A HIGH YIELDING, REPRODUCIBLE SYNTHESIS OF TRIMETHYLSILYLKETENE
ABSTRACT A two-step sequence for the preparation of trimethylsilylketene, from chloroacetaldehyde diethyl acetal via ethoxyacetylene, has been modified and optimized.
Polymerization of silyl ketenes using alkoxide initiators: a combined computational and experimental study
The atomic composition and chemical structure of polymers is fundamental to dictating properties and applications. While much work has addressed controlling pendant group functionalities and polymer molecular weight, much less work has focused on novel polymer backbone chemistries. Herein we report experimental and computational investigations of the polymerization of triisopropyl silyl (TIPS) ketene, and detail products formed. TIPS ketene reacts with an alkoxide initiator to give an enolate intermediate that propagates through either the carbon or oxygen atom, giving multiple functional groups in the resulting polymer backbone. This work indicates that silyl ketenes are suitable monomers for chain growth polymerizations, and that they can polymerize through both the CC and CO to prepare multiple polymer functionalities from a single monomer.
The role of early lithification in development of chalky porosity in calcitic micrites: Upper Cretaceous chalks, Egypt
Abstract Petrological and geochemical examination of Upper Cretaceous chalks from the Abu Roash area and Bahariya Oasis (Egypt) provide insights into factors which control porosity development in fine-grained calcitic carbonates. Petrological studies indicate that primary skeletal fabrics of coccoliths and foraminifera in micrites of Abu Roash are well preserved. In contrast, primary skeletal fabrics of the Bahariya Oasis chalks are pervasively altered. Geochemical analysis of these chalks reveals a striking contrast in composition. The high porosity chalks at Bahariya Oasis have depleted isotopic values ( δ 13 C = −5.0‰, δ 18 O = −8.9‰ PDB ) and low concentrations of trace elements (Sr and Na). In contrast, the low porosity chalks at Abu Roash are less depleted in terms of their isotopic values ( δ 13 C = 1.0‰, δ 18 O = −4.0‰ ) and possess elevated concentrations of Sr, Na, Fe and Zn. Importantly, fracture and collapse veins, present only at Abu Roash, are filled with calcite whose δ18O value is coincident with that of altered micrites at Bahariya Oasis. The lithic fragments cemented by this calcite, however, retain compositions identical to other lithified limestones at Abu Roash. Differences in fabric and chemistry of the pelagic marine micrites observed between Abu Roash and Bahariya Oasis reflect the degree of early lithification and compaction prior to exposure and meteoric diagenetic alteration associated with regional Late Cretaceous/pre-Eocene subaerial unconformity.