Die vorliegende Arbeit liefert einen Beitrag zum Verständnis der komplexen Struktur-/Eigenschaftsbeziehungen dünner Schichten hochverzweigter Polyester. Für die umfassende Charakterisierung wurde eine Vielzahl analytischer Methoden kombiniert. Des Weiteren wurde das Anwendungspotential dieser Schichten hinsichtlich möglicher Sensoranwendung anhand der Adsorption von Modellproteinen gewichtet. Dazu war es notwendig verschieden Methoden zur Stabilisierung dieser Schichten zu entwickeln.

Binäre Polymerbürsten bestehen aus zwei verschiedenen Polymertypen, die nebeneinander auf dem gleichen Trägermaterial verankert sind. Wenn diese Polymere unterschiedliche Benetzungseigenschaften haben, können damit schaltbare Oberflächen produziert werden. Abhängig vom Lösungsmittel, dem man die binäre Polymerbürste aussetzt, streckt sich entweder das hydrophile oder das hydrophobe Polymer zum Lösungsmittel hin, während die zweite Komponente nahe der Oberfläche verbleibt. Durch diese vertikale Phasenseparation kann temporär eine bestimmte Oberflächeneigenschaft erzeugt werden. Allerdings verschwindet diese sofort wieder, wenn ein anderes Lösungsmittel die binäre Bürste benetzt, sei es durch direkten Kontakt oder über die Gasphase. In der vorliegenden Arbeit wurde untersucht, ob es möglich ist, neuartige schaltbare binäre Polymerbürsten bestehend aus einem hydrophilen und einem hydrophoben Polymer angebunden auf Siliziumwafern herzustellen, deren Schaltfähigkeit durch photochemische Vernetzung unterbunden werden kann. Geprüft worden ist unter anderem, inwiefern sich hydrophober und hydrophiler Zustand der Schicht fixieren lassen und ob daraus resultierend, eine entsprechende Strukturierung der Oberfläche nach Bestrahlung durch eine geeignete Fotomaske oder durch fokussiertes Licht nachweisbar ist. Als hydrophobe Komponente wurden photovernetzbare Styren/2-(4’-Styryl)-inden-Copolymere verwendet, als hydrophile Komponente kam Polyvinylpyridin zum Einsatz. Mit einem speziellen Oberflächeninitiator konnten durch „Grafting from“ binäre Polymerbürsten mit bis zu 300 nm Schichtdicke erzeugt werden. Es ist gelungen, diese schaltbaren Schichten durch selektive photochemische Vernetzung einer der Bürstenkomponenten im hydrophilen oder im hydrophoben Zustand zu fixieren, was durch Kontaktwinkelmessung nachgewiesen werden konnte. Wie beabsichtigt, verlieren dabei die vernetzten Bereiche ihre Schaltfähigkeit. Es ließen sich feine Oberflächenstrukturen mittels Bestrahlung durch eine Fotomaske erzeugen, die sichtbar werden, wenn man sie mit Wasser benetzt bzw. Wasserdampf aussetzt.

Die Arbeit beschreibt die Synthese und Charakterisierung von amphiphilen Polyurethanen mit Emulgatoreigenschaften für die Polymerisation hydrophober Monomere in wässriger Phase. Der Emulgator wurde mit kolloid- und polymerchemischen Methoden hinsichtlich seiner grenzflächenaktiven Eigenschaften sowie einer Strukturbildung in wässriger Phase charakterisiert. Die Emulsionspolymerisation mit dem polymeren PU-Emulgator am Beispiel von Styrol ist untersucht worden. Dabei sind die Partikelgrössen und deren Verteilung in Abhängigkeit von Reaktionsparametern mittels Photonen-Korrelations-Spektroskopie und durch Fluss-Feldfluss-Fraktionierung (F-FFF) bestimmt worden. Weiterhin wurde mittels Dilatometrie und Reaktionskalometrie die Polymerisationskinetik untersucht. Die Partikelmorphologie konnte durch Festkörper-NMR modelliert werden. Durch Atomic Force Microscopy (AFM) im Tapping mode konnte die Oberfläche und die Phasenseparation der polymeren Phasen charakterisiert werden. / This paper describes the synthesis of a reactive amphiphilic polyurethane, and its use as an emulsifier for the emulsion polymerization of styrene. The colloid properties and the structure of the emulsifier in the aqueous phase have been investigated. When the acrylic polymerization is carried out with hydrophobic monomers, we obtain a composite particle structure. The variation of particle size and particle size distribution as a function of the reaction parameters was measured by light scattering methods and Flow-fieldflow-fractionation (F-FFF) . Through investigation by dilatometry and reaction calorimetry it was possible to compare the polymerization process with that of common emulsion polymerization. Solid State NMR analysis allowed us to develop a core-shell model for the composite particle structure, and to determine the presence of an interphase layer between core and shell. Atomic Force Microscopy (AFM) methods were used to characterize the surface of the films, and tapping mode AFM was used to characterize the polymer phase separation on the micro scale.

The thesis aims to synthesize hyperbranched poly(urea-urethane) polymers (HPU) in one-pot method using commercially available monomers which are 2,4-toluylene diisocyanate (TDI) as aromatic diisocyanate and isophorone diisocyanate (IPDI) and 2(3-isocyanatopropyl) cyclohexylisocyanate (IPCI) as aliphatic diisocyanates. Those proposed diisocyanates were reacted with diethanolamine (DEA) or diisopropanolamine (DIPA). Conditions of polymerisation reactions were optimised. Complete structural analysis using 1H and 13C NMR for the obtained aromatic polymers was carried out. Degree of branching up to 70% was calculated. Aliphatic polymers have spectra with overlapped signals therefore, no full structural analysis was possible. Molar masses were determined using SEC/RI detector which shows that the prepared polymers have Mw values between 1600 g/mol and 106000 g/mol. Thermal analysis for different polymer systems showed that aliphatic HPU are more thermally stable and have values of glass transition temperature higher than aromatic ones. Modification of the end groups in the prepared hyperbranched polymers was carried out using three different modifiers and degree of modification up to 100%. Linear polymers based on the same diisocyanate monomers were prepared to compare the properties of hyperbranched systems with their linear analogs. Measurements of solution viscosity showed that HPU have lower solution viscosity values than their linear analogs of comparable molar masses. Rheological measurement of some polymer samples of different systems were carried out and showed that our hyperbranched systems exhibit a more elastic behavior than the linear polymers. Surface studies for thin films prepared from different polymer systems (hyperbranched, linear and modified) were carried out and the obtained thin films were characterized using light microscope, microglider, GC-MS, and AFM. Contact angle measurements showed that HPU have a relatively hydrophilic character. The modified polymers have higher contact angle values than the unmodified ones due to the lack of OH end groups. Networks based on aliphatic and aromatic HPU were prepared through the reaction of HPU with trimer of 1,6-diisocyanatohexane and characterised by DSC, GC-MS, DMA and AFM. The domain size in aromatic networks was found to be larger than in aliphatic networks. Tensile test was carried out and it was found that aliphatic network is more elastic than aromatic one.

Multifunctional monomers on the basis of acryl- and methacryl derivatives were synthesized and different protective groups were used. After polymerization the protective groups were removed by different methods. Various initiators for the NMP of the monomers were synthesized and the reaction conditions were optimized. The results showed that NMP was not a suitable method for multifunctional acryl- and methacryl derivatives to achieve well-defined homopolymers, although it was successful for control of polymerization of styrene and block copolymerization of multifunctional acryl- and methacryl derivatives with alkoxyamine terminated polystyrene. The ATRP of multifunctional acrylates and methacrylates has been successfully performed, as well as the block copolymerization of multifunctional acrylates and methacrylates. Relatively low polydispersities of the corresponding polymers (PD=1.18-1.36) and reasonably high rates of polymerization could be achieved when Me6TREN and PMDETA were used as ligands. However, the ATRP of multifunctional acrylamides and methacrylamides failed. The RAFT-polymerization of styrene, acrylamide and acrylate using BDTB as a CTA and AIBN as an initiator afforded polymers with narrow molecular weight distribution (PD=1.13-1.26). A kinetic investigation and the further synthesis of block copolymers using dithioester-terminated homopolymers as macroCTAs showed that the RAFT polymerization of acrylamide M9b proceeded in a living manner. However, BDTB does not control the reaction of methacrylic monomers, such as methacrylates and methacrylamides. The bulk phase behavior of the block copolymers were examined by means of DSC and the surface behaviors of block copolymers as thin layers were examined with AFM. Two-phase transitions in the block copolymers were observed clearly by DSC, indicative of the appearance of phase separations, which were seen in an AFM image. In conclusion, multifunctional acryl- and methacryl derivatives failed to achieve well-defined homopolymers by NMP. However, this method was successful for block copolymerization of multifunctional acryl- and methacryl derivatives with alkoxyamine terminated polystyrene. Multifunctional acrylates and methacrylates were successfully homopolymerized and block copolymerized by ATRP. Multifunctional acrylates and acrylamides were suitable for homopolymerization and block copolymerization by the RAFT process. Thus far, it is difficult to homopolymerize multifunctional methacrylamides in controlled way.

The framework of this thesis aims to fabricate materials, which change surface characteristics in response to environmental conditions. This response may be employed to improve material characteristics as adhesion, wettability, interaction with cells etc. The mixed brushes introduce adaptive and switching behavior in different surrounding media. Two main approaches were employed to fabricate mixed polymer brushes: "grafting to" and "grafting from". Mixed PS/PVP polymer brushes were synthesized via step-by-step grafting of these two polymers from polyamide (PA) surfaces. NH3 plasma was used for the introduction of amino and OH functionalities on PA surfaces with following attachment of azo initiator of radical polymerizaton. The mixed brushes prepared on the surface of PA textiles combine both the switching effect and effect of composite surface (i.e. micrometer scale roughness) which substantially amplifies the switching range. Mixed polymer brushes prepared from P(S-b-2VP-b-EO) and P(S-b-4VP) block copolymers were grafted to both the flat surface of Si wafers and to the surface of silica nanoparticles via quaternization reaction of the pyridine nitrogen. This one step grafting technique has a substantial advantage over the multistep grafting of mixed polymer brushes. We have demonstrated that combination of the two level hierarchical organization of polymer films at macroscopic and nanoscopic levels resulted in the formation of self adaptive surfaces switchable in controlled environment from ultra-hydrophobic to hydrophilic energetic states. The PFS/PVP mixed brush was grafted onto the pre-treated PTFE surface (plasma etching) with the needle like topography. The size of vertical needles was at micron scale. If the brush is switched to the hydrophobic state the layer has shown a unique ultra-hydrophobic behavior (complete non-wetting) with the contact angle approaching value of 160o. If the mixed brush was switched into the hydrophilic state the surface became completely wetted due to the capillary forces in the pores formed by the needle like structure. Thus, the surface can be either highly wettable or completely non-wettable with the self cleaning properties.

Stimuli sensitive polymers and hydrogels respond with large property changes to small physical and chemical stimuli (e.g. temperature, pH, ionic strength). The bulk behavior of these polymers is widely studied and they show an isotropic swelling. However, thin hydrogel layers of polymers on a substrate show a swelling behavior, which is constrained in some way. Therefore, size, confinement, patternability, response time and transition temperature of thin hydrogel layers are the most important parameters in technological applications and this study focuses on the investigation of these above-mentioned parameters. The aim of this study involves synthesis, characterization and application of thin photo-crosslinked hydrogel layers. Dimethylmaleimide (DMI) moiety was incorporated in the polymers chains and was used to introduce photo-crosslinking by [2+2] cyclodimerization reaction in the presence of UV irradiation. The following photo-crosslinkers based on DMI group were synthesized ? - Acrylate photo-crosslinker (DMIAm) - Acrylamide photo-crosslinker (DMIAAm) - Polyol photo-crosslinker (DMIPA, DMIPACl) The conventional free radical polymerization of above listed photo-crosslinker with its respective monomer resulted in formation of photo-crosslinkable polymers of (a) HEMA, (b) DMAAm, (c) NIPAAm/DMAAm, (d) NIPAAm/Cyclam. The properties of these polymers were investigated by NMR, UV-VIS spectroscopy, GPC and SPR. Thin hydrogel layers were prepared by spin coating on gold-coated LaSFN9 glass. The covalent attachment to the surface was achieved through an adhesion promoter. Swelling behavior of the thin polymer layers was thoroughly investigated by Surface Plasmon Resonance (SPR) Spectroscopy and Optical Waveguide Spectroscopy (OWS). SPR and OWS gave a wide range of information regarding the film thickness, swelling ratio, refractive index, and volume degree of swelling of the thin hydrogel layer. For hydrophilic photo-crosslinked hydrogel layers of HEMA and DMAAm, it was observed that the volume degree of swelling was independent of temperature changes but was dependent on the photo-crosslinker mol-% in the polymer. These surface attached thin hydrogel layer exhibited an anisotropic swelling. For NIPAAm photo-crosslinked hydrogel layers with DMAAm as a hydrophilic monomer, it was observed that both transition temperature (Tc) and volume degree of swelling increases with increase in the mol-% of DMAAm. To study the effect of film thickness on Tc and volume degree of swelling, hydrogels with wide range of film thickness were prepared and investigated by SPR. These results provided vital information on the swelling behavior of surface attached hydrogel layer and showed the versatility of SPR instrument for studying thin hydrogel layers. Later part of project involved synthesis of multilayer hydrogel assembly involving a thermoresponsive polymer and a hydrophilic polymer. The combination of two layers with photo-crosslinkable DMAAm polymer as base layer and photo-crosslinkable NIPAAm polymer as top layer formulate a multilayer assembly where, the base layer only swells in response to temperature and the top layer shows temperature dependent swelling. Photo-crosslinked hydrogel layers of NIPAAm, DMAAm and HEMA shows a high-resolution patterns when irradiated by UV light through a chromium mask. At last this study focused on an important application of these hydrogel layers for cell attachment processes. Cell growth, proliferation and spreading shows a biocompatible nature of these hydrogel surfaces. Such thermoresponsive photo-crosslinkable multilayer structure forms bases for future projects involving their use in actuator material and cell-attachment processes.

Conducting polymers find variety of application in many areas in microelectronics. PPY and PT are among the most extensively studied intrinsically conducting polymers. The problem of poor adhesion of the electrochemically deposited conducting polymers was the main focus of this work. This easy peeling of the PPY layer from the oxide substrate was circumvented by design of novel adhesion promoters, which compatibilise the two incompatible surfaces- the polymer film and the oxide substrate. The first part of the research was focused on the synthesis of different classes of adhesion promoters. These monomers were based on monoheterocyclic derivative of 3-substituted pyrrole and a tricyclic derivative of 2,5-dithienylpyrrole. The synthesized monomers were bifunctional with a specified and defined task for each group. Pyrrole based monomers, 3-phenyl N-alkyl pyrrolyl phosphonic acids referred as C10PhP and C12PhP and the monomers based on 2,5-dithienylpyrrole were synthesized with different anchoring groups namely, -Si(OMe)3 and-PO3H2 and spacer groups (n= 4, 6, 10, 12, benzyl). SNSnP for [(2,5-dithiophen-2-yl-pyrrol-1-yl)-dodecyl]-phosphonic acid, SNSnTMS for [(2,5-dithiophen-2-yl-pyrrol-1-yl)-alkyl]-trimethoxysilane and ArP for 4-(2,5-di-thiophen-2-yl-pyrrol-1-yl)-1-yl)-benzyl]-phosphonic acid was used as acronym for further references. The adsorption and self-organisation process as well as the surface reactions of these adhesion promoters on different oxide surfaces have been investigated. The aim was to graft conducting polymer layers covalently on modified metal oxide surfaces. This novel molecule has the self-assembling property and can bind to the surface via acid-base interactions with the oxide surface. The pre-treated oxide substrates were modified by self-assembling technique from solution. Static contact angle gave the first indication of a successful adsorption. The kinetics of adsorption was monitored by Surface Plasmon Resonance Spectroscopy (SPR), Angle-Resolved X-Ray Photoelectron Spectroscopy (AR-XPS) confirms that the molecules are standing with the phosphonic acid group present in the inner part of the self-assembled monolayer (SAM), and the 2,5-dithienylpyrrole group is free on the top for further surface reactions. Such self-assembling molecules can find applications in grafting conducting polymer layers on metal oxide surfaces. The grafting process of conducting polymer was done either chemically or electrochemically with additional monomer. Thickness and morphology of the polymer films were studied by AFM and SEM. The film thickness could be adjusted between several hundreds of nanometer by varying the polymerization conditions. The tape-test confirms the strong adhesive bonding of the polymer to the modified substrate. Besides PPY, Poly(SNS) and Poly(SNSnP) were studied for their properties. The optical properties of Poly(SNS) were studied by UV-Vis spectroscopy. Electrochemically deposited polymer films of (Poly(SNS), Poly(SNSnTMS), Poly(ArP) and Poly(SNSnP)) was investigated by UV-Vis spectroscopy, XPS, grazing-angle FTIR spectroscopy, four-point conductivity and I-V and luminance - voltage characteristics. Grazing-angle FT-IR of the homopolymer, poly(SNSnP) showed interesting results. We observed the peaks due to P-OH at 1111 cm-1 indicating that the phosphonic acid is free on the top. This can find application as ion sensor because phosphonates are known to be good chelating agents. Comparison of the EIS and four-point conductivity measurements for the homopolymers of SNSnP and Poly(SNS) indicated a drop in the conductivity in case of substituted hompolymers. Poly(SNSnP) based LED device give white emission. EL spectra show broad bands, which cover the entire spectrum. They can be studied further for the development of light emitting diodes of different colours.

Oligomers and polymers based on functionalized Rf-amides were successfully synthesized for the fabrication of hydrophobic surfaces with either linear or network structure. Firstly, new functionalized Rf-amides (RfCONH-, Rf is a perfluoroalkyl segment) were developed in most cases by a one step reaction and a simple work-up procedure. The reaction behaviors of synthesized Rf-amides in polyreactions were well understood. New fluorinated oligoester polyols, blocked IPDI's, and end-hydroxyl terminated oligo(urea urethane)s have been synthesized, the detail structures and properties are well understood. These materials could be suitable components of powder coatings. On the other hand, the end-hydroxyl terminated oligo(urea urethane)s could be used as reactive additives in high solid content and water-borne coatings. Hydrophobic smooth surfaces based on linear polymers, poly(urea urethane)s and alternating MI copolymers, containing fluorinated side groups were successfully constructed. The attachment of fluorinated side groups into polymers can dramatically alter the surfaces of corresponding polymers from more hydrophilic to hydrophobic due to the enrichment of fluorinated side groups on the top of the surface. The backbone configuration, the polarity of backbones, and the thermal treatment on surfaces can influence the surface properties of corresponding materials. Finally, hydrophobic surfaces of cross-linked polyurethanes as model top coatings were constructed under melt condition at high temperature (180 and 190 oC) using the combination of fluorinated oligouretdiones and non-fluorinated oligoester polyols. It was found that the hydrophobicity of resulting cured films is a matter of the competition between the formation of cross-linking network and the segregation of fluoromoieties on the top of the surface.

Ziel dieser Arbeit ist die Darstellung funktioneller Materialien, die ein multi-sensitives Ansprechverhalten aufweisen. Die Charakterisierung des Quellverhaltens der Gele stellt die Voraussetzung dar, die phasenseparierten Polymerfilme als multi-sensitive Sensorschichten mit verbessertem Ansprechverhalten einzusetzen. Die Aufgabe dieser Arbeit besteht in der Synthese von AB-Blockcopolymeren, die im wässrigen Medium auf die Temperatur oder auf die Temperatur und den pH-Wert ansprechen. Unter Verwendung der Makroinitiator-Technik werden Blockcopolymere synthetisiert. Zunächst werden temperatur-sensitive Polymere mit einem wasserlöslichen Polyethylenglykol-Block (PEG) und N-Isopropylacrylamid (NIPAAm) mittels "Atom Transfer Radical Polymerization" (ATRP) hergestellt. Die Umsetzung der durch "Nitroxide Mediated Radical Polymerization" (NMRP) hergestellten pH-sensitiven Poly(2-vinylpyridin)-Blöcke (P2VP) mit NIPAAm führt zu multi-sensitiven Blockcopolymeren. Da die Polymere auf ihre Quelleigenschaften in dünnen Filmen hin untersucht werden sollen, ist die Verwendung eines Chromophors, der in den NIPAAm-Block einpolymerisiert wird, nötig. Die Vernetzung der Polymerfilme erfolgt photochemisch. Das Quellverhalten der Polymerschichten wurde mit der Methode der "Surface Plasmon Resonance"-Spektroskopie (SPR) charakterisiert. Im Rahmen dieser Arbeit ist es gelungen, multi-sensitive Polymere darzustellen und deren Sensitivität in dünnen Polymerfilmen nachzuweisen. Bei den synthetisierten Polymeren handelt es sich um neuartige und funktionelle Materialien.