MoCl<sub>5</sub>에 의한 페닐아세틸렌의 중합에서 2-프로핀-1-올의 영향

갈영순; 정발; 이원철; 최삼권

Polymer(Korea), Vol.17, No.4, 365-371, July, 1993

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MoCl₅에 의한 페닐아세틸렌의 중합에서 2-프로핀-1-올의 영향

The Effect of 2-Propyn-1-ol on the Polymerization of Phenylacetylene by MoCl₅

갈영순, 정발, 이원철, 최삼권

초록

MoCl₅-HC≡CCH₂OH촉매 시스템을 사용한 페닐아세틸렌의 중합을 여러가지 반응조건하에서 시도하였다. MoCl₅에 대한 HC≡CCH₂OH의 몰비, 활성화 온도 및 중합온도의 영향을 연구하였다. MoCl₅에 대한 HC≡CCH₂OH몰비가 5일 경우 가장 좋은 길과(중합수율=58%, Mw=7,200)를 얻었다. HC≡CCH₂OH에 대한 MoCl₅의 활성화 온도에 관계없이 넓은 온도범위에서 중합이 잘 진행되어 비교적 높은 수율을 보였다. HC≡CCH₂OH가 MoCl₅의 염소원소를 치환시켜 중합시에 활성촉매종으로 작용하는 몰리브데늄의 알콕사이드를 만드는 것으로 판단되었다. MoCl₅-HC≡CCH₂OH 촉매 시트템에 의해 합성된 폴리페닐아세틸렌의 구조를 NMR(¹H-, ¹³C-), IR, UV-visible등과 같은 분석장비로 규명하였으며 합성한 폴리(페닐아세틸렌)의 열특성에 관해서도 연구하였다.

The polymerization of phenylacetylene using MoCl₅-HC≡CCH₂OH catalyst system was carried out at various reaction conditions. The effects of the mole ratio of HC≡CCH₂OH to MoCl₅, the activation and polymerization temperatures, etc. were studied. The best result(polymer yield=58%, Mw=7200) was obtained when the mole ratio of HC≡CCH₂OH to MoCl₅ was 5. In a wide temperature range(20∼90℃), the polymerizations were well proceeded to give a relatively good yield, regardless of the activation temperature of MoCl₅ by HC-CCH₂OH. It was concluded that the hydroxyl group of HC≡CCH₂OH substituted the chlorine atom of MoCl₅ to make an alkoxide derivative of molybdenum which plays a role as an active catalytic species. The polymer structure of posy(phenylacetylene) prepared by MoCl₅-HC≡CCH₂OH catalyst system was also characterized by various instrumental methods such as NMR( ¹H-, ¹³C-), IR, UV-visible spectroscopies. The thermal properties were also studied.

[References]

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Schrock RR, Accounts Chem. Res., 23, 158 (1990)
Masuda T, Hasegawa KI, Higashimura T, Macromolecules, 7, 728 (1974)
Dragutan V, Balaban AT, Dimonie M, "Olefin Metathesis and Ring-Opening Polymerization of Cycloolefins," John Wiley & Sons (1985)
Natta G, Dall'Asta G, Mazzanti G, Angew. Chem.-Int. Edit., 3, 723 (1964)
Rossi R, Chim. Ind., 57, 242 (1975)
Mortreux A, Petit F, Blanchard M, Tetrahedron Lett., 4967 (1978)
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Bencheick A, Petit M, Mortreux A, Petit F, J. Mol. Catal., 15, 93 (1982)
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Masuda T, Mishima K, Fujimori JI, Nishida M, Muramatsu H, Higashimura T, Macromolecules, 25, 1401 (1992)
Gal YS, Jung B, Lee WC, Choi SK, Polym.(Korea), 16(5), 597 (1992)
Gal YS, Jung B, Lee WC, Choi SK, Bull. Korean Chem. Soc., 14, 171 (1993)
Taghizadeh N, Quignard F, Leconte M, Basset JM, Larroche C, Laval JP, Lattes A, J. Mol. Catal., 15, 219 (1982)
Gal YS, Cho HN, Choi SK, Polym.(Korea), 9(5), 361 (1985)
Gal YS, Cho HN, Kwon SK, Choi SK, Polym.(Korea), 12(1), 30 (1988)
Gal YS, Choi SK, J. Polym. Sci. C: Polym. Lett., 26, 115 (1988)
Masuda T, Hasegawa KI, Higashimuda T, Macromolecules, 7, 728 (1974)
Masuda T, Kawai M, Higashimura T, Polymer, 23, 744 (1982)
Abe Y, Masuda T, Higashimura T, J. Polym. Sci. A: Polym. Chem., 27, 4267 (1989)
Gal YS, Unpublished Data
Johnson CE, Bovey FA, J. Chem. Phys., 29, 1012 (1958)
Haigh CW, Mallion RB, Org. Mag. Mesonance, 4, 203 (1972)
Berlin AA, Cerkashin MI, Vysocomol. Soedin, A13, 2298 (1971)
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Chiang AC, Waters PF, Aldridge MH, J. Polym. Sci. A: Polym. Chem., 20, 1807 (1987)

[Referenced By]

[1] Ivin KJ, "Olefin Metathesis," Academic Press (1983)

[2] Dolgoplosk BA, Korshak YV, Russ. Chem. Rev., 53(1), 36 (1984)

[3] Schrock RR, Accounts Chem. Res., 23, 158 (1990)

[4] Masuda T, Hasegawa KI, Higashimura T, Macromolecules, 7, 728 (1974)

[5] Dragutan V, Balaban AT, Dimonie M, "Olefin Metathesis and Ring-Opening Polymerization of Cycloolefins," John Wiley & Sons (1985)

[6] Natta G, Dall'Asta G, Mazzanti G, Angew. Chem.-Int. Edit., 3, 723 (1964)

[7] Rossi R, Chim. Ind., 57, 242 (1975)

[8] Mortreux A, Petit F, Blanchard M, Tetrahedron Lett., 4967 (1978)

[9] Strelets VV, Tsarev VN, Efimov ON, Kinet. Katal., 22, 359 (1981)

[10] Bencheick A, Petit M, Mortreux A, Petit F, J. Mol. Catal., 15, 93 (1982)

[11] Higashimura T, Deng YX, Masuda T, Macromolecules, 15, 234 (1982)

[12] Masuda T, Yoshimura T, Higashimura T, Macromolecules, 22, 3804 (1989)

[13] Masuda T, Mishima K, Fujimori JI, Nishida M, Muramatsu H, Higashimura T, Macromolecules, 25, 1401 (1992)

[14] Gal YS, Jung B, Lee WC, Choi SK, Polym.(Korea), 16(5), 597 (1992)

[15] Gal YS, Jung B, Lee WC, Choi SK, Bull. Korean Chem. Soc., 14, 171 (1993)

[16] Taghizadeh N, Quignard F, Leconte M, Basset JM, Larroche C, Laval JP, Lattes A, J. Mol. Catal., 15, 219 (1982)

[17] Gal YS, Cho HN, Choi SK, Polym.(Korea), 9(5), 361 (1985)

[18] Gal YS, Cho HN, Kwon SK, Choi SK, Polym.(Korea), 12(1), 30 (1988)

[19] Gal YS, Choi SK, J. Polym. Sci. C: Polym. Lett., 26, 115 (1988)

[20] Masuda T, Hasegawa KI, Higashimuda T, Macromolecules, 7, 728 (1974)

[21] Masuda T, Kawai M, Higashimura T, Polymer, 23, 744 (1982)

[22] Abe Y, Masuda T, Higashimura T, J. Polym. Sci. A: Polym. Chem., 27, 4267 (1989)

[23] Gal YS, Unpublished Data

[24] Johnson CE, Bovey FA, J. Chem. Phys., 29, 1012 (1958)

[25] Haigh CW, Mallion RB, Org. Mag. Mesonance, 4, 203 (1972)

[26] Berlin AA, Cerkashin MI, Vysocomol. Soedin, A13, 2298 (1971)

[27] Simionescu CI, Percec V, Dumitrescu S, J. Polym. Sci. A: Polym. Chem., 15, 2497 (1977)

[28] Siskos MG, Bokaris EP, Zarkadis AK, Kyriakakou G, Eur. Polym. J., 28, 1127 (1992)

[29] Kern RJ, J. Polym. Sci. A: Polym. Chem., 7, 621 (1969)

[30] Simionescu CI, Dumitrescu S, Negulescu I, Percec V, Grigoras M, Diaconu I, Leanca M, Goras L, Vysokomol. Soedin, 16, 790 (1974)

[31] Simionescu CI, Dumitrescu S, Percec V, Polym. J., 8, 139 (1976)

[32] Dumitrescu S, Percec V, Simionescu CI, J. Polym. Sci. A: Polym. Chem., 15, 2893 (1977)

[33] Chiang AC, Waters PF, Aldridge MH, J. Polym. Sci. A: Polym. Chem., 20, 1807 (1987)