Article
  • Ring-opening Polymerization of Lactides Catalyzed by (Benzoimidazolylmethyl)amine Zinc(II) Complexes: Kinetics, Mechanism and Polymer Tacticity Studies
  • Attandoh NW, Ojwach SO
  • (Benzoimidazolylmethyl)amine Zinc(II) 착화합물에 의해 촉매화된 락타이드의 개환 중합: 반응속도, 메커니즘, 그리고 고분자 입체규칙성 연구
Abstract
Zinc(II) complexes of (benzoimidazolyl)amine ligands, N-(1H-benzoimidazol-2-ylmethyl)aniline (L1) and N-(1H-benzoimidazol-2-ylmethyl)-2-bromoaniline (L2), [Zn2(L1)2(OBz)4] (1), [Zn2(L2)2(OBz)4] (2) and [Zn(L1)2(OAc)2] (3) have been employed in the ring-opening polymerization of lactides. The complexes were found to form active catalysts in the polymerization of the D,L-lactide (D,L-LA) and L-lactide (L-LA) monomers. The polymerization kinetics proceeded via pseudo-first order mechanism with respect to the monomer. Low molecular weight polymers were obtained with relatively narrow molecular weight distribution of 1.30-1.50. The ligand architecture, the nature of the carboxylate anion and solvent system influenced the rate of lactide polymerization reactions. Polymerization reactions performed in methanol exhibited higher rates of reaction than those in toluene. The activation parameters measured for lactide polymerization using 3 were obtained as ΔH°=38.4±0.7 kJmol-1, ΔS°=-167.2±1.8 JK-1mol-1 and are consistent with a highly ordered transition state. The polymers produced were mainly atactic and isotactic.

Keywords: ring-opening polymerization; lactides; kinetics; tacticity

References
  • 1. Ju J, Chang JH, Polym. Korea, 38, 639 (2014)
  •  
  • 2. Tian H, Tang Z, Zhuang X, Chen X, Jing X, Prog. Polym. Sci, 37, 237 (2012)
  •  
  • 3. Sun H, Wang X, Zhang L, Polym. Korea, 38(4), 464 (2014)
  •  
  • 4. Albertsson AC, Varma IK, Biomacromolecules, 4(6), 1466 (2003)
  •  
  • 5. Yim JH, Kim DH, Ko YS, Polym. Korea, 39(3), 365 (2015)
  •  
  • 6. Chamberlain BM, Cheng M, Moore DR, Ovitt TM, Lobkovsky EB, Coates GW, J. Am. Chem. Soc., 123(14), 3229 (2001)
  •  
  • 7. Wu J, Pan X, Tang N, Lin CC, Eur. Polym. J., 43, 5040 (2007)
  •  
  • 8. Wu J, Yu TL, Chen CT, Lin CC, Coord. Chem. Rev., 250, 602 (2006)
  •  
  • 9. O’Keefe BJ, Hillmyer MA, Tolman WB, J. Chem. Soc.-Dalton Trans., 2215 (2001)
  •  
  • 10. Labet M, Thielemans W, Chem. Soc. Rev., 38, 3484 (2009)
  •  
  • 11. Aubrecht KB, Hillmyer MA, Tolman WB, Macromolecules, 35(3), 644 (2002)
  •  
  • 12. Dove AP, Gibson VC, Marshall EL, Rzepa HS, White AJP, Williams DJ, J. Am. Chem. Soc., 128(30), 9834 (2006)
  •  
  • 13. Yao W, Mu Y, Gao AH, Su Q, Liu YJ, Zhang YY, Polymer, 49(10), 2486 (2008)
  •  
  • 14. Liu YC, Ko BT, Lin CC, Macromolecules, 34(18), 6196 (2001)
  •  
  • 15. Davidson MG, Jones MD, Lunn MD, Mahon MF, Inorg. Chem., 45(5), 2282 (2006)
  •  
  • 16. Kim SH, Kim DJ, Go MJ, Ko YS, Lee J, Kim Y, J. Chem. Soc.-Dalton Trans., 41, 11619 (2012)
  •  
  • 17. Chmura AJ, Davidson MG, Jones MD, Lunn MD, Mahon MF, Johnson AF, Khunkamchoo P, Roberts SL, Wong SSF, Macromolecules, 39(21), 7250 (2006)
  •  
  • 18. Ning Y, Zhang Y, Rodriguez-Delgado A, Chen YX, Organometallics, 27, 5632 (2008)
  •  
  • 19. Gorczynski JL, Chen JB, Fraser CL, J. Am. Chem. Soc., 127(43), 14956 (2005)
  •  
  • 20. O'Keefe BJ, Breyfogle LE, Hillmyer MA, Tolman WB, J. Am. Chem. Soc., 124(16), 4384 (2002)
  •  
  • 21. Chen CT, Chan CY, Huang CA, Chen MT, Peng KF, J. Chem. Soc.-Dalton Trans., 4073 (2007)
  •  
  • 22. Gao AH, Yao W, Mu Y, Gao W, Sun MT, Su Q, Polyhedron, 28, 2605 (2009)
  •  
  • 23. Bunge SD, Lance JM, Bertke JA, Organometallics, 26, 6320 (2007)
  •  
  • 24. Lian B, Thomas CM, Casagrande OL, Lehmann CW, Roisnel T, Carpentier JF, Inorg. Chem., 46(1), 328 (2007)
  •  
  • 25. John A, Katiyar V, Pang K, Shaikh MM, Nanacati H, Hemant G, Ghosh P, Polyhedron, 26, 4033 (2007)
  •  
  • 26. Whitehorne TJJ, Schaper F, Chem. Commun., 48, 10334 (2012)
  •  
  • 27. Mazzeo M, Tramontano R, Lamberti M, Pilone A, Milione S, Pellecchia C, J. Chem. Soc.-Dalton Trans., 42, 9338 (2013)
  •  
  • 28. Agarwal S, Karl M, Dehnicke K, Seybert G, Massa W, Greiner A, J. Appl. Polym. Sci., 73(9), 1669 (1999)
  •  
  • 29. Zhang JJ, Jian CL, Gao Y, Wang L, Tang N, Wu JC, Inorg. Chem., 51(24), 13380 (2012)
  •  
  • 30. Chang YN, Liang LC, Inorg. Chim. Acta., 360, 136 (2007)
  •  
  • 31. Rong GZ, Deng MX, Deng C, Tang ZH, Piao LH, Chen XS, Jing XB, Biomacromolecules, 4(6), 1800 (2003)
  •  
  • 32. Ejfler J, Kobylka M, Jerzykiewicz LB, Sobota P, J. Chem. Soc.-Dalton Trans., 2047 (2005)
  •  
  • 33. Ojwach SO, Okemwa TT, Attandoh NW, Omondi B, J. Chem. Soc.-Dalton Trans., 42, 10735 (2013)
  •  
  • 34. Attandoh NW, Ojwach SO, Munro OQ, Eur. J. Inorg. Chem., 19, 3053 (2014)
  •  
  • 35. Darensbourg DJ, Karroonnirun O, Macromolecules, 43(21), 8880 (2010)
  •  
  • 36. Hormnirun P, Marshall EL, Gibson VC, Pugh RI, White AJP, Proc. Natl. Acad. Sci. U. S. A., 103, 15343 (2006)
  •  
  • 37. Williams CK, Brooks NR, Hillmyer MA, Tolman WB, Chem. Commun., 2132 (2002)
  •  
  • 38. Sung CY, Li CY, Su JK, Chen TY, Lin CH, Ko BT, J. Chem. Soc.-Dalton Trans., 41, 953 (2012)
  •  
  • 39. Wang L, Ma H, J. Chem. Soc.-Dalton Trans., 39, 7897 (2010)
  •  
  • 40. Sarazin Y, Liu B, Roisnel T, Maron L, Carpentier JF, J. Am. Chem. Soc., 133(23), 9069 (2011)
  •  
  • 41. Chisholm MH, Eilerts NW, Huffman JC, Iyer SS, Pacold M, Phomphrai K, J. Am. Chem. Soc., 122(48), 11845 (2000)
  •  
  • 42. Huang Y, Wang W, Lin CC, Blake MP, Clark L, Schwarz AD, Mountford P, J. Chem. Soc.-Dalton Trans., 42, 9313 (2013)
  •  
  • 43. Williams CK, Breyfogle LE, Choi SK, Nam W, Young VG, Hillmyer MA, Tolman WB, J. Am. Chem. Soc., 125(37), 11350 (2003)
  •  
  • 44. Martello MT, Burns A, Hillmyer M, ACS Macro Lett., 1, 131 (2012)
  •  
  • 45. Chisholm MH, Delbridge EE, New J. Chem., 27, 1177 (2003)
  •  
  • 46. Chisholm MH, Gallucci JC, Krempner C, Polyhedron, 26, 4436 (2007)
  •  
  • 47. Dubois P, Ropson N, Jerome R, Teyssie P, Macromolecules, 29(6), 1965 (1996)
  •  
  • 48. Song S, Ma H, Yang Y, J. Chem. Soc.-Dalton Trans., 42, 14200 (2013)
  •  
  • 49. Stanford MJ, Dove AP, Chem. Soc. Rev., 39, 486 (2010)
  •  
  • 50. Ajellal N, Carpentier JF, Guillaume C, Guillaume SM, Helou M, Poirier V, Sarazin Y, Trifonov A, J. Chem. Soc.-Dalton Trans., 39, 8363 (2010)
  •  
  • 51. Pilone A, Lamberti M, Mazzeo M, Milione S, Pellecchia C, J. Chem. Soc.-Dalton Trans., 42, 13036 (2013)
  •  
  • 52. Bourissou D, Martin-Vaca B, Dumitrescu A, Graullier M, Lacombe F, Macromolecules, 38(24), 9993 (2005)
  •  
  • 53. Jiang W, Huang W, Cheng N, Qi YB, Zong XP, Li H, Zhang QX, Polymer, 53(24), 5476 (2012)
  •  
  • 54. Dove AP, Li H, Pratt RC, Lohmeijer BGG, Culkin DA, Waymouth RM, Hedrick JL, Chem. Commun., 2881 (2006)
  •  
  • 55. Chisholm MH, Iyer SS, Matison ME, McCollum DG, Pagel M, Chem. Commun., 1999 (1997)
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2022 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 2016; 40(3): 347-354

    Published online May 25, 2016

  • 10.7317/pk.2016.40.3.347
  • Received on Sep 8, 2015
  • Accepted on Jan 23, 2016