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High molecular weight poly(e-caprolactone)s (PCL) were synthesized via zwitterionic polymerization of e-caprolactone initiated with N-heterocyclic carbenes. Ring-opening polymerization of e-caprolactone (1 M) with carbenes 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (1) or 1,3,4,5-tetramethylimidazol-2-ylidene (3) affords cyclic PCL with molecular weights up to Mn = 114 000 g/mol. Crystallization of the cyclic PCL was investigated by synchrotron small-angle X-ray scattering experiments and differential scanning calorimetry. High molecular weight cyclic poly(e-caprolactone) crystallizes with a similar lamellar thickness and long period spacing as linear poly(e-caprolactone), but the crystallization of cyclic poly(e-caprolactone) is faster than that of linear poly(e-caprolactone) for molecular weights greater than 75 000 g/mol. These results imply that the polymer topology does not have a significant influence on the crystal structure or morphology but can have a significant influence on the rate of crys...

The zwitterionic ring-opening polymerization of lactide initiated by N-heterocyclic carbenes generates cyclic polylactides with well-defined molecular weights between M(n) = 5000 and 30,000 g/mol with narrow polydispersities (M(w)/M(n) < or = 1.31). These zwitterionic polymerizations are extremely rapid (k(p) = 48.7 M(-1) s(-1)), but also exhibit exceptional control of molecular weight and molecular weight distribution. The unusual kinetic features of these zwitterionic polymerizations are illuminated with kinetic and mechanistic investigations, which implicate a mechanism that involves a slow initiation step (second order in [M]), a propagation step (first order in [M]) that is much faster than initiation (k(i) = 0.274 M(-2) s(-1)), cyclization (k(c) = 0.0575 s(-1)), and depropagation (k(d) = 0.208 s(-1)). Numerical and stochastic simulations of the kinetic data provide a kinetic rationale for the evolution of molecular weight with monomer conversion: the molecular weights increase with increasing monomer conversion, exhibit a nonzero intercept near 0% monomer conversion, and are relatively insensitive to the initial monomer-to-initiator ratio. The observed narrow molecular weight distributions are due to a high rate of propagation relative to cyclization and chain transfer. Kinetic simulations define the kinetic criteria under which the active zwitterions remain in solution; these simulations were substantiated by chain-extension experiments, which provide experimental evidence for chain extension of the zwitterions and reinitiation by the N-heterocyclic carbenes liberated upon macrocyclization. The kinetic model rationalizes some of the unique features of zwitterionic ring-opening polymerization and provides a useful mechanistic framework to optimize these polymerizations as a strategy to generate well-defined cyclic polyesters.

We report the synthesis of poly(e-caprolactone) utilizing N-heterocyclic carbene (NHC) organocatalysts. Sterically unencumbered NHCs were found to be highly effective for the living ring-opening polymerization of e-caprolactone under mild conditions. The NHCs were able to produce poly(e-caprolactone)s with controlled molecular weights, low polydispersities, and well-defined end groups derived from the alcohol initiator. Star-shaped poly(e-caprolactone)s with three and four arms were prepared using NHC organocatalysts and characterized by 1H NMR and GPC.

A systematic investigation of the microstructure of ethylene copolymers has been carried out as a function of the comonomer type and content, employing small-angle X-ray scattering (SAXS) experiments to study the lamellar structure, and solid-state NMR to study the local conformational freedom. The SAXS results clearly show that the major consequence of incorporating commonomers (butene and octene) is the absence of lamellar thickening during the crystallization. From solid-state NMR study, applying the rotor-encoded rotational echo double resonance technique (REREDOR), it is found that the extent of the orientational order in the noncrystalline region of semicrystalline polyethylene is substantial but this order is not significantly affected by the incorporation of comonomer units. Therefore, the major cause for the significant improvements of mechanical properties observed for ethylene copolymers is not a change in the thermodynamic state of the noncrystalline region, but most likely a significant change in the intermolecular topological structure due to the blocking of disentanglement processes required by the lamellar thickening step during crystallization.

We previously reported on a rheological study of Langmuir films of poly(tert-butyl methacrylate) (PtBMA), and this work describes further studies on this system. Here, surface pressure-area (Pi-A) isotherms and interfacial shear rheology experiments are performed to better understand the effects of two modifications: varying the temperature between 5 and 40 degrees C and introducing small amounts of carboxylic acid groups by partially hydrolyzing the polymer. Increased temperature produced isotherms with lower plateau surface pressures, Pip, and Pi values shifted to lower areas above Pip. Film properties transition from being primarily viscous to being dominated by elasticity as Pip is crossed for all temperatures studied, even as the value of Pip changes. Increasing the hydrolysis fraction leads to isotherms shifted to lower areas throughout the curve and higher Pip values. Both temperature variation and chemical modification are believed to affect the relative importance of polymer-polymer and polymer-subphase interactions.

We report spirocyclic imidazolidines derived from N-heterocyclic carbenes and β-lactones. These spirocycles are initiators for the zwitterionic ring-expansion polymerization of β-lactones to generate cyclic polyesters of well-defined molecular weight. The zwitterionic strategy based on the equilibrium between the zwitterionic intermediates and spiro macrocyclics enables the controlled synthesis of cyclic poly(β-lactone)s