Polymerization cyclic esters

Kowalski A, Duda A, Penczek S (1998) Kinetics and mechanism of cyclic esters polymerization initiated with tin(II) octoate, 1 Polymerization of e-caprolactone. Macromol Rapid Commun 19 567-572... 

Trollsas M, Lowenhiehn P, Lee VY, Mbller M, Miller RD, Hedrick JL (1999) New approach to hyperbranched polyesters self-condensing cyclic ester polymerization of bis (hydroxymethyl)-substituted e-caprolactone. Macromolecules 32 9062-9066... 

Tin(II) 2-ethylhexanoate is an important industrial initiator for cyclic ester polymerization [Duda and Penczek, 2001 Kricheldorf et al., 2001 Storey and Sherman, 2002]. Metal car-boxylates are useful initiators only in the presence of alcohols. The polymerization rate is very slow in the absence of alcohol, less than 1% of the rate in the presence of alcohol. The actual initiator is the metal alkoxide formed by the reaction between metal carboxylate and alcohol. 

Duda A Penczek S (2001) Thermodynamics, kinetics, and mechanisms of cyclic esters polymerization. In Polymers from renewable resources, vol 764. American Chemical Society, pp 160-198... 

Kowalski, A., Duda, A., Penczek, S. Mechanism of cyclic ester polymerization initiated with Tin(ll) octoate, 2. Macromolecules fitted with Tin(II) alkoxide species observed directly in MALDI-TOF spectra. Macromolecules. 2000, 33, 689-695. 

Niederberger M., Bard M.H., Stucky G.D. Benzyl alcohol and transition metal chlorides as a versatile reaction system for the nonaqueous and low-temperature synthesis of crystalline nano-objects with controlled dimensionality. J. Am. Chem. Soc. 2002 124 13642 O Keefe B.J., Breyfogle L.E., Hillmyer M.A., Tohnan W.B. Mechanistic comparison of cyclic ester polymerizations by novel iron(III)-alkoxide complexes Single vs multiple site catalysis. J. Am. Chem. Soc. 2002 124 4384... 

Ring-Chain Equilibria in Cyclic Ester Polymerizations 43... 

Mechanisms of ionic and coordination processes of aliphatic cyclic esters polymerizations have heen reviewed systematically since the late 1960s (see, e.g.. References 109-116), also including chapters in the first edition of the Comprehensive Polymer Science This chapter is based on the previous reviews coauthored hy the present author however, it is supplemented by additional and more recent data (until the beginning of 2011). 

Kowalski, A., Duda, A., and Penczek, S., 2000, Kinetics and Mechanism of Cyclic Esters Polymerization Initiated with Tin(II) Octoate. 3. Polymerization of L,L-Dilactide. Macromolecules 33 7359-7370. 

Keywords Aluminum Cyclic esters Polymerization Ziegler-Natta catalysts... 

Scheme 1.4 Mechanism of cyclic esters polymerization initiated by Sn(ll) octoate.

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