TY - JOUR A1 - Schreiber, Ulrike A1 - Hosemann, Benjamin A1 - Beuermann, Sabine T1 - 1H,1H,2H,2H-Perfluorodecyl-Acrylate-Containing block copolymers from ARGET ATRP JF - Macromolecular chemistry and physics N2 - Block copolymers of 1H,1H,2H,2H-perfluorodecyl acrylate (AC8) were obtained from ARGET ATRP. To obtain block copolymers of low dispersity the PAC8 block was synthesized in anisole with a CuBr(2)/PMDETA catalyst in the presence of tin(II) 2-ethylhexanoate as a reducing agent. The PAC8 block was subsequently used as macroinitiator for copolymerization with butyl and tert-butyl acrylate carried out in scCO(2). To achieve catalyst solubility in CO(2) two fluorinated ligands were employed. The formation of block copolymers was confirmed by size exclusion chromatography and DSC. KW - atom transfer radical polymerization (ATRP) KW - block copolymers KW - fluoropolymers KW - supercritical carbon dioxide Y1 - 2011 U6 - https://doi.org/10.1002/macp.201000307 SN - 1022-1352 VL - 212 IS - 2 SP - 168 EP - 179 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Vukicevic, Radovan A1 - Schwadtke, Ulrike A1 - Schmuecker, Simon A1 - Schaefer, Philipp A1 - Kuckling, Dirk A1 - Beuermann, Sabine T1 - Alkyne-azide coupling of tailored poly(vinylidene fluoride) and polystyrene for the synthesis of block copolymers JF - Polymer Chemistry N2 - The synthesis of block copolymers consisting of poly(vinylidene fluoride) (PVDF) and polystyrene (PS) is reported. Firstly, a propargyl-functionalized alkoxyamine initiator (PgOTIPNO) was prepared and subsequently used for the preparation of a propargyl-terminated PS homopolymer of different chain lengths with low dispersities via nitroxide-mediated radical polymerization. A tailored PVDF homopolymer with iodine end groups originating from iodine transfer polymerization was transformed to PVDF with azide end group. Then, alkyne-terminated PS with different molecular weights and azide-terminated PVDF were joined together via copper-catalyzed alkyne-azide coupling. The block copolymers were characterized using H-1-NMR, F-19-NMR, IR, SEC, and DSC. Y1 - 2012 U6 - https://doi.org/10.1039/c1py00427a SN - 1759-9954 VL - 3 IS - 2 SP - 409 EP - 414 PB - Royal Society of Chemistry CY - Cambridge ER - TY - CHAP A1 - Vukicevic, Radovan A1 - Schreiber, Ulrike A1 - Beuermann, Sabine T1 - Azide-terminated poly(vinylidene fluoride) as building block for nanocomposite materials and block copolymers T2 - Abstracts of papers : joint conference / The Chemical Institute of Cananda, CIC, American Chemical Society, ACS Y1 - 2011 SN - 0065-7727 VL - 242 IS - 16 PB - American Chemical Society CY - Washington ER - TY - CHAP A1 - Schreiber, Ulrike A1 - Vukicevic, Radovan A1 - Beuermann, Sabine T1 - Block copolymers of poly(vinylidene fluoride) obtained via 1,3 dipolar cycloaddition T2 - Abstracts of papers : joint conference / The Chemical Institute of Cananda, CIC, American Chemical Society, ACS Y1 - 2011 SN - 0065-7727 VL - 242 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Breininger, Eugenia A1 - Imran-ul-haq, Muhammad A1 - Tuerk, Michael A1 - Beuermann, Sabine T1 - Effect of polymer properties on poly(vinylidene fluoride) particles produced by rapid expansion of CO2 + polymer mixtures N2 - The generation of nanoscale primary poly(vinylidene fluoride) (PVDF) particles by rapid expansion of supercritical solutions (RESS) is reported. The experimental results show that RESS enables the formation of PVDF particles with median particle diameters ranging from 56 to 226 nm and that the size of PVDF particles can be influenced by polymer properties. The particle size can be decreased either by increasing molar mass, in case of identical polymer end groups, or by increasing the degree of crystallinity, in case of similar molar mass and different end groups. Y1 - 2009 UR - http://www.sciencedirect.com/science/journal/08968446 U6 - https://doi.org/10.1016/j.supflu.2008.09.016 SN - 0896-8446 ER - TY - JOUR A1 - Cockburn, Robert A. A1 - Siegmann, Rebekka A1 - Payne, Kevin A. A1 - Beuermann, Sabine A1 - McKenna, Timothy F. L. A1 - Hutchinson, Robin A. T1 - Free Radical Copolymerization Kinetics of gamma-Methyl-alpha-methylene-gamma-butyrolactone (MeMBL) JF - Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences N2 - The propagation kinetics and copolymerization behavior of the biorenewable monomer gamma-methyl-alpha-methylene-gamma-butyrolactone (MeMBL) are studied using the Pulsed laser polymerization (PLP)/size exclusion chromatography (SEC) technique. The propagation rate coefficent for MeMBL is 15% higher than that of its structural analogue, methyl methacrylate (MMA), with a similar activation energy of 21.8 kJ . mol(-1). When compared to MMA, MeMBL is preferentially incorporated into copolymers when reacted with styrene (ST), MMA, and n-butyl acrylate (BA); the monomer reactivity ratios fit from bulk MeMBL/ST, MeMBL/MMA, and MeMBL/BA copolymerizations are r(MeMBL) = 0.80 +/- 0.04 and r(ST) = 0.34 +/- 0.04, r(MeMBL), = 3.0 +/- 0.3 and r(MMA) = 0.33 +/- 0.01, and r(MeMBL) = 7.0 +/- 2.0 and r(BA) = 0.16 +/- 0.03, respectively. In all cases, no significant variation with temperature was found between 50 and 90 degrees C. The implicit penultimate unit effect (IPUE) model was found to adequately fit the composition-averaged copolymerization propagation rate coefficient, k(p,cop), for the three systems. Y1 - 2011 U6 - https://doi.org/10.1021/bm200400s SN - 1525-7797 VL - 12 IS - 6 SP - 2319 EP - 2326 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Vukicevic, Radovan A1 - Beuermann, Sabine T1 - Fullerenes decorated with poly(vinylidene fluoride) JF - Macromolecules : a publication of the American Chemical Society N2 - Fullerenes decorated with poly(vinylidene fluoride) (PVDF) were synthesized in a three-step procedure: Iodine transfer polymerization of vinylidene fluoride with C(6)F(12)I(2) as the chain transfer agent was carried out in supercritical carbon dioxide to synthesize iodine-terminated PVDF, which was subsequently transformed to azide-terminated polymer. Finally, azide-terminated PVDF chains were attached to a fullerene core under microwave irradiation at 160 degrees C in 1.5 h. The materials were characterized by NMR, FT-IR, UV/vis, GPC, elemental analysis, and DSC. On average, 4-5 PVDF chains are attached to one C(60) moiety. FT-IR spectra and DSC measurements indicate that the polymer end groups strongly affect the crystallinity of the material. For PVDF with azide end groups and PVDF attached to fullerenes the fraction of the beta polymorph is dominant while alpha polymorphs are almost absent. Y1 - 2011 U6 - https://doi.org/10.1021/ma102754c SN - 0024-9297 VL - 44 IS - 8 SP - 2597 EP - 2603 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Vukicevic, Radovan A1 - Hierzenberger, Peter A1 - Hild, Sabine A1 - Beuermann, Sabine T1 - Functionalization of carbon black nanoparticles with poly(vinylidene fluoride) N2 - The surface of carbon black (CB) nanoparticles was functionalized with poly(vinylidene fluoride) (PVDF) either by trapping of macroradicals or by cycloaddition. PVDF with two iodine end groups (I-PVDF-I) obtained from iodine transfer polymerization in supercritical CO2 was heated in the presence of CB and the C-I bond was cleaved resulting in a reaction between the macroradical and the CB surface. To allow for cycloaddition of PVDF to the CB surface for a number of polymers, the iodine end groups were replaced by azide end groups. In addition, microwave irradiation was applied to the functionalization. The influence of temperature, time, polymer concentration, and polymer molar mass on the functionalization reaction was examined. Y1 - 2010 UR - http://onlinelibrary.wiley.com/journal/10.1002/%28ISSN%291542-9369 U6 - https://doi.org/10.1002/Pola.24277 SN - 0887-624X ER - TY - JOUR A1 - Möller, Eleonore A1 - Beuermann, Sabine T1 - Homogeneous phase copolymerizations of vinylidene fluoride and hexafluoropropene in supercritical carbon dioxide JF - Macromolecular reaction engineering N2 - Copolymerizations of vinylidene fluoride (VDF) and hexafluoropropene (HFP) were carried out in homogeneous phase with supercritical carbon dioxide up to complete VDF conversion using conventional peroxide initiators. The HFP monomer feed ratios, f(HFP), were varied between 0.65 and 0.20. Depending on f(HFP) amorphous or semi-crystalline copolymers were obtained. f(HFP) also determines the minimum pressure required to allow for homogeneous phase reactions. For example, HFP-rich copolymerizations in 70 wt.-% CO(2) at 100 degrees C require a pressure of around 500 bar. Further, bulk copolymerizations in homogenous phase were feasible for f(HFP) 0.65 at 900 bar up to complete VDF conversion. Copolymerizations in the presence of perfluorinated hexyl iodide carried out at 75 degrees C gave access to low dispersity polymers. Due to homogeneous phase conditions the use of any surfactants or fluorinated cosolvent is avoided. KW - copolymerization KW - hexafluoropropene KW - phase behavior KW - supercritical CO(2) KW - vinylidene fluoride Y1 - 2011 U6 - https://doi.org/10.1002/mren.201000031 SN - 1862-832X VL - 5 IS - 1 SP - 8 EP - 21 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Siegmann, Rebekka A1 - Beuermann, Sabine T1 - Individual rate coefficients for 1H,1H,2H,2H-tridecafluorooctyl methacrylate radical polymerizations N2 - Kinetic data for radical polymerizations of 1H,1H,2H,2H-tridecafluorooctyl methacrylate (TDFOMA) in bulk is reported. Pulsed laser initiated polymerizations yield propagation rate coefficients, k(p), which are by a factor of 1.9 higher than methyl methacrylate k(p). The activation energy of TDFOMA k(p) is not significantly different from that of alkyl methacrylates. Chain-length averaged termination rate coefficients were estimated from chemically initiated polymerizations with in-line FT-NIR spectroscopic monitoring of monomer conversion. Up to 30% of monomer conversion TDFOMA termination rate coefficients are only slightly below MMA low conversion values. The result is suggested to be due to less interactions between the macroradicals compared to nonfluorinated systems. Y1 - 2010 UR - http://pubs.acs.org/journal/mamobx U6 - https://doi.org/10.1021/Ma902653b SN - 0024-9297 ER -