(2-Bromo-n-nonan-1-oxycarbonyl)ethyl acrylate was synthesized as an inimer for self-condensing vinyl polymerization (SCVP) to produce hyperbranched poly(n-nonyl acrylate), either as a homopolymer or as a copolymer with n-nonyl acrylate. The inimer was homopolymerized and copolymerized by atom transfer radical polymerization (ATRP) and activator generated by electron transfer ATRP to produce soluble polymers with broad polydispersities (up to Đ = 9.91), which is characteristic of hyperbranched polymers produced by SCVP. The resulting hyperbranched (co)polymers were crosslinked by atom transfer radical coupling in both one-pot and two-step procedures. The radical–radical crosslinking reaction is extremely efficient, resulting in hard plastic particles from the homopolymer of (2-bromo-n-nonan-1-oxycarbonyl)ethyl acrylate synthesized in bulk. Crosslinked organogels that swell in tetrahydrofuran were formed when the rate of crosslinking decreased using acetonitrile solutions. Dynamic shear and stress relaxation experiments demonstrated that the dry network behaves as a covalently crosslinked soft gel, with a glass transition at −50 °C according to differential scanning calorimetry. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2399–2410

2,3,4,5,6-Pentafluorostyrene (PFS) was copolymerized with 1-vinylnaphathalene (1VN) in bulk by radical copolymerization at 25 °C (r_1VNr_PFS = 0.070) using t-butylperoxy pivalate as the inititator, at 70 °C (r_1VNr_PFS = 0.11) using benzyol peroxide as the initiator, and at 120 °C (r_1VNr_PFS = 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 (r_2VNr_PFS = 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

“Three-arm star” poly[11-(4′-cyanophenyl-4′′-phenoxy)undecyl acrylate]s were synthesized by atom transfer radical polymerization (ATRP) of 11-(4′-cyanophenyl-4′′-phenoxy)undecyl acrylate using two new trifunctional initiators: 1,3,5-tri- (methyl 2-bromopropionate)benzene and 2,4,6-tri[4′-methyl(2′′-bromopropionate)phenoxymethyl]mesitylene. The polymers synthesized with 1,3,5-tri(methyl 2-bromopropionate)benzene (series II) contained 14–127 repeat units according to gel permeation chromatography relative to linear polystyrene (GPC_PSt) and 13–271 repeat units according to GPC with a light scattering detector (GPC_LS). Those synthesized with 2,4,6-tri[4′-methyl(2′′-bromopropionate)phenoxymethyl]mesitylene (series III) contained 14–87 repeat units according to GPC_PSt and 10–120 repeat units according to GPC_LS. The absolute molecular weight, size, and shape of both series of polymers were characterized by light scattering in CH₂Cl₂, and their thermotropic behavior was analyzed using differential scanning calorimetry; both types of properties were compared to those of the other architectures, especially the corresponding three-arm star poly[11-(4′-cyanophenyl-4′′-phenoxy)undecyl acrylate]s synthesized previously using 1,3,5-trisbromomethylmesitylene as the initiator. The size and shape of the three-arm star polymers in CH₂Cl₂ are similar, although the isotropization temperature in the solid state decreases and the breadth of the isotropization transition increases with increasing size and flexibility of the trifunctional core. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4363–4382, 2008