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  • Polymer and Materials Science  (30)
  • Astronomy  (1)
  • Biosensors  (1)
  • Cycloalkanes  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Assembly of polymer/lipid composite films on solids based on hairy rod LB-films (1997)
    Springer
    European biophysics journal 25 (1997), S. 249-259 
    Details
    ISSN: 1432-1017
    Keywords: Key words Supported membranes ; Soft interfaces ; Biosensors ; Polymer films ; Biomembranes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract The present work deals with the assembly of multilayers or rod-like polymers with hydrophobic side chains (called hairy rods) and their potential application as ultrathin polymer cushions for the build-up of self healing supported membranes on various solids (Si/SiO2-wafer, gold covered substrates). Three types of hairy rods were studied: Isopentyl cellulose (IPC), phtalocyaniatopolysiloxane with mixed alkane side chains (PCPS) and trimethylsilane cellulose (TMCS). Detailed analysis of the thickness of supported multilayers as a function of the number of deposited monolayers with ellipsometry, near infrared surface plasmon resonance (NIR-SPR), a quartz crystal microbalance (QCM) and reflection interference contrast microscopy (RICM), show that the basic building blocks of hairy rod multilayers are bilayers with the hydrophobic surfaces of the monolayers facing each other. Continuous and stable firms of hairy rods can be deposited if the hydrophobicities of the solid surface and the monolayer are matched. It is demonstrated by lateral diffusion measurements (using photobleaching techniques) that continuous phospholipid bilayers can be deposited onto multilayers of rigid rods of TMCS after hydrophilization by cleavage of trimethylsilane side chains in HCl-vapour, while stable lipid monolayers can be deposited onto hydrophobic surfaces of rigid rod layers. NIR-SPR allows the observation of double band reflectivity curves at interfaces separating different surface layers and thus offers the possibility of differential detection of ligand binding at the interface of differently functionalized domains.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s002490050037
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  • 2
    Electronic Resource
    Electronic Resource
    Packing of long-chain cycloalkanes in various crystalline modifications: an electron diffraction investigation (1988)
    Springer
    Colloid & polymer science 266 (1988), S. 419-428 
    Details
    ISSN: 1435-1536
    Keywords: Cycloalkanes ; phase transitions in oligomers ; electron diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The structure and thermal behavior of long-chain cycloalkanes (CH2)n with n= 48, 72, 96, 144 and 288 have been investigated by electron diffraction, WAXS and SAXS analysis. Five different modifications have been characterized by their subcells as a function of ring size, crystallization conditions and temperature. The rings adopt, in all modifications, a conformation with two straight stems connected by folds. Similarity with the polyethylene lattice is achieved only for n≥144. In this case, the stems are perpendicular to the layer surface and pack in the well-known orthorhombic subcell regardless of whether the rings are crystallized from solution or melt. (CH2)96 forms the same type of subcell when crystallized from the melt, but the stems are oblique to the layer surface. Rings of all sizes undergo a transition into a phase in which the stems are arranged similarly as in the “rotator phase” of linear paraffins. (CH2)72 and (CH2)96 exhibit additional transitions at lower temperatures. One significant feature of some transitions is the change of conformation and length of the folds.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01457258
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  • 3
    Electronic Resource
    Electronic Resource
    Synthesis of a metal containing ladder-polymer by solid-state polymerization of bis(1,3-pentadiynyl)mercury (1977)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 178 (1977), S. 1671-1677 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bis(1,3-pentadiynyl)mercury (3) polymerizes quantitatively in the solid-state if irradiated with UV-light or annealed at 100-200°C. The polymer shows resonant Raman frequencies at 1412, 1454, 2024, and 2070cm-1 typical for polymers containing butadiynyl (diacetylene) groups. The intensity of IR peaks due to the monomer triple bonds at 2098 and 2220 cm-1 decreases during polymerization and vanishes at completion. From experimental evidences it is inferred that the polymerization is lattice controlled and can be described, similar to the solid state polymerization of butadiynyl derivatives, by the formation of a ladder polymer of two strands of a poly(2-butynediylidene) linked together by mercury.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1977.021780607
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  • 4
    Electronic Resource
    Electronic Resource
    The relation between phase transition and crystallization behavior of 1,4-trans-poly(butadiene)Herrn Prof. Seefelder zum 60. Geburtstag gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1859-1874 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization behaviour of pure 1,4-trans-poly(butadiene) (1,4-PTBD) from dilute solutions in heptane and its relation to the phase transition phenomena in the solid state is investigated. Depending on whether the nucleation occurs in the high-temperature modification II or the low-temperature modification I two different regimes of crystallization behaviour are observed which in turn determine the crystal thickness as well as the phase transition and annealing behaviour of the crystals. The equilibrium phase transition temperature (I-II) is 356 K, the corresponding enthalpy is 144 J.g-1; the equilibrium melting temperature is 437 K and the enthalpy of melting is 69 J.g-1. The surface free energy terms are obtained relating the crystal thicknesses measured by SAXS and DSC to the temperatures of phase transition and melting, resp. Following Hoffman's theory of nucleation and growth the theoretical curves for the rate of nucleation and crystal growth are calculated and compared to the experimental results.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820626
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  • 5
    Electronic Resource
    Electronic Resource
    Investigation of the topochemical solid-state polymerization of a diacetylene by X-ray methods and brillouin-spectroscopy (1979)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 180 (1979), S. 1787-1795 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The topochemical polymerization of the substituted diacetylene, 2,4-hexadiynylene bis(p-toluenesulfonate) (1), has been followed by X-ray crystallography and by determination of the elastic constants of polymerizing crystals. For the first time the crystal structure of a polymerizable diacetylene monomer has been solved and the coordinates of all atoms prior and after the reaction have been determined. The length of the growing polymer chains and their distribution in the monomer matrix can be determined by the evaluation of the Brillouin spectra in terms of a model which considers the polymerizing crystal as a composite material of high-modulus rod-like macromolecules dispersed in the low-modulus matrix of the residual monomer.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1979.021800716
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  • 6
    Electronic Resource
    Electronic Resource
    Kinetische untersuchungen zur strahleninduzierten festkörperpolymerisation von trioxan und tetroxan IV. Mitt. der Reihe “kinetische und morphologische untersuchungen zur polymerisation von oxacyclischen monomeren im festen zustand” (1971)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 149 (1971), S. 197-220 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The radiation induced solid-state polymerization of tetroxane and trioxane was investigated. The influence of radiation-dose, reaction-time and temperature on yield and molecular weight was studied. Post-polymerization of both monomers shows a limiting conversion which increases with increasing reaction temperature. The activation energy of the post-polymerization was determined to 24 ± 2 (kcal/mole) in the case of tetroxane and was 36-38 (kcal/mole) in the case of trioxane. Time(t)-conversions(x)-curves for tetroxane could be described by the empirical equation: \documentclass{article}\pagestyle{empty}\begin{document}$$x = k_1 t/(1 + k_2 t)$$\end{document} whereby k1 and k2 are constants which could be evaluated by an appropriate plotting of the experimentally obtained data. Contrary to the post-polymerization of trioxane a pro-portionality between molecular weight, conversion and polymerization temperature was found in the case of tetroxane such that with increasing conversion higher molecular weights were obtained and an increase of reaction-temperature gave rise to higher molecular weights at constant conversion. The highest molecular weight obtained by post-polymerization of tetroxane was of the order of 8·105 and ca. 4·105 in the case of trioxane. The probability of chain-transfer is considerably higher with the polymerization of trioxane as compared with tetroxane.The morphology and texture of the originating polymers can be connected - at least qualitatively - with the reaction kinetics. It is highly probable that the kinetics of the polymerization of tetroxane are governed to some extent by relaxation processes of the growing polymer chains.
    Notes: Die strahlungsinduzierte Polymerisation von kristallinem Tetroxan und Trioxan wurde untersucht und der Einfluß von Strahlendosis, Reaktionszeit und -temperatur auf den Umsatz und das Molekulargewicht der entstehenden POM, insbesondere bei der Nachpolymerisation, studiert. Die Zeit-Umsatz-Kurven für die Nachpolymerisation laufen bei beiden Monomeren asymptotisch gegen einem Grenzwert des Umsatzes, der mit steigender Reaktionstemperatur ansteigt. Die Aktivierungsenergie der Nachpolymerisation wurde zu 24 ± 2 kcal/Mol für Tetroxan und zu 36-38 kcal/Mol für Trioxan bestimmt. Die Zeit(t)-Umsatz(x)-Kurven für Tetroxan lassen sich durch die empirische Gleichung: \documentclass{article}\pagestyle{empty}\begin{document}$$x = k_1 \cdot t/(1 + k_2 t)$$\end{document} beschreiben, wobei k1 und k2 Konstanten sind, die durch geeignete Auftragung der Meßwerte ermittelt werden können. Im Gegensatz zu Trioxan findet man bei Tetroxan eine Proportionalität zwischen Molekulargewicht, Umsatz und Polymerisationstemperatur in der Weise, daß mit steigendem Umsatz höhere Molekulargewichte beobachtet werden und bei konstantem Umsatz mit steigender Temperatur auch höhere Molekulargewichte auftreten. Bei der Nachpolymerisation von Tetroxan lagen die höchsten erreichbaren Molekulargewichte bei 8·105, während bei Trioxan nur Werte von 4·105 erreicht wurden. Die Wahrscheinlichkeit für übertragungsschritte ist bei der Polymerisation von Trioxan wesentlich höher als bei Tetroxan.Zwischen der morphologischen Beschaffenheit und Textur der entstehenden Polymeren und den kinetischen Befunden lassen sich qualitative Beziehungen herstellen. Danach wird die Reaktionskinetik im Fall der Polymerisation von Tetroxan wesentlich durch Relaxationsvorgänge an den sich bildenden Polymerketten beeinflußt.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1971.021490116
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  • 7
    Electronic Resource
    Electronic Resource
    Topochemical polymerization of monomers with conjugated triple bondsPart VI of the Series “Topochemical Reactions of Monomers with Conjugated Triple Bonds”.Main Lecture, Symposium M-14, IUPAC, Boston, July 1971XXIII IUPAC Symposium on Macromolecular Chemistry, Boston, 1971 (Macromolecular Preprint, Vol. II, p. 908). (1972)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 154 (1972), S. 35-48 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Festkörperpolymerisation von Monomeren mit konjugierten Dreifachbindungen ist eine vielseitige und einfache Methode zur Synthese von kristallinen Polymeren mit einer vollkommen konjugierten Hauptkette und hohem Molekulargewicht. Die Polymerisation läßt sich am besten als eine 1.4-Additionsreaktion der konjugierten Dreifachbindungen beschreiben. Dabei entsteht ein Polymeres mit 3 kumulierten Doppelbindungen pro Grundbaustein. Die trans-Konfiguration der Substituenten ergibt sich zwanglos aus dem Mechanismus der Festkörperpolymerisation und wird durch die Packung der Monomermoleküle im Kristallgitter vorherbestimmt. Aufgrund der Strukturdaten aus einer Röntgenstruktur-analyse des Polymeren aus 2.4-Hexadiin-1.6-diol-bis-phenylurethan muß angenommen werden, daß die polymeren Diacetylene entweder durch die Butatrien-Struktur oder eine mesomere en-in-Struktur beschrieben werden können. Die Polymerisation der farblosen Monomerkristalle wird durch Bestrahlung mit UV- oder energiereicher Strahlung oder aber durch Tempern der Monomerkristalle unterhalb ihres Schmelzpunktes bewirkt. Tief rot, blau oder schwarz gefärbte Polymerkristalle werden dabei erhalten, die einen starken Dichroismus aufweisen. Die Faserachse ist die Richtung der Hauptabsorption. Die Polymerkristalle sind Halbleiter. Die Aktivierungsenergie der Leitfähigkeit liegt in Abhängigkeit von den Substituenten an der konjugierten Hauptkette bei 0,6-1,0 eV.
    Notes: Solid-state polymerization of monomers with conjugated triple bonds turns out to be a versatile method for synthesis of crystalline polymers of high molecular weight exhibiting a fully conjugated backbone. The reaction is best described as an 1.4-addition polymerization of the conjugated triple bonds giving rise to a polymer with three cumulated double bonds per repeating unit. The all-trans configuration of the substituents is a consequence of the solid-state reaction mechanism and is already predetermined by the packing of the molecules in the monomer lattice. It was shown by X-ray analysis in the case of poly(2.4-hexadiin-1.6-diol-bis-phenylurethane) that the polymer diacetylenes can be described by either a butatriene structure or by a mesomeric en-in-structure. Polymerization of the colorless monomer crystals is achieved by irradiation with UV- or high-energy radiation or by simply annealing the monomer crystals below their melting point. Deep red, blue or black polymer crystals are obtained exhibiting strong dichroism with the fibre axis as the direction of main absorption. These crystals possess semiconducting properties (EA = 0.6-1.0 eV, depending on the substituents at the conjugated backbone).
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1972.021540103
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  • 8
    Electronic Resource
    Electronic Resource
    Analytik der morphologie von Mehrphasensystemen (1977)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 58 (1977), S. 37-83 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polymer multiphase systems are classified according to various points of view at first and the impact of supermolecular structure on physical and chemical properties is pointed out. Methods of analysis of the supermolecular structure are then discussed with emphasis on those in which chemical reactions are employed. Such methods are based on differences in either reactivity or accessibility of the different phases for specific reagents in a multiphase system. The following materials and methods are used as examples: selective dying of styrene-butadiene block copolymers and semicrystalline pol(ethylene) for electron microscopy; ordering phenomena and their characterization by mechanical spectroscopy and selective hydrolysis in segmented polyesters; chemical etching and GPC-analysis of the reaction products in order to elucidate the fine structure of the fold surfaces in semicrystalline polymers.The importance of such reactions for the present status of knowledge on the nature of supermolecular structure is extensively and critically discussed using poly(ethylene) as an example. Poly(ethylene terephthalate) is reviewed as an example for a more complicated and not fully understood case of a multiphase system. The last section deals with the problem of the distribution of comonomer units between crystalline and amorphous zones in random copolymers which have been partially crystallized It is deduced from experiments that comonomer units are built into the lattice to a fair amount. Theoretical understanding of this effect is not yet well developed.
    Notes: In der Einführung werden Typen von polymeren Mehrphasensystemen nach verschiedenen Gesichtspunkten klassifiziert, und es wird auf die Bedeutung der übermolekularen Struktur für physikalische und chemische Eigenschaften hingewiesen. Schwerpunktmäßig werden sodann solche Methoden der Analyse der Überstruktur besprochen, bei denen chemische Reaktionen eine Rolle spielen. Diese Methoden beruhen auf der unterschiedlichen Reaktionsfähigkeit bzw. Zugänglichkeit der verschiedenen Phasen eines Mehrphasen-systems für spezifische chemische Reagenzien. Als Beispiele werden die folgenden Stoff-klassen und Methoden behandelt: selektive Kontrastierung für elektronenmikroskopische Abbildungen bei Butadien-Styrol-Blockcopolymeren und bei teilkristallinem Polyäthylen; Ordnungsphänomene und deren Charakterisierung durch mechanische Spektroskopie und selektive Hydrolyse in segmentierten Blockcopolyestern; chemische Reaktionen und gelchromatographische Analyse der Reaktionsprodukte bei teilkristallinen Polymeren zum Zweck der Aufklärung der Feinstruktur der Faltbereiche.Die Bedeutung solcher Reaktionen für den Stand des Wissens über den Aufbau der Überstruktur wird am Beispiel des Polyäthylens ausführlich und kritisch behandelt und mit den Ergebnissen rein physikalischer Methoden verglichen. Polyäthylenterephthalat wird als Beispiel für einen komplizierten und noch nicht völlig verstandenen Fall eines Mehrphasensystems ausführlich gewürdigt. Im letzten Abschnitt wird das Problem der Verteilung der Comonomereinheiten zwischen kristalliner und amorpher Phase bei statistischen. kristallisationsfähigen Copolymeren betrachtet. Experimentell ergibt sich, daß Comonomereinheiten in beträchtlichem Ausmaß in das Gitter des Kristalliten eingebaut werden. Es fehlt aber noch an einer theoretischen Durchdringung dieses Sachverhalts.
    Additional Material: 19 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1977.050580102
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  • 9
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    Electronic Resource
    Structure and properties of segmented polyether-esters. II. Crystallization behavior of polyether-esters with random distribution of hard segment lengthHerrn Prof. Dr. Dr. h. c. Heinrich Hellmann zum 65. Geburtstag gewidmet (1978)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 74 (1978), S. 295-316 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Sechs verschiedene segmentierte Copolyetherester basierend auf Polybutylenterephthalat als hartem und Oligotetramethylenoxidglykol als weichem Segment wurden untersucht. Der Gewichtsbruch der Hartsegmente lag zwischen 0,26 und 0,72, und die Weichsegmente hatten Molgewichte von entweder 1000 oder 2000. Das Schmelz-, Rekristallisations- und Temperverhalten sowie Relaxationsphanomene wurden untersucht; letzteres mit Hilfe eines Torsionspendels.Die DSC-Daten zeigen, daI3 nur ein kleiner Teil aller Hartsegmente kristallisiert. Sequenzen, die kiirzer oder langer als die mittlere Sequenzlange sind, kristallisieren nicht, sondern bilden zusammen mit den Weichsegmenten eine homogene amorphe Matrix, in die die kristallinen Domanen eingebettet sind. Diese Domanen werden infolge kalten Flusses unter Spannung vollstandig zerstort, bilden sich jedoch bei Temperung der verstreckten Proben wieder aus. Man beobachtet ein exponentielles Anwachsen der Langperiode mit zunehmender Tempertemperatur, wobei der Schmelzpunkt konstant bleibt. Die Sequenzlangenverteilung scheint keinen EinfluB auf das Temperverhalten zu haben.
    Notes: Six different segmented copolyether-esters based on polybutyleneterephthalate as the hard and oligotetramethylene oxide glycols as the soft segments were studied. The weight fraction of the hard segments varied between 0.26 and 0.72 and the soft segment had an average molecular weight of either 1000 or 2000. The melting, recrystallization, and annealing behavior was studied as well as the relaxation behavior via measurement by a torsion pendulum. The DSC-data indicate that only a small fraction of all hard segment sequences crystallize. Sequences shorter or longer than the average sequence length do not crystallize but together with the soft segments form a homogeneous amorphous matrix in which the crystalline domains are embedded. These domains are completely destroyed by cold flow under stress but are formed again on annealing the stretched sample. An exponential increase of the long spacing is observed with increasing annealing temperature without change in melting temperature. The sequence distribution does not seem to influence the annealing behavior.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1978.050740119
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  • 10
    Electronic Resource
    Electronic Resource
    Synthese und Eigenschaften von Polyacetylen (1981)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 94 (1981), S. 105-117 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polyacetylene is important because it can be transferred into metallic conducting phases by treatment with strong oxidizing or reducing agents (“doping”). The influence of the reaction conditions, especially of the polymerization catalyst, are investigated. The polymers obtained under normal conditions are always crosslinked. The morphology is independent of the polymerization method and can be described as an aggregation of lamellar particles with typical dimensions of a few 100 Å. The polymer chains are oriented perpendicular to the surface and chain folding is observed. The crystal structures of cis and trans polyacetylene are given. The consequences of the morphology on the mechanism of doping and charge transport are discussed using general structural principles.
    Notes: Polyacetylen ist von Bedeutung, da es sich durch Behandlung mit starken Oxidations- oder Reduktionsmitteln („Dotieren“) in metallisch leitfähige Phasen überführen läßt. Der Einfluß der Polymerisationsbedingungen, besonders des Katalysators, auf die Eigenschaften wurde untersucht. Dabei zeigt es sich, daß das unter den normalen Bedingungen erhaltene Polyacetylen vernetzt ist. Die Morphologie ist unabhängig von der Polymerisationsmethode und kann als eine Aggregation lamellarer Teilchen mit typischen Abmessern von einigen 100 Å beschrieben werden. Die Ketten stehen senkrecht zur Deckfläche, und es wurde Kettenfaltung gefunden. Die Strukturen von cis-und trans-Polyacetylen werden gegeben. Die Auswirkungen der Morphologie auf die Chemie der Dotierung und den Mechanismus der Leitfähigkeit werden anhand allgemeiner Strukturprinzipien diskutiert.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1981.050940106
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