Influence of ionic interactions on the photoinduced Birefringence of poly[1-[4-(3-carboxy-4 hydroxyphenylazo) benzene sulfonamido]-1 2-ethanediyl, sodium salt] films

Electrostatic interactions govern most properties of polyelectrolyte films, as in the photoinduced bire-fringence of azo-containing polymers. In this paper we report a systematic investigation of optical storage characteristics of cast and layer-by-layer (LbL) films of poly[1 -[4-(3-carboxy-4 hydroxypheny-lazo) benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO). Birefringence was photoinduced faster in PAZO cast films prepared at high pHs, with the characteristic writing times decreasing almost linearly with the pH in the range between 4 and 9. This was attributed to an increased free volume for the azochromophores with the enhanced electrostatic repulsion in PAZO charged to a greater extent. In contrast, in LbL films of PAZO alternated with poly(allylamine hydrochloride) (PAH), the electrostatic interactions between the oppositely charged polymers hampered photoisomerization and molecular rearrangement, thus leading to a slower writing kinetics for highly charged PAH or PAZO.

On the equivalence of the mechanisms governing switching and hysteresis phenomena

The nucleation and growth model, which is usually applied to switching phenomena, is adapted for explaining surface potential measurements on the P(VDF-TrFE) (polyvinylidene fluoride-trifluoroethylene) copolymer obtained in a constant current corona triode. It is shown that the growth is one-dimensional and that the nucleation rate is unimportant, probably because surface potential measurements take much longer than the switching ones. The surface potential data can therefore be accounted for by a growth model in which the velocity of growth varies exponentially with the electric field. Since hysteresis loops can be obtained from surface potential measurements, it is suggested that similar mechanisms can be used when treating switching and hysteresis phenomena, provided that account is taken of the difference in the time scale of the measurements.

Thermal treatment effects on phase transitions in P(VDF-TrFE)

Differential scanning calorimetry (DSC) studies were performed for 60/40 P(VDF-TrFE). The results not only confirm the importance of thermal history but also show that the samples with various configurations in terms of ferroelectric phases can be obtained via thermal treatment.

Thermal analysis of conductive blends of PVDF and poly(o-methoxyaniline)

The thermal behavior of blends of poly(vinylidene fluoride), or PVDF, and poly(o-methoxyaniline) doped with toluene sulfonic acid was studied by thermogravimetic analysis, electrical conductivity measurements, differential scanning calorimetry, X-ray diffraction and scanning electron microscopy. Blends with thermal and electrical conductivity stabler than the conductive polymer alone were obtained. Nevertheless, degradation occurs after a long period of time (500 h) at high temperatures. The possible association of the conductivity decay with dopant loss, degradation and structural and morphological changes of the blend is discussed. (C) 2000 Elsevier Science Ltd.

Effects of thermal treatment on phase transitions and on the mechanical relaxation in poly(vinylidene fluoride)

This work reports on the effects from thermal treatment in poly(vinylidene fluoride), PVDF, obtained with differential scanning calorimetry (DSC) and dynamic thermal analysis (DMA) measurements. It is shown that in successive DMA measurements performed with one sample the α relaxation peak almost disappears while the γ′ peak appears. The α relaxation peak, at ∼100°C in DMA measurements, is attributed to the preferential orientation of chains in the amorphous phase while the γ′ relaxation peak, at ∼50°C, is related to the thermal treatment to which the sample was submitted.

Template-based fluoropolymer ferroelectrets with multiple layers of tubular channels

Significant efforts are devoted to developing new ferroelectrets with well-controlled void distributions or uniform voids and with good long-term and thermal stability of the piezoelectricity. Here, we describe the concept, the fabrication, and the most relevant properties of fluoropolymer ferroelectret systems with three separate films of fluoroethylenepropylene (FEP), alternating with two polytetrafluoroethylene (PTFE) templates. The FEP films are selectively fused by means of a lamination process. Two practically identical PTFE templates are used, which have parallel rectangular openings (1.5×30 mm 2) separated by PTFE ridges of 1.5 mm width. After removing the PTFE templates, a three-layer FEP-film sandwich with tubular channels is obtained. We demonstrate that such FEP-film systems exhibit significant and stable piezoelectricity after charging under a high DC voltage. The resulting piezoelectric effect may be further improved by carefully assembling and arranging the PTFE templates during preparation. ©2010 IEEE.

A New Fluorinated Polymer Having Two Connected Rings in the Main Chain: Synthesis and Characterization of Fluorinated Poly(1,3-cyclohexadiene)

The high electronegativity and small size of the fluorine atom and the high stability of C-F bonds impart interesting properties and applications to fluorine containing polymers. The unique properties of fluoropolymers include high thermal stability, improved chemical resistance, low surface energies, low coefficients of friction, and low dielectric constants. Applications of fluorinated polymers include use as noncorrosive materials, polymer processing aids, chemically resistant and antifouling coatings, as well as interlayer dielectrics. Fluorine-containing polymers can be directly synthesized via polymerization of fluorine-containing monomers or by post-polymerization modification. The latter method can be used to attach fluorinated species, such as perfluoroalkyl groups, onto conventional polymer chains, thereby imparting properties of fluorine-containing polymers into conventional polymers and widening their range of potential applications.

Photoinduced orientation in natural rubber

Azobenzene molecules and their derivatives have been widely investigated for their potential applications in optical and electrooptical devices. We have prepared a new guest-host system from natural rubber (NR) impregnated with azobenzene derivative Sudan Red B (SRB). The effects of stretching and immersion time on photoinduced orientation were investigated by birefringence signal measurements. We have found that the molecular orientation increase when the samples are stretched and decrease with the increase of immersion time. The first behavior was explained by using the random coil model and the latter was attributed to increase of the aggregation of SRB into NR matrix. (C) 2012 Published by Elsevier B.V.

Optically active photoresponsive multifunctional polymeric materials

In the last year [1], Angiolini and co-workers have synthesized and investigated methacrylic polymers bearing in the side chain the chiral cyclic (S)-3-hydroxypyrrolidine moiety interposed between the main chain and the trans-azoaromatic chromophore, substituted or not in the 4’ position by an electron-withdrawing group. In these materials, the presence of a rigid chiral moiety of one prevailing absolute configuration favours the establishment of a chiral conformation of one prevailing helical handedness, at least within chain segments of the macromolecules, which can be observed by circular dichroism (CD). The simultaneous presence of the azoaromatic and chiral functionalities allows the polymers to display both the properties typical of dissymmetric systems (optical activity, exciton splitting of dichroic absorptions), as well as the features typical of photochromic materials (photorefractivity, photoresponsiveness, NLO properties). The first part of this research was to synthesize analogue homopolymers and copolymers based on bisazoaromatic moiety and compare their properties to those of the above mentioned analogue derivatives bearing only one azoaromatic chromophore in the side chain. We focused also the attention on the effects induced on the thermal and chiroptical behaviours by the insertion of particulars achiral comonomers characterized by different side-chain mobility and grown hindrance (MMA, tert-BMA and TrMA). On the other hand carbazole containing polymers [2] have attracted much attention because of their unique features. The use of these materials in advanced micro- and nanotechnologies spreads in many different applications such as photoconductive and photorefractive polymers, electroluminescent devices, programmable optical interconnections, data storage, chemical photoreceptors, NLO, surface relief gratings, blue emitting materials and holographic memory. The second part of the work was focused on the synthesis and the characterization polymeric derivatives bearing in the side chain carbazole or phenylcarbazole moieties linked to the (S)- 2-hydroxy succinimide or the (S)-3-hydroxy pyrrolidinyl ring as chiral groups covalently linked to the main chain through ester bonds. The last objective of this research was to design, synthesize, and characterize multifunctional methacrylic homopolymers and copolymers bearing three distinct functional groups (i.e. azoaromatic, carbazole and chiral group of one single configuration) directly linked in the side chain. This polymeric derivatives could be of potential interest for several advanced application fields, such as optical storage, waveguides, chiroptical switches, chemical photoreceptors, NLO, surface relief gratings, photoconductive materials, etc.

Synthesen und Charakterisierungen Arylamin-haltiger Polymere: multifunktionelle hoch-T g-Copolymere für photorefraktive Anwendungen

Zusammenfassung Die vorliegenden Arbeit beschäftigt sich mit den Synthesen und Charakterisierungen multifunktioneller, Arylamin-haltiger Polymere, welche sich als photorefraktive(PR)-Materialien eignen. Die Glastemperaturen (Tg) der angestrebten Materialien liegen deutlich über Raumtemperatur, um so den Pockels-Mechanismus zum Aufbau des PR-Effektes zu favorisieren. Hierzu sind zwei synthetische Konzepte, basierend auf Maleinimid-Methylvinylisocyanat-Reaktiv-Polymeren und Triphenylamin-haltigen Polymeren, entwickelt worden. Im Rahmen des Reaktiv-Polymer-Konzeptes konnten PR-Materialien mit den bisher größten Beugungs-Effizienzen sowie den schnellsten Ansprechzeiten für multifunktionelle hoch-Tg-Polymere dargestellt werden. Hierfür wurden Maleinimid-Methylvinylisocyanat-Reaktiv-Polymere synthetisiert welche an der Imid-Position über Spacer-Gruppen mit Carbazol-Einheiten funktionalisiert sind. Die Tg´s der Polymere konnten zwischen 60°C und 194°C eingestellt werden. Die Isocyanat-Gruppen wurden dann polymeranlog mit hydroxyalkyl-funktionalisierten Chromophoren umgesetzt. Die Kinetik des PR-Effektes dieser Materialien wird durch die Ladungsträger-Beweglichkeiten in den Proben bestimmt. Eine Steigerung der Farbstoff-Konzentrationen erhöht die PR-Leistungen der Materialien, behindert jedoch deren Kinetik.Das Triphenylamin-Polymer-Konzept verwendet Triphenylamine als Lochleiter. Hierfür wurden die radikalischen Polymerisations-Verhalten der Monomere p-Diphenylaminostyrol (DPAS) und erstmals p-Ditoluylaminostyrol (DTAS) untersucht. Die Monomere wurden durch spontane, freie und kontrollierte radikalische Verfahren polymerisiert. Mittels eines TEMPO-Derivates gelang der Aufbau von Block-Copolymeren. Poly-DPAS konnte, im Gegensatz zu Poly-DTAS, polymeranlog tricyanovinyliert werden. Dadurch lassen sich PDPAS-block-PTPAS-Copolymere selektiv im PDPAS-Block tricyanovinylieren. Diese Materialien weisen eine Tendenzen zur Mikro-Phasen-Separation auf.Die Strukturierung von PDPAS konnte durch Photo-Polymerisation mit einer Auflösung von wenigen mm demonstriert werden. Carbazol und Triphenylamin-haltige Materialien wurden mittels Cyclo-Voltametrie untersucht.

Ionomere zum Aufbau funktioneller Oberflächen

Im ersten Teil der Arbeit wurden Ionomere durch aufeinanderfolgende polymeranaloge Reaktionen eines Reaktivesterpolymers mit verschiedenen primären bzw. sekundären Aminen synthetisiert. Polarisationsmikroskopische Untersuchungen zeigten, dass diese Ionomere sowohl über thermotrope als auch über lyotrope flüssigkristalline Eigenschaften verfügen. Anschließend wurden mit der 'self-assembly'-Methode Multischichtfilme aus den Ionomeren und hochgeladenen Polyelektrolyten sowie aus entgegengesetzt geladenen Ionomeren aufgebaut. Bei Röntgen-reflexionsmessungen an den Multischichtfilmen konnten winkelabhängige Modulationen der Strahlungsintensität beobachtet werden. Es ist zu vermuten, dass es sich bei diesen Modulationen um Überlagerungen von Kiessig-Ringen und Bragg-Peaks handelt, was ein Indiz dafür ist, dass regel-mäßige Subschichten in den Filmen existieren. Das Konzept der polymeranalogen Reaktionen eines Reaktivesterpolymers mit verschiedenen primären Aminen wurde außerdem dazu benutzt, Polymere zur Modifikation von Cadmiumselenid-Nanokristallen herzustellen. Hierbei konnte zum einen gezeigt werden, dass Nanokristalle direkt mit aminogruppenhaltigen Polymeren modifiziert werden können, zum anderen ist es auch möglich kationische Ionomere auf Nanokristallen mit Mercaptoessigsäure-Liganden zu adsorbieren. Im letzten Teil der Arbeit wurden ionische triazinhaltige Polymere hergestellt und elektrochemisch charakterisiert. Die hergestellten Polymere sind sehr leicht reduzierbar. Anschließend wurden aus den triazinhaltigen Polymeren und entgegengesetzt geladenen Polyelektrolyten ebenfalls Multischichtfilme hergestellt.

Synthesis and characterization of novel poly(imino ketone)s via palladium-catalyzed aryl amination

The challenge of the present work was to synthesize and to characterize new classes of N-containing polymers via palladium-catalyzed aryl amination. This work was inspired by a desire to combine the properties of high-performance polymers such as PEKs with those of N-containing conductive polymers such as polyaniline (PANI), poly(aromatic amides) (PAAs), and the ready synthesis of N-containing simple aromatic compound by the Buchwald-Hartwig reaction. Careful investigation of a model reaction was carried out to provide insights into the formation of side products which will have a negative effect upon the molecular weight or upon the materials properties of the desired polymers in the polycondensation reaction. In this thesis, five new different polymer classes namely, poly(imino ketone)s (PIKs), poly(imino acridine)s (PIAcs), poly(imino azobenzene)s (PIAzos), poly(imino fluorenone)s (PIFOs), and poly(imino carbazole)s (PICs) were synthesized and fully characterized by means of 1H-NMR, elemental analysis, UV, FT-IR, X-ray, GPC, TGA, DSC, DMA, and dielectric spectroscopy. To optimize the polycondensation process, the influence of the concentration, temperature, ligands and the reactivity of the halogen containing monomers were investigated. A temperature of 100-165 °C and a concentration of 30-36 % were found to be optimal for the palladium-catalyzed polycondensation to produce polymer with high molecular weight (Mn = 85 900, Mw = 474 500, DP = 126). Four different ligands were used successfully in the Pd-catalyzed process, of which the Pd/BINAP system was found to be the most effective catalyst, producing the highest yield and highest molecular weight polymers. It was found that the reactivity decreases strongly with increasing electronegativity of the halogen atoms, for example better yields, and higher molecular weights were obtained by using dibromo compounds than dichloro compounds while difluoro compounds were totally unreactive. Polymer analogous transformations, such as the protonation reaction of the ring nitrogens in PIAcs, or of the azobenzene groups of PIAzos, the photo and thermal cis-trans-isomerization of PIAzos, and of poly(imino alcohol)s were also studied. The values of the dielectric constants of PIKs at 1 MHz were in the range 2.71-3.08. These low values of the dielectric constant are lower than that of "H Film", a polyimide Kapton film which is one of the most preferred high-performance dielectrics in microelectronic applications having a dielectric constant of 3.5. In addition to the low values of the dielectric constants, PIKs have lower and glass transition temperatures (Tgs) than arimides such as Kapton which may make them more easily processable. Cyclic voltammetry showed that PICs exhibited low oxidation and reduction potentials and their values were shifted to low values with increasing degree of polymerization i.e. with increasing of the carbazole content in backbone of PICs (PIC-7, 0.44, 0.33 V, DP= 37, PIC-5, 0.63, 0.46, DP= 16, respectively).

Polimeri metacrilici contenenti ferrocene: sintesi mediante ATRP e proprietà

An investigation on the synthesis and properties of ferrocene-containing methacrylate monomer and polymer was carried out. Block copolymers of Ferrocenylmethyl Methacrylate with methyl, butil and esil methacrylate, were also prepared. The side-chain ferrocene-containing polymers and copolymers were prepared via atom transfer radical polymerization (ATRP). The glass transition temperature (Tg) values of the polymers and copolymers were measured by differential scan calorimetry (DSC).The thermal degradation behavior of copolymers was also studied and compared with the respective homopolymers. Cyclic voltammetry was employed to study the electrochemical properties. Preliminar electrochemical studies with a glassy carbon and Indium Tin Oxide electrodes modified with ferrocene-polymer conducted in aqueous and organic media are reported.

Hyperbranched polyether polyols as building blocks for complex macromolecular architectures

The present thesis deals with the development of new branched polymer architectures containing hyperbranched polyglycerol. Materials investigated include hyperbranched oligomers, hyperbranched polyglycerols containing functional initiator-cores at the focal point, well-defined linear-hyperbranched block copolymers and also negatively charged hyperbranched polyelectrolytes.rnHyperbranched oligoglycerols (DPn = 7 and 14) have been synthesized for the first time. The materials show narrow polydispersity (Mw/Mn ca. 1.45) and a very low content in cyclic homopolymers. 13C NMR evidences the dendritic structure of the oligomers and the DB could be calculated (44% and 52%). These new oligoglycerols were compared with the industrial products obtained by polycondensation which exhibit narrow polydispersity (Mw/Mn<1.3) butrnmultimodal distribution in SEC. Detailed 13C NMR and Maldi-ToF studies reveal the presence of branched units and cyclic compounds. In comparison, the hyperbranched oligoglycerols comprise a very low proportion of cyclic homopolymer which render them very interesting materials for biomedical applications for example.rnThe site isolation of the core moiety in dendritic structure offers intriguing potential with respect to peculiar electro-optical properties. Various initiator-cores (n-alkyl amines, UVabsorbing amines and benzophenone) for the ROMBP of glycidol have been tested. The bisglycidolized amine initiator-cores show the best control over the molecular weight and the molecular weight distribution. The photochemical analyses of the naphthalene containingrnhyperbranched polyglycerols show a slight red shift, a pronounced hypochromic effect (decrease of the intensity of the band) compared with the parent model compound and the formation of a relative compact structure. The benzophenone containing polymers adopt an open structure in polar solvents. The fluorescence measurements show a clear “dendritic effect” on the fluorescence intensities and the quantum yield of the encapsulated benzophenone.rnA convenient 3-step strategy has been developed for the preparation of well-defined amphiphilic, linear-hyperbranched block copolymers via hypergrafting. The procedure represents a combination of carbanionic polymerization with the alkoxide-based, controlled ring-opening multibranching polymerization of glycidol. Materials consisting of a polystyrene linear block and a hyperbranched polyglycerol block exhibit narrow polydispersity (1.01-1.02rnfor 5.4% to 27% wt. PG and 1.74 for 52% wt. PG) with a high grafting efficiency. The strategy was also extended to materials with a linear polyisoprene block.rnDetailed investigations of the solution properties of the block copolymers with linear polystyrene blocks show that block copolymer micelles are stabilized by the highly branched block. The morphology of the aggregates is depending on the solvent: in chloroform monodisperse spherical shape aggregates and in toluene ellipsoidal aggregates are formed. On graphite these aggregates show interesting features, giving promising potential applications with respect to the presence of a very dense, functional and stable hyperbranched block.rnThe bulk morphology of the linear-hyperbranched block copolymers has been investigated. The materials with a linear polyisoprene block only behave like complex liquids due to the low Tg and the disordered nature of both components. For the materials with polystyrene, only the sample with 27% wt. hyperbranched polyglycerol forms some domains showing lamellae.rnThe preparation of hyperbranched polyelectrolytes was achieved by post-modification of the hydroxyl groups via Michael addition of acrylonitrile, followed by hydrolysis. In aqueous solution materials form large aggregates with size depending on the pH value. After deposition on mica the structures observed by AFM show the coexistence of aggregates andrnunimers. For the low molecular weight sample (PG 520 g·mol-1) extended and highly ordered terrace structures were observed. Materials were also successfully employed for the fabrication of composite organic-inorganic multilayer thin films, using electrostatic layer-bylayer self-assembly coupled with chemical vapor deposition.

Injectable hydrogels with high fixed charge density and swelling pressure for nucleus pulposus repair:biomimetic glycosaminoglycan analogues

The load-bearing biomechanical role of the intervertebral disc is governed by the composition and organization of its major macromolecular components, collagen and aggrecan. The major function of aggrecan is to maintain tissue hydration, and hence disc height, under the high loads imposed by muscle activity and body weight. Key to this role is the high negative fixed charge of its glycosaminoglycan side chains, which impart a high osmotic pressure to the tissue, thus regulating and maintaining tissue hydration and hence disc height under load. In degenerate discs, aggrecan degrades and is lost from the disc, particularly centrally from the nucleus pulposus. This loss of fixed charge results in reduced hydration and loss of disc height; such changes are closely associated with low back pain. The present authors developed biomimetic glycosaminoglycan analogues based on sulphonate-containing polymers. These biomimetics are deliverable via injection into the disc where they polymerize in situ, forming a non-degradable, nuclear "implant" aimed at restoring disc height to degenerate discs, thereby relieving back pain. In vitro, these glycosaminoglycan analogues possess appropriate fixed charge density, hydration and osmotic responsiveness, thereby displaying the capacity to restore disc height and function. Preliminary biomechanical tests using a degenerate explant model showed that the implant adapts to the space into which it is injected and restores stiffness. These hydrogels mimic the role taken by glycosaminoglycans in vivo and, unlike other hydrogels, provide an intrinsic swelling pressure, which can maintain disc hydration and height under the high and variable compressive loads encountered in vivo. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.