A New Fluorinated Polymer Having Two Connected Rings in the Main Chain: Synthesis and Characterization of Fluorinated Poly(1,3-cyclohexadiene)

The high electronegativity and small size of the fluorine atom and the high stability of C-F bonds impart interesting properties and applications to fluorine containing polymers. The unique properties of fluoropolymers include high thermal stability, improved chemical resistance, low surface energies, low coefficients of friction, and low dielectric constants. Applications of fluorinated polymers include use as noncorrosive materials, polymer processing aids, chemically resistant and antifouling coatings, as well as interlayer dielectrics. Fluorine-containing polymers can be directly synthesized via polymerization of fluorine-containing monomers or by post-polymerization modification. The latter method can be used to attach fluorinated species, such as perfluoroalkyl groups, onto conventional polymer chains, thereby imparting properties of fluorine-containing polymers into conventional polymers and widening their range of potential applications.

Well-Defined Poly(4-vinylbenzocyclobutene): Synthesis by Living Anionic Polymerization and Characterization

Living anionic polymerization of 4-vinylbenzocylobutene was performed in benzene at room temperature using sec-butyllithium as the initiator. Results of the kinetic studies indicated the termination- and transfer-free nature of the polymerization. Homopolymers with predictable molecular weights and narrow molecular weight distributions were produced, excluding the interference of the cyclobutene rings during initiation and propagation. Thermogravimetric analysis of poly(4-vinylbenzocyclobutene) in air showed a small weight gain at ~200 °C, a rapid decomposition at ~455 °C, and a gradual decomposition at ~566 °C. This behavior was attributed to the formation of radicals from the pendent benzocyclobutene functionality through o-quinodimethane intermediates and simultaneous decomposition/cross-linking reactions at high temperature. The living nature of the polymerization was also examined via sequential copolymerization with butadiene to form diblock copolymers.

Deterministic Solutions for a Step-growth Polymerization

Chain topology, including branch node, chain link and cross-link dynamics that contribute to the number of elastically active strands and junctions, are calculated using purely deterministic derivations. Solutions are not coupled to population density distributions. An eigenzeit transformation assists in the conversion of expressions derived by chemical reaction principles from time to conversion space, yielding transport phenomena type expressions where the rate of change in the molar concentrations of branch nodes with respect to conversion is expressed as functions of the fraction of reactive sites on precursors and reactants. Analogies are hypothesized to exist in cross-linking space that effectively distribute branch nodes with i reacted moieties between cross-links having j bonds extending to the gel. To obtain solutions, reacted sites on nodes or links with finite chain extensions are examined in terms of stoichiometry associated with covalent bonding. Solutions replicate published results based on Miller and Macosko’s recursive procedure and results obtained from truncated weighted sums of population density distributions as suggested by Flory.