Abstract
Titanium complexes with dialkanolamine (1, 2) and salen ligands (3), as well as titanium alkoxide containing two fragments of an unsaturated alcohol (cis-but-2-ene-1,4-diol) asε-ligands (4), were studied in the anionic ring-opening bulk polymerization of ɛ-caprolactone (CL) at 80–130 °,C. All the catalysts involved initiate controlled polymerization and afford polyesters with a number-average molecular weight up to Mn = 20 000 g mol−1, which can be regulated by adjusting the [monomer]: [catalyst] ratio. Among the catalysts studied, complex 2 is most efficient in CL polymerization and affords polyesters with the narrowest molecular weight distribution (Mw/Mn < 1.2). In addition, complex 2 initiates the controlled polymerization of d,l-lactide (LA) and is effective in the synthesis of random and block copolymers of CL and LA.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
A. P. Gupta, V. Kumar, Eur. Polym. J., 2007, 43, 4053.
S. Penczek, M. Cypryk, A. Duda, P. Kubisa, S. Siomkowski, Prog. Polym. Sci., 2007, 32, 247.
A. C. Albertsson, I. K. Varma, Biomacromolecules, 2003, 4, 1466.
D. Mecerreyes, R. Jerome, P. Dubois, Adv. Polym. Sci., 1999, 147, 1.
M. A. Woodruff, D. W. Hutmacher, Prog. Polym. Sci., 2010, 35, 1217.
J.-M. Raquez, Y. Habibi, M. Murariu, P. Dubois, Prog. Polym. Sci., 2013, 38, 1504.
O. E. Teebken, A. Haverich, Eur. J. Vasc., Endovasc. Surg., 2002, 23, 475.
M. S. Kim, K. S. Seo, G. Khang, S. H. Cho, H. B. Lee, J. Biomed. Mater. Res., 2004, 70A, 154.
L. S. Nair, C. T. Laurencin, Prog. Polym. Sci., 2007, 32, 762.
P. Olsen, T. Borke, K. Odelius, A.-C. Albertsson, Biomacromolecules, 2013, 14, 2883.
O. Dechy-Cabaret, B. Martin-Vaca, D. Bourissou, Chem. Rev., 2004, 104, 6147.
R. A. Gross, B. Kalra, Science, 2002, 297, 803.
R. E. Drumright, P. R. Gruber, D. E. Henton, Adv. Mater., 2002, 12, 1841.
D. J. Darensbourg, O. Karroonnirun, Macromolecules, 2010, 43, 8880.
D. W. Grijpma, G. J. Zondervan, A. J. Pennings, Polym. Bull., 1991, 25, 327.
J.-L. Wang, J.-L. Dong, Macromol. Chem. Phys., 2006, 207, 554.
Y. Baimark, R. Molloy, Polym. Adv. Technol., 2005, 16, 332.
P. Li, A. Zerroukhi, J. Chen, Y. Chalamet, T. Jeanmaire, Z. Xia, J. Polym. Sci., Part A: Polym. Chem., 2008, 46, 7773.
P. Li, A. Zerroukhi, J. Chen, Y. Chalamet, T. Jeanmaire, Z. Xia, Polymer, 2009, 50, 1109.
J.-B. Fan, F. Long, M. P. Aldred, Y.-J. Li, Z.-W. Liang, M.-Q. Zhu, Macromol. Chem. Phys., 2012, 213, 1499.
J. Chen, L. L. Gorczynski, C. L. Fraser, Macromol. Chem. Phys., 2010, 211, 1272.
H. R. Kricheldorf, H. Hachmann-Thiessen, Macromol. Chem. Phys., 2005, 206, 758.
A. S. Karikari, W. F. Edwards, J. B. Mecham, T. E. Long, Biomacromolecules, 2005, 6, 2866.
N. Ding, B. Shentu, P. Pan, G. Shan, Y. Bao, Z. Weng, Ind. Eng. Chem. Res., 2013, 52, 12897.
W. Yuan, J. Yuan, F. Zhang, X. Xie, Biomacromolecules, 2007, 8, 1101.
S. Theiler, M. Teske, H. Keul, K. Sternbergand, M. Möller, Polym. Chem., 2010, 1, 1215.
A. Kowalski, A. Duda, S. Penczek, Macromol. Rapid Commun., 1998, 19, 567.
R. F. Storey, J. W. Sherman, Macromolecules, 2002, 35, 1504.
H. R. Kricheldorf, I. Kreiser-Saunders, A. Stricker, Macromolecules, 2000, 33, 702.
G. Deshayes, F. A. G. Mercier, P. Degée, I. Verbruggen, M. Biesemans, R. Willem, P. Dubois, Chem. Eur. J., 2003, 9, 4346.
A. Kowalski, J. Libiszowski, A. Duda, S. Penczek, Macromolecules, 2000, 33, 1964.
W. Yao, Y. Mu, A. Gao, Q. Su, Y. Liu, Y. Zhang, Polymer, 2008, 49, 2486.
D. Pappalardo, L. Annunziata, C. Pellecchia, Macromolecules, 2009, 42, 6056.
T. M. Ovitt, G. W. Coates, J. Am. Chem. Soc., 1999, 121, 4072.
T. M. Ovitt, G. W. Coates, J. Polym. Sci., Part A: Polym. Chem., 2000, 38, 4686.
A. Pilone, K. Press, I. Goldberg, M. Kol, M. Mazzeo, M. Lamberti, J. Am. Chem. Soc., 2014, 136, 1940.
N. Nomura, A. Akita, R. Ishii, M. Mizuno, J. Am. Chem. Soc., 2010, 132, 1750.
K. V. Zaitsev, Yu. A. Piskun, Y. F. Oprunenko, S. S. Karlov, G. S. Zaitseva, I. V. Vasilenko, A. V. Churakov, S. V. Kostjuk, J. Polym. Sci., Part A: Polym. Chem., 2014, 52, 1237.
H. R. Kricheldorf, Chem. Rev., 2009, 109, 5579.
J. Kasperczyk, M. Bero, Polymer, 2000, 41, 391.
F. Drouin, P. O. Oguadinma, T. J. Whitehorne, R. E. Prud’homme, F. Schaper, Organometallics, 2010, 29, 2139.
H.-Y. Chen, H.-Y. Tang, C.-C. Lin, Macromolecules, 2006, 39, 3745.
Y. Huang, W.-Ch. Hung, M.-Y. Liao, T.-E. Tsai, Y.-L. Peng, Ch.-Ch. Lin, J. Polym. Sci., Part A: Polym. Chem., 2009, 47, 2318.
M. Oshimura, A. Takasu, Macromolecules, 2010, 43, 2283.
C. Miola-Delaite, T. Hamaide, R. Spitz, Macromol. Chem. Phys., 1999, 200, 1771.
V. Simic, N. Spassky, L. G. Hubert-Pfalzgraf, Macromolecules, 1997, 30, 7338.
A. Amgoune, C. M. Tomas, J.-F. Carpentier, Macromol. Rapid Commun., 2007, 28, 693.
Y. Kim, J. G. Verkade, Macromol. Symp., 2005, 224, 105.
Y. Kim, J. G. Verkade, Macromol. Rapid Commun., 2002, 23, 917.
D. Takeuchi, T. Nokamura, T. Aida, Macromolecules, 2000, 33, 4608.
A. D. Asandei, G. Saha, Macromol. Rapid Commun., 2005, 26, 626.
S. Park, Y. S. Chi, I. S. Choi, J. Polym. Sci., Part A: Polym. Chem., 2006, 44, 3711.
F. Gornshtein, M. Kapon, M. Botoshansky, M. S. Eisen, Organometallics, 2007, 26, 497.
P. S. Umare, G. L. Tembe, K. V. Rao, U. S. Satpathy, B. Trivedi, J. Mol. Catal. A: Chem., 2007, 268, 235.
D. Takeuchi, T. Nokamura, T. Aida, Macromolecules, 2000, 33, 725.
Y. Kim, J. G. Verkade, Organometallics, 2002, 21, 2395.
D. Dakshinamoorthy, F. Peruch, J. Polym. Sci., Part A: Polym. Chem., 2011, 49, 5176.
K. V. Zaitsev, S. S. Karlov, A. A. Selina, Yu. F. Oprunenko, A. V. Churakov, B. Neumüller, J. A. K. Howard, G. S. Zaitseva, Eur. J. Inorg. Chem., 2006, 10, 1987.
I. V. Vasilenko, S. V. Kostjuk, K. V. Zaitsev, P. M. Nedorezova, D. A. Lemenovskii, S. S. Karlov, Polym. Sci., Ser. B (Engl. Transl.), 2010, 52, 136 [Vysokomol. Soedin., Ser. B, 2010, 52, 506].
K. V. Zaitsev, A. O. Kudlaev, S. S. Karlov, A. V. Churakov, S. V. Kostjuk, G. S. Zaitseva, Tezisy dokladov XXV Mezhdunarodnoi Chugaevskoi konferentsii po koordinatsionnoi khimii [Abstrs, XXV Chugaev Int. Conf. on Coordination Chemistry] (June 6–11, 2011, Suzdal), Institute of Solution Chemistry of the Russian Academy of Sciences, Suzdal, 2011, p. 389 (in Russian).
K. V. Zaitsev, M. V. Bermeshev, A. A. Samsonov, Y. F. Oprunenko, A. V. Churakov, J. A. K. Howard, S. S. Karlov, G. S. Zaitseva, New J. Chem., 2008, 32, 1415.
H. Chen, P. S. White, M. R. Gagne, Organometallics, 1998, 17, 5358.
A. Tsubery, E. Y. Tshuva, Inorg. Chem., 2012, 51, 1796.
E. F. DiMauro, A. Mamai, M. C. Kozlowski, Organometallics, 2003, 22, 850.
K. V. Zaitsev, S. S. Karlov, G. S. Zaitseva, E. Kh. Lermontova, A. V. Churakov, Acta Crystallogr., Sect. E: Struct. Rep. Online, 2013, 69, 626.
Y. A. Piskun, I. V. Vasilenko, S. V. Kostjuk, K. V. Zaitsev, G. S. Zaitseva, S. S. Karlov, J. Polym. Sci., Part A: Polym. Chem., 2010, 48, 1230.
D. Dakshinamoorthy, F. Peruch, J. Polym. Sci., Part A: Polym. Chem., 2012, 50, 2161.
W. Lin, G.-L. Dou, M.-H. Hu, C.-P. Cao, Z.-B. Huang, D.-Q. Shi, Org. Lett., 2013, 15, 1238.
Author information
Authors and Affiliations
Corresponding author
Additional information
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 0181–0188, January, 2015.
Rights and permissions
About this article
Cite this article
Piskun, Y.A., Vasilenko, I.V., Zaitsev, K.V. et al. Controlled homoand copolymerization of ε-caprolactone and d,l-lactide in the presence of TiIV complexes. Russ Chem Bull 64, 181–188 (2015). https://doi.org/10.1007/s11172-015-0840-7
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11172-015-0840-7