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Correlation of free radical copolymerization behavior and copolymer properties with the strength of π-π stacking interactions between aromatic fluorocarbons and aromatic hydrocarbons: Comparison of the copolymerization behavior of 2,3,4,5,6-pentafluorostyrene with styrene, 1-vinylnaphthalene and 2-vinylnaphthalene Part A Polymer chemistry

Pugh, Coleen, Paz-Pazos, Marta, Tang, Chau N.
Journal of polymer science 2009 v.47 no.2 pp. 331-345
composite polymers, differential scanning calorimetry, glass transition, least squares, perfluorocarbons, styrene, temperature
2,3,4,5,6-Pentafluorostyrene (PFS) was copolymerized with 1-vinylnaphathalene (1VN) in bulk by radical copolymerization at 25 °C (r₁VNrPFS = 0.070) using t-butylperoxy pivalate as the inititator, at 70 °C (r₁VNrPFS = 0.11) using benzyol peroxide as the initiator, and at 120 °C (r₁VNrPFS = 0.28) using t-butyl peroxide as the initiator; PFS was also copolymerized with 2-vinylnaphathalene (2VN) in bulk by radical copolymerization at 70 °C (r₂VNrPFS = 0.15) under similar conditions. Their reactivity ratios were determined at low monomer conversions using the nonlinear least-squares method of analysis, which demonstrated that both comonomer pairs tend to alternate, and that their alternating tendency increases with decreasing temperature, similar to the radical copolymerizations of PFS with styrene (St) in bulk. The glass transition temperatures determined by differential scanning calorimetry are elevated relative to their mole-average values, with the extent of elevation being greater for the 1VN-PFS copolymers than for the 2VN-PFS copolymers, which is greater than that for St-PFS copolymers.