The ring‐opening polymerization of ε‐caprolactone (ε‐CL) and δ‐valerolactone (δ‐VL) using nine catalytic systems consisting of a combination of three C2v zirconocene complexes and three borate cocatalysts is discussed. The polymerizations proceed in a well‐controlled manner, producing polymers with relatively high molecular weights and narrow molecular weight distributions. Kinetic experiments of the polymerization of ε‐CL with the catalytic system Cp2ZrMe2/B(C6F5)3 (1) showed a linear dependence between polymerization yield and molecular weight with time, as well as between the molecular weight with the molar ratio of the monomer over the catalyst [ε‐CL]/[Zr], indicating sufficient control of the polymerization reaction. The catalytic system (1) was utilized for the synthesis of well‐defined block copolymers of MMA with ε‐CL and δ‐VL. All samples were characterized by size exclusion chromatography, nuclear magnetic resonance, and differential scanning calorimetry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3524–3537, 2007

Well-defined diblock copolymers {PS-b-P(ϵ-CL)} and triblock terpolymers {PS-b-PI-b-P(ϵ-CL), PI-b-PS-b-P(ϵ-CL)} of polystyrene, PS, poly(ϵ-caprolactone), P(ϵ-CL), and polyisoprene, PI, were synthesized using CpTiCl2(OP) (P = PS, PS-b-PI, or PI-b-PS) as macroinitiator. Graft copolymers having polybutadiene, PBd, backbone and poly(n-hexyl isocyanate), PHIC, or P(ϵ-CL) branches {PBd-g-PHIC and PBd-g-P(ϵ-CL)} as well as block−graft terpolymers {PS-b-(PI-g-PHIC), PS-b-[PI-g-P(ϵ-CL)]} were also synthesized by performing hydroboration/oxidation reactions on the polydiene backbone and by transforming the introduced hydroxyl groups to initiation sites by reaction with CpTiCl3. Finally, PS(PHIC)2 and PS[P(ϵ-CL)]2 3-miktoarm star copolymers were synthesized using a heterofunctional initiator bearing one initiation site for atom transfer radical polymerization and two for titanium-mediated coordination polymerization. All intermediates and final products were characterized by size exclusion chromatography, equipped with refractive index and light scattering detectors, membrane osmometry, and 1H NMR spectroscopy.

Well‐defined ω‐cholesteryl poly(n‐hexyl isocyanate) (PHIC–Chol), as well as diblock copolymers of n‐hexyl isocyanate (HIC) with styrene, PS‐b‐PHIC [PS = polystyrene; PHIC = poly(n‐hexyl isocyanate)], and triblock terpolymers with styrene and isoprene, PS‐b‐PI‐b‐PHIC and PI‐b‐PS‐b‐PHIC (PI = polyisoprene), were synthesized with CpTiCl2(OR) (R = cholesteryl group, PS, or PS‐b‐PI) complexes. The synthetic strategy involved the reaction of the precursor complex CpTiCl3 with cholesterol or the suitable ω‐hydroxy homopolymer or block copolymer, followed by the polymerization of HIC. The ω‐hydroxy polymers were prepared by the anionic polymerization of the corresponding monomers and the reaction of the living chains with ethylene oxide. The reaction sequence was monitored by size exclusion chromatography, and the final products were characterized by size exclusion chromatography (light scattering and refractive‐index detectors), nuclear magnetic resonance spectroscopy, and, in the case of PHIC–Chol, differential scanning calorimetry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6503–6514, 2005

The polymerization behavior of cyclohexyl methacrylate and trimethylsilyloxyethyl methacrylate with the catalytic system Cp2ZrMe2/B(C6F5)3/ZnEt2 was examined. Block copolymers of these bulky methacrylates with methyl methacrylate (MMA), having high molecular weights and relatively narrow molecular weight distributions, were prepared. n‐Butyl acrylate and tert‐butyl acrylate were polymerized with various catalytic systems based on zirconocene complexes. These polymerizations seemed to proceed to a nonquantitative yield, producing polymers with high molecular weights and relatively low polydispersities. This behavior indicated the presence of termination reactions in the initiation step, which appeared to be faster than the propagation step. Block copolymers of these acrylates with MMA were synthesized with the catalytic system rac‐Et(Ind)2ZrMe2/[B(C6F5)4]−[Me2NHPh]+/ZnEt2, starting from the polymerization of MMA. The block copolymers produced were well defined in most cases, as indicated by size exclusion chromatography, NMR, and differential scanning calorimetry measurements. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3337–3348, 2005

Statistical copolymers of methyl methacrylate with cyclohexyl and trimethylsilyloxy ethyl methacrylate were synthesized with two different catalytic systems based on the zirconocene complex Cp2ZrMe2. The reactivity ratios of methyl methacrylate and these methacrylates were calculated with the Finemann–Ross, inverted Finemann–Ross, and Kelen–Tüdos graphical methods. The structural parameters of these copolymers were estimated from the calculation of the dyad monomer sequence fractions. Two different borate cocatalysts were employed, and their effect on the copolymerization process is discussed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3305–3314, 2005