyelectrolyte 微結構 複雜多變的主因，為探求PAni/polyelectrolyte 微結構形成的機制，必須先釐清高分 子電解質微結構變化的因素。分子量、溶劑、溶液的酸鹼值（PH value）、濃度及 溫度等等會影響此高分子電解質的微結構，我們所設計的高分子電解質因帶有磺 酸根而使水溶液為酸性，且隨著濃度升高而降低PH value，PH value 可能是影響的 主因，可以先改變高分子電解質水溶液的酸鹼度來探討PH value 與高分子電解質 微結構之間的關係，又或者改變溶液溫度等等。此系統是改變磺酸根濃度但固定 aniline 的量，可以固定 SO3H 與 aniline 的比例但改變絕對濃度進行 in situ
polymerization，探討絕對濃度跟微結構的關係。
此研究尚有許多未完善之處，例如 PAni 位於複合物的何處，aniline 吸附的機 制等等都需進一步的探討。除此之外，此複合物的熱性質或光電性質在工業上的 應用須靠後續的研究加以發展。
參考文獻
1. Shirakawa, H., et al., Synthesis of Electrically Conducting Organic Polymers - Halogen Derivatives of Polyacetylene, (Ch)X. Journal of the Chemical
Society-Chemical Communications, 1977(16): p. 578-580.
2. Terje A. Skotheim, R.L.E., John R. Reynolds, Handbook of conducting polymers ed. N.Y. M. Dekker. 1986.
3. Macdiarmid, A.G. and A.J. Heeger, Organic Metals and Semiconductors - the Chemistry of Polyacetylene, (Ch)X, and Its Derivatives. Synthetic Metals, 1980.
1(2): p. 101-118.
4. Zuo, F., et al., Solution Studies of the Emeraldine Oxidation-State of Polyaniline.
Synthetic Metals, 1989. 29(1): p. E445-E450.
5. Macdiarmid, A.G., et al., Polyaniline - a New Concept in Conducting Polymers.
Synthetic Metals, 1987. 18(1-3): p. 285-290.
6. Genies, E.M., et al., Polyaniline - a Historical Survey. Synthetic Metals, 1990.
36(2): p. 139-182.
7. Focke, W.W., G.E. Wnek, and Y. Wei, Influence of Oxidation-State, Ph, and Counterion on the Conductivity of Polyaniline. Journal of Physical Chemistry, 1987. 91(22): p. 5813-5818.
8. Macdiarmid, A.G., et al., Polyaniline - Protonic Acid Doping to the Metallic Regime. Molecular Crystals and Liquid Crystals, 1985. 125(1-4): p. 309-318.
9. Huang, J.X. and R.B. Kaner, The intrinsic nanofibrillar morphology of polyaniline. Chemical Communications, 2006(4): p. 367-376.
10. Huang, J.X. and R.B. Kaner, A general chemical route to polyaniline nanofibers.
Journal of the American Chemical Society, 2004. 126(3): p. 851-855.
11. Konyushenko, E.N., et al., Polyaniline nanotubes: conditions of formation.
Polymer International, 2006. 55(1): p. 31-39.
12. Stejskal, J., et al., Oxidation of aniline: Polyaniline granules, nanotubes, and oligoaniline microspheres. Macromolecules, 2008. 41(10): p. 3530-3536.
13. Osterholm, J.E., et al., Emulsion Polymerization of Aniline. Synthetic Metals, 1993. 55(2-3): p. 1034-1039.
14. Jing, L., et al., Micromorphology and electrical property of the HCl-doped and DBSA-doped polyanilines. Synthetic Metals, 2004. 142(1-3): p. 107-111.
15. Barra, G.M.O., et al., X-ray photoelectron spectroscopy and electrical conductivity of polyaniline doped with dodecylbenzenesulfonic acid as a function of the synthetic method. Journal of Applied Polymer Science, 2001.
80(4): p. 556-565.
16. Shreepathi, S. and R. Holze, Spectroelectrochemical investigations of soluble polyaniline synthesized via new inverse emulsion pathway. Chemistry of Materials, 2005. 17(16): p. 4078-4085.
17. Han, M.G., et al., Preparation and characterization of polyaniline nanoparticles synthesized from DBSA micellar solution. Synthetic Metals, 2002. 126(1): p.
53-60.
18. Han, D.X., et al., Reversed micelle polymerization: a new route for the synthesis of DBSA-polyaniline nanoparticles. Colloids and Surfaces a-Physicochemical and Engineering Aspects, 2005. 259(1-3): p. 179-187.
19. Jang, W.H., et al., Synthesis and electrorheology of camphorsulfonic acid doped polyaniline suspensions. Colloid and Polymer Science, 2001. 279(8): p.
823-827.
21. Gangopadhyay, R., A. De, and G. Ghosh, Polyaniline-poly (vinyl alcohol) conducting composite: material with easy processability and novel application potential. Synthetic Metals, 2001. 123(1): p. 21-31.
22. Chen, S.A. and W.G. Fang, Electrically Conductive Polyaniline Poly(Vinyl Alcohol) Composite Films - Physical-Properties and Morphological Structures.
Macromolecules, 1991. 24(6): p. 1242-1248.
23. Mirmohseni, A. and G.G. Wallace, Preparation and characterization of processable electroactive polyaniline-polyvinyl alcohol composite. Polymer, 2003. 44(12): p. 3523-3528.
24. Liu, J.M. and S.C. Yang, Novel Colloidal Polyaniline Fibrils Made by Template Guided Chemical Polymerization. Journal of the Chemical Society-Chemical Communications, 1991(21): p. 1529-1531.
25. Li, W.G., et al., Toward understanding and optimizing the template-guided synthesis of chiral polyaniline nanocomposites. Macromolecules, 2002. 35(27):
p. 9975-9982.
26. Dorey, S., et al., Ultrafine nano-colloid of polyaniline. Polymer, 2005. 46(4): p.
1309-1315.
27. Jayanty, S., et al., Polyelectrolyte templated polyaniline-film morphology and conductivity. Polymer, 2003. 44(24): p. 7265-7270.
28. Karakisla, M., M. Sacak, and U. Akbulut, Conductive polyaniline poly(methyl methacrylate) films obtained by electropolymerization. Journal of Applied Polymer Science, 1996. 59(9): p. 1347-1354.
29. Park, S.Y., et al., Polyaniline microsphere encapsulated by poly(methyl
methacrylate) and investigation of its electrorheological properties. Colloid and Polymer Science, 2003. 282(2): p. 198-202.
30. Cho, M.S., et al., Synthesis and electrorheological characteristics of polyaniline-coated poly(methyl methacrylate) microsphere: Size effect.
Langmuir, 2003. 19(14): p. 5875-5881.
31. Kim, B.J., et al., Preparation of PANI-coated poly(styrene-co-styrene sulfonate) nanoparticles. Polymer, 2002. 43(1): p. 111-116.
32. Barra, G.M.O., et al., Processing, characterization and properties of conducting polyaniline-sulfonated SEBS block copolymers. European Polymer Journal, 2004.
40(9): p. 2017-2023.
33. Stejskal, J., et al., Polyaniline dispersions 2. UV--Vis absorption spectra.
Synthetic Metals, 1993. 61(3): p. 225-231.