We report the synthesis of polymethylene waxes, a surrogate
of
PE waxes, by a controlled polymerization reaction in water at or near
r.t. and under atmospheric pressure. The monomer, dimethylsulfoxonium
methylide, is generated in situ from a salt, trimethylsulfoxonium
halide. The carbon sources for the polymerizations are C1 molecules,
which can be derived from nonpetroleum feedstock. DMSO serves as the
C1 carrier and is not consumed. The reaction is initiated and catalyzed
by trialkylboranes, compounds that are stable in water. A certain
degree of molecular weight control is achieved by adjusting the stoichiometry
of “salt” to organoborane. Polymethylene, the simplest
hydrocarbon polymer, is a semicrystalline material. The room temperature
polymerization produces a linear polymer approximately 100 °C
below its melting temperature (T
m). The
supercooled polymers rapidly crystallize into flat nanoparticles comprised
of stacked lamellae.
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