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

Abstract

Abstract2,3,4,5,6‐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. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 331–345, 2009

RAFT polymerization of alternating styrene‐pentafluorostyrene copolymers

“…Since stacking interactions between monomers can play a role in the degree of control over the monomer sequence through preorganization, 9,19,21 the influence of the solvent on both the degree of alternation and the control over molecular weight was investigated. Besides in 1,4-dioxane, the copolymerizations were also performed in N,N-dimethylformamide (DMF) and toluene.…”

“…Size-exclusion chromatography (SEC) analyses were carried out using a Shimadzu pump and Shimadzu UV and RI detectors with tetrahydrofuran (THF) as the eluent and a set of Polymer Standards columns (AM GPC gel, 10 mm, precolumn, 300 Å, and linear mixed bed). The flow rate used for all measurements was 1 mL min 21 . Commercially available PS standards were used for calibration.…”

Effect of Aromatic Co‐Solvents on the Efficiency of Atom Transfer Radical Coupling Reactions of Fluorinated and Non‐Fluorinated Vinyl Aromatic Polymers

“…As an example of exploiting these interactions, the free radical polymerization of styrene (S) and pentafluorostyrene (PFS) has been reported by Pugh et al to produce an alternating copolymer, attributed to pi–pi stacking between the two different monomeric units. The same group has also reported that copolymers consisting of PFS and vinylnaphthalene possess the same alternating configurations of monomeric units along the backbone, presumably for the same reason . In another study, Weck et al reported the RAFT copolymerization of S and its para‐substituted derivatives with PFS, and found an inclination of the monomers to alternate that coincided with the electron donating ability of the para substituent on the S derivative …”

“…There are two types of face‐to‐face interactions that can occur: a sandwich configuration and a parallel, displaced configuration. Of the two, the displaced configuration is slightly preferred due to greater binding energy as a result of smaller inter‐planar distance between the benzene and the HFB . This attraction has a short lifetime, with molecular dynamics simulations estimating it to be between 33 ps at 126 K and 17 ps at 158 K .…”

Fluorescent monomers as building blocks for dye labeled polymers: synthesis and application in energy conversion, biolabeling and sensors

“…139 Moreover, the p-p stacking behavior of copolymers composed of pentafluorostyrene (PFS) and N3 or N4, respectively, was examined by the group of Pugh. 140 So far, polymers based on polymerizable naphthalenes were applied in mixed ligand monolith capillary column material. 141 The composition (including octadecyl acrylate (ODA), N2 and trimethylolpropane trimethacrylate (TRIM) crosslinker) of the column material was altered.…”