Highly active and cis-1,4 selective polymerization of 1,3-butadiene catalyzed by cobalt(II) complexes bearing α-diimine ligands

doi:10.1016/S1872-2067(12)60625-1

Abstract

Abstract: A series of cobalt(II) complexes bearing α-diimine ligands were synthesized and characterized by elemental and spectroscopic analysis. These complexes had the general formulas [ArN=C(Me)-(Me)C=NAr]CoCl₂ (Ar=C₆H₅, 3a; 4-MeC₆H₄, 3b; 4-MeOC₆H₄, 3c; 4-FC₆H₄, 3d; 4-ClC₆H₄, 3e; 2-MeC₆H₄, 3f; 2-EtC₆H₄, 3g; 2-ⁱPrC₆H₄, 3h; 2,4,6-Me₃C₆H₂, 3i; 2,6-Et₂C₆H₃, 3j; 2,6-ⁱPrC₆H₃, 3k). 2,6-Bis[(2,6-diisopropylphenylimino)ethyl]pyridine CoCl₂ (4a) was also synthesized for comparison. The structures of complexes 3i, 3k, and 4a were further analyzed by X-ray crystallography. When the Co(II) complexes were activated with ethylaluminum sesquichloride, they exhibited high catalytic activity for 1,3-butadiene polymerization. The polymers produced have high cis-1,4 stereoregularity (up to 98.0%) and high molecular weights (M_n=1×10⁴-1×10⁵). The substituent ligand affected both catalytic activity and stereoselectivity through an electronic effect while steric hindrance by the substituent was not important. The effects of the polymerization conditions, such as polymerization time, temperature, different alkylaluminum compounds used as cocatalyst, and [Al]/[Co] molar ratio, on polymerization behavior were investigated.

Key words: Cobalt, α-Diimine, 1,3-Butadiene, Polybutadiene, Polymerization

Xiangyu Jia, Heng Liu, Yanming Hu, Quanquan Dai, Jifu Bi, Chenxi Bai, Xuequan Zhang. Highly active and cis-1,4 selective polymerization of 1,3-butadiene catalyzed by cobalt(II) complexes bearing α-diimine ligands[J]. Chinese Journal of Catalysis, 2013, 34(8): 1560-1569.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(12)60625-1

https://www.cjcatal.com/EN/Y2013/V34/I8/1560

References

[1] Ricci G, Sommazzi A, Masi F, Ricci M, Boglia A, Leone G. Coord Chem Rev, 2010, 254: 661

[2] Shen Z Q. Inorg Chim Acta (沈之荃. 无机化学学报), 1987, 140: 7

[3] Friebe L, Nuyken O, Obrecht W. Adv Polym Sci, 2006, 204: 1

[4] Fischbach A, Anwander R. Adv Polym Sci, 2006, 204: 155

[5] Pan L, Zhang K Y, Nishiura M, Hou Z M. Angew Chem Int Ed, 2011, 50: 12012

[6] Du G X, Wei Y L, Ai L, Chen Y Y, Xu Q, Liu X A, Zhang S W, Hou Z M, Li X F. Organometallics, 2011, 30: 160

[7] Nishiura M, Hou Z M. Nat Chem, 2010, 2: 257

[8] Thiele S K H, Wilson D R. J Macromol Sci, Polym Rev, 2003, C43: 581

[9] Miyazawa A, Kase T, Hashimoto K, Choi J C, Sakakura T, Ji Z J. Macromolecules, 2004, 37: 8840

[10] Meppelder G J M, Fan H T, Spaniol T P, Okuda J. Inorg Chem, 2009, 48: 7378

[11] Qiao Y L, Zhu H, Wu Y X, Wang J, Xu R W, Wu G Y, Yang W T. Acta Polym Sin (乔雨露, 朱寒, 吴一弦, 王金, 徐日炜, 武冠英, 杨万泰. 高分子学报), 2010: 640

[12] Gong D R, Wang B L, Bai C X, Bi J F, Wang F, Dong W M, Zhang X Q, Jiang L S. Polymer, 2009, 50: 6259

[13] Appukuttan V, Zhang L, Ha C S, Kim I. Polymer, 2009, 50: 1150

[14] Gao W, Cui D M. J Am Chem Soc, 2008, 130: 4984

[15] Kaita S, Hou Z M, Wakatsuki Y. Macromolecules, 1999, 32: 9078

[16] Zhang L X, Suzuki T, Luo Y, Nishiura M, Hou Z M. Angew Chem Int Ed, 2007, 46: 1909

[17] Arndt S, Beckerle K, Zeimentz P M, Spaniol T P, Okuda J. Angew Chem Int Ed, 2005, 44: 7473

[18] Kaita S, Yamanaka M, Horiuchi A C, Wakatsuki Y. Macromolecules, 2006, 39: 1359

[19] Kaita S, Hou Z M, Wakatsuki Y. Macromolecules, 2001, 34: 1539

[20] Fischbach A, Meermann C, Eickerling G, Scherer W, Anwander R. Macromolecules, 2006, 39: 6811

[21] Evans W J, Giarikos D G, Ziller J W. Organometallics, 2001, 20: 5751

[22] Wang D, Li S H, Liu X L, Gao W, Cui D M. Organometallics, 2008, 27: 6531

[23] Colamarco E, Milione S, Cuomo C, Grassi A. Macromol Rapid Commun, 2004, 25: 450

[24] Nakayama Y, Baba Y, Yasuda H, Kawakita K, Ueyama N. Macromolecules, 2003, 36: 7953

[25] Cariou R, Chirinos J, Gibson V C, Jacobsen G, Tomov A K, Elsegood M R J. Macromolecules, 2009, 42: 1443

[26] Ricci G, Forni A, Boglia A, Sommazzi A, Masi F. J Organomet Chem, 2005, 690: 1845

[27] Ricci G, Forni A, Boglia A, Motta T, Zannoni G, Canetti M, Bertini F. Macromolecules, 2005, 38: 1064

[28] Ricci G, Forni A, Boglia A, Sonzogni M. Organometallics, 2004, 23: 3727

[29] Hu Y M, Dong W M, Jiang L S, Zhang X Q, Yu G, Cao L H. Chin J Catal (胡雁鸣, 董为民, 姜连升,张学全, 郭玉, 曹丽辉. 催化学报), 2004, 25: 664

[30] Gong D R, Dong W M, Hu Y M, Bi J F, Zhang X Q, Jiang L S. Polymer, 2009, 50: 5980

[31] Lu J, Hu Y M, Zhang X Q, Bi J F, Dong W M, Jiang L S, Huang B T. J Appl Polym Sci, 2006, 100: 4265

[32] Jang Y C, Kim P, Lee H. Macromolecules, 2002, 35: 1477

[33] Cai Z G, Shinzawa M, Nakayama Y, Shiono T. Macromolecules, 2009, 42: 7642

[34] Cariou R, Chirinos J J, Gibson V C, Jacobsen G, Tomov A K, Britovsek G J P, White A J P. Dalton Trans, 2010, 39: 9039

[35] Furukawa J. Pure Appl Chem, 1975, 42: 495

[36] Cooper W. Ind Eng Chem Prod Res Devel, 1970, 9: 457

[37] Smirnova L V, Yatsenko L A, Boldyrev A G, Panasyuk S L, Kropacheva Y N. Vysokomol Soedin A, 1991, 33: 1905

[38] Oehme A, Gebauer U, Gehrke K, Lechner M D. Angew Makromol Chem, 1996, 235: 121

[39] Nath D C D, Shiono T, Ikeda T. Macromol Chem Phys, 2002, 203: 1171

[40] Sharaev O K, Kostitsyna N N, Glebova N N, Bondarenko G N, Yakovlev V A. Polym Sci Ser B, 2006, 48: 274

[41] Nath D C D, Shiono T, Ikeda T. Macromol Chem Phys, 2003, 204: 2017

[42] Endo K, Kitagawa T, Nakatani K. J Polym Sci Part A, 2006, 44: 4088

[43] Chandran D, Kwak C H, Ha C S, Kim I. Catal Today, 2008, 131: 505

[44] Gong D R, Wang B L, Cai H G, Zhang X Q, Jiang L S. J Organomet Chem, 2011, 696: 1584

[45] Gong D R, Jia X Y, Wang B L, Zhang X Q, Jiang L S. J Organomet Chem, 2012, 702: 10

[46] Appukuttan V, Zhang L, Ha J Y, Chandran D, Bahuleyan B K, Ha C S, Kim I. J Mol Catal A, 2010, 325: 84

[47] Nobbs J D, Tomov A K, Cariou R, Gibson V C, White A J P, Britovsek G J P. Dalton Trans, 2012, 41: 5949

[48] Ai P F, Chen L, Guo Y T, Jie S Y, Li B G. J Organomet Chem, 2012, 705: 51

[49] Jie S Y, Ai P F, Li B G. Dalton Trans, 2011, 40: 10975

[50] Johnson L K, Killian C M, Brookhart M. J Am Chem Soc, 1995, 117: 6414

[51] Killian C M, Johnson L K, Brookhart M. Organometallics, 1997, 16: 2005

[52] Svejda S A, Brookhart M. Organometallics, 1999, 18: 65

[53] Elgert K F, Quack G, Stutzel B. Polymer, 1974, 15: 612

[54] Elgert K F, Quack G, Stutzel B. Polymer, 1975, 16: 154

[55] Chung C K, Grubbs R H. Org Lett, 2008, 10: 2693

[56] Dieck H T, Svoboda M, Greiser T. Z Naturforsch B, 1981, 36: 823

[57] Pesch J, Harms K, Bach T. Eur J Org Chem, 2004: 2025

[58] Quintanilla E, Di Lena F, Chen P. Chem Commun, 2006: 4309

[59] Quevedo-Sanchez B, Nimmons J F, Coughlin E B, Henson M A. Macromolecules, 2006, 39: 4306

[60] Porri L, Giarrusso A, Ricci G. Prog Polym Sci, 1991, 16: 405