Effects of ligand and cosolvent on oxidative coupling polymerization of 2,6 -dimethylphenol catalyzed by chelating amine-copper(II) complexes

Mingu Kim; Xinhui Feng; Yong Tae Kim; Joong-In Kim; Jaesook Yun

Macromolecular Research, Vol.21, No.10, 1054-1058, October, 2013

DOI10.1007/s13233-013-1150-2 Export Citation

Effects of ligand and cosolvent on oxidative coupling polymerization of 2,6 -dimethylphenol catalyzed by chelating amine-copper(II) complexes

Mingu Kim, Xinhui Feng, Yong Tae Kim¹, Joong-In Kim¹, and Jaesook Yun^†

Department of Chemistry and Institute of Basic Science, Sungkyunkwan University, Gyeonggi, 440-746, Korea
¹Corporate Research Institute, Samsung Cheil Industries Inc, Gyeonggi, 437-711, Korea

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The influence of chelating amine ligands, copper precursors, and solvent composition on copper-catalyzed oxidative coupling of 2,6-dimethylphenol was investigated. The most efficient catalytic reaction was conducted with CuCl2-di-tert-butylethylenediamine (Dt-BEDA) complex in anisole or toluene with alcohol cosolvent. Slight structural changes in the N-substituent, backbone, or coordination atom of the ligand significantly dropped catalytic activities, leading to a low polymer yield. Alcohol cosolvent was necessary to synthesize a polymer of high molecular weight (M n - >10,000) with the copper(II) catalyst in toluene. With increasing alcohol ratios, the isolated yields and M n - values of the resulting polymers gradually decreased. However, the use of sterically bulky t-butanol produced polymers of the desired molecular weight ranges with low polydispersity indexes (PDI, <2) and without a significant drop in isolated yield.

Keywords:copper;chelating amine ligand;2,6-dimethylphenol;poly(2,6-dimethyl-1,4-phenylene ether)

[References]

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Endres GF, Hay AS, Eustance JW, J. Org. Chem., 28, 1300 (1963)
Hay AS, J. Polym. Sci. A: Polym. Chem., 36(4), 505 (1998)
Uyama H, Kobayashi S, Chemotechnology, 22 (1999)
Yee AF, Polym. Eng. Sci., 17, 213 (1977)
Wellinghoff ST, Baer E, J. Appl. Polym. Sci., 22, 2025 (1978)
Krijgsman J, Gaymans RJ, Polymer, 44(25), 7589 (2003)
Olabisi O, Obeson LM, Shaw MT, Polymer-Polymer Miscibility, Academic Press, New York, 1979, and references therein.
Baesjou PJ, Driessen WL, Challa G, Reedijk J, Macromolecules, 32(2), 270 (1999)
Gamez P, Gupta S, Reedijk J, C. R. Chim., 10, 295 (2007)
Kobayashi S, Higashimura H, Prog. Polym. Sci, 28, 1015 (2003)
Higashimura H, Kubota M, Oouchi K, Fukushima D, Tanaka K, Sumitomo Kagaku, 2, 1 (2008)
Chen W, Challa G, Eur. Polym. J., 26, 1211 (1990)
Aubel PG, Khokhar SS, Driessen WL, Challa G, Reedijk J, J. Mol. Catal. A-Chem., 175(1-2), 27 (2001)
Camus A, Garozzo MS, Marsich N, Mari M, J. Mol. Catal. A-Chem., 112, 353 (1996)
Chung YM, Ahn WS, Lim PK, J. Mol. Catal. A-Chem., 148, 117 (1999)
White DM, Klopfer HJ, J. Polym. Sci., 10, 1565 (1972)
Denk MK, Krause MJ, Niyogi DF, Gill NK, Tetrahedron, 59, 7565 (2003)
Roche SP, Teyssot ML, Gautier A, Tetrahedron Lett., 51, 1265 (2010)
Kliegman JM, Barnes RK, Tetrahedron, 26, 2555 (1970)
Ando A, Shioiri T, Tetrahedron, 45, 4969 (1989)
Hay AS, Macromolecules, 2, 107 (1969)
Viersen FJ, Challa G, Reedijk J, Polymer, 31, 1368 (1990)
Mobley DP, J. Polym. Sci., 22, 3203 (1984)
Chung YM, Ahn WS, Lim PK, Appl. Catal. A: Gen., 192(2), 165 (2000)
Cho HY, Han BH, Kim I, Paik HJ, Macromol. Res., 14(5), 539 (2006)
Guieu SJA, Lanfredi AMM, Massera C, Pachon LD, Gamez P, Reedijk J, Catal. Today, 96(4), 259 (2004)
Triethylamine itself was reported ineffective as well in the Cu(I)-TMEDA catalyzed polymerization due to its steric bulkiness. See ref. 2(a).
Finkbeiner H, Hay AS, Blanchard HS, Endres GF, J. Org. Chem., 31, 549 (1966)
Shibasaki Y, Nakamura M, Ishimaru R, Kondo JN, Ueda M, Chem. Lett., 34(5), 662 (2005)

[1] Hay AS, Blanchard HS, Endres GF, Eustance JW, J. Am. Chem. Soc., 81, 6335 (1959)

[2] Endres GF, Hay AS, Eustance JW, J. Org. Chem., 28, 1300 (1963)

[3] Hay AS, J. Polym. Sci. A: Polym. Chem., 36(4), 505 (1998)

[4] Uyama H, Kobayashi S, Chemotechnology, 22 (1999)

[5] Yee AF, Polym. Eng. Sci., 17, 213 (1977)

[6] Wellinghoff ST, Baer E, J. Appl. Polym. Sci., 22, 2025 (1978)

[7] Krijgsman J, Gaymans RJ, Polymer, 44(25), 7589 (2003)

[8] Olabisi O, Obeson LM, Shaw MT, Polymer-Polymer Miscibility, Academic Press, New York, 1979, and references therein.

[9] Baesjou PJ, Driessen WL, Challa G, Reedijk J, Macromolecules, 32(2), 270 (1999)

[10] Gamez P, Gupta S, Reedijk J, C. R. Chim., 10, 295 (2007)

[11] Kobayashi S, Higashimura H, Prog. Polym. Sci, 28, 1015 (2003)

[12] Higashimura H, Kubota M, Oouchi K, Fukushima D, Tanaka K, Sumitomo Kagaku, 2, 1 (2008)

[13] Chen W, Challa G, Eur. Polym. J., 26, 1211 (1990)

[14] Aubel PG, Khokhar SS, Driessen WL, Challa G, Reedijk J, J. Mol. Catal. A-Chem., 175(1-2), 27 (2001)

[15] Camus A, Garozzo MS, Marsich N, Mari M, J. Mol. Catal. A-Chem., 112, 353 (1996)

[16] Chung YM, Ahn WS, Lim PK, J. Mol. Catal. A-Chem., 148, 117 (1999)

[17] White DM, Klopfer HJ, J. Polym. Sci., 10, 1565 (1972)

[18] Denk MK, Krause MJ, Niyogi DF, Gill NK, Tetrahedron, 59, 7565 (2003)

[19] Roche SP, Teyssot ML, Gautier A, Tetrahedron Lett., 51, 1265 (2010)

[20] Kliegman JM, Barnes RK, Tetrahedron, 26, 2555 (1970)

[21] Ando A, Shioiri T, Tetrahedron, 45, 4969 (1989)

[22] Hay AS, Macromolecules, 2, 107 (1969)

[23] Viersen FJ, Challa G, Reedijk J, Polymer, 31, 1368 (1990)

[24] Mobley DP, J. Polym. Sci., 22, 3203 (1984)

[25] Chung YM, Ahn WS, Lim PK, Appl. Catal. A: Gen., 192(2), 165 (2000)

[26] Cho HY, Han BH, Kim I, Paik HJ, Macromol. Res., 14(5), 539 (2006)

[27] Guieu SJA, Lanfredi AMM, Massera C, Pachon LD, Gamez P, Reedijk J, Catal. Today, 96(4), 259 (2004)

[28] Triethylamine itself was reported ineffective as well in the Cu(I)-TMEDA catalyzed polymerization due to its steric bulkiness. See ref. 2(a).

[29] Finkbeiner H, Hay AS, Blanchard HS, Endres GF, J. Org. Chem., 31, 549 (1966)

[30] Shibasaki Y, Nakamura M, Ishimaru R, Kondo JN, Ueda M, Chem. Lett., 34(5), 662 (2005)