Addition Polymerization of 5-Ethylidene-2-norbornene by Cationic Palladium Cationic Complex and Subsequent Derivatization

Luhai Wang; Xiaoya Wang; Min Yang; Yige Wang; Li Li; Binyuan Liu; Il Kim

Macromolecular Research, Vol.19, No.10, 1071-1076, October, 2011

DOI10.1007/s13233-011-1011-9 Export Citation

Addition Polymerization of 5-Ethylidene-2-norbornene by Cationic Palladium Cationic Complex and Subsequent Derivatization

Luhai Wang^{1, 2}, Xiaoya Wang^{1, 3}, Min Yang^{1, 3}, Yige Wang^{1, 3}, Li Li^{1, 3}, Binyuan Liu^{1, 3, †}, and Il Kim^{4, †}

¹School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin, 300130, China, Korea
²DaQing Chemical Research Center, The Petrochemical Research Institute, Petrochina, Daqing, China
³, Korea
⁴The WCU Center for Synthetic Polymer Bioconjugate Hybrid Materials, Department of Polymer Science and Engineering, Pusan National University, Busan, 609-735, Korea

E-mail:,

Poly(5-ethylidene-2-norbornene) (PENB) was synthesized via a vinylic pathway using a cationic palladium-based catalyst, displaying high activity up to 1.06×106 g-PENB/mol Pd. The effects of the monomer to catalyst ratio, temperature, reaction time, and concentration on the polymerization were investigated systematically. The control tests and spectroscopic analyses of the PENB indicate that 5-ethylidene-2-norbornene is polymerized via an addition polymerization using endocyclic double bonds. The post-modification was also performed using a free radical graft polymerization. The resulting PENB copolymers were characterized by IR, 1H NMR, and GPC analyses.

Keywords:5-ethylidene-2-norbornene;palladium complex;addition polymerization;graft polymerization;transition metal chemistry.

[References]

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Muller K, Kreiling S, Dehnicke K, Allgaier J, Richter D, Fetters LJ, Jung Y, Yoon DY, Greiner A, Macromol. Chem. Phys., 207, 193 (2006)
Myagmarsuren G, Lee KS, Jeong OY, Ihm SK, Polymer, 46(11), 3685 (2005)
Myagmarsuren G, Jeong OY, Ihm SK, Appl. Catal. A: Gen., 296(1), 21 (2005)
Dorkenoo KD, Pfromm PH, Rezac ME, J. Polym. Sci. B: Polym. Phys., 36(5), 797 (1998)
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Sesca S, J. Polym. Sci., Macromol. Rev., 10, 1 (1975)
Kim I, React. Funct. Polym., 49(3), 197 (2001)
Marathe S, Sivaram S, Macromolecules, 27(5), 1083 (1994)
Endo K, Fujii K, Otsu T, Macromol. Chem. Phys., 197, 97 (1996)
Lasarov H, Pakkanen TT, Macromol. Rapid Commun., 22(6), 434 (2001)
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[3] Goodall BL, Benedikt GM, Mcintosh LH, Barnes DA, Rhodes LF, U. S. Patent, 5,468,819 (1995).

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[6] Myagmarsuren G, Lee KS, Jeong OY, Ihm SK, Polymer, 46(11), 3685 (2005)

[7] Myagmarsuren G, Jeong OY, Ihm SK, Appl. Catal. A: Gen., 296(1), 21 (2005)

[8] Dorkenoo KD, Pfromm PH, Rezac ME, J. Polym. Sci. B: Polym. Phys., 36(5), 797 (1998)

[9] Breunig S, Risse W, Makromol. Chem., 193, 2915 (1992)

[10] Reinmuth A, Mathew JP, Melia J, Risse W, Macromol. Rapid Commun., 17(3), 173 (1996)

[11] Mathew JP, Reinmuth A, Melia J, Swords N, Risse W, Macromolecules, 29(8), 2755 (1996)

[12] Heinz BS, Heitz W, Krugel SA, Raubacher F, Wendorff JH, Acta Polym., 48, 385 (1997)

[13] Okoroanyanwu U, Shimokawa T, Byers JD, Willson CG, J. Mol. Catal. A-Chem., 133, 93 (1998)

[14] Jung IG, Seo J, Chung YK, Shin DM, Chun SH, Son SU, J. Polym. Sci. A: Polym. Chem., 45(14), 3042 (2007)

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[18] Heitz W, Krugel SA, Madan R, Wendorff JH, Macromol. Chem. Phys., 200, 338 (1999)

[19] Liu BY, Yang L, Mathews AS, Wang Y, Yan WD, Abraham S, Ha CS, Park DW, Kim I, React. Funct. Polym., 68(12), 1619 (2008)

[20] Fujiwara T, Shinba Y, Sugimoto K, Mori Y, Tomikawa M, J. Photopolym Sci. Technol., 18, 289 (2005)

[21] Arrowsmith D, Kaminsky W, Schauwienold AM, Weingarten U, J. Mol. Catal. A-Chem., 160(1), 97 (2000)

[22] Bavarian N, Baird MC, Parent JS, Macromol. Chem. Phys., 202, 3248 (2001)

[23] Ver Strate G, Encycl. Polym. Sci., 6, 523 (1986)

[24] Sesca S, J. Polym. Sci., Macromol. Rev., 10, 1 (1975)

[25] Kim I, React. Funct. Polym., 49(3), 197 (2001)

[26] Marathe S, Sivaram S, Macromolecules, 27(5), 1083 (1994)

[27] Endo K, Fujii K, Otsu T, Macromol. Chem. Phys., 197, 97 (1996)

[28] Lasarov H, Pakkanen TT, Macromol. Rapid Commun., 22(6), 434 (2001)

[29] Zhao CT, Ribeiro MD, Portela MF, J. Mol. Catal. A-Chem., 185(1-2), 81 (2002)

[30] Janiak C, Lassahn PG, J. Mol. Catal. A-Chem., 166(2), 193 (2001)

[31] Li HC, Li JC, Zhang YT, Mu Y, Polymer, 49(12), 2839 (2008)

[32] Green M, Hancock RI, J. Chem. Soc. A, 2054 (1967)

[33] Mutch A, Leconte M, Lefebvre F, Basset JM, J. Mol. Catal. A-Chem., 133, 191 (1998)

[34] Pasquale A, Karro R, Allen RD, Long TE, Polym. Prepr., 41, 1931 (2001)