Silicone release liners are silicone coatings on top of papers or films that are used in the adhesives industry to prevent adhesion before the final use of the adhesive e.g. labels. The process of production of release liners involves the casting of molten polysiloxanes on top of the substrates that crosslink by hydrosilylation reaction forming silicone networks. The quality of the release liner can be assessed by diverse methods usually performed when the coating process has been finished. Rarely an online control of the reaction is possible. Fluorescence spectroscopy was found to be a non-invasive useful method to control the reaction during the whole process by introducing very small concentration of fluorescent molecules in the polymer formulations; those fluorophores are sensitive to environmental changes as the silicone polymer molecules crosslink. In response to that stimulus, the fluorescence intensity varies along the time upon reaction allowing the identification of the gel point and further modifications or molecules rearrangements in a post-curing stage within weeks that are non-observable with conventional quality control methods. It was found that the fluorescent molecules do not require to be attached covalently to the polysiloxanes, thus fluorescence spectroscopy is a simple method to implement for controlling the production of silicone coatings. Moreover, the characterization of several silicone formulations was performed to find the optimal conditions for the production of release liners and to understand the effect of every component in the formulation on the performance of the silicones. The kinetics of the reaction was also studied and even a mechanism for the hydrosilylation reaction was proposed.

Die RAFT-Polymerisation ("Reversible Addition-Fragmentation Chain Transfer") ist eine radikalische Polymerisation, die auf dem Prinzip des degenerativen Kettentransfers basiert. Es können Polymere hergestellt werden, die eine niedrige Dispersität aufweisen und komplexe makromolekulare Strukturen ausbilden. Für die Funktionalisierung von Polymerketten bietet sich die RAFT-Polymerisation ebenfalls an, da idealerweise jede auf diese Art hergestellte Polymerkette eine RAFT-Einheit trägt und so eine vollständige Funktionalisierung gewährleistet ist. Im Fokus dieser Arbeit stand die Funktionalisierung von Polybutadien und 1,3-Butadien enthaltenden Copolymeren mit gezielt eingebauten schwefelhaltigen Gruppen. Dabei wurden zwei verschiedene Ansätze verfolgt: Die α,ω-Funktionalisierung der Polymerketten mittels modifizierter RAFT-Agenzien sowie eine Funktionalisierung entlang der Polymerkette mit Hilfe von speziellen Monomeren. Da diese Polymere in technischen Anwendungen Verwendung finden sollen, standen einfache Synthesen, die sich gut auf den Technikums- und Industriemaßstab übertragen lassen, im Vordergrund. Da es sich bei der RAFT-Einheit auch um eine schwefelhaltige Gruppe handelt, wurden Strategien zur Funktionalisierung der Abgangsgruppe erarbeitet und experimentell untersucht, um so ein α,ω-funktionalisiertes Polymer zu erhalten. Neben klassischen RAFT-Agenzien wurden auch neuartige Makro-RAFT-Agenzien verwendet, bei denen die schwefelhaltige Gruppe während einer Polymerisation in situ angebunden wird. Darüber hinaus konnten erfolgreich Monomere synthetisiert werden, die wegen ihrer styrolähnlichen Struktur und der Ähnlichkeit der Monomere Styrol und 1,3-Butadien in ihrem Polymerisationsverhalten gut mit 1,3-Butadien copolymerisieren und dabei die schwefelhaltige Gruppe entlang der Polymerkette einbauen. Das Hauptaugenmerk weiterer Untersuchungen lag auf den Copolymerisationseigenschaften der Monomere. Dazu wurden umfangreiche Untersuchungen mit Styrol als Modellsystem für 1,3-Butadien durchgeführt und die gewonnenen Erkenntnisse in einer Copolymerisation der funktionalisierten Monomere mit 1,3-Butadien verifiziert. Es konnte weiterhin gezeigt werden, dass sich schaltbare RAFT-Agenzien für die Synthese von Poly(butadien)-block-poly(vinylacetat) eignen, obwohl es sich um zwei Monomere mit stark unterschiedlichen elektronischen Eigenschaften handelt, die in einer konventionellen radikalischen Polymerisation kein Copolymer bilden würden. Aufgrund der Ähnlichkeit der Monomere Vinylacetat und Ethylen eröffnet dies neue Wege in der kontrollierten radikalischen Polymerisation von Polybutadien-block-polyethylen und erweitert so das Spektrum der unpolaren Monomere in der RAFT-Polymerisation zur Herstellung von Blockcopolymeren.

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Mechanochromic polymers respond to external force by changing their color. This can be achieved by the incorporation of a molecular switch such as spiropyran (SP) into polymers. SPs can be isomerized by mechanical force from their colorless form into colored merocyanines. Main chain copolymerization of spiropyrans allows investigation of their mechanochromic behavior and potential use as force sensors. So far, several covalent polymer matrices have been used to investigate the mechanochromic response of SPs, among them poly(ε caprolactone) (PCL). Less investigated is how the mechanochromic response can be fine-tuned by substituent effects. First, PCL with differently substituted spiropyrans at the chain’s midpoint were used in order to investigate the effect of different substituents and their regiochemistry on the isomerization behavior of SPs under mechanical stress. A low activation barrier was observed for NO2 substitution of “ortho”-spiropyrans compared to no substitution (R = H). In order to investigate phenyl-substituted “para,para” spiropyrans, a newly developed kinked polyarylene was employed as covalent matrix material. This new polyarylene (PmmpP) has a meta,meta,para connection in its backbone and exhibits excellent mechanical properties. Its high strength allows the isomerization of this molecular switch with a large activation barrier. The phenyl-substituted “para,para” spiropyran showed transient mechanochromism and was switched 25 times in force-and-release cycles. The synthesis of PmmpP was carried out by a Suzuki polycondensation in three steps from commercial starting materials. To further capitalize on the simplicity and properties of PmmpP, a two step synthesis of a semifluorinated kinked polyarylene was demonstrated by direct arylation polycondensation with tetrafluorobenzene (F4). This partially fluorinated PmmpF4 was synthesized with a variety of side-chains. Resulting polymers exhibited a large range of glass transition temperatures, allowing for the production of tailor-made smart materials.

This doctoral thesis focuses on synthesis of rigid star-shaped and rod-like viologen oligomers. The work is divided in two parts: synthesis, characterization and electropolymerization of star-shaped (i) and rod-like viologens oligomers (ii). In the first part the synthesis of viologen stars consisting of a phenyl core with triple 1,3,5-branching, each branch consisting of a linear alternating series of diphenyl (PhV++) and dibenzyl (BnV++) viologens and a variety of peripheral groups –X (Br, OH), is presented. A new electrochemical method of electrode modification (Gold, GC, ITO and CNTs) with viologen derivatives based on a benzyl radical coupling mechanism is described. The radicals are excessively generated at the star periphery resulting in a highly cross-linked polyviologen film with persisting star subunits. It is characterized by CV, STM and UV-Vis methods. Redox-titration experiments monitored by UV-Vis reveals that the reduction of the viologen stars begins at the periphery with the formation of PhV+•, continues with generation of BnV+• and ends with the reduction of the radical cations in the same sequence. Thus, viologen stars combine the unique redox and electrochromic property of isolated phenyl and benzyl viologen in one molecule. The second part of the thesis focuses on the step-wise synthesis of a library of rigid rod-like conjugated difunctional viologen/diphenyl oligomers with varying chain lengths including different side chain substitution. All oligomers are soluble in DMSO or MeOH depending on the counter anion (PF6- or Cl-). In order to tune the solubility of the oligomers, the side chains are tailored as methoxy, butoxy and oligo(ethylene oxide). The most solubilizing side-chains are of the oligo(ethylene oxide) type. All viologen oligomers are characterized by means of 1H-NMR, 13C-NMR, elemental analysis, optical spectroscopy and cyclic voltammetry. A simple surface functionalization and grafting technique has been developed for covalent binding of the viologen oligomers onto various conductive substrates e.g.: Au, GC and ITO. These modified electrodes are suitable for potential applications in designing field-effect transistors, sensors and supercapacitors. The polymer layers are characterized by means of FT-IR, STM, XPS and CV. The combined results presented in thesis represent a major advance in electrode functionalization by n-dopable viologen polymers and herald a variety of potential applications that make use of n-type semiconductors.

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