%0 Journal Article
%A Pugh, Coleen
%A Tang, Chau N.
%A Paz-Pazos, Marta
%A Samtani, Om
%A Dao, Adam H.
%D 2007
%T Correlation of Free Radical Copolymerization Behavior and
Copolymer Properties with the Strength of π−π Stacking Interactions
between Aromatic Fluorocarbons and Aromatic Hydrocarbons:
Copolymerization of Styrene and Fluorinated Styrenes at the Two
Extreme Levels of Fluorination
%U https://acs.figshare.com/articles/journal_contribution/Correlation_of_Free_Radical_Copolymerization_Behavior_and_Copolymer_Properties_with_the_Strength_of__Stacking_Interactions_between_Aromatic_Fluorocarbons_and_Aromatic_Hydrocarbons_Copolymerization_of_Styrene_and_Fluorinated_Styrenes_at_the_Two_Extreme_Lev/2975083
%R 10.1021/ma062617s.s001
%2 https://acs.figshare.com/ndownloader/files/4675555
%K copolymers
%K NMR spectroscopy results
%K ethylene glycol contact angles
%K Free Radical Copolymerization Behavior
%K copolymerization
%K styrene
%K St
%K bulk
%K 4 FS
%K rStrFS
%K PFS
%X In order to determine if the alternating tendency of styrene with fluorinated styrenes in free radical
copolymerizations correlates with the strength and/or extent of π−π stacking interactions between aromatic
fluorocarbons and aromatic hydrocarbons, styrene (St) was copolymerized with 2,3,4,5,6-pentafluorostyrene (PFS)
and 4-fluorostyrene (4FS) under a variety of conditions. For the copolymerization of styrene with PFS at 25 °C,
rStrFS = 0.048 and 0.069 in bulk and toluene, respectively, using tert-butylperoxy pivalate as the initiator. For the
copolymerization of styrene with PFS at 70 °C using benzoyl peroxide as the initiator, rStrFS = 0.17 in bulk and
rStrFS = 0.14 in toluene. For the copolymerization of styrene with 4FS, rStrFS = 0.69 at 25 °C under redox
conditions and rStrFS = 0.62 at 70 °C in bulk. As confirmed by 1H, 13C, and 19F one-dimensional NMR and
1H−13C heteronuclear single quantum coherence and 1H−H nuclear Overhauser effect two-dimensional NMR
spectroscopy results, St and 4FS tend to form random copolymers whereas the St-PFS copolymers tend to alternate
with the alternating tendency increasing with decreasing temperature. The glass-transition temperatures determined
by differential scanning calorimetry of the St-PFS copolymers are elevated relative to their mole-average values,
whereas those of the corresponding homopolymer blends and the St-4FS copolymers occur at mole-average values.
The water and ethylene glycol contact angles of both the St-PFS and St-4FS copolymer films occur at their
mole-average values.
%I ACS Publications