@misc{SchoenemannLaschewskyRosenhahn2018, author = {Sch{\"o}nemann, Eric and Laschewsky, Andr{\´e} and Rosenhahn, Axel}, title = {Exploring the long-term hydrolytic behavior of zwitterionic polymethacrylates and polymethacrylamides}, series = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe}, journal = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe}, number = {1091}, issn = {1866-8372}, doi = {10.25932/publishup-47305}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-473052}, pages = {25}, year = {2018}, abstract = {The hydrolytic stability of polymers to be used for coatings in aqueous environments, for example, to confer anti-fouling properties, is crucial. However, long-term exposure studies on such polymers are virtually missing. In this context, we synthesized a set of nine polymers that are typically used for low-fouling coatings, comprising the well-established poly(oligoethylene glycol methylether methacrylate), poly(3-(N-2-methacryloylethyl-N,N-dimethyl) ammoniopropanesulfonate) ("sulfobetaine methacrylate"), and poly(3-(N-3-methacryamidopropyl-N,N-dimethyl)ammoniopropanesulfonate) ("sulfobetaine methacrylamide") as well as a series of hitherto rarely studied polysulfabetaines, which had been suggested to be particularly hydrolysis-stable. Hydrolysis resistance upon extended storage in aqueous solution is followed by ¹H NMR at ambient temperature in various pH regimes. Whereas the monomers suffered slow (in PBS) to very fast hydrolysis (in 1 M NaOH), the polymers, including the polymethacrylates, proved to be highly stable. No degradation of the carboxyl ester or amide was observed after one year in PBS, 1 M HCl, or in sodium carbonate buffer of pH 10. This demonstrates their basic suitability for anti-fouling applications. Poly(sulfobetaine methacrylamide) proved even to be stable for one year in 1 M NaOH without any signs of degradation. The stability is ascribed to a steric shielding effect. The hemisulfate group in the polysulfabetaines, however, was found to be partially labile.}, language = {en} } @article{SchoenemannLaschewskyRosenhahn2018, author = {Sch{\"o}nemann, Eric and Laschewsky, Andre and Rosenhahn, Axel}, title = {Exploring the long-term hydrolytic behavior of zwitterionic polymethacrylates and polymethacrylamides}, series = {Polymers}, volume = {10}, journal = {Polymers}, number = {6}, publisher = {MDPI}, address = {Basel}, issn = {2073-4360}, doi = {10.3390/polym10060639}, pages = {23}, year = {2018}, abstract = {The hydrolytic stability of polymers to be used for coatings in aqueous environments, for example, to confer anti-fouling properties, is crucial. However, long-term exposure studies on such polymers are virtually missing. In this context, we synthesized a set of nine polymers that are typically used for low-fouling coatings, comprising the well-established poly(oligoethylene glycol methylether methacrylate), poly(3-(N-2-methacryloylethyl-N,N-dimethyl) ammoniopropanesulfonate) (sulfobetaine methacrylate), and poly(3-(N-3-methacryamidopropyl-N,N-dimethyl)ammoniopropanesulfonate) (sulfobetaine methacrylamide) as well as a series of hitherto rarely studied polysulfabetaines, which had been suggested to be particularly hydrolysis-stable. Hydrolysis resistance upon extended storage in aqueous solution is followed by H-1 NMR at ambient temperature in various pH regimes. Whereas the monomers suffered slow (in PBS) to very fast hydrolysis (in 1 M NaOH), the polymers, including the polymethacrylates, proved to be highly stable. No degradation of the carboxyl ester or amide was observed after one year in PBS, 1 M HCl, or in sodium carbonate buffer of pH 10. This demonstrates their basic suitability for anti-fouling applications. Poly(sulfobetaine methacrylamide) proved even to be stable for one year in 1 M NaOH without any signs of degradation. The stability is ascribed to a steric shielding effect. The hemisulfate group in the polysulfabetaines, however, was found to be partially labile.}, language = {en} } @phdthesis{Hildebrand2016, author = {Hildebrand, Viet}, title = {Twofold switchable block copolymers based on new polyzwitterions}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-101372}, school = {Universit{\"a}t Potsdam}, pages = {xvi, 170, LXXX}, year = {2016}, abstract = {In complement to the well-established zwitterionic monomers 3-((2-(methacryloyloxy)ethyl)dimethylammonio)propane-1-sulfonate ("SPE") and 3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate ("SPP"), the closely related sulfobetaine monomers were synthesized and polymerized by reversible addition-fragmentation chain transfer (RAFT) polymerization, using a fluorophore labeled RAFT agent. The polyzwitterions of systematically varied molar mass were characterized with respect to their solubility in water, deuterated water, and aqueous salt solutions. These poly(sulfobetaine)s show thermoresponsive behavior in water, exhibiting upper critical solution temperatures (UCST). Phase transition temperatures depend notably on the molar mass and polymer concentration, and are much higher in D2O than in H2O. Also, the phase transition temperatures are effectively modulated by the addition of salts. The individual effects can be in parts correlated to the Hofmeister series for the anions studied. Still, they depend in a complex way on the concentration and the nature of the added electrolytes, on the one hand, and on the detailed structure of the zwitterionic side chain, on the other hand. For the polymers with the same zwitterionic side chain, it is found that methacrylamide-based poly(sulfobetaine)s exhibit higher UCST-type transition temperatures than their methacrylate analogs. The extension of the distance between polymerizable unit and zwitterionic groups from 2 to 3 methylene units decreases the UCST-type transition temperatures. Poly(sulfobetaine)s derived from aliphatic esters show higher UCST-type transition temperatures than their analogs featuring cyclic ammonium cations. The UCST-type transition temperatures increase markedly with spacer length separating the cationic and anionic moieties from 3 to 4 methylene units. Thus, apparently small variations of their chemical structure strongly affect the phase behavior of the polyzwitterions in specific aqueous environments. Water-soluble block copolymers were prepared from the zwitterionic monomers and the non-ionic monomer N-isopropylmethacrylamide ("NIPMAM") by the RAFT polymerization. Such block copolymers with two hydrophilic blocks exhibit twofold thermoresponsive behavior in water. The poly(sulfobetaine) block shows an UCST, whereas the poly(NIPMAM) block exhibits a lower critical solution temperature (LCST). This constellation induces a structure inversion of the solvophobic aggregate, called "schizophrenic micelle". Depending on the relative positions of the two different phase transitions, the block copolymer passes through a molecularly dissolved or an insoluble intermediate regime, which can be modulated by the polymer concentration or by the addition of salt. Whereas, at low temperature, the poly(sulfobetaine) block forms polar aggregates that are kept in solution by the poly(NIPMAM) block, at high temperature, the poly(NIPMAM) block forms hydrophobic aggregates that are kept in solution by the poly(sulfobetaine) block. Thus, aggregates can be prepared in water, which switch reversibly their "inside" to the "outside", and vice versa.}, language = {en} } @phdthesis{Stephan2007, author = {Stephan, Niels}, title = {Ph{\"a}nomenologische Untersuchungen zur Feuchteempfindlichkeit der elektrischen Eigenschaften von d{\"u}nnen Polymerfilmen und deren Verwendung f{\"u}r neuartige Feuchtesensoren}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-13853}, school = {Universit{\"a}t Potsdam}, year = {2007}, abstract = {Ziel dieser Arbeit ist die ph{\"a}nomenologische Untersuchung der Feuchteempfindlichkeit der elektrischen Eigenschaften d{\"u}nner Polymerschichten. Diese Untersuchungen stellen gleichzeitig Vorarbeiten zur Entwicklung von Prototypen von zwei polymeren D{\"u}nnschicht-Feuchtesensoren dar, die sich durch die spezielle Auswahl der feuchtesensitiven Materialien jeweils durch eine besondere Eigenschaft gegen{\"u}ber kommerziellen Massenprodukten auszeichnen. Ziel der Entwicklungsarbeiten f{\"u}r den ersten Prototypen war die Konstruktion eines schnellen Feuchtesensors, der pl{\"o}tzliche und sprunghafte Feuchte{\"a}nderungen in der umgebenden Atmosph{\"a}re m{\"o}glichst rasch detektieren kann. Daf{\"u}r wurden d{\"u}nne Schichten von Poly-DADMAC auf Interdigitalstrukturen aufgebracht, die einen m{\"o}glichst direkten Kontakt zwischen feuchtesensitiver Schicht und umgebender, feuchter Atmosph{\"a}re gew{\"a}hrleisten. Als Messgr{\"o}ßen dienten die Wechselstromgr{\"o}ßen Widerstand und Kapazit{\"a}t der Schichten. Die Feuchtekennlinien der Schichten zeigen gute Konstanz und hohe Reproduzierbarkeit. Der Widerstand der Schichten {\"a}ndert sich durch den Einfluss von Feuchte je nach Schichtdicke um 3 bis 5 Gr{\"o}ßenordnungen und eignet sich als Messgr{\"o}ße f{\"u}r die Feuchtigkeit im gesamten Feuchtebereich. Die Hysterese der Filme konnte auf kleiner als 2,5\% r.F. bestimmt werden, die Reproduzierbarkeit auf besser als 1\% r.F. Die Ansprechzeit der Schichten l{\"a}sst sich schichtdickenabh{\"a}ngig zu 1 bis 10 Sekunden bestimmen. Hierbei zeigen besonders die d{\"u}nnen Schichten kurze Ansprechzeiten. Zielstellung f{\"u}r den zweiten Feuchtesensor war die Entwicklung eines Prototypen, dessen sensitive Schicht sich biostatisch und biozid verh{\"a}lt, so dass er in biotischen Umgebungen eingesetzt werden kann. Es wurden f{\"u}nf Polysulfobetaine synthetisiert, deren Biozidit{\"a}t und Biostatik mit dem Kontakttest nach R{\"o}nnpagel, dem ISO846-Test und Abbautests bestimmt wurde. Zwei Polymere - Poly-DMMAAPS (BT2) und Poly-[MSA-Styren-Sulfobetain] (BT5) - erwiesen sich als ausreichend biozid und biostatisch. Schichten dieser Polymere wurden auf Interdigitalstrukturen aufgezogen, anschließend wurden die Kennlinien dieser Proben aufgenommen. Die Messwerte zeigen f{\"u}r beide Polymere gute Konstanz und eine hohe Reproduzierbarkeit. BT2-Proben sind zwischen 20\% und 80\% r.F. besonders empfindlich und zeigen {\"u}ber einen Monat keine Langzeitdrift. Vernetzte Proben zeigen bis 50°C keinen temperaturbedingten Abfall der Feuchteempfindlichkeit. Der Einsatz vernetzter BT5-Schichten als kapazitiver Feuchtesensor ist bis etwa 70°C m{\"o}glich, die Schichten sind selbst nach Lagerung im Hochvakuum und mehrfacher Betauung stabil. Damit liegen zwei funktionsf{\"a}hige Prototypen von Feuchtesensoren vor, f{\"u}r die die meisten Kennwerte denen von vergleichbaren kommerziellen Feuchtesensoren entsprechen. Gleichzeitig zeichnen sie sich aber durch eine sehr niedrige Ansprechzeit bzw. eine ausreichende Lebensdauer unter biotischen Bedingungen aus.}, language = {de} }