本文是以乳化聚合法合成具有不同奈米級與次微米級顆粒大小和不同外殼組成的核殼型橡膠(CSR)添加劑，以作為不飽和聚酯樹脂(UP)及乙烯基酯樹脂(VER)的抗體積收縮劑(LPA)及增韌劑，吾人並合成三種不同化學結構之UP,包括MA-PG型,MA-PA-PG型及vinyl ester resin (VER) ,進而設計出具不同相溶性之苯乙烯(St)/UP/CSR三成份系統.吾人先以半批次進料方式聚合丙烯酸正丁酯(BA)，形成PBA軟質核心，再以批次進料方式聚合甲基丙烯酸甲酯(MMA)，形成PMMA硬質外殼，CSR之外殼並且不加或加入交聯劑(EGDMA)進行改質，以合成外殼未交聯或交聯之PBA/PMMA核殼型橡膠。另外,CSR之外殼吾人亦以醋酸乙烯(Vinyl acetate VAC)共單體改質,以增加CSR外殼之極性.吾人利用Debye’s eq.及基團貢獻法，計算出UP、VER與CSR之外殼的偶極矩，以解釋St／UP／CSR三成份系在25℃及110℃下未反應前之相溶性。吾人亦利用掃描式電子顯微鏡(SEM)來觀測St／UP／CSR三成份系在110℃下聚合固化後樣品破壞面的微觀型態，藉以瞭解CSR的外殼化學組成與顆粒大小對St／UP／CSR三成份系在聚合固化過程中之相溶性影響。不同之CSR添加量，對St/UP/CSR三成份系統在聚合固化過程中之相容性影響，亦在文中探討。

Acrylic type of core-shell rubbers (CSR) , with varied nano-scale and submicron-scale particle size and shell chemical composition, as low-profile additives (LPA) and tougheners for unsaturated polyester resins (UP) and vinyl ester resin (VER) have been synthesized by two-stage seeded emulsion polymerizations . Three types of unsaturated polyester resin with different chemical structures, namely, MA-PG type, MA-PA-PG type, and vinyl ester resin (VER) ,have also been synthesized so that styrene (St) /UP /CSR ternary systems with different miscibility can be designed. In the synthesis of the core-shell rubber, a semi-batch process was used to synthesize the soft core, which was made from poly(butyl acrylate) (PBA) , whereas a batch process was to employed to synthesize the hard shell , which was composed of poly(methyl methacrylate) (PMMA) . Also, the shell of the CSR was modified with or without a crosslinking agent, ethylene glycol dimethacrylate (EGDMA). In addition, the shell of CSR has also been modified by introducing vinyl acetate (VAc) as a comonomer to increase the molecular polarity for the shell of the CSR. By using Debye’s equation and the group contribution method, the dipole moments of UP and the shell component of the CSR can be calculated, which can then explain the phase characteristics of the St/UP/CSR ternary system prior to the reaction at 25℃ and 110℃ . Also , the effect of the shell composition of CSR and CSR particle size on the compatibility of the St/UP/CSR ternary system during the cure at 110℃ has been investigated by the cured sample morphology as observed by scanning electron microscopy (SEM) . The effects of CSR content on the compatibility of different St/UP/CSR ternary systems during the cure have been dealt with as well.

1. R.B. Burns , “Polyester Molding Compounds ,” Marcel Dekker , New York , 1982.
2. H.G. Kia , ed., “Sheet Molding Compound : Science and Technology ,” Hanser Publishers , New York , 1993.
3. E.J. Bartkus and C. H. Kroekel, J. Appl. Polym. Sci., Appl. Polym. Symp., 15, 113 (1970).
4. Y.J. Huang, T.S. Chen, J.G. Huang and F.H. Lee, J. Appl. Polym. Sci., 89, 3336(2003).
5. V.A. Pattison, R.R. Hindersinn and W.T. Schwartz, J. Appl. Polym. Sci., 18, 2763 (1974).
6. W. Funke, R. Kolitz, and W. Straehle, Makromol. Chem., 180, 2797 (1979).
7. W. Funke, and K. Walther, Polymer J., 17, 1, 179 (1985).
8. W. Funke, Br. Polym. J., 21, 107 (1989).
9. L. Liang and W. Funke, Macromolecules, 29 ,8685 (1996).
10. 郭庭蓁, 碩士論文, 國立台灣科技大學, 2006.
11. J.P. Dong, J.H. Lee, D.H. Lai and Y.H. Huang, J. Appl. Polym. Sci., 98, 246(2005).
12. E. Martuscelli, P. Musto, G. Ragosta, G. Scarinz and E. Bertotti, J. Polym. Sci., Part B: Polym. Phys., 31, 619 (1993).
13. S.B. Pandit and V.M. Nadkarni, Ind. Eng. Chem. Res.,33,2778 (1994).
14. The B.F. Goodrich Co., WO93/21274 (Oct. 28, 1993).
15. Crc for Polymers Pty. Ltd, WO97/43339 (Nov. 20,1997).
16. The B.F.Goodrich Co,Wo 93/21274(Oct.28,1993).
17. J. Wang, M. Lee, X. Yu, J. Ji and K. Yao, J. Mater. Sci. Technol., 20, 5, 522 (2004).
18. J. Wang, M. Lee, K. Yao, J. Ji and X. Yu, J. Mater. Sci. Technol., 20, 6, 787 (2004).
19. J.Y. Qian, R. A. Pearson, V. L. Dimonie and M. S. El-Aasser, J. Appl. Polym. Sci., 58, 439 (1995).
20. K.F. Lin and Y.D. Shieh, J. Appl. Polym. Sci., 69, 2069 (1998).
21. K.F. Lin and Y.D. Shieh, J. Appl. Polym. Sci., 70, 2313 (1998).
22. C.L Lee, K.R Lin and W.Y. Chiu, J. Appl. Polym. Sci., 51, 1621 (1994).
23. 梁景冠，碩士論文，國立台灣科技大學，2003.

24. C.B. Arends, ed., “Polymer Toughening,” Marcel Dekker, New York, 1996.
25. Y.J. Huang, J.H. Wu, J.G. Liang, M.W. Hsu, and J.K. Ma, J. Appl. Polym. Sci, 107, 939 (2008).
26. Y.S.Yang and L.J.Lee,Polymer,29,1793(1988).
27.K.Horie,I.Mita,and H.Kambe,J.Polym.Sci.PartA-1:Polym.
Chem.,7,2561(1969).
28.江文慶，碩士論文，國立台灣科技大學，1996.
29.Y.C. Chen , V. L. Dimonie , and M.S. El-Aasser , J. Appl.
Polym. Sci. , 42 , 1049(1991).
30.J.Berg.D.C.Sundberg, and B.Kronberg , Polym. Mater. Sci.
Eng. , 54 , 367 , (1986).
31. D.C.Sundberg , A.J.Cassasa , J.Pantazopoulos , M.R.
Muscato ,B.K.Kronberg , and J.Berg , J. Appl. Polym. Sci. ,
41 , 1425(1990).
32. Y. J. Huang and C. C. Su, J. Appl. Polym. Sci., 55, 323
(1995).
33. Y. J. Huang and L. D. Chen, Polymer, 39, 7049 (1998).
34. Y. J. Huang and W. C. Jiang, Polymer, 39, 6631 (1998).
35.J. Simitzis, Eur. Polym. J., 24, 87 (1988).
36.R. Subramaniam and F. J. McGarry, 48th Annual Conference,
Composites Institute, SPI, Session 14-C (Feb. 8-11, 1993).
37.B. R. Bogner and M. Kallaur, in “Sheet Molding Compounds:
Science and Technology,” ed. H. G. Kia, Hanser, New York,
1993, Ch.2.
38.Amoco Chemical Co., “Processing Unsaturated Polyesters
Based on Amoco Isophthalic Acid,” IP-43b, 1989.
39.E. F. Cariston and G. B. Johnson, U. S. Patent 2, 904, 533
(1959).
40.N. Agarwal, I. K. Varma, and V. Choudhary, J. of Appl. Polym.
Sci., 99, 2424(2006).
41.B. Gawdzik, and T. Matynia, J. of Appl. Polym. Sci., 81,
2062(2001).
42.P. Penczek, J. Sodhi, and R. Osrysz, J. of Appl. Polym. Sci.,
101, 2627(2006).
43.P. F. Bruins, Ed., “Unsatruated Polyester Technology, ”
Gordon and Breach, New York, p315-342.
44.The Dow Chemical Company , WO86/07067(Dec. 4, 1986).
45.彭俊昇, 碩士論文，國立台灣科技大學，2000.
46.G. Odian,”Principle of Polymerization ,”3rd
Edition,Wiley,New York,1991.
47.廖平喜，聚合物化學，高立圖書有限公司，台北， 1997.
48.H.R. Allcock and F.W. Lampe.,”Contemporary Polymer
Chemistry”,2nd Ed., Prentice Hall, Englewood Cliffs, New Jersey,1990, p. 50.
49.吳嘉鴻, 碩士論文, 台灣科技大學, 2003.
50.J.W.Vanderhoff, “Science and Technology of Polymer
Colloids”, G. W.Poehlein, H.O. and J. W.Goodwin
Eds., Vol.I.1983
51.V.I.Yeliseyeva, in ”Emulsion Polymerization”, chap.7,
Academic Press, 1982.
52.H.One and H.Saeki, Br.Polym.J, 7, 21(1975)
53.M.S.Juang and I.M.Krieger, J.Polym.Sci., Polym.Chem.Ed.
,14, 2089(1976).
54.S.A.Chen and H.S.Chang, J.Polym.Sci., Polym.Chem.Ed., 23,
2615(1985).
55.D.H.Napper and A.G.Parts, J.Polym.Sci., 16, 113(1962).
56.R.M.Fitch, Br.Polym.J., 5, 467(1973).
57.J.H.Bayendale, M.G.Evans and J.K.Kilham, Trans.Faraday
Soc., 42, 688(1946).
58.J.W.Goodwin, J.Hearn, C.C.Ho and R.H.Ottewill, Br.Polym.
J., 5, 347(1973).
59.許繼強, 碩士論文, 台灣科技大學, 2000.
60.W. Thomson (L. Kelvin), Procedings of the Royal Society,
Edinburgh, 7, 63 (1871).
61.A. S. Kablnov, K. N. Makarov, A. V. Pertzov and E. D.
Shchukin, J. Colloid Interface Sci., 138, 98 (1990).
62.A. S. Kabalnov, A. V. Pertzov and E. D. Shchukin, Colloids
Surfaces, 124, 19 (1987).
63.P. Taylor, Colloids Surfaces A: Phys. Chem. Eng. Aspects,
99, 175 (1995).
64.A. S. Kabalnov and E. D. Shchukin, Adv. in Colloid Interface
Sci, 138, 69 (1992).
65.W. L. Grimm, T. I. Min, M. S. El-Aasser and J. W. Vanderhoff,
J. Colloid Interface Sci., 94, 531 (1983).
66.Y. T. Choi, “Formation and Stabilization of Miniemulsions
and Latexes”, Ph. D. Dissertation, Lehigh University
(1986).
67.W. L. Grimm, “The Use of Mixed-Emulsifier Systems in the
Preparation and Stabilization of Emulsions and Latexes”,
M. S. Thesis, Lehigh University (1986).
68.M. S. El-Aasser, C. D. Lack, Y. T. Choi, T. I. Min, J. W.
Vanderhoff and F. M. Fowkes, Colloids Surfaces, 12, 79
(1984).
69. S.L. Rosen, “Fundamental Principles of Polymeric
Materials,” 2nd Ed., Wiley, New York, 1993.
70.蔡明洲, 碩士論文, 台灣科技大學, 2006.
71.曾國棟, 碩士論文, 台灣科技大學, 2005.
72.Y. J. Huang and J. C. Horng, Polymer, 39, 3683 (1998).
73.J. P. Lecointe, J. P. Pascault, L. Suspene, and Y. S. Yang,
Polymer, 33, 3223 (1992).
74.L. Suspene, D. Fourquier, and Y. S. Yang, Polymer, 33, 1593
(1991).

75.Y. J. Huang and C. C. Su, J. Appl. Polym. Sci., 55, 305
(1995).
76.Y. J. Huang, C. J. Chu, and J. P. Dong, J. Appl. Polym.
Sci.,78, 543 (2000).
77.廖德章, 高分子實驗法, 高立圖書有限公司, 民國79.
78.W. Ming, F.N. Jones, and S. Fu, Macromol. Chem. Phys. 199,
1075 (1998).
79.A. Hammond, P.M. Budd, and C. Price, Progr. Colloid Polym.
Sci,113, 142(1993).
80. W Funke. Brit. Polymer. J., 1989,21, 107.
81. L Liang; W Funke. Macromolecules, 1996, 29, 8650.
82. A.S.Djiuard; M.S. Thesis, National Taiwan University of
science and Technology, 2008.
83.E.A. Collins, J. Bares, F.W. Billmeyer, “Experiments in
Polymer Science”, J. Wiley＆Sons, N.Y., 1973 p.334.
84.阮峻維, 碩士論文, 國立台灣科技大學, 1999.
85.V. Nelliappan, A. Klein, E.S. Daniels, and I.E. Roberts, J.
Of Polym. Sci. Part A, Vol34, 3183-3190(1996).

86.K. Landfester, C. Boeffel, M.Lamble, H.W. Spiess, Ecole
d’Application des Hauts Polymers/CNRS, 29,
5972-5980(1996).
87.D.W.V. Krevlen, ”Properties of polymers: their correlation
with chemical structure, their numerical estimation and
prediction from additive group contributions”, 3rd Ed.,
Elserier, Amsterdam 1990.