테트라하이드로퓨란의 개환 중합반응에 의해 변형된 12-몰리브도인산의 특성 및 촉매 반응성

박교익; 이화영; 송인규

Journal of the Korean Industrial and Engineering Chemistry, Vol.9, No.7, 1018-1022, December, 1998

Characteristics and Catalytic Activities of 12-Molybdophosphoricacid Modified by Ring Opening Polymerization of Tetrahydrofuran

박교익, 이화영, 송인규

초록

본 연구에서는 테트라하이드로퓨란(THF)의 개환중합반응에 의해 변형된 12-몰리브도인산의 특성 및 촉매 반응성을 살펴보았다. 기상 에탄올 전화반응에서 THF에 의해 변형된 12-몰리브도인산은 모산 촉매보다 매우 우수한 전환율 및 생성물 수율을 보였다. 변형된 12-몰리브도인산의 증가된 반응성은 변형된 헤테로폴리음이온의 구조적 유연성과 약화된 수소결합에 기인하는 것으로 판단된다. THF는 양성자 또는 결정수를 매개로 헤테로폴리산과 상호작용을 하는 것으로 나타났는데, 결정수를 중심으로 한 THF와 헤테로폴리음이온간의 상호작용이 변형된 12-몰리브도인산의 촉매 활성을 결정하는 주된 요인이었다.

Characteristics and catalytic activities of 12-molybdophosphoricacid catalysts modified by ring opening polymerization of tetrahydrofuran (THF) were studied in this work. 12-Molybdophosphoricacid catalysts modified by THF showed higher conversions and product yields than the mother acid in the vapor-phase ethanol conversion. It was believed that the enhanced catalytic activities of modified 12-molybdophosphoricacids were due to structural flexibility of heteropolyanions and weakened hydrogen bond around heteropolyanions. THF interacted with protons and crystalline water molecules of heteropolyacids. The interaction between THF and heteropolyanoins, which crystalline water molecules act as intermediary, was the dominant factor deciding the catalytic activities of modified 12-molybophosphoricacids.

Keywords:12-molybdophosphoricacid;Tetrahydrofuran;Ethanol;Heteropolyanion;Polymerization

[References]

Okuhara T, Mizuno N, Misono M, Adv. Catal., 41, 113 (1996)
Misono M, Catal. Rev.-Sci. Eng., 29, 269 (1987)
Kozhevnikov IV, Matveev KI, Appl. Catal., 5, 135 (1983)
Aoshima A, Yamamatsu S, Yamaguchi T, Nippon Kagaku Kaishi, 1763 (1987)
Aoshima A, Tonomura S, Ymamatsu S, Polym. Adv. Technol., 2, 127 (1990)
Lee KY, Arai T, Nakata S, Asaoka S, Okuhara T, Misono M, J. Am. Chem. Soc., 114, 2836 (1992)
Kim HC, Moon SH, Lee WY, Chem. Lett., 447 (1991)
Ai M, Appl. Catal., 4, 245 (1982)
Ai M, J. Catal., 85, 324 (1984)
Pron A, Synth. Met., 46, 277 (1992)
Lee JK, Song IK, Lee WY, J. Mol. Catal., 120, 207 (1997)
Song IK, Lee JK, Park GI, Lee WY, Stud. Surf. Sci. Catal., 110, 1183 (1997)
Lee WY, Song IK, Lee JK, Park GI, Lim SS, Korean J. Chem. Eng., 14(6), 432 (1997)
Ueda W, Suzuki Y, Lee W, Imaoka S, Stud. Surf. Sci. Catal., 101, 1065 (1996)
Lee JK, Song IK, Park GI, Lee WY, HWAHAK KONGHAK, 35(2), 237 (1997)
Nakamoto K, "Infrared Spectra of Inorganic and Coordination Compounds," p. 185, John Wiley & Sons, New York (1963)
Brown GM, Neo-Spirlet MR, Busing WR, Levy HA, Acta Crystallogr. Sect. B-Struct. Sci., 33, 1038 (1977)
Kozhevnikov IV, Sinnema A, Vanbekkum H, Catal. Lett., 34(1-2), 213 (1995)

[Referenced By]

[1] Okuhara T, Mizuno N, Misono M, Adv. Catal., 41, 113 (1996)

[2] Misono M, Catal. Rev.-Sci. Eng., 29, 269 (1987)

[3] Kozhevnikov IV, Matveev KI, Appl. Catal., 5, 135 (1983)

[4] Aoshima A, Yamamatsu S, Yamaguchi T, Nippon Kagaku Kaishi, 1763 (1987)

[5] Aoshima A, Tonomura S, Ymamatsu S, Polym. Adv. Technol., 2, 127 (1990)

[6] Lee KY, Arai T, Nakata S, Asaoka S, Okuhara T, Misono M, J. Am. Chem. Soc., 114, 2836 (1992)

[7] Kim HC, Moon SH, Lee WY, Chem. Lett., 447 (1991)

[8] Ai M, Appl. Catal., 4, 245 (1982)

[9] Ai M, J. Catal., 85, 324 (1984)

[10] Pron A, Synth. Met., 46, 277 (1992)

[11] Lee JK, Song IK, Lee WY, J. Mol. Catal., 120, 207 (1997)

[12] Song IK, Lee JK, Park GI, Lee WY, Stud. Surf. Sci. Catal., 110, 1183 (1997)

[13] Lee WY, Song IK, Lee JK, Park GI, Lim SS, Korean J. Chem. Eng., 14(6), 432 (1997)

[14] Ueda W, Suzuki Y, Lee W, Imaoka S, Stud. Surf. Sci. Catal., 101, 1065 (1996)

[15] Lee JK, Song IK, Park GI, Lee WY, HWAHAK KONGHAK, 35(2), 237 (1997)

[16] Nakamoto K, "Infrared Spectra of Inorganic and Coordination Compounds," p. 185, John Wiley & Sons, New York (1963)

[17] Brown GM, Neo-Spirlet MR, Busing WR, Levy HA, Acta Crystallogr. Sect. B-Struct. Sci., 33, 1038 (1977)

[18] Kozhevnikov IV, Sinnema A, Vanbekkum H, Catal. Lett., 34(1-2), 213 (1995)