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  • 1
    facet.materialart.
    Unbekannt
    Publikationsdatum: 2020-12-11
    Beschreibung: Im Mai 2009 wurde Wolfram|Alpha gestartet, ein Service, der seinen Namen von seinem Entwickler, dem britischen Mathematiker Stephen Wolfram, ableitet. Dem Benutzer soll nicht nur eine Liste von Webseiten als Ergebnis auf Anfragen geliefert werden, sondern Antworten auf konkrete Fragen geben. In diesem Report soll gezeigt werden, warum sichWolframjAlpha von Suchmaschinen abgrenzt und was die Berechnung von Antworten auf natürlichsprachliche Fragen möglich machen kann.
    Beschreibung: Wolfram|Alpha was started in May 2009 and it's a service whose name derives from the british mathematician Stephen wolfram. As a result for a request the user is not just supported with a list of websites but with answers for concrete questions. In this report it will be shown why Wolfram|Alpha seperates from search engines and moreover what makes the computation of answers for natural language queries possible.
    Schlagwort(e): ddc:004
    Sprache: Deutsch
    Materialart: reportzib , doc-type:preprint
    Format: application/pdf
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  • 2
    facet.materialart.
    Unbekannt
    Publikationsdatum: 2016-06-30
    Beschreibung: Executing applications in the Grid often requires access to multiple geographically distributed resources. In a Grid environment, these resources belong to different administrative domains, each employing its own scheduling policy. That is, at which time an activity (e.g., compute job, data transfer) is started, is decided by the resource's local management system. In such an environment, the coordinated execution of distributed applications requires guarantees on the quality of service (QoS) of the needed resources. Reserving resources in advance is an accepted means to obtain QoS guarantees from a single provider. The challenge, however, is to coordinate advance reservations of multiple resources. This work presents a system architecture and mechanisms to coordinate multiple advance reservations -- called co-reservations -- for delivering QoS guarantees to complex applications. We formally define the co-reservation problem as an optimization problem. The presented model supports three dimensions of freedom: the start time, the duration and the service level of a reservation. Requests and resources are described in a simple language. After matching the static properties and requirements of either side in a mapping, the reservation mechanism probes information about the future status of the resources. The versatile design of the probing step allows the efficient processing of requests, but also lets the resources express their preferences among the myriads of reservation candidates. Next, the best mapping is found through an implementation of the formal co-reservation model. Then, the mapping has to be secured, i.e., resources need to be allocated to a co-reservation candidate with all-or-nothing semantics. We study several goal-driven sequential and concurrent allocation mechanisms and define schemes for handling allocation failures. Finally, we introduce the concept of virtual resources for seamlessly embedding co-reservations into Grid resource management.
    Beschreibung: Die Ausführung von Anwendungen erfordert oft mehrere, geographisch verteilte Ressourcen. In Grid-Umgebungen gehören diese Ressourcen zu verschiedenen administrativen Organisationen, wobei jede ihre eigene Schedulingregeln verwendet. Das bedeutet, zu welcher Zeit eine Aktivität gestartet wird (z.B. ein Rechenjob), wird vom lokalen Ressourcenmanagementsystem entschieden. Die koordinierte Ausführung von verteilten Anwendungen erfordert Dienstgütegarantien für die benötigten Ressourcen. Das Reservieren von Ressourcen im Voraus ist ein Mittel, um Dienstgütegarantien von einem einzelnen Ressourcenanbieter zu erhalten. Die Herausforderung in dieser Arbeit ist, Vorausreservierungen von mehreren Ressourcen zu koordinieren. Es wird ein System für die Koordinierung mehrerer Vorausreservierungen -- Co-Reservierungen genannt -- für die Bereitstellung von Dienstgütegarantien vorgestellt. Wir definieren das Co-Reservierungsproblem als Optimierungsproblem. Das vorgestellte Modell unterstützt drei Freiheitsgrade: die Startzeit, die Dauer und die Dienstgüte einer Reservierung. Anfragen und Ressourcen werden in einer einfachen Sprache beschrieben. Nachdem statische Eigenschaften und Anforderungen beider Seiten überprüft wurden, ermittelt der Reservierungsmechanismus Informationen über den zukünftigen Zustand der Ressourcen. Dieser Schritt ist so allgemein gehalten, daß er sowohl ein effizientes Bearbeiten der Anfragen erlaubt als auch den Ressourcen ermöglicht ihre Präferenzen auszudrücken. Im Anschluss wird die optimale Zuweisung von Anfragen zu Ressourcen ermittelt. Im letzten Schritt muss diese Zuweisung umgesetzt werden, d.h., entweder alle oder keine Ressource wird allokiert. Es werden mehrere sequentielle und parallele Allokationsverfahren vorgestellt sowie deren Auswirkung auf verschiedene Metriken untersucht. Die Einbettung von Co-Reservierungen in das Grid-Ressourcenmanagement wird anhand des Konzeptes der virtuellen Ressource dargestellt.
    Schlagwort(e): ddc:004
    Sprache: Englisch
    Materialart: doctoralthesis , doc-type:doctoralThesis
    Format: application/pdf
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  • 3
    Publikationsdatum: 2016-06-30
    Beschreibung: Aktuelle Entwicklungen zeigen, dass Peer-to-Peer (P2P) Anwendungen wie Skype oder Bittorrent im Internet immer mehr an Bedeutung gewinnen. In den letzten Jahren hat es einen explosionsartigen Anstieg an Nutzern und Daten in solchen Netzen gegeben. Dabei stellt der eigentliche Dateitransfer zwischen zwei Rechnern kein großes Problem mehr dar und auch der Speicherbedarf für die große Menge an Daten kann durch die Weiterentwicklung der Hardware gut gedeckt werden. Das eigentliche Problem liegt vielmehr darin, den Rechner zu finden, der die gewünschten Daten hat. Client-Server Architekturen, wie zum Beispiel Napster, haben sich als ungünstig herausgestellt. Wenige Server, die eine große Anzahl an Clients bedienen müssen, sind einerseits sehr anfällig gegenüber Angriffen und Ausfällen (Single Point of Failure)und kommen auch nicht mit der ständig wachsenden Anzahl an Nutzern zurecht. Verteilte Hashtabellen (DHT) bieten hier einen guten Lösungsansatz, der mit einer großen Anzahl an Nutzern skaliert und ausfallsicher ist. Andere dezentrale Lösungen, wie zum Beispiel das P2P Netzwerk Gnutella haben zwar das Problem des Single Point of Failure gelöst, jedoch haben sie starke Nachteile bei der Suche nach Keys. Bei einer Suche wird ein Broadcast verwendet (jeder schickt die Anfrage an jeden weiter) und damit ein enormer Netzwerkverkehr erzeugt. In "Why Gnutella Can't Scale. No, Really" wird erklärt, dass eine Suchanfrage bei Standardeinstellungen in der Clientsoftware einen Netzwerkverkehr von 17MB erzeugt. Deswegen wird zusätzlich eine Lösung benötigt, die Keys und Values geordnet verteilt, damit sie gezielt gesucht werden können. Aus diesem Grund beschäftigt sich die folgende Arbeit mit einer völlig dezentralen Architektur, die außerdem eine sinnvolle Platzierung der Keys vornimmt. Die dezentrale Architektur hat den Vorteil, dass die Endgeräte den Hauptteil des Dienstes selbst erbringen und damit jeder zusätzliche Teilnehmer seine eigenen Ressourcen beisteuert. Diese Arbeit präsentiert Chord#, eine dezentrale, skalierbare und selbstorganisierende verteilte Hashtabelle. Chord# wurde ausgewählt, da in dieser Arbeit auch Wert auf Bereichsabfragen gelegt wurde. Diese sind zum Beispiel bei dem Chord Algorithmus nicht möglich, da dieser eine Hashfunktion für die Keys verwendet und somit die Daten zwar gleichmäßig aber unsortiert auf die Teilnehmer verteilt. Es wird in dieser Arbeit gezeigt, dass mit Hilfe von Chord# auch ohne die Hashfunktion gute Ergebnisse erzielt werden. Außerdem können durch den Verzicht auf die Hashfunktion Bereichsabfragen ermöglicht werden. Dafür wird der Chord# Algorithmus in Java implementiert (ca. 1500 Zeilen Code) und in dem Forschungsnetz PlanetLab ausführlich auf Laufzeiten, Instandhaltungskosten und Skalierung getestet.
    Beschreibung: Recent developments show that peer-to-peer (p2p) applications, such as Skype or Bittorrent have become increasingly important in the internet. Over the last years there has been a rapid growth of both users and data in such networks. However, the actual file transfer between two peers is not really an issue anymore. The same holds true for data storage, since the new hardware grants users enough space to store their data. The real problem is finding the peers that possess the desired data. Client-server architectures like Napster have proven to be ineffective addressing that problem. One or few servers being responsible for many peers are vulnerable to attacks or failures (single point of failure). Additionally, they are unable to cope with the rapidly growing number of peers. Distributed hashtables (DHT) are a good approach to solve these problems, since they scale nicely with large numbers of peers and provide a high tolerance for errors. Other decentralized solutions like the p2p network Gnutella solved the problem of Single Point of Failure but show considerable disadvantages when searching for keys. The peers in Gnutella use a broadcast (sending the message to all peers they know)resulting in massive traffic. According to "Why Gnutella Can't Scale. No, Really.", each search using standard client settings yields 17MB traffc. This calls for a different solution, distributing keys and values to peers quickly and efficiently so they can be found fast. For that reason this thesis focuses on a fully distributed architecture using organized key placement. One major advantage of distributed architecture is the fact, that the peers do most of the work themselves. This way, new peers joining the network add resources to it. This thesis presents Chord#, a scalable, self-organizing and completely decentralized DHT. It has been chosen due to its capability to allow range queries. The regular Chord algorithm does not support range queries, because of the hashfunction it uses to evenly distribute the keys among the peers. This results in similar or logical coherent keys most likely not being close together in the network. This thesis shows Chord# achieving same results as Chord - regarding performance costs - without the hashfunction. In dropping the hashfunction this algorithm allows the use of range queries. The Chord# algorithm is implemented in Java (about 1500 lines of code) and thoroughly tested in the research network PlanetLab. The results are evaluated regarding performance, maintenance and scalability.
    Schlagwort(e): ddc:004
    Sprache: Deutsch
    Materialart: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 4
    facet.materialart.
    Unbekannt
    Publikationsdatum: 2017-11-02
    Beschreibung: One of the biggest impacts on the performance of a Distributed Hash Table (DHT), once established, is its ability to balance load among its nodes. DHTs supporting range queries for example suffer from a potentially huge skew in the distribution of their items since techniques such as consistent hashing can not be applied. Thus explicit load balancing schemes need to be deployed. Several such schemes have been developed and are part of recent research, most of them using only information locally available in order to scale to arbitrary systems. Gossiping techniques however allow the retrieval of fairly good estimates of global information with low overhead. Such information can then be added to existing load balancing algorithms that can use the additional knowledge to improve their performance. Within this thesis several schemes are developed that use global information like the average load and the standard deviation of the load among the nodes to primarily reduce the number of items an algorithm moves to achieve a certain balance. Two novel load balancing algorithms have then been equipped with implementations of those schemes and have been simulated on several scenarios. Most of these variants show better balance results and move far less items than the algorithms they are based on. The best of the developed algorithms achieves a 15-30% better balance and moves only about 50-70% of the number of items its underlying algorithm moves. This variation is also very robust to erroneous estimates and scales linearly with the system size and system load. Further experiments with self-tuning algorithms that set an algorithm’s parameter according to the system’s state show that even more improvements can be gained if additionally applied. Such a variant based on the algorithm described by Karger and Ruhl shows the same balance improvements of 15-30% as the variant above but reduces the number of item movements further to 40-65%.
    Schlagwort(e): ddc:004
    Sprache: Englisch
    Materialart: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 5
    Publikationsdatum: 2020-12-15
    Beschreibung: Entwurf und Entwicklung eines eingebetteten Hauptspeicher-Datenbanksystems mit Snapshot-Reads.
    Beschreibung: Design and implementation of an embedded main memory database with snapshot reads.
    Schlagwort(e): ddc:004
    Sprache: Deutsch
    Materialart: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 6
    Publikationsdatum: 2016-06-30
    Beschreibung: Das Ziel dieser Arbeit ist die Schaffung einer Zugriffs-Komponente für das Grid-Datenmanagement-System ZIB-DMS, das dessen transparente Einbindung in den Verzeichnisbaum eines Linux-Systems erlaubt. Dazu wird unter Verwendung des FUSE-Rahmenwerkes ein Userspace-Dateisystem mit Anbindung an das ZIB-DMS konzipiert und implementiert. Im Fokus stehen dabei die Abbildung der erweiterten Verwaltungsmechanismen des Systems auf die limitierte Schnittstelle hierarchischer Dateisysteme und die dazu notwendigen Änderungen am ZIB-DMS.
    Beschreibung: The goal of this work is to create an access component for the Grid data management system ZIB-DMS, that allows a transparent integration into the directory tree of a Linux system. For this purpose the FUSE framework is used to design and implement a userspace file system with connections to the ZIB-DMS. The focus is on the mapping of the extended management mechanisms of the system to the limited interface of hierarchical file systems and the therefore necessary changes to ZIB-DMS.
    Schlagwort(e): ddc:004
    Sprache: Deutsch
    Materialart: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 7
    Publikationsdatum: 2021-01-22
    Beschreibung: We present a framework for transactional data access on data stored in a DHT. It allows to atomically read and write items and to run distributed transactions consisting of a sequence of read and write operations on the items. Items are symmetrically replicated in order to achieve durability of data stored in the SON. To provide availability of items despite the unavailability of some replicas, operations on items are quorum-based. They make progress as long as a majority of replicas can be accessed. Our framework processes transactions optimistically with an atomic commit protocol that is based on Paxos atomic commit. We present algorithms for the whole framework with an event based notation. Additionally we discuss the problem of lookup inconsistencies and its implications on the one-copy serializability property of the transaction processing in our framework.
    Schlagwort(e): ddc:004
    Sprache: Englisch
    Materialart: reportzib , doc-type:preprint
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  • 8
    Publikationsdatum: 2020-12-11
    Beschreibung: When planning teams for projects with specific goals, employees of a company have to group together so well, that all necessary knowledge for conquering the project’s challenges are met within the member’s skills. A tool that facilitates semantic web technologies can support the team recruiter, who is responsible for chosing the members of the team, in terms of finding the most efficient combinations of the company’s employees based on their expertises.
    Schlagwort(e): ddc:004
    Sprache: Englisch
    Materialart: reportzib , doc-type:preprint
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  • 9
    Publikationsdatum: 2021-01-22
    Beschreibung: Key/value stores which are built on structured overlay networks often lack support for atomic transactions and strong data consistency among replicas. This is unfortunate, because consistency guarantees and transactions would allow a wide range of additional application domains to benefit from the inherent scalability and fault-tolerance of DHTs. The Scalaris key/value store supports strong data consistency and atomic transactions. It uses an enhanced Paxos Commit protocol with only four communication steps rather than six. This improvement was possible by exploiting information from the replica distribution in the DHT. Scalaris enables implementation of more reliable and scalable infrastructure for collaborative Web services that require strong consistency and atomic changes across multiple items.
    Schlagwort(e): ddc:004
    Sprache: Englisch
    Materialart: reportzib , doc-type:preprint
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  • 10
    Publikationsdatum: 2022-07-19
    Beschreibung: Basierend auf einem vorhandenen Ansatz zur Einführung von anisotropen Tetraedern im Randbereich eines reinen Tetraedergitters wird ein Gittergenerator für hybride Gitter implementiert. Das hybride Gitter besteht in Randnähe primär aus anisotropen Prismen und im Inneren der Geometrie aus isotropen Tetraedern. Eine erhöhte Auflösung im Randbereich soll zu besseren Ergebnissen von numerischen Strömungssimulationen führen, für welche eine problemangepasste Diskretisierung des zu untersuchenden Gebietes benötigt wird. In dem zuvor genannten Ansatz wird eine Reihe von Übergangselementen vorgeschlagen, die an scharfen Kanten der Oberfläche platziert werden sollen. Im Rahmen dieser Diplomarbeit wird die Idee der Übergangselemente aufgegriffen und bei hybriden Gittern eingesetzt, um auch komplexe Eingabegeometrien vergittern zu können. Der ursprüngliche Gittergenerierungprozess wird überarbeitet und erweitert. Eine neue Menge an Übergangselementen wird eingeführt, es werden gekrümmte Extrusionsvektoren verwendet und es wird die Auswertung der medialen Oberfläche vorgenommen, um Überschneidungen im hybriden Gitter zu vermeiden. Der Gittergenerator wird als Modul in das Visualisierungs- und Analyseprogramm Amira implementiert und die erstellten hybriden Gitter werden auf ihre Elementqualität und die Güte der Strömungssimulationsergebnisse hin überprüft.
    Beschreibung: Based on an existing approach for the introduction of anisotropic tetrahedra near the surface boundary of a tetrahedral grid a grid generator for hybrid grids is implemented. The hybrid grid consists near the surface boundary primarily of anisotropic prisms and inside the geometry of isotropic tetrahedra. An increased resolution near the boundary should lead to better results of numerical flow simulations, which needs a problem specific discretization of the analyzed domain. In the aforementioned approach a set of transition elements is suggested, which should be placed at sharp surface corners. As a part of this diploma thesis the concept of using transition elements is applied for creating hybrid grids even for very complex input geometries. The initial grid generation process is revised and enhanced. A new set of transition elements is introduced, curved extrusion vectors are used and the medial surface is evaluated to avoid intersections in the hybrid grid. The grid generator is implemented as a module for the visualization and analysis tool Amira and the element quality of the generated hybrid grids and the quality of flow simulations performed on the grids are tested.
    Schlagwort(e): ddc:004
    Sprache: Deutsch
    Materialart: masterthesis , doc-type:masterThesis
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  • 11
    Publikationsdatum: 2016-06-30
    Beschreibung: We study performance and scaling of the Berlin Quantum Chromodynamics Program (BQCD) on the SGI Altix 4700 at Leibniz Supercomputing Centre (LRZ). We employ different communication methods (MPI, MPI with two OpenMP threads per process, as well as the shmem library) and run the MPI version on the two types of nodes of that machine. For comparison with other machines we made performance measurements on an IBM p690 cluster and a Cray XT4.
    Schlagwort(e): ddc:004
    Sprache: Englisch
    Materialart: reportzib , doc-type:preprint
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  • 12
    Publikationsdatum: 2022-07-19
    Beschreibung: In dieser Arbeit wird eine Serie von Remeshing-Verfahren um die Berücksichtigung von nicht-mannigfaltigen Dreiecksvernetzungen und Merkmalskantenzügen erweitert. Die betrachteten Verfahren arbeiten im Wesentlichen lokal. Daher können die im Rahmen dieser Arbeit entwickelten Erweiterungen, die nicht-mannigfaltige Kantenzüge und Merkmalskantenzüge betreffen, separat beschrieben werden. Dabei wird ein Ansatz verfolgt, beide Arten von besonderen Kantenzügen aufgrund ihrer Gemeinsamkeiten einheitlich zu behandeln. Dieser besteht zum einen darin, eine Korrespondenz zwischen Kantenzügen auf der Eingabe- und der Ausgabefläche zu erhalten, indem die Remeshing-Operationen auf den Kantenzügen in entsprechend eingeschränkter Weise verwendet werden. Zum anderen wird beschrieben, wie die Abtastdichte der Kantenzüge dynamisch an die Abtastdichte der Umgebung angepasst werden kann, um für weitgehende Isotropie in der Nähe von Merkmalskantenzügen zu sorgen.
    Beschreibung: A unified approach for consistent remeshing of arbitrary non-manifold triangle meshes with additional user-defined feature lines is presented. The method is based on local operations only and produces meshes of high regularity and triangle quality while preserving the geometry as well as topology of the feature lines as well as the input mesh.
    Schlagwort(e): ddc:004
    Sprache: Deutsch
    Materialart: masterthesis , doc-type:masterThesis
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  • 13
    Publikationsdatum: 2022-07-19
    Beschreibung: This work introduces a novel streamline seeding technique based on dual streamlines that are orthogonal to the vector field, instead of tangential. The greedy algorithm presented here produces a net of orthogonal streamlines that is iteratively refined resulting in good domain coverage and a high degree of continuity and uniformity. The algorithm is easy to implement and efficient, and it naturally extends to curved surfaces.
    Beschreibung: In dieser Arbeit wird eine neue Strategie zur Platzierung von Stromlinien vorgestellt. Hierzu werden zusätzliche duale Stromlinien verwendet, die --im Gegensatz zur üblichen Definition-- orthogonal zum Vektorfeld verlaufen. Der vorgestellte Greedy-Algorithmus berechnet ein Netz aus orthogonalen Stromlinien, welches iterativ verfeinert wird, was zu einer guten Abdeckung der Domäne und einer gleichmäßigen Verteilung der Stromlinien führt. Es handelt sich um einen einfach zu implementierenden und effizienten Algorithmus, der direkt auf gekrümmten Oberflächen anwendbar ist.
    Schlagwort(e): ddc:004
    Sprache: Englisch
    Materialart: reportzib , doc-type:preprint
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  • 14
    Publikationsdatum: 2020-12-11
    Beschreibung: In dieser Diplomarbeit wird untersucht, wie auf der Basis von Literaturreferenzen ein Zitationsgraph durch ein automatisches Verfahren aufgebaut werden kann. Zur Lösung des Problems werden Probabilistische Relationale Modelle herangezogen. Eine problemspezifische Erweiterung des Modells ermöglicht es, dass bestehende Unsicherheiten im Zitationsgraphen mit Hilfe eines Inferenzverfahrens aufgelöst werden können. Zur Evaluierung des Verfahren werden Experimente auf dem Cora-Datensatz durchgeführt.
    Schlagwort(e): ddc:004
    Sprache: Deutsch
    Materialart: masterthesis , doc-type:masterThesis
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  • 15
    Publikationsdatum: 2016-06-30
    Beschreibung: Die Diplomarbeit präsentiert ein Transaktionsverfahren für strukturierte Overlay-Netzwerke, das an die Erfordernisse verteilter Informationssysteme mit relationalem Datenmodell angepasst ist. Insbesondere wird der Einsatz von Transaktionen für verteilte Wikis betrachtet, die moderne Funktionalitäten, wie Metadaten und zusätzliche Indexe für die Navigation, unterstützen. Konsistenz und Dauerhaftigkeit der gespeicherten Daten erfordert die Behandlung von Knotenausfällen. Die Arbeit schlägt dafür das Zellenmodell vor: Das Overlay wird aus replizierten Zustandsmaschinen gebildet, um Verfügbarkeit zu gewährleisten. Das Transaktionsverfahren baut darauf auf und verwendet Two-Phase-Commit mit Fehlererkennung und Widerherstellung von ausgefallenen Transaktionsmanagern. Anwendungen wird eine Auswahl an pessimistischen und hybrid-optimistischen Nebenläufigkeitskontrollverfahren geboten, die die Minimierung von Latenzeffekten und die schnelle Ausführung von Nur-Lese-Transaktionen ermöglichen. Für die Beispielanwendung Wiki wird der erforderliche Pseudocode angegeben und die verschiedenen Nebenläufigkeitskontrollverfahren hinsichtlich ihrer Nachrichtenkomplexität verglichen.
    Beschreibung: The diploma thesis presents a transaction processing scheme for structured overlay networks and uses it to develop a distributed Wiki application based on a relational data model. The Wiki supports rich metadata and additional indexes for navigation purposes. Ensuring consistency and durability requires handling of node failures. Such failures are masked by providing high availability of nodes. This in turn is achieved by constructing the overlay from replicated state machines (cell model). Atomicity is realized using two phase commit with additional support for failure detection and restoration of the transaction manager. The developed transaction processing scheme provides the application with a mixture of pessimistic, hybrid optimistic and multiversioning concurrency control techniques to minimize the impact of replication on latency and optimize for read operations. The pseudocode of the relevant Wiki functions is presented and the different concurrency control techniques are evaluated in terms of message complexity.
    Schlagwort(e): ddc:004
    Sprache: Deutsch
    Materialart: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 16
    Publikationsdatum: 2016-06-30
    Beschreibung: Die Arbeit präsentiert ein Transaktionsverfahren für strukturierte Overlay-Netzwerke, das an die Erfordernisse verteilter Informationssysteme mit relationalem Datenmodell angepasst ist. Insbesondere wird der Einsatz von Transaktionen für verteilte Wikis betrachtet, die moderne Funktionalitäten, wie Metadaten und zusätzliche Indexe für die Navigation, unterstützen. Konsistenz und Dauerhaftigkeit der gespeicherten Daten erfordert die Behandlung von Knotenausfällen. Die Arbeit schlägt dafür das Zellenmodell vor: Das Overlay wird aus replizierten Zustandsmaschinen gebildet, um Verfügbarkeit zu gewährleisten. Das Transaktionsverfahren baut darauf auf und verwendet Two-Phase-Commit mit Fehlererkennung und Widerherstellung von ausgefallenen Transaktionsmanagern. Anwendungen wird eine Auswahl an pessimistischen und hybrid-optimistischen Nebenläufigkeitskontrollverfahren geboten, die die Minimierung von Latenzeffekten und die schnelle Ausführung von Nur-Lese-Transaktionen ermöglichen. Für die Beispielanwendung Wiki wird der erforderliche Pseudocode angegeben und die verschiedenen Nebenläufigkeitskontrollverfahren hinsichtlich ihrer Nachrichtenkomplexität verglichen.
    Beschreibung: The report presents a transaction processing scheme for structured overlay networks and uses it to develop a distributed Wiki application based on a relational data model. The Wiki supports rich metadata and additional indexes for navigation purposes. Ensuring consistency and durability requires handling of node failures. Such failures are masked by providing high availability of nodes. This in turn is achieved by constructing the overlay from replicated state machines (cell model). Atomicity is realized using two phase commit with additional support for failure detection and restoration of the transaction manager. The developed transaction processing scheme provides the application with a mixture of pessimistic, hybrid optimistic and multiversioning concurrency control techniques to minimize the impact of replication on latency and optimize for read operations. The pseudocode of the relevant Wiki functions is presented and the different concurrency control techniques are evaluated in terms of message complexit
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    Sprache: Deutsch
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  • 17
    Publikationsdatum: 2016-06-30
    Beschreibung: Berlin als Stadtstaat ist Kommune und Land der Bundesrepublik zugleich und Standort vieler renommier-ter Wissenschafts- und Kultureinrichtungen. In enger Zusammenarbeit der Wissenschaftseinrichtungen mit dem IT-Dienstleistungszentrum Berlin (ITDZ, ehemals Landesbetrieb für Informationstechnik), der für die Behörden Berlins zuständigen Einrichtung, wurde seit 1993 ein landeseigenes Glasfasernetz mit einer derzeitigen Länge von 856 km Glasfaserkabel (je Kabel bis zu 144 Einzelfasern) zur gemeinsamen Nutzung von Wissenschaft und Verwaltung errichtet und weiter ausgebaut. 1994 erfolgte der offizielle Start des Berliner Wissenschaftsnetzes BRAIN (Berlin Research Area Information Network), als durch einen Beschluss des Senats von Berlin die Nutzung des landeseigenen Glasfasernetzes durch die Wissen-schaftseinrichtungen festgeschrieben wurde. Bereits 1995 wurden durch die Wissenschaftseinrichtungen auf diesem Glasfasernetz die ersten sieben Anschlüsse in ATM-Technik (Classical BRAIN-ATM) in Betrieb genommen, 1999 wurden anschließend auch erste Strecken in Ethernet-Technik (Classical BRAIN-GE) betrieben. Diese heterogenen Netze mit unterschiedlichen Netzgeräten wurden dezentral von den Netzadministratoren der beteiligten Einrichtungen nach globalen Absprachen betreut. Die dezentrale Administration erschwerte das Management und die Erweiterungen der Gesamtnetze. Basierend auf den vorliegenden Erfahrungen vereinbarten die Berliner Wissenschaftseinrichtungen, ein technisch neues Verbundnetz in Gigabit-Ethernet-Technik mit einheitlichen Geräten und einem zentralen Netzwerkmana-gement aufzubauen und zu betreiben. Seit November 2003 betreibt BRAIN auf dem landeseignen Glasfasernetz ein auf MPLS-Technik basie-rendes Gigabit-Ethernet-Netz, das „BRAIN-Verbundnetz“, mit den Diensten LAN-to-LAN-Kopplung der Einrichtungen, regionaler IP-Verkehr, Übergang zum Verwaltungsnetz und WiN-Backup. Das BRAIN-Verbundnetz löste die dezentral betreuten Vorläufernetze komplett ab. Von den derzeit 27 BRAIN-Teilnehmern nutzen 24 Einrichtungen an 53 in der Stadt verteilten Standorten die Dienste des BRAIN-Verbundnetzes, 18 Standorte sind mit 1000 Mbit/s und 35 Standorte mit 100 Mbit/s angeschlossen. Für verteilte Standorte einer Einrichtung besteht zudem die Möglichkeit, diese über dedizierte Fasern oder Bandbreiten miteinander zu vernetzen. Seit dem 2. Quartal 2007 wird im Rahmen eines Pilotprojekts der Nutzen eines zentral gemanagten Fibre Channel-Netzwerks "BRAIN-SAN" ermittelt, um Möglichkeiten einer verteilten Datenhaltung der Berliner Hochschulen und wissenschaftlichen Einrichtungen zu schaf-fen. Zusätzlich zu den vorgenannten Diensten nutzt der DFN-Verein die BRAIN-Struktur für die Verbindun-gen der X-WiN-Kernnetzknoten in Berlin und Potsdam untereinander und für Zugangsleitungen zu den Anwendern. Mit Stand 2007 nutzt das Berliner Wissenschaftsnetz BRAIN vom landeigenen Glasfasernetz 2100 km Einzelfasern und verbindet insgesamt 43 Einrichtungen (BRAIN-Teilnehmer und DFN-Anwender) aus Wissenschaft, Bildung und Kultur mit 129 Standorten. Der Betrieb von BRAIN wird im wesentlichen durch seine Nutzer finanziert. Das Land Berlin trägt aller-dings pauschal die überwiegenden Kosten für die Wartung des Glasfasernetzes, soweit es vom ITDZ be-reit gestellt wird. Zentrales Planungs- und Steuerungsorgan für BRAIN ist die von der Senatsverwaltung für Bildung, Wis-senschaft und Forschung eingerichtete BRAIN-Planungsgruppe. Sie besteht aus Mitarbeitern der Rechen-zentren der drei Berliner Universitäten und des ZIB. Nach außen wird BRAIN in rechtlicher und wirtschaftlicher Hinsicht treuhänderisch vom ZIB vertreten, die BRAIN-Geschäftsstelle befindet sich ebenfalls im ZIB.
    Beschreibung: Berlin as a city state is both local authority and federal state of the Federal Republic, as well as a location of many renowned institutions of research and culture. In close cooperation of the institutions of research with the IT service centre Berlin (ITDZ, the former Landesbetrieb für Informationstechnik) - which is the appropriate facility for the authorities of Berlin - a glass fibre network of a total extension of 856 kilome-tres of fibre optics (144 fibres each cable optic) for the common use of research and administration has been established and advanced since 1993. In 1994, when a resolution of the Senate of Berlin laid down the use of the appropriate fibre networks by the research facilities, this was the official beginning of the Berlin Research Area Information Network (BRAIN). The first seven interfaces in this fibre network in ATM technology (Classical BRAIN-ATM) were already established by the research facilities in 1995. In 1999, first systems run in Ethernet technology (Classical BRAIN-GE). These heterogeneous networks with different interfaces have been supported locally by the network administrators of the research facili-ties following global agreements. Management and advancement of the overall networks were encum-bered by these local administrations. Based on the existing experience, Berlin's research facilities agreed on the building and advancement of a technically new integrated network in gigabit Ethernet technology with standardised facilities and a centrally managed network. Since November 2003 the Berlin Research Area Information Network established a Gigabit Ethernet - called “BRAIN Integrated Network” - based on MPLS technology, including LAN to LAN linking of the facilities, local IP traffic, interface to the administration's network and WIN back-up. This BRAIN Inte-grated Network has completely replaced the locally administered predecessor networks. 24 of 27 BRAIN participants use the services of the BRAIN Integrated Network on 53 locations spread all over the city. 18 locations are connected with 1000 Mbit/s and 35 locations with 100 Mbit/s. Moreover, spread locations of a single facility have the possibililty to communicate by dedicated fibres or bandwidths. From the 2nd quarter 2007 within the scope of a pilot scheme, the advantage of a centrally administered fibre channel network "BRAIN-SAN" will be determined in order to accomplish possibilities of a spread data manage-ment of Berlin's universities and research facilities. In addition to the aforementioned services the DFN association makes use of BRAIN's structure for the connection of the X-WiN-core network nodes in Berlin and Potsdam und for access pathways to the us-ers. As from 2007, Berlin's research network BRAIN uses 2100 kilometres of single fibres from the country's fibre glass network and connects a total of 43 facilities (BRAIN participants and DFN users) from re-search, education and culture with 129 locations. The operations of BRAIN are funded basically by its users. However, the country of Berlin bears most of the costs for the maintenance of the glass fibre network, as far as it is provided by ITDZ. Central planning and steering body for BRAIN is the BRAIN planning group, which has been arranged by the administration of the Senatsverwaltung für Bildung, Wissenschaft und Forschung. It consists of staff from the computing centres of Berlin's three universities and of ZIB. BRAIN is represented legally and economically on a trust basis by the ZIB, where the BRAIN office is located also.
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  • 18
    Publikationsdatum: 2022-07-19
    Beschreibung: For medical diagnosis, visualization, and model-based therapy planning three-dimensional geometric reconstructions of individual anatomical structures are often indispensable. Computer-assisted, model-based planning procedures typically cover specific modifications of “virtual anatomy” as well as numeric simulations of associated phenomena, like e.g. mechanical loads, fluid dynamics, or diffusion processes, in order to evaluate a potential therapeutic outcome. Since internal anatomical structures cannot be measured optically or mechanically in vivo, three-dimensional reconstruction of tomographic image data remains the method of choice. In this work the process chain of individual anatomy reconstruction is described which consists of segmentation of medical image data, geometrical reconstruction of all relevant tissue interfaces, up to the generation of geometric approximations (boundary surfaces and volumetric meshes) of three-dimensional anatomy being suited for finite element analysis. All results presented herein are generated with amira ® – a highly interactive software system for 3D data analysis, visualization and geometry reconstruction.
    Schlagwort(e): ddc:004
    Sprache: Englisch
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  • 19
    Publikationsdatum: 2022-07-19
    Beschreibung: This work introduces novel internal and external memory algorithms for computing voxel skeletons of massive voxel objects with complex network-like architecture and for converting these voxel skeletons to piecewise linear geometry, that is triangle meshes and piecewise straight lines. The presented techniques help to tackle the challenge of visualizing and analyzing 3d images of increasing size and complexity, which are becoming more and more important in, for example, biological and medical research. Section 2.3.1 contributes to the theoretical foundations of thinning algorithms with a discussion of homotopic thinning in the grid cell model. The grid cell model explicitly represents a cell complex built of faces, edges, and vertices shared between voxels. A characterization of pairs of cells to be deleted is much simpler than characterizations of simple voxels were before. The grid cell model resolves topologically unclear voxel configurations at junctions and locked voxel configurations causing, for example, interior voxels in sets of non-simple voxels. A general conclusion is that the grid cell model is superior to indecomposable voxels for algorithms that need detailed control of topology. Section 2.3.2 introduces a noise-insensitive measure based on the geodesic distance along the boundary to compute two-dimensional skeletons. The measure is able to retain thin object structures if they are geometrically important while ignoring noise on the object's boundary. This combination of properties is not known of other measures. The measure is also used to guide erosion in a thinning process from the boundary towards lines centered within plate-like structures. Geodesic distance based quantities seem to be well suited to robustly identify one- and two-dimensional skeletons. Chapter 6 applies the method to visualization of bone micro-architecture. Chapter 3 describes a novel geometry generation scheme for representing voxel skeletons, which retracts voxel skeletons to piecewise linear geometry per dual cube. The generated triangle meshes and graphs provide a link to geometry processing and efficient rendering of voxel skeletons. The scheme creates non-closed surfaces with boundaries, which contain fewer triangles than a representation of voxel skeletons using closed surfaces like small cubes or iso-surfaces. A conclusion is that thinking specifically about voxel skeleton configurations instead of generic voxel configurations helps to deal with the topological implications. The geometry generation is one foundation of the applications presented in Chapter 6. Chapter 5 presents a novel external memory algorithm for distance ordered homotopic thinning. The presented method extends known algorithms for computing chamfer distance transformations and thinning to execute I/O-efficiently when input is larger than the available main memory. The applied block-wise decomposition schemes are quite simple. Yet it was necessary to carefully analyze effects of block boundaries to devise globally correct external memory variants of known algorithms. In general, doing so is superior to naive block-wise processing ignoring boundary effects. Chapter 6 applies the algorithms in a novel method based on confocal microscopy for quantitative study of micro-vascular networks in the field of microcirculation.
    Beschreibung: Die vorliegende Arbeit führt I/O-effiziente Algorithmen und Standard-Algorithmen zur Berechnung von Voxel-Skeletten aus großen Voxel-Objekten mit komplexer, netzwerkartiger Struktur und zur Umwandlung solcher Voxel-Skelette in stückweise-lineare Geometrie ein. Die vorgestellten Techniken werden zur Visualisierung und Analyse komplexer drei-dimensionaler Bilddaten, beispielsweise aus Biologie und Medizin, eingesetzt. Abschnitt 2.3.1 leistet mit der Diskussion von topologischem Thinning im Grid-Cell-Modell einen Beitrag zu den theoretischen Grundlagen von Thinning-Algorithmen. Im Grid-Cell-Modell wird ein Voxel-Objekt als Zellkomplex dargestellt, der aus den Ecken, Kanten, Flächen und den eingeschlossenen Volumina der Voxel gebildet wird. Topologisch unklare Situationen an Verzweigungen und blockierte Voxel-Kombinationen werden aufgelöst. Die Charakterisierung von Zellpaaren, die im Thinning-Prozess entfernt werden dürfen, ist einfacher als bekannte Charakterisierungen von so genannten "Simple Voxels". Eine wesentliche Schlussfolgerung ist, dass das Grid-Cell-Modell atomaren Voxeln überlegen ist, wenn Algorithmen detaillierte Kontrolle über Topologie benötigen. Abschnitt 2.3.2 präsentiert ein rauschunempfindliches Maß, das den geodätischen Abstand entlang der Oberfläche verwendet, um zweidimensionale Skelette zu berechnen, welche dünne, aber geometrisch bedeutsame, Strukturen des Objekts rauschunempfindlich abbilden. Das Maß wird im weiteren mit Thinning kombiniert, um die Erosion von Voxeln auf Linien zuzusteuern, die zentriert in plattenförmigen Strukturen liegen. Maße, die auf dem geodätischen Abstand aufbauen, scheinen sehr geeignet zu sein, um ein- und zwei-dimensionale Skelette bei vorhandenem Rauschen zu identifizieren. Eine theoretische Begründung für diese Beobachtung steht noch aus. In Abschnitt 6 werden die diskutierten Methoden zur Visualisierung von Knochenfeinstruktur eingesetzt. Abschnitt 3 beschreibt eine Methode, um Voxel-Skelette durch kontrollierte Retraktion in eine stückweise-lineare geometrische Darstellung umzuwandeln, die als Eingabe für Geometrieverarbeitung und effizientes Rendering von Voxel-Skeletten dient. Es zeigt sich, dass eine detaillierte Betrachtung der topologischen Eigenschaften eines Voxel-Skeletts einer Betrachtung von allgemeinen Voxel-Konfigurationen für die Umwandlung zu einer geometrischen Darstellung überlegen ist. Die diskutierte Methode bildet die Grundlage für die Anwendungen, die in Abschnitt 6 diskutiert werden. Abschnitt 5 führt einen I/O-effizienten Algorithmus für Thinning ein. Die vorgestellte Methode erweitert bekannte Algorithmen zur Berechung von Chamfer-Distanztransformationen und Thinning so, dass diese effizient ausführbar sind, wenn die Eingabedaten den verfügbaren Hauptspeicher übersteigen. Der Einfluss der Blockgrenzen auf die Algorithmen wurde analysiert, um global korrekte Ergebnisse sicherzustellen. Eine detaillierte Analyse ist einer naiven Zerlegung, die die Einflüsse von Blockgrenzen vernachlässigt, überlegen. In Abschnitt 6 wird, aufbauend auf den I/O-effizienten Algorithmen, ein Verfahren zur quantitativen Analyse von Mikrogefäßnetzwerken diskutiert.
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    Sprache: Englisch
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  • 20
    Publikationsdatum: 2022-07-19
    Beschreibung: One crucial step in virtual drug design is the identification of new lead structures with respect to a pharmacological target molecule. The search for new lead structures is often done with the help of a pharmacophore, which carries the essential structural as well as physico-chemical properties that a molecule needs to have in order to bind to the target molecule. In the absence of the target molecule, such a pharmacophore can be established by comparison of a set of active compounds. In order to identify their common features,a multiple alignment of all or most of the active compounds is necessary. Moreover, since the “outer shape” of the molecules plays a major role in the interaction between drug and target, an alignment algorithm aiming at the identification of common binding properties needs to consider the molecule’s “outer shape”, which can be approximated by the solvent excluded surface. In this thesis, we present a new approach to molecular surface alignment based on a discrete representation of shape as well as physico-chemical properties by points distributed on the solvent excluded surface. We propose a new method to distribute points regularly on a surface w.r.t. a smoothly varying point density given on that surface. Since the point distribution algorithm is not restricted to molecular surfaces, it might also be of interest for other applications. For the computation of pairwise surface alignments, we extend an existing point matching scheme to surface points, and we develop an efficient data structure speeding up the computation by a factor of three. Moreover, we present an approach to compute multiple alignments from pairwise alignments, which is able to handle a large number of surface points. All algorithms are evaluated on two sets of molecules: eight thermolysin inhibitors and seven HIV-1 protease inhibitors. Finally, we compare the results obtained from surface alignment with the results obtained by applying an atom alignment approach.
    Beschreibung: Die Identifizierung neuer Leitstrukturen (lead structures) zur Entwicklung optimierter Wirkstoffe ist ein äußerst wichtiger Schritt in der virtuellen Wirkstoffentwicklung (virtual drug design). Die Suche nach neuen Leitstrukturen wird oft mit Hilfe eines Pharmakophor-Modells durchgeführt, welches die wichtigsten strukturellen wie auch physiko-chemischen Eigenschaften eines bindenden Moleküls in sich vereint. Ist das Zielmolekül (target) nicht bekannt, kann das Pharmakophor-Modell mit Hilfe des Vergleiches aktiver Moleküle erstellt werden. Hier ist insbesondere die gleichzeitige Überlagerung (multiple alignment) aller oder nahezu aller Moleküle notwendig. Da bei der Interaktion zweier Moleküle die "äußere Form" der Moleküle eine besondere Rolle spielt, sollte diese von jedem Überlagerungsalgorithmus, der sich mit der Identifizierung von Bindungseigenschaften befasst, berücksichtigt werden. Dabei kann die "äußere Form" durch eine bestimmte Art von molekularer Oberfläche approximiert werden, die man als solvent excluded surface bezeichnet. In dieser Arbeit stellen wir einen neuen Ansatz zur Überlagerung molekularer Oberflächen dar, der auf einer diskreten Repräsentation sowohl der Form als auch der molekularen Eigenschaften mittels Punkten beruht. Um die Punkte auf der molekularen Oberfläche möglichst regulär entsprechend einer gegebenen Punktdichte zu verteilen, entwickeln wir eine neue Methode. Diese Methode ist nicht auf Moleküloberflächen beschränkt und könnte daher auch für andere Anwendungen von Interesse sein. Basierend auf einem bekannten Point-Matching Verfahren entwickeln wir einen Point-Matching Algorithmus für Oberflächenpunkte. Dazu erarbeiten wir u.a. eine effiziente Datenstruktur, die den Algorithmus um einen Faktor von drei beschleunigt. Darüberhinaus stellen wir einen Ansatz vor, der Mehrfachüberlagerungen (multiple alignments) aus paarweisen Überlagerungen berechnet. Die Herausforderung besteht hierbei vor allem in der großen Anzahl von Punkten, die berücksichtigt werden muss. Die vorgestellten Algorithmen werden an zwei Gruppen von Molekülen evaluiert, wobei die erste Gruppe aus acht Thermolysin Inhibitoren besteht, die zweite aus sieben HIV-1 Protease Inhibitoren. Darüberhinaus vergleichen wir die Ergebnisse der Oberflächenüberlagerung mit denen einer Atommittelpunktüberlagerung.
    Schlagwort(e): ddc:004
    Sprache: Englisch
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  • 21
    Buch
    Buch
    Boston :Birkhäuser,
    Titel: Sampling, wavelets, and tomography /
    Beteiligte Person(en): Benedetto, John , Zayed, Ahmed I.
    Verlag: Boston :Birkhäuser,
    Erscheinungsjahr: 2003
    Seiten: p. cm
    Serie: Applied and computational harmonic analysis
    ISBN: 0-8176-4304-4 , 3-7643-4304-4
    Materialart: Buch
    Sprache: Englisch
    Schlagwort(e): Hamonic analysis ; Wavelets (Mathematics) ; Fourier analysis ; Sampling (Statistics) ; Tomography
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  • 22
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 703-712 
    ISSN: 0887-624X
    Schlagwort(e): synthesis ; homopolymerization ; block copolymerization ; N-ethyl-2-ethyl-pyridinium ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A novel acetylenic monomer 2-N-ethyl pyridinium trifluoromethane sulfonate (2EPyEtTf) was synthesized and polymerized. Diblock copolymers of 2EPyEtTf with styrene and with butadiene were prepared. Initiation of the polymerization by living anionic polystyryl--Li+ and polybutadienyl--Li+ (Scheme 1) resulted in polystyrene-block-poly(N-ethyl-2-ethynylpyridinium trifluoromethanesulfonate) (PS57PA8), and polybutadiene -block-poly(N-ethyl-2-ethynylpyridinium trifluoromethanesulfonate) (PB30PA8). These amphiphilic block molecules contain rigid, conjugated, and strongly hydrophilic polyacetylene chain fragments attached to hydrophobic polystyrene or flexible polybutadiene chain fragments. The structure of these copolymers was studied by FTIR, UV-visible, and NMR spectroscopy. GPC and viscometry were also used to obtain information on the molecular mass and the molecular mass distribution. Thermal behavior was investigated by means of TGA and DSC. Both block copolymers were shown to form stable monolayers at the air-water interface. The positively charged rigid polyacetylene portion of the copolymer is believed to be partially submerged, while the more flexible hydrophobic chains are forced out of the water. Multilayers of PB30PA8 deposited using the Langmuir-Blodgett technique were found to be less uniform than in the case of the previously reported polystyrene-block-poly(2EPyMeTf) (PS12PA4) copolymer (Balogh et al., Macromolecules, 29, 1996). Polycation-polyanion self-assembly deposition was also investigated, using polystyrenesulfonate (PSS) as polyanion. While PS57PA8/PSS layer-by-layer deposition was not uniform, it was found that PB30PA8/PSS gave homogenous and stable films on hydrophilic glass substrates. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 703-712, 1998
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 23
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 737-748 
    ISSN: 0887-624X
    Schlagwort(e): inverse microemulsion polymerization ; MADQUAT ; nucleation ; photopolymerization ; molecular weights ; flocculants ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The polymerization of inverse microemulsions of 2-methacryloyl oxyethyl trimethyl ammonium chloride stabilized by a blend of nonionic emulsifiers (a sorbitan sesquioleate and a sorbitan monooleate) and initiated by UV light in the presence of Azobis(isobutyronitrile) (AIBN) was investigated. The effect of initiator concentration, light intensity, emulsifier concentration, and dispersed phase weight fraction on the polymerization rate (Rp), number of polymer particles (Np), and polymer molecular weight (Mw) was studied. The application of this process to tubular reactors is discussed. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 737-748, 1998
    Zusätzliches Material: 15 Ill.
    Materialart: Digitale Medien
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  • 24
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1127-1156 
    ISSN: 0887-624X
    Schlagwort(e): emulsion polymerization ; crosslinking and long-chain branching ; molecular weight distribution ; compartmentalization ; gel formation ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A kinetic model for evaluating the chain length distribution of a branched polymer produced in emulsion was developed. Chain branching occurring through any intermolecular mechanism is considered, namely, crosslinking, chain transfer to polymer and propagation to terminal double bond. The model accounts for active chain compartmentalization and, when coupled to a model able to describe the evolution of the polymerization system, allows evaluation of the cumulative properties of the produced polymer both in the pregel and postgel phases. The numerical difficulties related to the description of a rather wide polymer chain population and of gel formation are overcome by using the ‘numerical fractionation’ technique. A parametric analysis of both instantaneous and cumulative properties is reported and discussed, with special attention to the role of radical compartmentalization in determining the molecular weight properties of a polymer produced in emulsion. Significant differences with the molecular weights computed using models developed for homogeneous (non compartmentalized) systems have been found. A comparison with the predictions of Flory's statistical theory is also reported in terms of gel point and gel weight fraction. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1127-1156, 1998
    Zusätzliches Material: 12 Ill.
    Materialart: Digitale Medien
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  • 25
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 861-871 
    ISSN: 0887-624X
    Schlagwort(e): 2-methylene-1,3-dioxane ; 4-methyl-2-methylene-1,3-dioxane ; 4,4,6-trimethyl-2-methylene-1,3-dioxane ; 2-methylene-1,3-dioxolane ; 4-methyl-2-methylene-1,3-dioxolane ; 4,5-dimethyl-2-methylene-1,3-dioxolane ; cationic copolymerization ; reactivity ratio ; relative reactivity ; ring-retained polymerization ; cyclic ketene acetals ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Cationic copolymerizations of 4-methyl-2-methylene-1,3-dioxane, 2 (M1), with 2-methylene-1,3-dioxane, 1 (M2); of 4,4,6-trimethyl-2-methylene-1,3-dioxane, 3 (M1), with 2-methylene-1,3-dioxane, 1 (M2); of 4-methyl-2-methylene-1,3-dioxolane, 5 (M1), with 2-methylene-1,3-dioxolane, 4 (M2); and of 4,5-dimethyl-2-methylene-1,3-dioxolane, 6 (M1), with 2-methylene-1,3-dioxolane, 4 (M2) were conducted. The reactivity ratios for these four types of copolymerizations were r1 = 1.73 and r2 = 0.846; r1 = 2.26 and r2 = 0.310; r1 = 1.28 and r2 = 0.825; r1 = 2.23 and r2 = 0.515, respectively. The relative reactivities of these monomers towards cationic polymerization are: 3 〉 2 〉 1; and 6 〉 5 〉 4. With both five- and six-membered ring cyclic ketene acetals, the reactivity increased with increasing methyl substitution on the ring. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 861-871, 1998
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 26
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 883-888 
    ISSN: 0887-624X
    Schlagwort(e): temperature sensitive ; particle ; emulsion polymerization ; morphology ; adsorption ; enzyme ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Two kinds of temperature-sensitive composite polymer particles were prepared by seeded emulsion copolymerizations of (dimethylamino)ethyl methacrylate and ethylene glycol dimethacrylate with 0.14 μm-sized polystyrene and 0.26 μm-sized poly(methylmethacrylate) seed particles. To evaluate the usefulness as a carrier for biomolecules, the enzymatic activities of trypsin adsorbed on these two composite polymer particles were measured at temperatures above and below each lower critical solution temperature (LCST). In both cases, adsorbed trypsin retained its enzymatic activity during repeated adsorption/desorption measurements. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 883-888, 1998
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 27
    ISSN: 0887-624X
    Schlagwort(e): (1→6)-2,5-anhydro-D-glucitol ; HPLC ; optical resolution ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The cyclopolymerization of 3,4-di-O-allyl-1,2 : 5,6-dianhydro-D-mannitol (1) was carried out using BF3·OEt2 and t-BuOK. The polymer obtained by the polymerization with BF3·OEt2 mainly consisted of (1→6)-bonded 3,4-di-O-allyl-2,5-anhydro-D-glucitol as the five-membered constitutional repeating unit, though it contained a small amount of other cyclic repeating units. On the other hand, during the polymerization using t-BuOK, the stereoregular polymer (1→6)-linked 3,4-di-O-allyl-2,5-anhydro-D-glucitol (2) was synthesized via a regio- and stereoselective mechanism. Cleavage of the allyl ether linkage in polymer 2 occurred to produce the polymer consisting of only 2,5-anhydro-D-glucitol units, i.e., (1→6)-2,5-anhydro-D-glucitol (3). Chromatographic enantioseparation of chloroquine and tröger base has been performed on (3,5-dimethylphenyl)carbamate and 4-methylbenzoate derivatives of 3 as a chiral stationary phase for high-performance liquid chromatography. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 901-909, 1998
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 28
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 939-947 
    ISSN: 0887-624X
    Schlagwort(e): fluorine ; perfluoropolyether ; polyester ; segmented ; thermoplastic ; interfacial synthesis ; thermal transitions ; dynamic-mechanical properties ; chemical resistance ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Linear segmented polyesters containing soft perfluoropolyether (PFPE) and hard aromatic segments are obtained by an interfacial polycondensation reaction of an acyl chloride-ended fluorinated prepolymer with various aromatic diphenols in the presence of phase transfer catalysts (PTC) as accelerators. Experimental conditions for reaching high molecular weights are discussed. The calorimetric analysis (DSC) of all the polyesters synthesized shows a typical biphasic morphology, where a very low Tg (〈 -110°C) corresponding to the segregated PFPE moiety, is always accompanied by another Tg or a higher melting temperature, depending on the nature of the hard phase. Dynamic-mechanical analysis (DMA) has been carried out confirming the DSC results and suggesting diversified mechanical behaviors at the various temperatures in line with the amorphous or semicrystalline nature of the polymer. Chemical resistance was finally tested by dipping in several solvents and chemicals. The new polyesters show high contact angles, a moderate swelling in many organic solvents and excellent stability in aggressive hydrolytic environments. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 939-947, 1998
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 29
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 979-984 
    ISSN: 0887-624X
    Schlagwort(e): lactitol ; hydrogel ; polyether polyol ; PEO and PPO linkage ; swelling degree ; thermosensitivity ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A series of new thermosensitive polymer hydrogels were prepared by reacting acylated poly(ethylene glycol) bis(carboxymethyl) ether (PEGBCOCl) with lactitol-based polyether polyols (LPEP). The polyether polyols were generated from propoxylation of lactitol and have molecular weights ranging from 1337 to 4055 g/mol. The hydrogels absorb water up to 1000% of their dry weight and expel free water at temperatures at and above 30°C. The wide ranging swelling behavior and excellent thermosensitivity depend closely on the degree of crosslinking and the propylene oxide lengths in the polyols. Differential scanning calorimetry of the hydrogels showed two endotherms associated with the phase transitions of PO and EO segments in the hydrogel structures. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 979-984, 1998
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 30
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1017-1029 
    ISSN: 0887-624X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: This paper discusses the poly(ethylene-co-p-methylstyrene) copolymers prepared by metallocene catalysts, such as Et(Ind)2ZrCl2 and [C5Me4(SiMe2NtBu)]-TiCl2, with constrained ligand geometry. The copolymerization reaction was examined by comonomer reactivity (reactivity ratio and comonomer conversion versus time), copolymer microstructure (DSC and 13C-NMR analyses) and the comparisons between p-methylstyrene and other styrene-derivatives (styrene, o-methylstyrene and m-methylstyrene). The combined experimental results clearly show that p-methylstyrene performs distinctively better than styrene and its derivatives, due to the cationic coordination mechanism and spatially opened catalytic site in metallocene catalysts with constrained ligand geometry. A broad composition range of random poly(ethylene-co-p-methylstyrene)copolymers were prepared with narrow molecular weight and composition distributions. With the increase of p-methylstyrene concentration, poly(ethylene-co-p-ethylstyrene)copolymer shows systematical decrease of melting point and crystallinity and increase of glass transition temperature. At above 10 mol % of p-methylstyrene, the crystallinity of copolymer almost completely disappears. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1017-1029, 1998
    Zusätzliches Material: 8 Ill.
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  • 31
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1473-1480 
    ISSN: 0887-624X
    Schlagwort(e): thermotropic polymers ; liquid crystalline polymers ; semirigid spacers ; melt spinning ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A thermotropic, liquid crystalline copolyester, based on 2-chlorohydroquinone, 1,4-cyclohexanedimethanol and terephthaloyl chloride, has been synthesized and melt spun. The cyclohexanedimethylene moiety acts as a semirigid spacer, introducing flexibility while preserving the thermotropic nature of the polymer. Melt-spun fibers were observed to have a high degree of molecular alignment owing to the nematic nature of the melt. Both polymer and fiber properties have been characterized. Characterization techniques used to this end include elemental analysis, hot-stage polarized light microscopy, scanning electron microscopy, dilute solution viscometry, Fourier transform infrared spectroscopy, nuclear magnetic resonance, differential scanning calorimetry, and thermogravimetric analysis. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1473-1480, 1998
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 32
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1481-1490 
    ISSN: 0887-624X
    Schlagwort(e): ibuprofen ; ketoprofen ; naproxen ; copolymer reactivity ; thermal stability ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Three nonsteroidal antiinflammatory drugs, 2-(4-isobutylphenyl)-propionic acid (ibuprofen), 2-(3-benzoylphenyl)-propionic acid (ketoprofen), and 2-(6-methoxy-2-naphthyl)-propionic acid (naproxen), were covalently linked with 2-hydroxyethyl methacrylate (HEMA). The drug-linked HEMA (M1) (ibuprofen-linked HEMA abbreviated as HI; ketoprofen-linked HEMA as HK, and naproxen-linked HEMA as HN), were respectively copolymerized with methacrylic acid (M2), MA, to obtain macromolecular prodrugs. The compositions of the copolymers were determined by means of a 1H-NMR spectroscopy and monomer reactivity ratios were estimated using the Kelen-Tüdös linear differential equation. The reactivity ratios are: r1 = 0.101 ± 0.012, r2 = 1.071 ± 0.065 for HI-MA; r1 = 0.344 ± 0.066, r2 = 0.966 ± 0.032 for HN-MA, and r1 = 0.650 ± 0.182, r2 = 1.032 ± 0.106 for HK-MA, respectively. The monomer reactivity toward to MA radical estimated from 1/r2 values is almost same for all three monomers (1/r2 ∼ 1). The glass transition temperatures of three drug-linked homopolymers go hand in hand with the steric hindrance of three drugs, i.e., ketoprofen 〉 naproxen ≫ ibuprofen calculated the minimum energy by computer molecular modeling. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1481-1490, 1998
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 33
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1363-1371 
    ISSN: 0887-624X
    Schlagwort(e): liquid chromatography ; column packing ; bare silica gel ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Liquid chromatography of macromolecules at the critical adsorption point (LC CAP) presents a potentially very powerful method for molecular characterization of complex polymers. However, LC CAP applicability is limited due to various experimental problems. The pore sizes and surface chemistry of the column packings belong to the most important weak points of the method. The LC CAP behavior of poly(methyl methacrylate)s was investigated using bare silica gels of 6, 12, and 100 nm pore sizes and with various amounts of surface silanols. Tetrahydrofuran as the adsorption suppressing liquid and toluene as the adsorption promoting liquid were mixed to form the “nearly critical” eluents. Both pore size and surface chemistry of silica were found to strongly influence the retentive characteristics of the system in the critical adsorption area. Macromolecules that were large enough to be excluded from the packing pores hardly followed the LC CAP rules: their retention volumes changed irregularly with the polymer molar mass and their recovery dropped sharply. The narrow pore silica gel-packed column governed the elution patterns of the whole column set composed of silica gels with different pore sizes. This makes the conventional LC CAP characterization of common polymers with broader molar mass distribution impractical and even not feasible. A hybrid column system was proposed containing narrow pore nonadsorptive column added in series to the meso- and macroporous LC CAP silica gels. This narrow pore column would allow separation of gas, impurities, and system peaks from the polymer peaks. The possible successive changes of the surface of silica gel, e.g., due to formation of silanols by hydrolysis or due to irreversible adsorption of some admixtures from the sample or eluent may make the LC CAP irrepeatable. Pronounced peak broadening was observed in the critical adsorption area and this effect increased strongly with the polymer molar mass. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1363-1371, 1998
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 34
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1397-1405 
    ISSN: 0887-624X
    Schlagwort(e): hyperbranched polyesters ; nematic phase ; phloritic acid ; vectra ; melt rheology ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Two classes of liquid crystalline hyperbranched copolyesters were prepared by the copolycondensation of silylated 3,5-bis(acetoxy)benzoic acid with mixtures of mesogenic difunctional monomers. The first class of LC-copolyesters was obtained from 1 : 1 mixtures (molar ratio) of silylated β-(4-acetoxyphenyl)propionic acid and silylated 4-acetoxybenzoic acid (poly(HPPA/HBA)). The second class of LC-copolyesters was obtained by additional copolycondensation of silylated 6-acetoxy-2-naphthoic acid. The hyperbranched copolyesters of this ternary system poly(HPPA/HBA/HNA) proved to be less crystalline in contrast to the binary system. In both classes of LC-copolyesters the degree of branching was varied via the feed ratio of 3,5-dihydroxybenzoic acid. A minimum segment length of 6 difunctional monomer units between the branching points is required to establish a nematic phase. However, a greater segment length is needed to obtain a homogeneous LC-phase. The poly(HPPA/HBA) copolyesters were also characterized by melt rheology. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1397-1405, 1998
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 35
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1417-1424 
    ISSN: 0887-624X
    Schlagwort(e): 2-hydroxyethyl acrylate ; poly(2-hydroxyethyl acrylate) ; atom transfer radical polymerization (ATRP) ; controlled free radical polymerization ; MALDI-MS ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The application of atom transfer radical polymerization (ATRP) to the homopolymerization of 2-hydroxyethyl acrylate, a functional monomer, is reported. The polymerizations exhibit first-order kinetics, and molecular weights increase linearly with conversion. Polydispersities remain low throughout the polymerization (Mw/Mn ≈ 1.2). Reactions were conducted in bulk and in 1 : 1 (by volume) aqueous solution; the latter demonstrates the resilience of ATRP to protic media. Analysis of poly(2-hydroxyethyl acrylate) by MALDI-MS and 1H-NMR shows Mn,exp to be much closer to Mn,th than those observed by SEC using polystyrene standards. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1417-1424, 1998
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 36
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1599-1606 
    ISSN: 0887-624X
    Schlagwort(e): bivalent organolanthanides ; polymerization ; methyl methacrylate ; stereomultiblock polymer ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Bivalent organolanthanides with unbridged substituted indenyl or fluorenyl ligands (1-SiMe3Ind)2YTHF (I), (9-SiMe3Flu)2YTHF (II), were found to efficiently catalyze the stereoregular polymerization of methyl methacrylate. The microstructure of resultant polymers was shown to be dependent of a conformation that the ligands adopt at the polymerization temperature. The formation of isotactic rich PMMAs from complex II was proposed to be associated with the fluctuation of the 9-trimethylsilylfluorenyls around a C2 symmetric twisted-conformation. The formation of the multi(syndioPMMA-block-iso-PMMA) polymers from the mixture of rac- and meso-isomers of I was rationalized on the basis of competing conjugate addition and inversion of the metallocene conformation. Surprisingly, both rac- and meso-isomers of I were found to operate with similar activity and stereospecifity, although the stereospecific operation of the meso-form was not completely understandable. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1599-1606, 1998
    Zusätzliches Material: 1 Ill.
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  • 37
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1491-1494 
    ISSN: 0887-624X
    Schlagwort(e): sulfonyl isocyanate ; acrylamide ; hydrogen-transfer polymerization ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: No abstract.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 38
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1495-1500 
    ISSN: 0887-624X
    Schlagwort(e): acryloyl-L-proline methyl ester (A-ProOMe) ; methacryloyl-L-proline methyl ester (MA-ProOMe) ; porous gel membranes ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Thermoresponsive porous gel membranes were synthesized by a simultaneously occurring process consisting of radiation-induced polymerization and crosslinking in aqueous solutions at various concentrations of acryloyl-L-proline methyl ester(A-ProOMe) without a crosslinker. Permeation of p-nitrophenol (PNP) through a thermoresponsive porous gel membrane obtained at a monomer concentration of 80% (w/w) drastically reduced around 14°C, the lower critical solution temperature (LCST) of linear poly(A-ProOMe) in water, from 0.60 × 10-3 cm/min at 10°C to no permeation at 18°C, accompanied by changes in both size and shape of pores associated with gel shrinkage. Moreover, it was found that porous gel membranes with a porosity of approximately 60% had a greater PNP permeability constant through porous gel membranes with mutually connected pores obtained at a monomer concentration of 50% (w/w) than individually supported pores obtained at a monomer concentration of 70% (w/w). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1495-1500, 1998
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 39
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1509-1513 
    ISSN: 0887-624X
    Schlagwort(e): methylene blue ; dye-sensitized photopolymerization ; magnetic field ; triplet state ; acrylamide ; methyl methacrylate ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Methylene blue sensitized photopolymerization of acrylamide (AM) and methyl methacrylate (MMA) using triethanolamine or the sodium salt of EDTA as a reducing agent has been investigated under the influence of a magnetic field (0-7.3 kG). There was no effect of the magnetic field (MF) on the polymerization of AM and MMA in aqueous medium. However, in the water-methanol mixture (1 : 1) the yield of polymer decreases and the molecular weight increases in both cases under MF. This has been explained on the basis of the triplet mechanism. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1509-1513, 1998
    Zusätzliches Material: 5 Tab.
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  • 40
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1543-1551 
    ISSN: 0887-624X
    Schlagwort(e): polymer microspheres ; monodisperse ; crosslinked ; porosity ; porogen ; precipitation polymerization ; divinylbenzene ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The precipitation polymerization of commercial divinylbenzene in acetonitrile containing up to 40 vol. % toluene or other cosolvents is shown to produce novel porous monodisperse poly(divinylbenzene) microspheres. These microspheres have diameters between 4 and 7 μm, total pore volumes of up to 0.52 cm3/g, and surface areas of up to 800 m2/g. As no surfactant nor stabilizer was used in the preparation of these particles, their surfaces are free of any such residues. The particles were slurry-packed into stainless steel columns for size exclusion chromatography evaluation, and the results show an exclusion limit at molecular weights of 500 g/mol. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1543-1551, 1998
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 41
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1593-1597 
    ISSN: 0887-624X
    Schlagwort(e): MMA ; polymerization ; (diisopropylamido)bis(methylcyclopentadienyl)lanthanides ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: It was first found that (diisopropylamido)bis(methylcyclopentadienyl)lanthanides (MeC5H4)2LnN(i-Pr)2(THF) (Ln = Yb (1), Er (2), Y (3)) exhibit extremely high catalytic activity in the polymerization of methyl methacrylate. The reactions can be carried out over a quite broad range of polymerization temperatures from -78 to 40°C. The catalytic activity of the complexes increases with an increase of ionic radii of the metal elements, i.e. Y 〉 Er 〉 Yb. The results of GPC (gel permeation chromatography) indicate that the number-average molecular weights (Mn) of polymers obtained exceed 100 × 103 and the molecular weight distribution (Mw/Mn) becomes broad with the increase of temperature. Furthermore highly syndiotactic PMMA (87.7%) can be obtained by lowering the reaction temperature to -78°C. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1593-1597, 1998
    Zusätzliches Material: 1 Ill.
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  • 42
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1607-1613 
    ISSN: 0887-624X
    Schlagwort(e): sol-gel ; hybrid material ; poly(styrene-co-maleic anhydride) ; tetraethoxysilane ; (3-aminopropyl)triethoxysilane ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Poly(styrene-co-maleic anhydride)/silica hybrid material has been successfully prepared from styrene-maleic anhydride copolymer and tetraethoxysilane (TEOS) in the presence of a coupling agent (3-aminopropyl)triethoxysilane (APTES) by an in situ sol-gel process. It was observed that the gel time of sol-gel solution was dramatically influenced by the amount of APTES. The hybrid material exhibits optical transparency almost as good as both silica gel and the copolymer. The covalent bonds between organic and inorganic phases were introduced by the aminolysis reaction of the amino group with maleic anhydride units of copolymer to form a copolymer bearing trimethoxysilyl groups, which undergo hydrolytic polycondensation with TEOS. The differential scanning calorimetry (DSC) showed that the glass transition temperature of the hybrid materials increases with increasing of SiO2 composition. Photographs of scanning electron microscopy (SEM) and atomic force microscopy (AFM) inferred that the size of the inorganic particles in the hybrid materials was less than 20 nm. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1607-1613, 1998
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 43
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1639-1648 
    ISSN: 0887-624X
    Schlagwort(e): poly(ethylene terephthalate) (PET) ; plasma ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The influence of different types of low and atmospheric pressure plasma on poly(ethylene terephthalate) (PET) has been studied in terms of changes in molar mass and molar mass distribution. Apart from a variation of plasma gases (oxygen, helium) different types of plasma (microwave, radio frequency, corona discharge) were used for the plasma surface modification. The changes in molar mass and types of functional end groups of lower molar mass products were investigated by means of matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOFMS), whereas the high-molar mass fraction was analyzed by means of size-exclusion chromatography (SEC). The formation of crosslinked products during exposure to a helium plasma, which emits preponderately energy-rich and intense ultraviolet radiation, was proved by means of thermal field-flow fractionation (ThFFF). This method combined with a multiangle laser light scattering (MALLS) detector allows detection of weakly crosslinked polymers and microgels. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1639-1648, 1998
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 44
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1657-1665 
    ISSN: 0887-624X
    Schlagwort(e): 2,6-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride ; poly(ether imide)s ; thermal behavior ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A new naphthalene unit-containing bis(ether anhydride), 2,6-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride, was synthesized in three steps starting from the nucleophilic nitrodisplacement reaction of 2,6-dihydroxynaphthalene and 4-nitrophthalonitrile in N,N-dimethylformamide (DMF) solution in the presence of potassium carbonate, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). High-molar-mass aromatic poly(ether imide)s were prepared using a conventional two-step polymerization process from the bis(ether anhydride) and various aromatic diamines. The intermediate poly(ether amic acid)s had inherent viscosities of 0.65-2.03 dL/g. The films of poly(ether imide)s derived from two rigid diamines, i.e. p-phenylenediamine and benzidine, crystallized during the thermal imidization process. The other poly(ether imide)s belonged to amorphous materials and could be fabricated into transparent, flexible, and tough films. These aromatic poly(ether imide) films had yield strengths of 104-131 MPa, tensile strengths of 102-153 MPa, elongation to break of 8-87%, and initial moduli of 1.6-3.2 GPa. The glass transition temperatures (Tg's) of poly(ether imide)s were recorded in the range of 220-277°C depending on the nature of the diamine moiety. All polymers were stable up to 500°C, with 10% weight loss being recorded above 550°C in both air and nitrogen atmospheres. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1657-1665, 1998
    Zusätzliches Material: 2 Ill.
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  • 45
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1683-1683 
    ISSN: 0887-624X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 46
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1847-1854 
    ISSN: 0887-624X
    Schlagwort(e): polyhydrazides ; poly-1,3,4-oxadiazoles ; thermal behavior ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Two flexible dicarboxylic acid monomers, 4,4′-[isopropylidenebis(1,4-phenylene)dioxy]dibenzoic acid (1) and 4,4′-[hexafluoroisopropylidenebis(1,4-phenylene)-dioxy]dibenzoic acid (3), were synthesized from readily available compounds in two steps in high yields. High molecular-weight polyhydrazides and poly(amide-hydra-zide)s were directly prepared from dicarboxylic acids 1 and 3 with terephthalic dihydrazide (5), isophthalic dihydrazide (6), and p-aminobenzhydrazide (7) by the phosphorylation reaction by means of diphenyl phosphite (DPP) and pyridine in N-methyl-2-pyrrolidone (NMP)/LiCl, or prepared from the diacyl chlorides of 1 and 3 with the hydrazide monomers 5-7 by the low-temperature solution polycondensation in NMP/LiCl. Less favorable results were obtained when using triphenyl phosphite (TPP) instead of DPP in the direct polycondensation reactions. Except for those derived from terephthalic dihydrazide, the resulting polyhydrazides and poly(amide-hydrazide)s could be cast into colorless, flexible, and tough films with good tensile strengths. All the hydrazide polymers and copolymers are amorphous in nature and are readily soluble in various polar solvents such as NMP and dimethyl sulfoxide (DMSO). Their Tgs were recorded in the range of 162-198°C and could be thermally cyclodehydrated into the corresponding polyoxadiazoles and poly(amide-oxadiazole)s approximately in the region of 300-380°C, as evidenced by the DSC thermograms. The oxadiazole polymers and copolymers showed a dramatically decreased solubility and higher Tg when compared to their respective hydrazide prepolymers. They exhibited Tgs of 190-216°C and were stable up to 450°C in air or nitrogen. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1847-1854, 1998
    Zusätzliches Material: 4 Ill.
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  • 47
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1891-1899 
    ISSN: 0887-624X
    Schlagwort(e): polyisobutylene ; poly(dimethylsiloxane) ; hydrosilation ; bicomponent networks ; molecular weight between crosslinks ; network functionality ; sol fraction ; extractables ; model networks ; end-linking ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The synthesis of novel polyisobutylene (PIB)/poly(dimethylsiloxane) (PDMS) bicomponent networks is described. The synthesis strategy (see Figure 1) was to prepare well-defined and -characterized allyl-tritelechelic polyisobutylenes [φ(PIB - C - C=C)3] and SiH-ditelechelic poly(dimethylsiloxanes) (HSi-PDMS-SiH) and then crosslink these moieties by hydrosilation. The φ(PIB - C - C=C)3 was prepared by living isobutylene polymerization followed by end-quenching with allyltrimethylsilane, whereas the HSi-PDMS-SiH was obtained by equilibrium polymerization of octamethylcyclotetrasiloxane and tetramethyldisiloxane. The detailed structures of the starting polymers were characterized by GPC and 1H-NMR spectroscopy. A series of PIB/PDMS bicomponent networks of varying compositions and average molecular weights between crosslinks (Mc) of ∼ 20,000 g/mol were assembled. Optimum crosslinking conditions were defined in terms of H2PtCl6 catalyst concentration, nature of solvent, time, temperature, and stoichiometry of ∼ CH2CH=CH2/∼SiH groups, allowing for the convenient synthesis of well-defined model bicomponent networks. Swelling studies and elemental analysis confirm the correctness of the synthetic strategy. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1891-1899, 1998
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 48
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1901-1910 
    ISSN: 0887-624X
    Schlagwort(e): polyisobutylene ; poly(dimethylsiloxane) ; bicomponent networks ; network structure ; molecular weight between crosslinks ; network properties ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The first part of this series concerned the synthesis of novel polyisobutylene (PIB)/poly(dimethylsiloxane) (PDMS) bicomponent networks; the present paper concerns the structure and property characterization of a series of bicomponent networks of varying compositions (PIB wt %/PDMS wt % = 92/8, 70/30, 50/50, 35/65) having average molecular weights between crosslinks (Mc) of ˜ 20,000 g/mol. According to network structure analysis by uniaxial equilibrium stress-strain measurements, the experimental Mc's are in excellent agreement with theoretical values. Hydrosilation end-linking efficiency was quantitated by the amount of sol and functional group analysis by 1H-NMR spectroscopy. NMR evidence indicates double-bond isomerization during hydrosilation. Network compositions by elemental analysis together with the low sol fractions indicate efficient crosslinking. These data suggest highly efficient network formation and well-defined bicomponent network structures. While PIB and PDMS showed Tg's at -72 and -124°C, respectively, the bicomponent network did not exhibit clearly discernible phase transitions. The heat stability of bicomponent networks increased slightly with increasing PDMS content showing initial (10%) degradation temperatures at ˜ 380°C in nitrogen and ˜ 320°C in air. Tensile strengths and elongations were dependent on composition and varied in the 0.6-3.8 MPa and 600-1100% ranges, respectively. The swelling behavior was not much affected by composition. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1901-1910, 1998
    Zusätzliches Material: 8 Ill.
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  • 49
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1785-1790 
    ISSN: 0887-624X
    Schlagwort(e): carbon monoxide ; norbornene ester ; glass transition temperature ; palladium catalyst ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In this article we will discuss the synthesis of the new copolymers of norbornene derivatives with an ester group and carbon monoxide, using Pd(CH3CN)4(BF4)2 as a catalyst and 2,2′-bipyridine as a ligand in nitromethane/methanol at 60°C. Elementary analysis, infrared spectra, and NMR spectra indicated that copolymers contain ketone, ester, and bicyclic structures. Methanol functions as the coinitiator and chain transfer agent in copolymerization. A decrease in the molar ratio of [CH3OH]/[Pd] caused an increase in molecular weight and a decrease in yield of the copolymer. The number-average molecular weight of copolymers (Mn) ranged from 3800 to 5300, and the glass transition temperature (Tg) ranged from -32 to 117°C. Thermal analysis revealed that both T10%d and Tmaxd exceeded 180 and 230°C, respectively. Linear long-chain substituents such as n-C11H23C(O)—O—CH2— drastically reduced Tg to a value of -32°C. In general, copolymers having a longer linear side-chain substituents of ester on norbornene have a more desirable solubility. Moreover, X-ray diffraction demonstrated that the degree of crystallinity decreases with an increasing length of side chain substituents. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1785-1790, 1998
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 50
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1813-1820 
    ISSN: 0887-624X
    Schlagwort(e): poly(ester-imide)s ; poly(ethylene terephthalate) ; transesterification, nematic phase ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Four series of copoly(ester-imide)s (co-PEIs) were prepared by transesterification of poly(ethylene terephthalate), PET, with N-(4-carboxyphenyl)trimellitimide and an acetylated diphenol. Methylhydroquinone, tert. butylhydroquinone, phenylhydroquinone, and 2,7-dihydroxynaphthalene were used as diphenols. The chemical structures of these co-PEIs were characterized by chemical analyses, 1H-, and 13C-NMR spectra. A low degree of crystallinity was observed when the PET content was above 85% mol %. Between 60 and 80 mol % PET all co-PEIs are biphasic, whereas below 60 mol % the co-PEIs form a homogeneous nematic melt and below the glass transition temperature (Tg) a nematic glass. The Tgs vary continously with the molar composition but the mechanical properties drop sharply when the nematic phase changes to an isotropic one. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1813-1820, 1998
    Zusätzliches Material: 7 Ill.
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  • 51
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1821-1827 
    ISSN: 0887-624X
    Schlagwort(e): morphology ; grafting ; oxazoline-functionalized polymer particles ; carbolic acids ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Oxazoline-functionalized, crosslinked PMMA-particles, prepared by free radical nonaqueous dispersion polymerization, were grafted with n-decanoic acid and carboxylic acid-terminated polystyrene. Oxazoline groups, separated by an alkylspacer from the PMMA backbone, showed enhanced mobility with respect to the backbone, as evaluated by solid-state NMR spectroscopy using a dipolar filter. As a function of molecular mass of the carboxylic acid, the oxazoline conversion varied from 70 mol % for n-decanoic acid to 1% for monocarboxylate-terminated polystyrene CT-PS with Mn: 15,900 g/mol. Morphological studies, performed by TEM, showed that reaction with acid terminated polystyrene results exclusively in interfacial grafting at the particle surface. At low grafting levels a raspberry-like morphology was obtained, whereas grafting levels exceeding 14 wt % CT-PS resulted in core-shell morphology. Core-shell morphology was also verified by static light scattering using toluene solvent, which is isorefractive to the PMMA core. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1821-1827, 1998
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 52
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1573-1582 
    ISSN: 0887-624X
    Schlagwort(e): amic acid ; secondary amine ; maleic anhydride ; melt reaction kinetics ; model compounds ; polymer-bound functional groups ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: This study examines the legitimacy of using the reaction kinetics of low molecular weight model compounds in solution to predict the chemical kinetics of polymer-bound species in a homogeneous melt. The reaction under study takes place between an aliphatic secondary amine, diisooctadecylamine (DiOA), and a 5-membered anhydride ring, saturated maleic anhydride (MA), forming an amic acid product. The MA species was present as a pendant graft on either a model compound, dodecane-g-(maleic anhydride) (dodecane-g-MA), or a polymer chain, linear low-density polyethylene-g-(maleic anhydride) (LLDPE-g-MA). Pseudo-second-order kinetics of the anhydride consumption are followed by infrared spectroscopy, either in situ in dodecane solution or by scanning frozen film samples taken from a linear low-density polyethylene melt. It was found that the LLDPE-g-MA/DiOA system reacted at a slightly slower rate than the dodecane-g-MA/DiOA system in the low-viscosity solution at 140°C. In the melt, the dodecane-g-MA/DiOA system experienced a small decrease in the overall reaction rate compared to the same reaction carried out in dodecane. However, the LLDPE-g-MA/DiOA system underwent a 65% decrease in the observed second-order rate constant on going from a solution to the melt. To explain these phenomena, the effects of diffusion, miscibility, and chain entanglements in the melt are examined here. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1573-1582, 1998
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 53
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 31-38 
    ISSN: 0887-624X
    Schlagwort(e): triblock copolymers ; polycondensations ; telechelic character ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Telechelic oligo(ether-ketone)s containing two trimethylsiloxy end groups and one methyl group per repeating unit were prepared by polycondensation of 4-fluoro-2′-methyl-4′-(trimethylsiloxy)benzophenone. The telechelic character was achieved by cocondensation of a small amount of silylated bisphenol-P. The end groups of the silylated oligo(ether-ketone)s were acetylated by means of acetyl chloride. On the basis of 1H-NMR end group analyses two samples of α,ω-bis(acetoxy) oligo(ether-ketone)s with DP = 14 and DP ∼ 28 were obtained. These oligo(ether-ketone)s and a 70 or 140 fold molar amount of silylated 3,5-bis(acetoxy)benzoic acid were polycondensed at 270°C in bulk. The resulting A-B-A triblock copolymers were fractionated by dissolution in tetrahydrofuran. In three out of four experiments a small fraction of precipitated material rich in oligo(ether-ketone) was isolated. The purified triblock copolymers were characterized by inherent viscosities and NMR spectra. For those samples containing the long oligo(ether-ketone) block a low degree of crystallinity was observed after annealing. Four additional polycondensations were conducted with an initial reaction temperature of 290°C. In this way a completely soluble and amorphous triblock copolymer was obtained. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 31-38, 1998
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 54
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 21-29 
    ISSN: 0887-624X
    Schlagwort(e): liquid crystalline polymers ; epoxy resins ; thermotropic ; polymer chain extension ; catalytic polyaddition ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: This work is a continuation of the authors' earlier investigations of liquid crystalline epoxy resins prepared from diglycidyl ether of 4,4′-dihydroxybiphenyl (DGE-DHBP), which was used as a mesogenic agent, and aliphatic dicarboxylic compounds, which were used as flexible spacers. In this paper, the synthesis and characterization of liquid crystalline epoxy resins, prepared from DGE-DHBP and difunctional aromatic compounds are described. Three series of liquid crystalline epoxy resins were prepared by chain extension of DGE-DHBP with isomeric hydroxybenzoic and benzenedicarboxylic acids as well as diphenols. An isophthalic-terminated polyether was applied to decrease the temperature of phase transitions. The syntheses were carried out by catalytic polyaddition in the melt. Triphenylphosphine was applied as the catalyst. The resulting epoxy resins were investigated by DSC, polarizing microscope as well as by X-ray and IR spectroscopy. The phase transition temperatures and the type of mesophase of the resulting products depend on the character of the functional groups in the chain extender and on the position of the functional groups in the aromatic ring. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 21-29, 1998
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 55
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2021-2027 
    ISSN: 0887-624X
    Schlagwort(e): 2,2′-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride ; aromatic polyimides ; solubility ; thermal behavior ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A new aromatic tetracarboxylic dianhydride having a crank and twisted noncoplannar structure, 2,2′-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, was synthesized by the reaction of 4-nitrophthalonitrile with biphenyl-2,2′-diol, followed by hydrolysis and cyclodehydration. The biphenyl-2,2′-diyl-containing aromatic polyimides having inherent viscosities up to 0.66 dL/g were obtained by the conventional two-step procedure starting from the dianhydride monomer and various aromatic diamines. Most of the polyimides were readily soluble in amide-type solvents such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone. The aromatic polyimides had glass transition temperatures in the range of 205-242°C, and began to lose weight around 415°C, with 10% weight loss being recorded at about 500°C in air. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2021-2027, 1998
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 56
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2069-2079 
    ISSN: 0887-624X
    Schlagwort(e): Candida antarctica lipase ; Novozym 435® ; polyester ; enzymatic polymerization ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Preliminary enzymatic polymerization studies in the simple stoichiometric adipic acid/butane-1,4-diol system using lipase B from Candida antarctica, immobilized as Novozym 435®, suggest that in solvent-free conditions a step-growth mechanism operates involving the sequential addition of an AB synthon by esterification mode only. Conversely, in toluene as solvent there is a change to the more facile transesterification mode in line with the conventional polyesterification procedure, pointing to a change in specificity of the lipase. Evidence is drawn from qualitative studies using a series of synthetic intermediates, enabling authentication of product mixtures together with an indication of the comparative reactivity of species along the proposed reaction pathway. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2069-2080, 1998
    Zusätzliches Material: 5 Ill.
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  • 57
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2111-2117 
    ISSN: 0887-624X
    Schlagwort(e): dendritic polymer ; blends ; coatings ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Hybrid blends of poly(amidoamine) PAMAM dendrimers with two linear high polymers, poly(vinyl chloride), PVC, and poly(vinyl acetate), PVAc, are reported. The interaction between the blend components was studied using dynamic mechanical analysis, xenon nuclear magnetic resonance (NMR) spectroscopy, and tensile property measurements. The data suggest a much higher degree of interaction between components of PVAc-containing blends compared to those containing PVC. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2111-2117, 1998
    Zusätzliches Material: 4 Ill.
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  • 58
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2135-2146 
    ISSN: 0887-624X
    Schlagwort(e): SCLC polyurethanes ; azobenzene mesogenic group ; alkyl spacer ; bilayer smectic phases ; hydrogen bonding ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A series of side chain liquid crystal polyurethanes (CnCNPs), in which the spacer length was varied from 2 to 12 methylene units, were synthesized by the addition polymerization of α-[bis(2-hydroxyethyl)amino]-ω-(4-cyanoazobenzene-4′-oxy)alkanes (CnCN-diols) with hexamethylene diisocyanate. The liquid crystalline properties of CnCNPs were characterized by means of differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction. Polyurethanes with spacer length 4 or higher exhibited mesomophic properties. C4CNP and C5CNP exhibited an enantiotropic nematic mesophase, while C6-C12CNPs exhibited enantiotropic bilayer smectic mesophases. CnCNPs have a high tendency to crystallize; crystallization is kinetically controlled. Polyurethane's backbone crystallization is closely related to hydrogen bonding. To establish the role of hydrogen bonding in mesophase formation as well as crystallization, Fourier transform infrared spectroscopy studies of CnCNPs were carried out at different temperatures focusing on H-bonds between the N—H and C=O groups of the urethane backbone. With increasing temperature, C=O and N—H stretching bands were evenly shifted to higher wavenumbers, with two exceptions (C4CNP and C5CNP) discussed in detail in the text. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2135-2146, 1998
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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  • 59
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2169-2176 
    ISSN: 0887-624X
    Schlagwort(e): free radical ; initiation ; styrene ; acrylonitrile ; copolymerization ; nitroxide trapping ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The competitive reactions of cyanoisopropyl radicals with the mixed monomers styrene and acrylonitrile have been investigated using the nitroxide radical trapping technique. When the trap concentration is kept low, second, third, and even fourth generation (in terms of successive monomer addition) carbon radicals have been observed as trapped products. The ratio of rate constants for the addition of styrene and acrylonitrile to cyanoisopropyl radicals is 2.7 at 75°C and 5.3 at 105°C. These values are compared with the ratios for reactions of these two monomers with a number of other radicals and discussed in terms of the polarities of the radicals and monomers. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2169-2176, 1998
    Zusätzliches Material: 1 Ill.
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  • 60
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2301-2307 
    ISSN: 0887-624X
    Schlagwort(e): 1,4-bis(4-trimellitimidophenoxy)-2-tert-butylbenzene (BTTB) ; direct polycondensation ; poly(amide-imide)s ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: New poly(amide-imide)s were prepared from a diimide-dicarboxylic acid, 1,4-bis(4-trimellitimidophenoxy)-2-tert-butylbenzene (BTTB), with various diamines by the direct polycondensation in N-methyl-2-pyrrolidinone (NMP) using triphenyl phosphite and pyridine as condensing agents. The new diimide-dicarboxylic acid BTTB containing an ether linkage and tert-butyl substituent was synthesized by the condensation reaction of 1,4-bis(4-aminophenoxy)-2-tert-butylbenzene with trimellitic anhydride. All the polymers were obtained in quantitative yields with inherent viscosities of 0.62-1.06 dL g-1. The polymers were amorphous, and most of them were readily soluble in aprotic polar solvents such as NMP, N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF), as well as in less polar solvents such as dimethyl sulfoxide (DMSO), m-cresol, pyridine, and γ-butyrolactone, and also even in tetrahydrofuran. The glass transition temperatures of the polymers were determined by DSC method, and they were in the range of 238-279°C. These polymers were stable up to 408-449°C in air and 451-483°C in nitrogen and lose 10% weight in the range of 479-525°C in air and 480-528°C in nitrogen atmosphere. The polymer films had a tensile strength range of 71-115 MPa, an elongation at break range of 4-14%, and a tensile modulus range of 2.3-3.1 GPa. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2301-2307, 1998
    Zusätzliches Material: 5 Tab.
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  • 61
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2331-2338 
    ISSN: 0887-624X
    Schlagwort(e): poly(ether urethane) ; surface modification ; heparin immobilization ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Novel poly(ether urethanes) containing diester groups in the side chains (PU) were synthesized from 4,4′-diphenylmethyl diisocyanate, polytetramethylene glycol, and diethyl bis(hydroxymethyl)malonate as a chain extender. The surface modification of the PU film was carried out by a hydrolysis reaction, poly(ethylene oxide) (PEO) grafting, and heparin immobilization, and the surface-modified PUs were then characterized by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, electron spectroscopy for chemical analysis (ESCA), and a contact angle goniometer. The concentration of carboxylic acid groups introduced on the PU surfaces as determined by the rhodamine interaction method was 61 nmol/cm2 when treated with 4N NaOH/methanol (1 : 2 v/v) for 30 min and subsequently with a citric acid-methanolic aqueous solution. The amounts of heparin coupled to the carboxyl groups on the PU surfaces and to the terminus amino groups on the PU-PEO were 0.92 and 0.84 μ g/cm2, respectively. There was almost no heparin released from the immobilized surface of a physiological solution for 100 h, thereby indicating the strong stability of immobilized heparin. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2331-2338, 1998
    Zusätzliches Material: 5 Ill.
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  • 62
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2229-2235 
    ISSN: 0887-624X
    Schlagwort(e): polyarylates ; aromatic polyether ; 2,2-bis(4-hydroxyphenyl)-1,2-diphenylethanone ; solubility ; thermal behavior ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: New polyarylates having benzopinacolone units were synthesized from 2,2-bis(4-hydroxyphenyl)-1,2-diphenylethanone and aromatic dicarboxylic acid chlorides. The polymers having an inherent viscosity of 0.71-0.94 dL/g were obtained by the two-phase method using toluene as an organic solvent. The polymers were easily soluble in various organic solvents and had high glass transition temperatures in the range of 200-240°C. An aromatic polyether having benzopinacolone unit was also prepared. However, its inherent viscosity was low because of the occurrence of a side reaction. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2229-2235, 1998
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 63
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2247-2259 
    ISSN: 0887-624X
    Schlagwort(e): pervaporation ; plasma graft polymerization ; membrane ; glycidyl methacrylate ; morphology ; porous polyethylene ; benzene/cyclohexane separation ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Composite membranes were prepared by plasma-induced graft polymerization of vinyl monomers onto porous substrates of high density polyethylene, and the relationship between the polymerization conditions and morphological structure and pervaporation performance toward benzene/cyclohexane mixtures was investigated in detail. The morphological structures of the plasma-grafted membranes depended on the monomer reactivity, plasma treatment manner, and graft polymerization conditions. Pervaporation properties were closely related to the graft monomers and the morphological structures. The poly(glycidyl methacrylate)-grafted membranes prepared by homogeneous both sides plasma treatment and under mild polymerization conditions showed the highest pervaporation performance with a permeation flux of 0.3 kg/(m2 h) and separation factor of 22 at 60 wt % benzene and 70°C. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2247-2259, 1998
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 64
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2269-2274 
    ISSN: 0887-624X
    Schlagwort(e): dinuclear ansa-zirconocene catalyst ; diastereomers ; biphenyl and phenyl ligands ; polymerization of ethene and propene ; copolymerization of ethene and 1-octene ; thermal stability of active species ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Both the rac- and meso-dinuclear ansa-zirconocene catalysts (μ-C12H8{[SiPh(Ind)2]ZrCl2}2) were prepared by a coupling reaction between 2 equiv of diindenylphenylchlorosilane (rac- and meso-isomers) and 1 equiv of p-dilithiobiphenyl in diethyl ether at -80°C, followed by a successive reaction with ZrCl4 · 2THF in THF at -78°C. Polymerizations of ethene and propene were conducted in a 1 dm3 high-pressure glass reactor equipped with a mechanical stirrer at 60, 80, 100, 120, and 150°C using methylalumoxane (MAO) as cocatalyst and toluene or decahydronaphthalene as the solvent. Copolymerization of ethene and 1-octene was also checked in brief. For ethene polymerization, the meso-catalyst was found to be more active, which displayed an extremely high activity to give linear polyethene with a high molecular weight and a narrow molar mass distribution (MMD). The apparent activity increased monotonously with rising polymerization temperature from 60°C up to 150°C, indicating that the active species are stable even at a high temperature. On the other hand, both the rac- and meso-catalysts showed very poor activities for propene polymerization. However, copolymerization of ethene and 1-octene proceeded at a high speed. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2269-2274, 1998
    Zusätzliches Material: 4 Ill.
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  • 65
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2291-2299 
    ISSN: 0887-624X
    Schlagwort(e): poly(o-toluidine) ; (POT) ; poly(m-toluidine) ; (PMT) ; polystyrene (PSt) ; blends ; emulsion pathway ; spectroscopy ; thermal stability ; conductivity ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Conducting poly(o-toluidine) (POT) and poly(m-toluidine) (PMT) blends containing 10, 30, 50, 70, and 90 % wt/wt of polystyrene (PSt) were prepared by employing a two-step emulsion pathway. The bands characteristic of both polystyrene and POT/PMT are present in the IR spectra of POT-PSt and PMT-PSt blends. The UV-visible spectra of POT-PSt and PMT-PSt blends exhibit two bands around 313 and 610 nm, confirming that some amount of POT/PMT base is present in the blends. The EPR parameters such as line width and spin concentration reveal the presence of POT/PMT salt in the respective blends. The TGA, DTA, and DSC results suggest a higher thermal stability for the POT and PMT blends than that for the respective salts. The conductivity values of POT(70)-PSt(30) and POT(90)-PSt(10) blends are almost the same (1.1 × 10-2 and 1.3 × 10-2 S cm-1, respectively) and these values are very close to that of pure POT salt, suggesting that POT can be blended with up to 30% wt/wt of PSt to improve its mechanical properties without a significant drop in its conductivity. The conductivity values of PMT-PSt blends are lower than those of the corresponding POT-PSt blends by two to three orders of magnitude, indicating that POT is a better system than PMT to prepare blends by this method. The dielectric constant and tan δ values of the blends increase with the amount POT/PMT and are greater than that of polystyrene. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2291-2299, 1998
    Zusätzliches Material: 4 Ill.
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  • 66
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2521-2530 
    ISSN: 0887-624X
    Schlagwort(e): poly(methylphenylsiloxane) ; poly(methyl methacrylate) ; graft copolymer ; spin-spin relaxation ; degradation ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Poly(methylphenylsiloxane)-poly(methyl methacrylate) graft copolymers (PSXE-g-PMMA) were prepared by condensation reaction of poly(methylphenylsiloxane)-containing epoxy resin (PSXE) with carboxyl-terminated poly(methyl methacrylate) (PMMA), and they were characterized by gel permeation chromatography (GPC), infrared (IR), and 29Si and 13C nuclear magnetic resonance (NMR). The microstructure of the PSXE-g-PMMA graft copolymer was investigated by proton spin-spin relaxation T2 measurements. The thermal stability and apparent activation energy for thermal degradation of these copolymers were studied by thermogravimetry and compared with unmodified PMMA. The incorporation of poly(methylphenylsiloxane) segments in graft copolymers improved thermal stability of PMMA and enhanced the activation energy for thermal degradation of PMMA. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2521-2530, 1998
    Zusätzliches Material: 11 Ill.
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  • 67
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2563-2570 
    ISSN: 0887-624X
    Schlagwort(e): thioxanthone derivatives ; water-compatible photoinitiator ; absorption spectrum ; fluorescence ; photopolymerization ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Six amine-linked thioxanthones, i.e., 2-(2-hydroxy-3-[bis(2-hydroxyethyl)amino]propoxy)thioxanthone (HAPTX) and its 4-methyl, 1,3-dimethyl, 1,4-dimethyl, 3,4-dimethyl, and 1,3,4-trimethyl substituted derivatives, were synthesized as water-compatible photoinitiators and identified with FTIR, MS, NMR, and elementary analysis. The absorption and fluorescence properties were studied. Their photoinitiating polymerization efficiencies were tested with a recording dilatometer utilizing acrylamide as monomer in aqueous solution. The results show that the six amine-linked thioxanthones can independently initiate acrylamide polymerization efficiently without additional external amines as co-initiators. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2563-2570, 1998
    Zusätzliches Material: 1 Ill.
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  • 68
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2593-2600 
    ISSN: 0887-624X
    Schlagwort(e): phenylenediamine ; oxidative polymerization ; enzyme ; horseradish peroxidase ; CD spectrum ; organic solvent ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Ortho-, meta-, and para-phenylenediamines were polymerized using hydrogen peroxide as an oxidant and horseradish peroxidase as a catalyst in mixed solvents of 1,4-dioxane and water. The yield of the polymers was strongly dependent on solvent composition, and maximum yields were obtained at 15-30% 1,4-dioxane. The analysis of circular dichroic spectra of the enzyme suggested that enzyme structure was significantly modified at high 1,4-dioxane contents, which may be responsible for the decrease of catalytic activity of the enzyme. On the basis of IR and electronic spectra of the polymers, it was considered that o- and p-phenylenediamine polymers retain disubstituted benzene nuclei, which suggests that the polymerization proceeded mainly via N - N coupling. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2593-2600, 1998
    Zusätzliches Material: 6 Ill.
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  • 69
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2667-2668 
    ISSN: 0887-624X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 70
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2691-2698 
    ISSN: 0887-624X
    Schlagwort(e): N-substituted pyrrole ; liquid crystalline polymer ; polypyrrole ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Three liquid crystalline N-substituted pyrroles were synthesized from 6-(1-pyrrolyl)hexanol with phenolic derivatives having a mesogenic core of cyclohexylbenzene or biphenyl by Mitsunobu reaction. These pyrroles had two anodic peaks at 1.4 and 1.8 V (vs. SCE). The former was due to an oxidation of the pyrrole moiety and the latter was due to an oxidation of the mesogenic moiety. These pyrrole monomers were polymerized by electrochemical and chemical methods. The potentiostatic method and the chemical method using FeCl3 gave a soluble and fusible polymer, respectively. A polymer having a mesogenic core of cyclohexyl benzene obtained by the chemical method and a polymer having a mesogenic core of biphenylketone obtained by the potentiostatic method had a liquid-crystalline phase. The phase was identified as smectic A by polarizing microscopy and XRD analysis. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2691-2698, 1998
    Zusätzliches Material: 5 Ill.
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  • 71
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 207-208 
    ISSN: 0887-624X
    Schlagwort(e): photoinitiated polymerization ; initiator absorbance ; metal complex ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: No abstract.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 72
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    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 209-213 
    ISSN: 0887-624X
    Schlagwort(e): end-reactive oligomer ; terminal vinylidene ; thermal degradation ; polystyrene ; temperature dependence ; chemical recycle ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: No abstract.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 73
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 215-215 
    ISSN: 0887-624X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: No abstract.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 74
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 225-231 
    ISSN: 0887-624X
    Schlagwort(e): silacyclobutane ; polysilabutane ; oligooxyethylene ; polycarbosilane ; anionic polymerization ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A new class of polar polysilabutanes with mono- or tri-(oxyethylene)phenyl groups on the silicon atom have been synthesized by anionic polymerization of silacyclobutanes having ω-(t-butyldimethylsilyl-protected) mono- or tri-(oxyethylene)phenyl groups and subsequent deprotection of the silyl groups. The monomers were synthesized by treatment of 1,1-dichlorosilacyclobutane with ω-(t-butyldimethylsilyl-protected) mono- or tri-(oxyethylene)phenyl Grignard reagents. Anionic polymerization of silacyclobutane was performed with butyllithium initiator in THF. t-Butyldimethylsilyl-protecting groups at polymer pendant groups were hydrolyzed with tetrabutyl ammonium fluoride in water-containing THF. The obtained polysilabutanes were soluble in a polar organic solvent such as methanol, and their mass distributions were analysed by matrix-assisted laser-desorption-ionization mass spectrometry (MALDI TOF MS). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 225-231, 1998
    Zusätzliches Material: 2 Ill.
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  • 75
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 233-239 
    ISSN: 0887-624X
    Schlagwort(e): silicone rubber ; insulation ; ablation ; thermal decomposition ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Ablation characteristics of silicone insulation were examined in an induced air combustion chamber and by thermogravimetric analysis. The rate of ablation increased with the combustion pressure. Although the flame temperature was less effective in increasing the ablation rate, the ablation rate below 1160 K was much smaller than expected. The decomposition kinetics of the silicone insulation was significantly altered at this temperature range. The stability of the char layer was much higher below approximately 1000 K. Since the lower ablation rate was obtained in higher mass flow rate condition, the heat input from the boundary layer to the insulation surface was decreased at this condition. The expended insulation consisted of a virgin zone, reaction zone, and char layer. These degraded materials were generated at relatively narrow temperature ranges. The char layer maintained a silicone backbone structure even though it experienced severe conditions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 233-239, 1998
    Zusätzliches Material: 9 Ill.
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  • 76
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 217-223 
    ISSN: 0887-624X
    Schlagwort(e): aromatic polyacetylene ; Rh complex catalyst ; cis-transoid ; pressure ; isomerization ; solitons ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: This study reports that stereospecific polymerization of aromatic acetylenes, e.g., p-methoxyphenylacetylene (pMOPA) and p-ethoxyphenylacetylene (pEOPA)was successfully performed to give polyacetylene selectively bearing cis-transoid forms in high yield when a Rh complex catalyst, [Rh(norbornadiene)Cl]2 was used in the presence of triethylamine as the polymerization solvent together with a detailed characterization of the resulting polymers, before and after compression. Compression of these polymers induced a cis-trans isomerization at room temperature under vacuum even in the solid state. Based on data collected before and after compression it is estimated that the trans conjugated length, (C=C)n, produced as a result of the compression is n = 26 for PpMOPA and n = 40 for PpEOPA polymers, respectively. We further found that g values in the ESR spectra of the pristine polymer were shifted to higher magnetic field by compression, indicating that unpaired electrons called solitons are stabilized in the trans conjugation length as mobile electrons, although in the pristine polymers the unpaired electrons are stabilized in the less conjugated chain, showing large g value, suggesting a magnetic interaction between oxygen in the alkoxy group of phenyl moiety and unpaired electrons in the cis form. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 217-223, 1998
    Zusätzliches Material: 4 Ill.
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  • 77
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. v 
    ISSN: 0887-624X
    Schlagwort(e): electron photoejection ; electron transfer ; radical anion disproportionation ; initiation ; anionic polymerization ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The principle of the electron photoejection technique is explained. This approach leads to the formation of transient spectra of unstable intermediates, allowing their recording and providing their extinction coefficients. Moreover, it permits determination of their electron affinities and the rates of their reactions, whether spontaneous or with some added substrates. Application of this technique to studies of disproportionation of radical anions has been most profitable. It led to the determination of the forward and backward rate constants of disproportionation of a variety of radical anions, and to discovery and quantification of some subtle features of these reactions. The electron photoejection technique provided the data characterizing the electron transfer initiation of anionic polymerization and clarified some of its features. Other opportunities provided by the electron photoejection in studies of electron transfer processes are suggested. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: v-xiii, 1998
    Zusätzliches Material: 15 Ill.
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  • 78
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 241-247 
    ISSN: 0887-624X
    Schlagwort(e): neodymium tricarboxylate ; polymerization of butadiene or styrene ; copolymerization of butadiene and styrene ; cis-1,4 polymerization mechanism ; back-biting coordination model ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Homo- and copolymerizations of butadiene (BD) and styrene (St) with rare-earth metal catalysts, including the most active neodymium (Nd)-based catalysts, have been examined, and the cis-1,4 polymerization mechanism was investigated by the diad analysis of copolymers. Polymerization activity of BD was markedly affected not only by the ligands of the catalysts but also by the central rare-earth metals, whereas that of St was mainly affected by the ligands. In the series of Nd-based catalysts [Nd(OCOR)3:R = CF3, CCl3, CHCl2, CH2Cl, CH3], Nd(OCOCCl3)3 gave a maximum polymerization activity of BD, which decreased with increasing or decreasing the pKa value of the ligands. This tendency was different from that for Gd(OCOR)3 catalysts, where the CF3 derivative led to the highest polymerization activity of BD. For the polymerization of St and its copolymerization with BD, the maximum activities were attained at R = CCl3 for both Nd- and Gd-based catalysts. The copolymerization of BD and St with Nd(OCOCCl3)3 catalyst was also carried out at various monomer feed ratios, to evaluate the monomer reactivity ratios as rBD = 5.66 and rSt = 0.86. The cis-1,4 content in BD unit decreased with increasing St content in copolymers. From the diad analysis of copolymers, it was indicated that Nd(OCOCCl3)3 catalyst controls the cis-1,4 structure of the BD unit by a back-biting coordination of the penultimate BD unit. Furthermore, the long range coordination of polymer chain by the neodymium catalyst was suggested to assist the cis-1,4 polymerization. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 241-247, 1998
    Zusätzliches Material: 8 Ill.
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  • 79
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    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 249-256 
    ISSN: 0887-624X
    Schlagwort(e): polysulfonate ; reactive chloromethyl groups ; polyaddition ; bisepoxide ; disulfonyl chloride ; quaternary onium salt ; catalyst ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Polysulfonates with reactive pendant chloromethyl groups were synthesized by polyadditions of bisepoxides with disulfonyl chlorides. The polyaddition of bisphenol A diglycidyl ether (BPGE) with m-benzene disulfonyl chloride (m-BDSC) occurred in anisole without any catalyst at 130°C for 24 h. However, polymer with high molecular weight was not obtained. On the other hand, the polyadditions of BPGE with m-BDSC proceeded very smoothly with high yield (81-91%) to give polymers with relatively high molecular weights in anisole at 130°C for 24 h when quaternary phosphonium salts were used as catalysts. The polyaddition was also enhanced by the addition of certain crown ether complexes. However, the catalytic activity of these compounds was less than those of quaternary phosphonium salts. Furthermore, polyadditions of certain bisepoxides with disulfonyl chlorides were also carried out to produce the corresponding polymers under the same reaction conditions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 249-256, 1998
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 80
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2463-2471 
    ISSN: 0887-624X
    Schlagwort(e): ring-opening reaction ; ring-opening polymerization ; alcohol ; cyclic carbonate ; activated monomer mechanism ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Ring-opening reactions of 1,3-dioxepan-2-one (1) and 1,3-dioxan-2-one (2) with several alcohols were examined. The reactions proceeded without trifluoroacetic acid (TFA) in low conversions, while they proceeded smoothly with TFA to afford the ring-opened adducts and oligomers. Ring-opening polymerizations of 1 and 2 were also carried out by alcohol-acid catalysts to afford the corresponding polycarbonates (Mn = 2500-6800). The molecular weights increased with increase of the conversions of 1 and 2. The observed polymerization rates of 1 and 2 were determined as 24.4 × 10-6 and 0.8 × 10-6 s-1, respectively. Mechanistic aspects were studied by NMR spectroscopy. The methylene protons α and β to the carbonate moieties shifted to lower fields in 0.06-0.11 ppm in the 1H-NMR spectra by the addition of TFA. Downfield shifts of the carbonyl carbon signals of 1 and 2 were observed in 3.94-4.15 ppm in the 13C-NMR spectra. These results strongly suggest that the cyclic carbonates are activated by TFA. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2463-2471, 1998
    Zusätzliches Material: 5 Ill.
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  • 81
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 263-267 
    ISSN: 0887-624X
    Schlagwort(e): rigid-rod ; liquid crystalline ; polymers ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The synthesis and the characterization of a set of polymers obtained by polycondensation of n-alkoxyterephthalic acid (n = 1, 3, 5, 7) and 4,4′-dihydroxybiphenyl are reported. The n-alkoxy insertion promotes the processability of the material by lowering the melting temperature. All polymers show the nematic phase at about 300°C, almost independently of the length of lateral substituent. The isotropization is not observed up to 450°C, where thermal decomposition occurs. The temperature of glass transition decreases with increasing n, ranging from 170°C (n = 5) to 220°C (n = 1). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 263-267, 1998
    Zusätzliches Material: 2 Ill.
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  • 82
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 269-276 
    ISSN: 0887-624X
    Schlagwort(e): living radical polymerization ; methylstyrene ; MTEMPO ; stability ; aminoxy chain end ; steric hindrance ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Radical polymerization of 2-, 3-, and 4-methylstyrenes (MeSts) was investigated with benzoyl peroxide (BPO) as an initiator, in the presence of 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO). The polymerization was performed in bulk for 3.5 h at 95°C, and then continued for a defined time at 125°C, to give the corresponding poly(MeSt)s with narrow polydispersity in high yield. It was found that the polymerization proceeded in accordance with a living mechanism, because the molecular weight of the resulting polymers was proportional to the conversion, and to the reciprocal of the initial concentration of MTEMPO. It was found that steric hindrance between the methyl group of 2-MeSt, and the tetramethyl ones of MTEMPO, significantly contributed to the rate of polymerization, and to the stability of the growing polymer chain end. The stability decreased in the order of 2- 〉 3- 〉 4-MeSt, by occurrence of decomposition, which was caused by disproportionation of the growing chain end. However, the steric hindrance had no effect on the tacticity of the resulting polymer. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36, 269-276, 1998
    Zusätzliches Material: 7 Ill.
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  • 83
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 277-281 
    ISSN: 0887-624X
    Schlagwort(e): poly(benzazoles) ; bicyclo[2.2.2]octane ; aromatization ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Poly(benzobisoxazoles) (PBOs), poly(benzobisthiazoles) (PBTs) and copolymers thereof containing the 2,5-dihydroxybicyclo[2.2.2]octane moiety have been prepared and studied. The homopolymers were synthesized by the polycondensation of 2,5-dihydroxybicyclo[2.2.2]octane-1,4-dicarboxylic acid with 4,6-diamino-1,3-benzenediol dihydrochloride or 2,5-diamino-1,4-benzenedithiol dihydrochloride in poly(phosphoric acid). Random and block copolymers (PBO-PBT) were also prepared. The polymers were characterized by solubility, X-ray diffraction, spectroscopy (infrared and solid-state 13C nuclear magnetic resonance), and thermal analysis such as differential scanning calorimetry and thermogravimetric analysis. Thermogravimetric analysis showed thermal stability of the polymers above 375°C in air and under argon atmosphere. The polymers exhibited high resistance to organic and inorganic solvents. The polymers were converted to the more stable aromatic polymers via dehydration and retro Diels-Alder reactions of the 2,5-dihydroxybicyclo[2.2.2]octyl moiety by pyrolysis. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 277-281, 1998
    Zusätzliches Material: 3 Ill.
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  • 84
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 283-289 
    ISSN: 0887-624X
    Schlagwort(e): polyurea ; azoaromatic group ; surface relief grating ; holographic material ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We have synthesized two classes of polyureas with mono- and bisazoaromatic groups in their main chains via reactions between isophorone diisocyanate and the corresponding diamines. Holographic gratings were fabricated on azoaromatic polyurea films prepared by spin-coating from solutions. The effect of high glass transition temperature and dipole moment of azo groups on the formation of gratings was investigated. Although the two polymers have relatively high glass transition temperatures (197 and 236°C), chromophore alignment was induced by laser beam irradiation at modest light intensities. Regularly spaced surface relief gratings on the polymer film were also recorded upon exposure to an interference pattern of two polarized argon laser beams. Erasure could be achieved by heating above Tg or by exposure to one of the beams in a manner similar to low-Tg side-chain azo polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 283-289, 1998
    Zusätzliches Material: 3 Ill.
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  • 85
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 301-307 
    ISSN: 0887-624X
    Schlagwort(e): polyimides ; electrooptics ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Aromatic polyimides with side chain nonlinear optical chromophores have been investigated through a facile two-step synthetic route. First, various poly(hydroxy imide)s have been synthesized by direct thermal imidization of diaminophenol dihydrochloride salt and aromatic dianhydride monomers. The resulting polyimides bearing phenolic hydroxy groups were found to react easily with the terminal hydroxy group on the chromophores via the Mitsunobu condensation to give corresponding polyimides with high optical nonlinearities and good solubility in common organic solvents. Detailed physical properties showed that these polyimides have a molecular weight (Mw) of 31,000 and high glass transition temperature above 220°C, ensuring a long-term alignment stability at elevated temperature. The electrooptic coefficients, r33, of the electrically poled polymer films were in the range 1.8-7.6 pm/V at 1.3 μm. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 301-307, 1998
    Zusätzliches Material: 3 Ill.
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  • 86
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 3165-3172 
    ISSN: 0887-624X
    Schlagwort(e): carbon black ; surface grafting of polymer ; living radical polymerization ; TEMPO-terminated polystyrene ; radical trap ; dispersibility ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The grafting of polystyrene with controlled molecular weight and narrow molecular weight distribution onto the carbon black surface through the trapping of polymer radicals formed by the thermal dissociation of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-terminated polystyrene (PSt-TEMPO) by the carbon black surface was investigated. PSt-TEMPO was prepared by living radical polymerization of St with the benzoyl peroxide/TEMPO system. When PSt having no terminal TEMPO moiety was heated with carbon black, no grafting of PSt onto the surface was observed. On the contrary, by the heating of PSt-TEMPO with carbon black in m-xylene at 125°C, PSt with controlled molecular weight and narrow molecular weight distribution was grafted onto the surface: the percentage grafting of PSt (Mn = 3.2 × 103;Mw/Mn = 1.07) onto furnace black was determined to be 16.0%. On the basis of the above results, it is concluded that PSt radicals formed by the thermal dissociation of the C—ON bond between PSt and TEMPO are trapped by polycondensed aromatic rings of carbon black. The mole number of grafted PSt chains on the carbon black surface decreased with increasing molecular weight of PSt-TEMPO. PSt-grafted carbon black gave a stable colloidal dispersion in THF. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3165-3172, 1998
    Zusätzliches Material: 7 Ill.
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  • 87
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2735-2740 
    ISSN: 0887-624X
    Schlagwort(e): Ti(BFA)2Cl2/MgCl2 catalyst (BFA = 4,4,4-trifluoro-1-phenyl-1,3-butanedione) ; activation by trialkylaluminum with or without diisopropyldimethoxysilane ; copolymerization of ethene with propene ; homogeneity of active species ; homogeneity of copolymers ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The Ti(BFA)2Cl2/MgCl2-Al(C2H5)3 catalyst (BFA = 4,4,4-trifluoro-1-phenyl-1,3-butanedione) modified by DIPDMS (diisopropyldimethoxysilane), which had been proved to yield an extremely high isotactic polypropene in high selectivity, was tested for the copolymerization of ethene with propene. The analysis of resulting copolymers by CFC (cross fractionation chromatography) indicated the formation of a small quantity of ethene-rich copolymers as a byproduct, suggesting that the catalyst possesses not only Ti(III) species but a small portion of Ti(II) species. Whereas, the same catalyst without being modified by an external donor selectively yielded propene-rich random copolymers resulting from Ti(III) species in high yields. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2735-2740, 1998
    Zusätzliches Material: 5 Ill.
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  • 88
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2763-2774 
    ISSN: 0887-624X
    Schlagwort(e): free radical grafting ; glycidyl methacrylate ; polyethylene ; styrene ; reactive extrusion ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Glycidyl methacrylate (GMA) is a very useful monomer as it bears an epoxy group which is capable of reacting with various other functional groups. However, its melt free radical grafting reactivity onto a polymer backbone is low. In this study, we show that the use of styrene (St) as a comonomer greatly promotes both GMA's grafting yield and grafting rate onto polyethylene (PE). It is proposed that, in the presence of St, the dominant mechanism of the free radical grafting of GMA onto PE is that St reacts first with PE secondary macroradicals and the resulting styryl macroradicals then copolymerize with GMA leading to grafted GMA. We also show that the contribution of St is not related to an improved solubility of GMA in the molten PE. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2763-2774, 1998
    Zusätzliches Material: 20 Ill.
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  • 89
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2793-2798 
    ISSN: 0887-624X
    Schlagwort(e): highly branched radial block copolymers ; dendritic initiation ; alipatic polyesters ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Living ring opening polymerization of ε-caprolactone initiated from the numerous chain-end hydroxymethyl groups of the analogous dendrimeric and hyperbranched polyesters derived from 2,2-bis(hydroxymethyl) propionic acid is described. By controlling the size of the dendritic macromolecule and the molar ratio of ε-caprolactone, a variety of highly branched radial block copolymers are obtained. Comparison of the results obtained for the dendrimeric and hyperbranched initiators demonstrates that the reactivity of the chain-end hydroxymethyl groups in the dendrimer are significantly greater than in the isomeric hyperbranched case. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2793-2798, 1998
    Zusätzliches Material: 2 Ill.
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  • 90
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2827-2837 
    ISSN: 0887-624X
    Schlagwort(e): stimuli-responsive polymers ; trans-cis isomerization ; NMR spectroscopy ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The low-temperature polycondensation of trans-azobenzene-4,4′-dicarbonyl chloride with (S)-(-)-1,1′-binaphthyl-2,2′-diamine and/or 1,4-bis(3-aminophenoxy-4′-benzoyl)benzene afforded a new series of poly(aryl ether ketone amide)s with both fixed and photoinducible kinking elements positioned randomly along the main chain. In their lower energy, trans-azobenzene configurations, the orange, film-forming materials were amorphous, highly tractable, and thermally stable under air or nitrogen up to about 420°C. Variants endowed with higher loadings of the bent binaphthyl monomer were soluble in a variety of organic solvent media including THF and acetone. The introduction of cis-azobenzene backbone kinks into these materials was carried out by irradiating the polymer solutions with near-UV light. Up to 70% of the azobenzene moieties in these polymers were capable of assuming the higher energy cis-configuration, thus greatly increasing the number of bent or kinked sites positioned along each polymer backbone. In solution, reverse cis → trans isomerization reactions were triggered thermally and were quantitatively tracked by both optical absorbance and 1H NMR spectroscopies. Activation parameters calculated for cis → trans reorganization of the polymer backbone were not dependent upon the chemical composition or molecular weight of the polymers but did exhibit a small dependence upon the nature of the solvent medium used to conduct the isomerization experiment. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2827-2837, 1998
    Zusätzliches Material: 7 Ill.
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  • 91
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2881-2887 
    ISSN: 0887-624X
    Schlagwort(e): fluorinated poly(arylene ether) ; phenyl ethynyl ; polymer optical waveguide ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Crosslinkable fluorinated poly(arylene ethers) (FPAE-Fn-PEP) with high transparency and high thermal stability have been investigated for low-loss optical waveguide materials. FPAE-Fn-PEP bearing phenyl ethynyl moiety at the polymer chain end were synthesized by the reaction of 4,4′-(hexafluoro-isopropylidene)diphenol with an excess decafluorobiphenyl, followed by the reaction of 4-phenyl ethynyl phenol. The Mns and Mw/Mns of the polymers determined by GPC with polystyrene standard were in the range of 6200 to 19,400 and 1.4 to 2.04, respectively. The resulting polymers were thermally crosslinked at 320°C for 2 h. The cured polymers show good chemical resistance and high thermal stability up to 510°C under nitrogen. The refractive indices of their films were controlled between 1.495 and 1.530 at 1.55 μm by adjusting molecular weight. A single-mode channel waveguide made of FPAE-F20-PEP was fabricated by conventional photolithography and O2 reactive ion etching (RIE). The propagation loss of the channel waveguide was measured and found to be less than 0.2 dB/cm at 1.55 μm. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2881-2887, 1998
    Zusätzliches Material: 4 Ill.
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  • 92
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2873-2880 
    ISSN: 0887-624X
    Schlagwort(e): polyaddition ; bis(oxetane) ; aromatic dithiol ; catalyst ; quaternary onium salt ; crown ether complex ; new reactive polymer ; pendant primary hydroxyl group ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Addition reaction of (3-methyl-3-oxetanyl)methyl acetate (MOMA) with bis(4-mercaptophenyl) sulfide (BMPS) was examined in certain organic solvents. When the reaction of MOMA with BMPS was performed without any catalyst in hexamethylphosphoric triamide (HMPA) and N-methyl-2-pyrrolidone (NMP) at 130°C for 24 h, conversions of the corresponding adduct were 96 and 36%, respectively, which was confirmed by 1H-NMR spectra. On the other hand, when the reaction was carried out using tetraphenylphosphonium bromide (TPPB) as a catalyst under the same conditions, conversions of the adduct were 96 and 81% in HMPA and NMP, respectively. This result shows that although the addition reaction of oxetane compound with aromatic dithiol proceeds without any catalyst in HMPA, the reaction was strongly enhanced by adding TPPB in NMP. On the basis of the above results, polyadditions of bis((3-methyl-3-oxetanyl)methyl) terephthalate (BMOT) and bis((3-ethyl-3-oxetanyl)methyl) terephthalate with BMPS were performed using TPPB as the catalyst in NMP at 130°C for 24 h. As a result, the corresponding high molecular weight polymers 1 (Mn = 22,400) and 2 (Mn = 12,800) with pendant primary hydroxyl groups were obtained in 83 and 89% yields without any gel products, respectively. Furthermore, a low molecular weight oligomer was obtained from the polyaddition of BMOT with aliphatic dithiol, bis(mercaptomethyl)benzene, under the same reaction conditions. The catalytic activity on the polyaddition of BMOT with BMPS was also examined, and it was found that thermally stable TPPB and crown ether complexes at the reaction temperature (130°C) have higher catalytic activity than tetrabutylammonium bromide and tetrabutylphosphonium bromide to produce polymer 1 with high molecular weight. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2873-2880, 1998
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  • 93
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2979-2983 
    ISSN: 0887-624X
    Schlagwort(e): dendrimer ; nomenclature ; fractal ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Dendrimeric and related molecules that have the same atomic connectivity from exterior to core, P-C1-J1-C2- … Z (P peripheral group, J juncture, C connector, Z core) can be described completely by a highly compact fractal notation, which is of the general form PfJ1,J2 … (C1.C2 …)Z. In this paper, we show how to describe molecules that deviate slightly from the symmetry of a related parent molecule, by use of parenthetic expressions (iX), (dX), and (YrX) which designate atoms or molecular groups that are inserted, deleted, or replaced by other groups in the parent. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2979-2983, 1998
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  • 94
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2995-2995 
    ISSN: 0887-624X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: No abstract.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 95
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 3035-3043 
    ISSN: 0887-624X
    Schlagwort(e): nanoencapsulation ; tyrosine ; dyes ; poly(isodecyl acrylate) ; nanoparticles ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The polymerization of isodecyl acrylate (ISODAC) in vesicles of sodium di-2-ethylhexyl phosphate (SEHP) loaded with dyes or tyrosine was achieved. The study of the polymerization rate-conversion curve of the monomer confirmed that this polymerization was different from other polymerizations known, as it was proposed previously. Then the entrapment of hydrophilic molecules such as tyrosine or brilliant cresyl blue and lipophilic molecules such as sudan III into the nanoparticles was evaluated and confirmed by different methods. While tyrosine was not retained, brilliant cresyl blue and sudan III were entrapped inside nanoparticles. The size and the polarity of the molecules to be encapsulated, which are related to their diffusion coefficients and partition coefficients between water and the nanoparticle, seem to be the parameters responsible of the entrapment. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3035-3043, 1998
    Zusätzliches Material: 7 Ill.
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  • 96
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 3063-3072 
    ISSN: 0887-624X
    Schlagwort(e): polypropylene ; metallocenes ; Ziegler-Natta ; catalysts ; polymerization ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Propylene was polymerized with metallocene and Ziegler-Natta mixed-catalytic systems to obtain reactor blends of metallocene and Ziegler-Natta-derived propylene homopolymers. The two catalytic systems are able to act jointly, providing individual polymers with different melting and crystallization temperatures. Compatibility between the components of the mixed-catalytic systems and the influence of the components on the polymerization process and on the properties of the reactor blends were studied. Thermal, mechanical, viscoelastic, rheological, and optical properties of the blends were tested and compared with those of conventional polypropylene grades. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3063-3072, 1998
    Zusätzliches Material: 5 Ill.
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  • 97
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 401-411 
    ISSN: 0887-624X
    Schlagwort(e): novolac resin ; poly(ethylene oxide) ; interpolymer complexes ; crosslinkable ; polymer morphology ; thermal properties ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Crosslinkable interpolymer complexes of novolac resin and poly(ethylene oxide) (PEO) were prepared by mutual mixing ethanol solutions of novolac and PEO. Fourier transform infrared (FTIR) studies revealed that the driving force for the formation of novolac/PEO complex is hydrogen bonding interaction between the hydroxyl groups of novolac and the ether oxygens of PEO. The morphology and thermal properties of the complexes before and after curing were investigated by optical microscopy and differential scanning calorimetry (DSC). It was found that the uncured novolac/PEO complexes had a single composition-dependent glass transition temperature (Tg). The curing with 15 wt % hexamine (HMTA) (relative to novolac content) resulted in disappearing of Tg behaviour for both the neat novolac and the novolac-rich complexes, owing to less mobility of the novolac chain segments. The melting temperature (Tm) and crystallization rate of the HMTA-cured novolac/PEO complexes decreased with increasing novolac content, and no Tm was observed for the cured complexes with PEO content less than 50%. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 401-411, 1998
    Zusätzliches Material: 11 Ill.
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  • 98
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    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 413-419 
    ISSN: 0887-624X
    Schlagwort(e): liquid crystalline polymer ; polyarylates ; 4-hydroxy-2,3,5,6-tetrafluorobenzoic acid ; 6-hydroxy-2-naphthoic acid ; fine structure ; thermal property ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 4-Hydroxy-2,3,5,6-tetrafluorobenzoic acid/6-hydroxy-2-naphthoic acid copolymers (FHBA/HNA copolymer) with different copolymer compositions were prepared and the influence of FHBA residue on the thermal properties and structures of the copolymers were investigated. Introduction of FHBA decreased the crystal/nematic phase transition temperatures(TCNs) of the FHBA/HNA copolymers. TCNs of the copolymers were in the temperature range between 200 and 250°C, depending on the copolymer composition. They are approximately 40°C lower than those of 4-hydroxybenzoic acid/HNA copolymers. FHBA/HNA copolymers exhibited low crystallinity, and annealing treatment hardly influenced the crystalline natures. FHBA residue possibly interferes with the recrystallization during annealing. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 413-419, 1998
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 99
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 421-428 
    ISSN: 0887-624X
    Schlagwort(e): poly(siloxane)-supported zirconocene catalysts ; polymerizations of ethene and propene ; copolymerization of ethene with 1-octene ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Poly(siloxane)s with bisindenyl, bisfluorenyl, bis(1,2,3,4-tetramethylcyclopentadienyl), bis(2,4,7-trimethylindenyl) and monoindenylmethyl side groups were synthesized by condensation of the corresponding dichlorosilanes and water. For reference, diphenylsilanediol or hydroquinone was also employed in place of water. A series of poly(siloxane)-supported zirconocene catalysts were then prepared from these precursors and applied to ethene and propene polymerizations as well as to the copolymerization of ethene with 1-octene in the presence of methylalumoxane. The polymerization activity of the new supported metallocenes depends drastically upon the substituents in the siloxane backbone. The zirconocene catalysts supported on poly(bisindenylsiloxane) and poly(bisfluorenylsiloxane) give the highest activities for ethene and propene polymerizations, respectively. The weight-average molecular weights of the polymers are also markedly dependent upon the substituents. On the other hand, the molecular mass distributions (MMD) are generally not so sharp, suggesting that the active species formed in these supported catalysts are not uniform. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 421-428, 1998
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 100
    ISSN: 0887-624X
    Schlagwort(e): cationic polymerization ; living polymerization ; vinyl ether ; initiator ; acetic acid ; tin tetrabromide ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Cationic polymerization of isobutyl vinyl ether (IBVE) with acetic acid (CH3COOH)/tin tetrahalide (SnX4: X = Cl, Br, I) initiating systems in toluene solvent at 0°C was investigated, and the reaction conditions for living polymerization of IBVE with the new initiating systems were established. Among these tin tetrahalides, SnBr4 was found to be the most suitable Lewis acid to obtain living poly(IBVE) with a narrow molecular weight distribution (MWD). The polymerization with the CH3COOH/SnBr4 system, however, was accompanied with the formation of a small amount of another polymer fraction of very broad MWD, probably due to the occurrence of an uncontrolled initiation by SnBr4 coupled with protonic impurity. Addition of 1,4-dioxane (1-1.25 vol %) or 2,6-di-tert-butylpyridine (0.1-0.6mM) to the polymerization mixture completely eliminated the uncontrolled polymer to give only the living polymer with very narrow MWD (Mw/Mn ≤ 1.1; Mw, weight-average molecular weight; Mn, number-average molecular weight). The Mn of the polymers increased in direct proportion to monomer conversion, continued to increase upon sequential addition of a fresh monomer feed, and was in good agreement with the calculated values assuming that one CH3COOH molecule formed one polymer chain. Along with these results, kinetic study and direct 1H-NMR observation of the living polymerization indicated that CH3COOH and SnBr4 act as so-called “initiator” and “activator”, respectively, and the living polymerization proceeds via an activation of the acetate dormant species. The basic additives such as 1,4-dioxane and 2,6-di-tert-butylpyridine would serve mainly as a “suppressor” of the uncontrolled initiation by SnBr4. The polymers produced after quenching the living polymerization with methanol possessed the acetate dormant terminal and they induced living polymerization of IBVE in conjunction with SnBr4 in the presence of 1,4-dioxane. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3173-3185, 1998
    Zusätzliches Material: 12 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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