Abstract
In the present study, we have discussed the bulk ring opening polymerization (ROP) of rac-lactide (rac-LA) and ε-caprolactone (ε-CL) using Cd(OAc)2. Cd(OAc)2 appeared to be a good catalyst for the polymerization of rac-LA and ε-CL yielding high molecular weight (M n) polymers with narrow molecular weight distributions (MWDs). The catalytic activity of the system can be increased markedly upon using catalytic amount of BnOH as external alcoholic initiator. There is a first order dependence of the rate constant with respect to monomer concentrations as understood from the kinetic studies. The rate was found to be faster in the presence of BnOH. The polymerization process was controlled. The polymerization proceeded via the coordination-insertion mechanism without BnOH as well as activated monomer mechanism in the presence of BnOH. In the absence of BnOH, the acetyl group initiated the polymerization as understood from the 1H NMR and MALDI-TOF analysis. The benzyloxy group initiated the polymerization in the presence of BnOH. Moderate activity towards the polymerization of ethylene was observed using MAO as alkyl aluminum activator. The polymerization parameters towards the polymerization of ethylene were widely investigated.
Similar content being viewed by others
References
Luckachan GE, Pillai CKS (2011) J Polym Environ 19:637–676
Ahmed J, Varshney SK (2011) Int J Food Prop 14:37–58
Inkinen S, Hakkarainen M, Albertsson AC, Södergård A (2011) Biomacromolecules 12:523–532
Whitehorne TJJ, Schaper F (2013) Inorg Chem 52:13612–13622
Albertsson AC, Varma IK (2003) Biomacromolecules 4:1466–1486
Oh JK (2011) Soft Matter 7:5096–5108
Chen F, Hayami JWS, Amsden BG (2014) Biomacromolecules 15:1593–1601
Stanford MJ, Dove AP (2010) Chem Soc Rev 39:486–494
Zhong Z, Dijkstra PJ, Feijen J (2003) J Am Chem Soc 125:11291–11298
Tschan MJL, Brulé E, Haquette P, Thomas CM (2012) Polym Chem 3:836–851
Wu J, Yu TL, Chen CT, Lin CC (2006) Coord Chem Rev 250:602–626
Drumright RE, Gruber PR, Henton DE (2000) Adv Mater 12:1841–1846
Mandal M, Chakraborty D (2016) J Polym Sci A Polym Chem 54:809–824
Roymuhury SK, Chakraborty D, Ramkumar V (2015) Dalton Trans 44:10352–10367
Ghosh S, Chakraborty D, Ramkumar V (2015) J Polym Sci A Polym Chem 53:1474–1491
Ghosh S, Chakraborty D, Varghese B (2015) Eur Polym J 62:51–65
Al-Khafaji Y, Sun X, Prior TJ, Elsegood MRJ, Redshaw C (2015) Dalton Trans 44:12349–12356
Mandal M, Chakraborty D, Ramkumar V (2015) RSC Adv 5:28536–28553
Yu XF, Zhang C, Wang ZX (2013) Organometallics 32:3262–3268
Prasad AV, Stubbs LP, Ma Z, Yinghuai Z (2012) J Appl Polym Sci 123:1568–1575
Kamber NE, Jeong W, Waymouth RM, Pratt RC, Lohmeijer BGG, Hedrick JL (2007) Chem Rev 107:5813–5840
Dove AP, Pratt RC, Lohmeijer BGG, Waymouth RM, Hedrick JL (2005) J Am Chem Soc 127:13798–13799
Myers M, Connor EF, Glauser T, Möck A, Nyce G, Hedrick JL (2002) J Polym Sci A Polym Chem 40:844–851
Saha TK, Chakraborty D (2013) Polym Int 62:1507–1516
Tsai CY, Du HC, Chang JC, Huang BH, Ko BT, Lin CC (2014) RSC Adv 4:14527–14537
Saha TK, Mandal M, Thunga M, Ramkumar V, Chakraborty D (2013) Dalton Trans 42:10304–10314
Saha TK, Mandal M, Chakraborty D, Ramkumar V (2013) New J Chem 37:949–960
Saha TK, Ramkumar V, Chakraborty D (2011) Inorg Chem 50:2720–2722
Sánchez-Barba LF, Garcés A, Fernández-Baeza J, Otero A, Alonso-Moreno C, Lara-Sánchez A, Rodríguez AM (2011) Organometallics 30:2775–2789
Chakraborty D, Mandal M (2016) Indian Pat Appl IN 2014KO01271 A 20160610.
Gowda RR, Chakraborty D (2010) J Mol Catal A Chem 333:167–172
Gowda RR, Chakraborty D (2011) J Mol Catal A Chem 349:86–93
Ziegler K, Holzkamp E, Breil H, Martin H (1955) Angew Chem 67:541–547
Natta G, Pino P, Corradini P, Danusso F, Mantica E, Mazzanti G, Moraglio G (1955) J Am Chem Soc 77:1708–1710
Meknight AL, Waymouth RM (1998) Chem Rev 98:2587–2598
Coates GW, Waymouth RM (1995) Science 267:217–219
Hauptman E, Waymouth RM, Ziller JW (1995) J Am Chem Soc 117:11586–11587
Gibson VC, Redshaw C, Solan GA (2007) Chem Rev 107:1745–1776
Nomura K, Zhang S (2011) Chem Rev 111:2342–2362
Zhang W, Sun WH, Redshaw C (2013) Dalton Trans 42:8988–8997
Kawai K, Fujita T (2009) Top Organomet Chem 26:3–46
Makio H, Kashiwa N, Fujita T (2002) Adv Synth Catal 344:477–493
Matsui S, Mitani M, Saito J, Tohi Y, Makio H, Matsukawa N, Takagi Y, Tsuru K, Nitabaru M, Nakano T, Tanaka H, Kashiwa N, Fujita T (2001) J Am Chem Soc 123:6847–6856
Barakat I, Dubois P, Jérôme R, Teyssié P (1993) J Polym Sci A Polym Chem 31:505–514
Kricheldorf HR, Mang T, Jonte JM (1984) Macromolecules 17:2173–2181
Stevels WM, Ankone MJ, Dijkstra PJ, Feijen J (1996) Macromolecules 29:6132–6138
Chamberlain BM, Jazdzewski BA, Pink M, Hillmyer MA, Tolman WB (2000) Macromolecules 33:3970–3977
Wu JC, Yu TL, Chen CT, Lin CC (2006) Coord Chem Rev 250:602–626
Williams CK, Choi LE, Nam W, Young Jr VG, Hillmyer MA, Tolman WB (2003) J Am Chem Soc 125:11350–11359
O’Keefe BJ, Breyfogle LE, Hillmyer MA, Tolman WB (2002) J Am Chem Soc 124:4384–4393
Baśko M, Kubisa P (2006) J Polym Sci A Polym Chem 44:7071–7081
Kubisa P (2003) J Polym Sci A Polym Chem 41:457–468
Gowda RR, Chakraborty D (2009) J Mol Catal A Chem 301:84–92
Li D, Peng Y, Geng C, Liu K, Kong D (2013) Dalton Trans 42:11295–11303
Gendler S, Segal S, Goldberg I, Goldschmidt Z, Kol M (2006) Inorg Chem 45:4783–4790
Buffet JC, Wanna N, Arnold TAQ, Gibson EK, Wells PP, Wang Q, Tantirungrotechai J, O’Hare D (2015) Chem Mater 27:1495–1501
Li A, Ma H, Huang J (2013) Organometallics 32:7460–7469
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
ESM 1
(DOCX 1188 kb)
Rights and permissions
About this article
Cite this article
Mandal, M., Monkowius, U. & Chakraborty, D. Cadmium acetate as a ring opening polymerization catalyst for the polymerization of rac-lactide, ε-caprolactone and as a precatalyst for the polymerization of ethylene. J Polym Res 23, 220 (2016). https://doi.org/10.1007/s10965-016-1099-x
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s10965-016-1099-x