TY - THES A1 - Imran ul-haq, Muhammad T1 - Synthesis of fluorinated polymers in supercritical carbon dioxide (scCO₂) T1 - Synthese von Fluorpolymeren in überkritischem Kohlendioxid (scCO₂) N2 - For the first time stabilizer-free vinylidene fluoride (VDF) polymerizations were carried out in homogeneous phase with supercritical CO₂. Polymerizations were carried out at 140°C, 1500 bar and were initiated with di-tert-butyl peroxide (DTBP). In-line FT-NIR (Fourier Transform- Near Infrared) spectroscopy showed that complete monomer conversion may be obtained. Molecular weights were determined via size-exclusion chromatography (SEC) and polymer end group analysis by 1H-NMR spectroscopy. The number average molecular weights were below 104 g∙mol−1 and polydispersities ranged from 3.1 to 5.7 depending on DTBP and VDF concentration. To allow for isothermal reactions high CO₂ contents ranging from 61 to 83 wt.% were used. The high-temperature, high-pressure conditions were required for homogeneous phase polymerization. These conditions did not alter the amount of defects in VDF chaining. Scanning electron microscopy (SEM) indicated that regular stack-type particles were obtained upon expansion of the homogeneous polymerization mixture. To reduce the required amount of initiator, further VDF polymerizations using chain transfer agents (CTAs) to control molecular weights were carried out in homogeneous phase with supercritical carbon dioxide (scCO₂) at 120 °C and 1500 bar. Using perfluorinated hexyl iodide as CTA, polymers of low polydispersity ranging from 1.5 to 1.2 at the highest iodide concentration of 0.25 mol·L-1 were obtained. Electrospray ionization- mass spectroscopy (ESI-MS) indicates the absence of initiator derived end groups, supporting livingness of the system. The “livingness” is based on the labile C-I bond. However, due to the weakness of the C-I bond perfluorinated hexyl iodide also contributes to initiation. To allow for kinetic analyses of VDF polymerizations the CTA should not contribute to initiation. Therefore, additional CTAs were applied: BrCCl3, C6F13Br and C6F13H. It was found that C6F13H does not contribute to initiation. At 120°C and 1500 bar kp/kt0.5~ 0.64 (L·mol−1·s−1)0.5 was derived. The chain transfer constant (CT) at 120°C has been determined to be 8·10−1, 9·10−2 and 2·10−4 for C6F13I, C6F13Br and C6F13H, respectively. These CT values are associated with the bond energy of the C-X bond. Moreover, the labile C-I bond allows for functionalization of the polymer to triazole end groups applying click reactions. After substitution of the iodide end group by an azide group 1,3 dipolar cycloadditions with alkynes yield polymers with 1,2,3 triazole end groups. Using symmetrical alkynes the reactions may be carried out in the absence of any catalyst. This end-functionalized poly (vinylidene fluoride) (PVDF) has higher thermal stability as compared to the normal PVDF. PVDF samples from homogeneous phase polymerizations in supercritical CO₂ and subsequent expansion to ambient conditions were analyzed with respect to polymer end groups, crystallinity, type of polymorphs and morphology. Upon expansion the polymer was obtained as white powder. Scanning electron microscopy (SEM) showed that DTBP derived polymer end groups led to stack-type particles whereas sponge- or rose-type particles were obtained in case of CTA fragments as end groups. Fourier-Transform Infrared spectroscopy and wide angle X-ray diffraction indicated that the type of polymorph, α or β crystal phase was significantly affected by the type of end group. The content of β-phase material, which is responsible for piezoelectricity of PVDF, is the highest for polymer with DTBP-derived end groups. In addition, the crystallinity of the material, as determined via differential scanning calorimetry is affected by the end groups and polymer molecular weights. For example, crystallinity ranges from around 26 % for DTBP-derived end groups to a maximum of 62 % for end groups originating from perfluorinated hexyl iodide for polymers with Mn ~2200 g·mol–1. Expansion of the homogeneous polymerization mixture results in particle formation by a non-optimized RESS (Rapid Expansion from Supercritical Solution) process. Thus, it was tested how polymer end groups affect the particles size distribution obtained from RESS process under controlled conditions (T = 50°C and P = 200 bar). In all RESS experiments, small primary PVDF with diameters less than 100 nm without the use of liquid solvents, surfactants, or other additives were produced. A strong correlation between particle size and particle size distribution with polymer end groups and molecular weight of the original material was observed. The smallest particles were found for RESS of PVDF with Mn~ 4000 g·mol–1 and PFHI (C6F13I) - derived end groups. N2 - Erstmalig gelang es, stabilisatorfreie Vinylidenfluorid (VDF)-Polymerisationen in homogener Phase mit überkritischem CO₂ (scCO₂) bis zu vollständigem Monomerumsatz durchzuführen. Die Homogenität während der Polymerisation wurde durch in-line Fourier-Transform Nahinfrarot Spektroskopie beobachtet. Für Polymerisationen bei 140 °C und 1500 bar wurde Di-tert-butylperoxid (DTBP) als Initiator verwendet. Es wurden Polymere mit einem Zahlenmittel der Molmasse kleiner 104 g·mol–1 und Polydispersitäten zwischen 3.1 und 5.7. erhalten. Um isotherme Reaktionen zu ermöglichen, wurden CO₂-Gehalte zwischen 61 und 83 wt.% verwendet. Die für die homogene Reaktionsführung erforderlichen hohen Drücke und Temperaturen haben keinen Einfluss auf die Mikrostruktur des Polymers. Zur Verringerung der Initiatorkonzentration wurden weitere Polymerisationen unter Verwendung von Kettentransferreagenzien (CTA) bei 120 °C und 1500 bar in homogener Phase mit scCO₂ durchgeführt. Perfluoriertes Hexyliodid als CTA ermöglicht kontrollierte radikalische Polymerisationen, wobei Polymere mit geringer Polydispersität zwischen 1.5 und 1.2 erhalten wurden. Endgruppenanalyse mit Elektronenspray-Ionisations-Massen¬spektro¬metrie (ESI-MS) zeigte, dass keine Initiatorendgruppen im Polymer enthalten sind. Diese Beobachtung unterstützt den lebenden Charakter der Polymerisationen und basiert auf einer labilen C-I-Bindung im Polymer. Aufgrund der schwachen C-I-Bindung trägt das perfluorierte Hexyliodid (C6F13I) auch zur Initiierung bei. Polymerisationen in Gegenwart von BrCCl3, C6F13Br und C6F13H zeigten, dass nur C6F13H keinen Beitrag zur Initiierung leistet. Bei 120 °C und 1500 bar wurde ein kp/kt0.5 von ~ 0.64 (L·mol−1·s−1)0.5 bestimmt, wobei kp der Wachstums- und kt der Terminierungsgeschwindigkeitskoeffizient sind. Die Kettentransfer¬konstanten (CT) bei 120°C betragen 8·10−1, 9·10−2 und 2·10−4 für C6F13I, C6F13Br und C6F13H. Die Änderung der CT-Werte lässt sich mit der zunehmenden Bindungsenergie in der Reihe C-I, C-Br und C-H erklären. Die labile C-I-Bindung ermöglicht eine Funktionalisierung des Polymers durch Click-Reaktionen. Nach Substitution der Iodid-Endgruppe durch eine Azidgruppe erfolgte eine katalysatorfreie 1,3-dipolare Cyclaoaddition mit Alkinen zu Polymeren mit 1,2,3-Triazol-Endgruppen. Dieses endfunktionalisierte PVDF besitzt im Vergleich zu konventionellem PVDF eine höhere thermische Stabilität. Nach der Expansion der Polymerisationsmischung mit scCO₂ auf Umgebungsbedingungen lag das Polymer als weißes Pulver vor, das im Hinblick auf z.B. Polymerendgruppen, Kristallinität, Gestalt und Größe der Partikel untersucht wurde. Rasterelektronenmikroskopie zeigte, dass Polymere mit DTBP-Endgruppen zu stapelförmigen Partikeln führen, während bei CTA-Fragmenten als Endgruppen schwamm- oder rosenartige Partikel erhalten wurden. Ergebnisse der FT-IR Spektroskopie und Weitwinkelröntgenbeugung zeigten, dass der höchste Gehalt an β-phasigem Material, der für die Piezoelektrizität des PVDF verantwortlich ist, für PVDF mit Initiatorendgruppen erhalten wurde. DSC (Differential Scanning Calorimetry) Messungen ergaben zudem, dass der Kristallinitätsgrad durch Endgruppen und Polymermasse beeinflusst wird. Die Expansion der homogenen Polymermischung kann als nicht-optimierter RESS-Prozess (Rapid Expanison from Supercritical Solution,) angesehen werden. Aus RESS Experimenten unter kontrollierten Bedingungen wurden jeweils nanoskalige primäre PVDF-Partikel ohne Verwendung von Lösungsmitteln, Tensiden oder anderen Additiven erhalten. Es besteht ein enger Zusammenhang zwischen einerseits der Partikelgröße und der Partikelgrößenverteilung und andererseits der Polymerkonzentration in scCO₂ vor der Expansion, bestimmt durch Polymerendgruppen und Molmassen der eingesetzten Materialien. KW - Synthese KW - Fluorpolymere KW - überkritisches Kohlendioxid (scCO₂) KW - Synthesis KW - fluorinated polymers KW - supercritical carbon dioxide (scCO₂) Y1 - 2008 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-19868 ER - TY - THES A1 - Bivigou Koumba, Achille Mayelle T1 - Design, Synthesis and Characterisation of Amphiphilic Symmetrical triblock copolymers by the RAFT process : their self-organisation in dilute and concentrated aqueous solutions T1 - Design, Synthese und Charakterisierung von amphiphilen symmetrischen Triblock-Copolymeren anhand des RAFT Prozesses : ihre Selbstorganisation in wässrigen verdünnten und höher konzentrierten Lösungen N2 - This work presents the synthesis and the self-assembly of symmetrical amphiphilic ABA and BAB triblock copolymers in dilute, semi-concentrated and highly concentrated aqueous solution. A series of new bifunctional bistrithiocarbonates as RAFT agents was used to synthesise these triblock copolymers, which are characterised by a long hydrophilic middle block and relatively small, but strongly hydrophobic end blocks. As hydrophilic A blocks, poly(N-isopropylacrylamide) (PNIPAM) and poly(methoxy diethylene glycol acrylate) (PMDEGA) were employed, while as hydrophobic B blocks, poly(4-tert-butyl styrene), polystyrene, poly(3,5-dibromo benzyl acrylate), poly(2-ethylhexyl acrylate), and poly(octadecyl acrylate) were explored as building blocks with different hydrophobicities and glass transition temperatures. The five bifunctional trithiocarbonates synthesised belong to two classes: the first are RAFT agents, which position the active group of the growing polymer chain at the outer ends of the polymer (Z-C(=S)-S-R-S-C(=S)-Z, type I). The second class places the active groups in the middle of the growing polymer chain (R-S-C(=S)-Z-C(=S)-S-R, type II). These RAFT agents enable the straightforward synthesis of amphiphilic triblock copolymers in only two steps, allowing to vary the nature of the hydrophobic blocks as well as the length of the hydrophobic and hydrophilic blocks broadly with good molar mass control and narrow polydispersities. Specific side reactions were observed among some RAFT agents including the elimination of ethylenetrithiocarbonate in the early stage of the polymerisation of styrene mediated by certain agents of the type II, while the use of the RAFT agents of type I resulted in retardation of the chain extension of PNIPAM with styrene. These results underline the need of a careful choice of RAFT agents for a given task. The various copolymers self-assemble in dilute and semi-concentrated aqueous solution into small flower-like micelles. No indication for the formation of micellar clusters was found, while only at high concentration, physical hydrogels are formed. The reversible thermoresponsive behaviour of the ABA and BAB type copolymer solutions in water with A made of PNIPAM was examined by turbidimetry and dynamic light scattering (DLS). The cloud point of the copolymers was nearly identical to the cloud point of the homopolymer and varied between 28-32 °C with concentrations from 0.01 to 50 wt%. This is attributed to the formation of micelles where the hydrophobic blocks are shielded from a direct contact with water, so that the hydrophobic interactions of the copolymers are nearly the same as for pure PNIPAM. Dynamic light scattering measurements showed the presence of small micelles at ambient temperature. The aggregate size dramatically increased above the cloud point, indicating a change of aggregate morphology into clusters due to the thermosensitivity of the PNIPAM block. The rheological behaviour of the amphiphilic BAB triblock copolymers demonstrated the formation of hydrogels at high concentrations, typically above 30-35 wt%. The minimum concentration to induce hydrogels decreased with the increasing glass transition temperatures and increasing length of the end blocks. The weak tendency to form hydrogels was attributed to a small share of bridged micelles only, due to the strong segregation regime occurring. In order to learn about the role of the nature of the thermoresponsive block for the aggregation, a new BAB triblock copolymer consisting of short polystyrene end blocks and PMDEGA as stimuli-responsive middle block was prepared and investigated. Contrary to PNIPAM, dilute aqueous solutions of PMDEGA and of its block copolymers showed reversible phase transition temperatures characterised by a strong dependence on the polymer composition. Moreover, the PMDEGA block copolymer allowed the formation of physical hydrogels at lower concentration, i.e. from 20 wt%. This result suggests that PMDEGA has a higher degree of water-swellability than PNIPAM. N2 - Die Arbeit behandelt die Synthese und das Selbstorganisationsverhalten von neuen funktionellen symmetrischen "stimuli-responsiven" Triblockcopolymeren ABA und BAB in wässrigen verdünnten und höher konzentrierten Lösungen. Neue symmetrische, bifunktionelle Bistrithiocarbonate wurden als RAFT-Agentien benutzt, um Triblockcopolymere mit langen hydrophilen (A) Innen- und kurzen hydrophoben (B) Außenblöcken zu synthetisieren. Als hydrophile A Blöcke wurden Poly(N-isopropylacrylamid) PNIPAM und Poly(methoxy diethylene glykol acrylat) PMDEGA benutzt, während als hydrophobe Blöcke B Poly(4-tert-butyl styrol), Polystyrol, Poly(3,5-dibromo benzyl acrylat), Poly(2-ethylhexyl acrylat), und Poly(octadecyl acrylat) als Bausteine mit unterschiedlicher Glasübergangstemperatur untersucht wurden. Die Selbstorganisation von ABA und BAB Copolymeren in Wasser mit A Blöcken aus PNIPAM wurde anhand von Trübungsphotometrie, dynamischer Lichtstreuung (DLS) und Rheologie untersucht. Die amphiphilen Blockcopolymere sind direkt wasserlöslich. Bei Konzentrationen von 0.01 bis 50 wt% zeigen Trübungsmessungen bei den Blockcopolymeren wie bei den Homopolymeren eine Übergangstemperatur bei 28-32 °C. Zurückzuführen ist dies auf die Bildung von Mizellen, bei der die hydrophoben Blöcke von einem direkten Kontakt mit Wasser abgeschirmt werden. DLS zeigt kleine Mizellen bei niedrigen Temperaturen und Aggregate mit großem hydrodynamischem Durchmesser bei Temperaturen oberhalb der Übergangstemperatur. Die rheologische Untersuchung von BAB Polymeren zeigt die Bildung von Hydrogelen bei höheren Konzentrationen (über 30-35 wt%). Die minimal benötigte Konzentration, bei der die von Hydrogelen auftreten, nimmt mit wachsender Glasübergangstemperatur ab, und nimmt mit der Länge der hydrophoben Blöcke B zu. Im Unterschied zu PNIPAM zeigen wässrige Lösungen von PMDEGA und seinen Blockcopolymeren reversible Übergangstemperaturen abhängig von der chemischen Struktur. Außerdem bilden PMDEGA Blockcopolymere Hydrogele bei niedriger Konzentration (ab 20 wt%). Dieses Ergebnis deutet darauf hin, dass PMDEGA stärker Wasser bindet als PNIPAM. KW - Design KW - Synthese KW - Charakterisierung KW - Triblock-Copolymere KW - RAFT KW - Design KW - Synthesis KW - Characterisation KW - Triblock Copolymers KW - RAFT Y1 - 2009 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-39549 ER - TY - JOUR A1 - Shainyan, Bagrat A. A1 - Tolstikova, Ljudmila L. A1 - Schilde, Uwe T1 - Simple methods for the preparation of N-triflyl guanidines and the structure of compounds with the CF3SO2N=C-N fragment JF - Journal of fluorine chemistry N2 - Two novel and simple approaches to N-triflyl guanidines are elaborated. Owing to very strong conjugation the formally double C=N bond of TIN=C(NHR)(2) is longer than the formally single N-C bonds. Energetic effect of the triflylgroup on the conjugation in the N-C=N moiety is estimated to be >= 150 kcal/mol. KW - N-triflyl guanidines KW - Synthesis KW - Structure KW - X-ray KW - MP2 calculations Y1 - 2012 U6 - https://doi.org/10.1016/j.fluchem.2011.12.004 SN - 0022-1139 VL - 135 IS - 1 SP - 261 EP - 264 PB - Elsevier CY - Lausanne ER - TY - JOUR A1 - Laschewsky, André T1 - Recent trends in the synthesis of polyelectrolytes JF - Current opinion in colloid & interface science : current chemistry N2 - Recent developments in the synthesis of polyelectrolytes are highlighted, with respect to the nature of the ionic groups, the polymer backbones, synthetic methods, and additional functionality given to the polyelectrolytes. In fact, the synthesis of new polyelectrolytes is mostly driven by material aspects, currently. The article pays particular attention to strong polyelectrolytes, and the new methods of controlled polymerization. These methods and the so-called click reactions have enabled novel designs of polyelectrolytes. Nevertheless, the polymerization of unprotected ionic monomers is still challenging and limits the synthetic possibilities. The structural aspects are complemented by considerations with respect to the aspired uses of the new polyelectrolytes. KW - Polyelectrolytes KW - Synthesis KW - Ionic monomers KW - Controlled polymerization KW - "click" chemistry Y1 - 2012 U6 - https://doi.org/10.1016/j.cocis.2011.08.001 SN - 1359-0294 VL - 17 IS - 2 SP - 56 EP - 63 PB - Elsevier CY - London ER - TY - JOUR A1 - Schwarze, Thomas A1 - Traeger, Juliane A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Holdt, Hans-Jürgen T1 - Macrocyclic dithiomaleonitriles for an efficient PdCl2 coordination JF - Inorganica chimica acta : the international inorganic chemistry journal N2 - We have synthesized a set of new unsaturated macrocyclic dithioethers with an increasing number of flexible methylene units 1-7 (Scheme 2) to investigate the correlation between the ring size of these ligands, the chelation effect and the consequences for an efficient PdCl2 coordination. The dithioethers 1-7 and the complex [PdCl2(4)]center dot CHCl3 were characterized by X-ray diffraction analysis. The crystal structures of 1-7 show that 2-7 are better preorganized chelating ligands for an exocyclic PdCl2 coordination than 1. The chelation effect of 1-7, the orientation of the sulfur atoms and the S center dot center dot center dot S donor distances, are influenced by the flexibility of the methylene units. In this series the unsaturated macrocyclic ligands 5 and 6 are the best chelating ligands for an efficient PdCl2 coordination. Comparative solvent extraction experiments with mn-12S(2)O(2) (mn = maleonitrile) reveal that the low interface activity of the new ligands reduces the extraction rate. However, a comparison with open-chain dithiomaleonitriles shows the impact of the macrocyclic effect of 4 and 5 on the extraction yield. KW - Thioether ligands KW - Palladium KW - Synthesis KW - X-ray diffraction KW - Chelation effect KW - Extraction Y1 - 2013 U6 - https://doi.org/10.1016/j.ica.2013.08.020 SN - 0020-1693 SN - 1873-3255 VL - 408 IS - 2 SP - 53 EP - 58 PB - Elsevier CY - Lausanne ER - TY - JOUR A1 - Chmielewski, Frank M. A1 - Baldermann, Susanne A1 - Götz, Klaus Peter A1 - Homann, Thomas A1 - Gödeke, Kristin A1 - Schumacher, Fabian A1 - Huschek, Gerd A1 - Rawel, Harshadrai Manilal T1 - Abscisic acid related metabolites in sweet cherry buds (Prunus avium L.) JF - Journal of Horticulture N2 - As our climate changes, plant mechanisms involved for dormancy release become increasingly important for commercial orchards. It is generally believed that abscisic acid (ABA) is a key hormone that responds to various environmental stresses which affects bud dormancy. For this reason, a multi-year study was initiated to obtain data on plant metabolites during winter rest and ontogenetic development in sweet cherry buds (Prunus avium L.). In this paper, we report on metabolites involved in ABA synthesis and catabolism and its effect on bud dormancy in the years 2014/15-2016/17. In previous work, the timings of the different phases of para-, endo-, ecodormancy and ontogenetic development for cherry flower buds of the cultivar ‘Summit’ were determined, based on classical climate chamber experiments and changes in the bud’s water content. Based on these time phases, we focused now on the different aspects of the ABA-metabolism. The results show that there is a continual synthesis of ABA about 5 weeks before leaf fall, and a degradation of ABA during ecodormancy and bud development until the phenological stage ‘open cluster’. This is confirmed by relating the ABA content to that of the total precursor carotenoids, neoxanthin and violaxanthin. The tentative monitoring of individual intermediate metabolites revealed that dihydroxyphaseic acid is the most abundant catabolite of ABA and ABA glucosyl ester is in terms of mass intensity, the most abundant ABA metabolite observed in this study. The results suggest that the direct route for ABA biosynthesis from farnesyl pyrophosphate may also be relevant in cherry flower buds. KW - Dormancy KW - Abscisic acid KW - Synthesis KW - Catabolism KW - Prunus avium L. KW - Flower buds Y1 - 2018 U6 - https://doi.org/10.4172/2376-0354.1000221 SN - 2376-0354 VL - 5 IS - 1 ER - TY - JOUR A1 - Sperlich, Eric A1 - Köckerling, Martin T1 - [Nb6Cl12(CH3OH)4(OCH3)2] ⋅ DABCO ⋅ 1.66 CH2Cl2 BT - cluster units wrapped in a network of hydrogen bonds JF - Zeitschrift für anorganische und allgemeine Chemie : ZAAC = Journal of inorganic and general chemistry N2 - An easy-to-do synthesis for the hexanuclear niobium cluster compound [Nb6Cl12(CH3OH)(4)(OCH3)(2)] . DABCO . 1.66 CH2Cl2 has been developed. An one-pot reaction between the cluster precursor [Nb6Cl14(H2O)(4)] . 4H(2)O and methanol with the addition of DABCO leads to the crystallization of the title compound in high yield within a few minutes. The single-crystal X-ray structure of this cluster compound has been determined. Very strong, nearly symmetric intercluster hydrogen bonds Nb-6-MeO...H...OMe-Nb-6 are present between the cluster units. A bridging co-crystalline DABCO molecule is also involved in a three-dimensional hydrogen-bonding network. KW - Niobium KW - Cluster KW - Hydrogen Bonds KW - Synthesis KW - Structure Determination Y1 - 2021 U6 - https://doi.org/10.1002/zaac.202100138 SN - 0044-2313 SN - 1521-3749 VL - 647 IS - 18 SP - 1759 EP - 1763 PB - Wiley-VCH CY - Weinheim ER -