PEN 필름 중의 유기용매 확산과 용매유도 결정화

김성중; 이영목; 남주영; 임승순

Polymer(Korea), Vol.23, No.1, 81-90, January, 1999

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PEN 필름 중의 유기용매 확산과 용매유도 결정화

The Solvent Induced Crystallization and Diffusion Behavior of Solvents in Poly(ethylene 2,6-naphthalate) Film

김성중, 이영목, 남주영, 임승순

초록

Poly(ethylene 2,6-naphthalate) (PEN)의 용매에 의한 결정화 거동을 규명하기 위하여 PEN과 dioxane 그리고 DMF의 상용성 확산거동의 변화로부터 결정화를 발생케 하는 주원인을 살퍼보았다. 40 ℃에서 dioxane의 확산거동은 Fickian거동을 나타내었으며, 20 ℃와 30 ℃에서의 확산거동은 Cass Ⅱ거동을 나타내었다. 그러나 이런 확산들은 결정화에 의해 지배되는 겉보기 Fickian, Cass Ⅱ확산이었다. 40℃의 dioxane에서 처리된 시료는 α-crystal에서 나타나는 구정조직을 형성하였으며, Cass Ⅱ거동을 나타내는 20 ℃에서 처리된 시료는 결정구조가 β-crystal이고 morphology는 amoeba 형태를 보였다. DMF의 확산거동은 dioxane의 확산거동과 유사한 거동을 나타내었으나 PEN과의 상요성은 dioxane보다 더 좋았다. 그러나 DMF와 혼합용매에서 처리된 시료는 모두 α-crystal을 형성하므로, 용매유도 결정화에서 결정형태의 차이는 온도에 따른 확산거동의 차이와 용매의 특성에 기인한다고 생각된다.

The solvent induced crystallization (SINC) behavior of poly (ethylene 2,6-naphthalate) (PEN) films is investigated by monitoring the diffusion behavior of dioxane and DMF in PEN films. The diffusion behavior of dioxane at 40 ℃ is not pure Fickian but apparent Fickian at which diffusion is controlled by crystallization. The diffusion behavior at 20 ℃ and 30 ℃ is not pure Care Ⅱ. The samples treated in dioxane at 40 ℃, which show the Fickian diffusion behavior, exhibits α-crystal and spherulitic texture. The sample treated in dioxane 20 ℃, which shows Case Ⅱ diffusion behavior, exhibits β-crystal and the amoeba structure. The diffusion behavior of DMF is similar to that of dioxane. However, the samples treated with DMF only show the α-crystal irrespective of treatment temperature. And then, the compatibility of DMF to PEN is better than that of dioxane to PEN. According to the above results, we think that the difference of crystalline structure in solvent induced crystallization is caused to the difference of diffusion behavior according to treatment temperature and the characteristic of solvent.

Keywords:poly(ethylene 2,6-naphthalate) (PEN);SINC;case Ⅱ;β-crystal

[References]

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Vrentas JS, Duda JL, Macromolecules, 9, 785 (1976)
Astarita G, Sarti GC, Polym. Eng. Sci., 18, 388 (1978)
Gostoli C, Sarti GC, Polym. Eng. Sci., 22, 1018 (1982)
Thomas NL, Windle AH, Polymer, 21, 613 (1980)
Thomas NL, Windle AH, Polymer, 23, 529 (1982)
Jameel H, Waleman J, Rebenfeld L, J. Appl. Polym. Sci., 26, 1795 (1981)
Jameel H, Noether HD, Rebenfeld L, J. Appl. Polym. Sci., 27, 773 (1982)
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Lee YM, Lee SH, In SS, Kim JW, Polym.(Korea), 17(5), 569 (1993)
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Bell VL, Pezdirtz GF, J. Polym. Sci. A: Polym. Chem., 21, 3083 (1983)
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van Krevelen DW, "Properties of Polymers," p. 219, Elsevier, Inc., Amsterdam (1990)
Kelley FN, Bueche F, J. Polym. Sci., 1, 549 (1961)
Kim JC, Ph.D. Thesis, Univ. of Akron (1995)

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[2] Frisch HL, J. Polym. Sci. A: Polym. Chem., 2, 7 (1969)

[3] Hopfenberg HB, Stannett VT, Folk GM, Polym. Eng. Sci., 15, 261 (1975)

[4] Ware RA, Tirtowidyjojo S, Cohen C, J. Appl. Polym. Sci., 26, 2975 (1981)

[5] Crank J, Park GS, "Diffusion in Polymers," Academic Press, New York (1975)

[6] Durning CJ, Rebenfeld L, Russel WD, Weigmann HD, J. Polym. Sci. B: Polym. Phys., 24, 1321 (1986)

[7] Desai AB, Wilkes GL, J. Polym. Sci. Polym. Symp., 46, 29 (1974)

[8] Hildebrand JH, Scott RL, "The Solubility of Non-Electrolytes," 3rd Ed., Dover, New York (1949)

[9] Hansen CM, J. Paint Technol., 39, 104 (1967)

[10] Crank J, "The Mathematics of Diffusion," 2nd Ed., p. 105, Oxford University Press, Bristol, England (1975)

[11] Vrentas JS, Jarzebski CM, Duda JL, AIChE J., 21, 894 (1975)

[12] Vrentas JS, Duda JL, Macromolecules, 9, 785 (1976)

[13] Astarita G, Sarti GC, Polym. Eng. Sci., 18, 388 (1978)

[14] Gostoli C, Sarti GC, Polym. Eng. Sci., 22, 1018 (1982)

[15] Thomas NL, Windle AH, Polymer, 21, 613 (1980)

[16] Thomas NL, Windle AH, Polymer, 23, 529 (1982)

[17] Jameel H, Waleman J, Rebenfeld L, J. Appl. Polym. Sci., 26, 1795 (1981)

[18] Jameel H, Noether HD, Rebenfeld L, J. Appl. Polym. Sci., 27, 773 (1982)

[19] Im SS, Lee HS, J. Appl. Polym. Sci., 37, 1801 (1989)

[20] Lee YM, Kim KH, Im SS, Polym.(Korea), 17(3), 275 (1993)

[21] Lee YM, Lee SH, In SS, Kim JW, Polym.(Korea), 17(5), 569 (1993)

[22] Lee YM, Im SS, J. Korean Fiber Soc., 32, 697 (1995)

[23] Lee YM, Lee KW, Im SS, J. Korean Fiber Soc., 33, 412 (1996)

[24] Lee YM, Im SS, Polym.(Korea), 21(4), 605 (1997)

[25] Makarewicz PJ, Wilkes GL, J. Polym. Sci., 16, 1529 (1978)

[26] Bell VL, Pezdirtz GF, J. Polym. Sci. A: Polym. Chem., 21, 3083 (1983)

[27] Mencik Z, Chem. Prim., 17(2), 78 (1967)

[28] Zachmann HG, Wiswe D, Gehrke R, Riekel C, Makromol. Chem. Suppl., 12, 175 (1985)

[29] Buchner S, Chen D, Gehrke R, Zachmann HG, Mol. Cryst. Liq. Cryst., 155, 357 (1988)

[30] Markarewicz PJ, Wilkes GL, J. Appl. Polym. Sci., 22, 3347 (1978)

[31] Desai AB, Wilkes GL, J. Polym. Sci. Polym. Symp., 46, 291 (1974)

[32] van Krevelen DW, "Properties of Polymers," p. 219, Elsevier, Inc., Amsterdam (1990)

[33] Kelley FN, Bueche F, J. Polym. Sci., 1, 549 (1961)

[34] Kim JC, Ph.D. Thesis, Univ. of Akron (1995)