HI/I<sub>2</sub> 촉매로 중합되는 Alkyl Vinyl Ether의 양이온 리빙 중합에 있어서 Tacticity 본석으로 본 중합활성점의 구조적 특성

조창기; McGrath JE

Polymer(Korea), Vol.16, No.1, 29-35, January, 1992

HI/I₂ 촉매로 중합되는 Alkyl Vinyl Ether의 양이온 리빙 중합에 있어서 Tacticity 본석으로 본 중합활성점의 구조적 특성

Tacticity Analysis and the Nature of Active Propagating Species in the Living Cationic Polymerization of Alky Vinyl Ethers Initiated by HI/I₂ Catalyst

조창기, McGrath JE

초록

리빙 중합조건하에서 HI/I₂ 촉매에 의하여 합성된 poly(ethyl vinyl ether)와 poly(n-butyl vinyl ether)의 tactility를 탄소 핵자기 공명을 이용하여 분석하였으며, 그 분석결과를 BF₃OEt₂나 SbCl₅가 사용된 리빙 중합이 아닌 중합계에서 얻어진 고분자의 분석결과와 비교하였다. HI/I₂ 촉매에 의하여 얻어진 polymer의 sequence distribution은 Bernoullian 통계를 따르지 않았고 반면에 BF₃OE_t2를 사용하여 얻어진 것은 random statistics를 따르고 있었다. 중합온도가 감소할 때. 얻어진 고분자의 isotacticity는 증가하였고 random statistics로부터의 deviation은 증가하였다.

Ethyl vinyl ether(EVE) and n-butyl vinyl ether(nBVE) were polymerized by HI/I₂ catalyst under living polymerization conditions, and the tacticities of the obtained polymers were determined by carbon-13 NMR spectroscopy. The tacticity result was analyzed and compared with reported data which were obtained from nonliving polymerization systems catalyzed by BF₃OEt₂ or SbCl₅. Sequence distribution of a polymer obtained with HI/I₂ catalyst did not follow Bernoullian statistics, whereas that of the polymer obtained from BF₃OEt₂ catalyst system followed the random statistics. As the polymerization temperature decreased, the isotacticity of the polymer obtained increased, and the deviation from random statistics became larger.

[References]

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[2] Faust R, Kennedy JP, Polym. Bull., 19, 29 (1988)

[3] Kojima K, Sawamoto M, Higashimura T, J. Polym. Sci. A: Polym. Chem., 28, 3007 (1990)

[4] Faust R, Kennedy JP, Polym. Bull., 15, 317 (1986)

[5] Miyamoto M, Sawamoto M, Higashimura T, Macromolecules, 17, 265 (1984)

[6] Sawamoto M, Okamoto C, Higashimura T, Macromolecules, 20, 2693 (1987)

[7] Aoshima S, Higashimura T, Polym. Bull., 15, 417 (1986)

[8] Higashimura T, Kishimoto Y, Aoshima S, Polym. Bull., 18, 111 (1987)

[9] Cho CG, Feit BA, Webster OW, Macromolecules, 23, 1918 (1990)

[10] Kazas G, Puskas JE, Chen CC, Kennedy JP, Polym. Bull., 20, 413 (1988)

[11] Zsuga M, Kennedy JP, Polym. Bull., 21, 5 (1989)

[12] Nuyken O, Kroener H, Makromol. Chem., 191, 1 (1990)

[13] Cho CG, McGrath JE, J. Macromol. Sci.-Chem., A25, 499 (1988)

[14] Kennedy JP, Marechal E, "Carbocationic Polymerization," Wiley-Interscience, New York (1982)

[15] Young WG, Winstein S, Goering HL, J. Am. Chem. Soc., 73, 1958 (1951)

[16] Mueller MA, Stickler M, Makromol. Chem. Rapid Commun., 7, 575 (1986)

[17] Zambelli A, Tosi C, Adv. Polym. Sci., 15, 31 (1974)

[18] Carrick WL, Adv. Polym. Sci., 12, 65 (1973)

[19] Ketley AD, "Stereospecific Polymerization of Vinyl Ethers," in A.D. Ketley, Ed., "The Stereochemistry of Macromolecules," Vol. 2, p. 37-109, Marcel-Dekker, Inc., New York (1967)

[20] Sikkema DJ, Angad-Gaur H, Makromol. Chem., 181, 2259 (1980)

[21] Kunitake T, Tsugawa S, Macromolecules, 8, 709 (1975)

[22] Ledwith A, Chiellini E, Solaro R, Macromolecules, 12, 240 (1979)

[23] Kunitake T, Takarabe K, Makromol. Chem., 182, 817 (1981)

[24] Higashimura T, Suzuoki K, Okamura S, Makromol. Chem., 86, 259 (1965)

[25] Hatada K, Kitayama T, Matsuo N, Yuki H, Polym. J., 15, 719 (1983)

[26] Matsuzaki K, Ito H, Kawamura T, Uryu T, J. Polym. Sci. A: Polym. Chem., 11, 971 (1973)

[27] Angad-Gaur H, Sikkema DJ, Makromol. Chem., 181, 2385 (1980)

[28] Bovey FA, "High Resolution NMR of Macromolecules," Academic Press, New York (1972)

[29] Koenig JL, "Chemical Microstructure of Polymer Chains," Wiley-Interscience, New York (1980)

[30] Higashimura T, Yonezawa T, Okamura S, Fukui K, J. Polym. Sci., 39, 487 (1959)

[31] Cram DJ, Kopecky KR, J. Am. Chem. Soc., 81, 2748 (1959)

[32] Kunitake T, Takarabe K, Tsugawa S, Polym. J., 8, 363 (1976)

[33] Mayr H, Schneider R, Schade C, Makromol. Chem. Macrmol. Symp., 13-14, 43 (1988)