Synthesis of α-methylene-δ-valerolactone and its selective polymerization from a product mixture for concurrent separation and polymer production.

We report the continuous, gas-phase synthesis of α-methylene-δ-valerolactone (MVL) from δ-valerolactone (DVL) and formaldehyde (FA) over alkaline earth oxide catalysts. MgO, CaO, and BaO supported on silica (∼5 wt%) were active for MVL production (613 K, 0.4 kPa DVL, 1.

.

The design of facile synthetic routes to well-defined block copolymers (BCPs) from direct polymerization of one-pot comonomer mixtures, rather than traditional sequential additions, is both fundamentally and technologically important. Such synthetic methodologies often leverage relative monomer reactivity toward propagating species exclusively and therefore are rather limited in monomer scope and control over copolymer structure. The recently developed compounded sequence control (CSC) by Lewis pair polymerization (LPP) utilizes synergistically both thermodynamic () and kinetic () differentiation to precisely control BCP sequences and suppress tapering and misincorporation errors.

9-fluorenemethanol: an internal electron donor to fine tune olefin polymerization activity.

A new MgCl2 based molecular adduct has been synthesized with 9-fluorenemethanol (9FM) as a novel internal electron donor (IED), along with ethanol (EtOH) (MgCl2·n9FM·xEtOH). The above molecular adduct has been subjected to a variety of structural, spectroscopic and morphological characterization techniques. The results of the solid state (13)C CPMAS NMR technique suggests the coordination of 9FM to MgCl2.

Group IV complexes containing the benzotriazole phenoxide ligand as catalysts for the ring-opening polymerization of lactides, epoxides and as precatalysts for the polymerization of ethylene.

A series of Ti(IV), Zr(IV) and Hf(IV) benzotriazole phenoxide (BTP) complexes were synthesized and characterized by various spectroscopic techniques, elemental analysis and X-ray crystallography. The monosubstituted Zr(IV) BTP complexes [(μ-L)Zr(O(i)Pr)3]2 1-3 [L = (C1)BTP-H (1), (TCl)BTP-H (2), (pent)BTP-H (3)] and tetrasubstituted Zr(IV), Hf(IV) complexes ZrL4 4-6 [L = (C1)BTP-H (4), (TCl)BTP-H (5), (pent)BTP-H (6)] and HfL4 7-9 [L = (C1)BTP-H (7), (TCl)BTP-H (8), (pent)BTP-H (9)] were prepared by the reaction of Zr(O(i)Pr)4·((i)PrOH) and Hf(O(t)Bu)4 in toluene with the respective ligands in different stoichiometric proportions. The reaction between BTP and TiCl4 and ZrCl4 and HfCl4 in a 2 : 1 stoichiometric reaction resulted in the formation of disubstituted group IV chloride complexes L2MCl2 10-12 [L = (C1)BTP-H, M = Ti, Zr and Hf].