No description available.

This thesis describes studies directed to the ring opening metathesis polymerisation of macromonomers and mesogenic monomers to produce graft copolymers and side chain liquid crystalline polymers respectively. The necessary background information relevant to the work described in this thesis is presented in chapter-1 and consists of four sections; namely, descriptions of metathesis polymerisation, anionic polymerisation, synthesis of graft copolymers and synthesis of side chain liquid crystalline polymers. The synthesis of the end capping reagent exo-5-norbomene-2- carbonyl chloride is described in chapter-2. The synthesis and characterisation of exo- 5-norbomene-2-poly(styrylcarboxylate) macromonomers by living anionic polymerisation is discussed in chapter-3. Chapter-4 reports the synthesis, characterisation and properties of graft copolymers prepared by ring opening metathesis polymerisation of exo-5-norbomene-2-poly(styrylcarboxylate) macromonomers. Chapters-5 describes the synthesis of the mesogenic monomer; (5)- (-)-2-methylbutyl-4-(4-(l 0-(3-cyclopentenylmethoxy) decyloxy) phenylcarbonyloxy) benzoate, suitable for ring opening metathesis polymerisation to produce side chain liquid crystalline polymer. The attempted synthesis of side chain liquid crystalline polymer by ring opening metathesis polymerisation of the mesogenic monomer; (5)-(- )-2-methylbutyl-4-(4-( 10-(3 -cyclopentenylmethoxy) decyloxy) phenylcarbonyloxy) benzoate is reported in chapter-6. Finally chapter-7 summarises the conclusions and makes some suggestions for future work.

No description available.

The work described in the thesis is concerned with making new polymeric materials via ring opening metathesis polymerisation (ROMP) using a well-defined ruthenium carbene as an initiator. The object of the study was to provide a process for producing shaped articles by introducing a reactive liquid mixture into a mould in which the reacting liquid mixture undergoes ROMP in the bulk to produce the moulded article. Mono- and difunctional imidonorbomene derivatives were used as monomer and crosslinker respectively. The properties of the cured samples were determined by sol-gel analysis, DSC, TGA, nmr and IR spectrometry. Gel fraction, Tg and content of unreacted monomer were used to characterise the cured samples. The results indicated a strong dependence of the polymers appearance and properties on the polymerization formulation and protocol, i.e. the monomer, the crosslinker and the polymerization conditions. The relative reactivity of the exo- and endo-monomers was investigated using the 'Hnmr technique since the initiation and propagation steps of the polymerisations can be followed in detail by this technique. The results showed that the polymerisations are living and the exo-isomer is more reactive than endo-isomer. A wider range of polymers can be prepared from solution polymerisation as compared to bulk polymerisation. The polymers derived from solid monomers, the monofunctional monomer with short N-alkyl pendant groups and all the difunctional monomers, could be prepared more easily in solution than in bulk polymerisation. The endo-monomer and the monofunctional monomer with long N-alkyl pendant group showed very low reactivity and were not suitable for ROMP in bulk but underwent solution polymerisation. It was found that the thermal properties of the linear polymers depend upon the amount of each monomer isomer incorporated into the polymer chain and the ength of the N-alkyl pendant groups. All linear polymers are soluble in chlorinated solvents from which clear films can be cast. The work described establishes conditions for production of fully crosslinked solids with only traces of the sol fraction.

Die Polymerisation lichthärtender Komposite wurde bisher vor allem mit Halogenlichtgeräten durchgeführt. Eine neue Geräteentwicklung beruht auf der LED (Light Emitting Diodes)-Technologie: Hierbei werden die benötigten Lichtwellen mithilfe der Halbleitertechnik generiert und von Dioden ausgestrahlt. Das emittierte Spektrum ist genau auf den Fotoinitiator Kampferchinon abgestimmt. Im Gegensatz zu Halogengeräten ist daher die Filterung des blauen Lichtes überflüssig. Mit dem höheren Wirkungsgrad und der längeren Lebensdauer vereinen LED-Geräte wesentliche Vorteile gegenüber herkömmlichen Lichthärtegeräten. Jedoch muss jede neu entwickelte Technik in ihrer Anwendung untersucht werden, um die Qualität im klinischen Ergebnis gewährleisten zu können. Ziel dieser Studie war es daher, LED-Technik und Halogenpolymerisation zu vergleichen. Zielgröße dieses Vergleiches war die Durchhärtungstiefe (DHT) der belichteten Komposite, die für die Füllungsqualität von großer Bedeutung ist. Sechs kommerziell erhältliche Materialien (Filtek Supreme, Filtek Z250, Point 4, TPH Spectrum, Definite, Tetric Ceram) wurden mit jeweils einem sehr lichtintensiven (Optilux 501 bzw. Freelight 2) und einem standardmäßig ausgestatteten Halogen- und LED-Polymerisationsgerät (Elipar Trilight, Ultralume LED 2) ausgehärtet. Die Polymerisation fand in Probenherstellungsformen aus transluzentem PTFE-Material und in Stahlformen statt. Außerdem wurden zur Überprüfung der Eignung des Versuchsaufbaus Proben in einem Echtzahnmodell hergestellt, wobei Kunststoff- und Stahlmatrizen zur Anwendung kamen. Die Belichtungszeit betrug bei den leistungsstarken Geräten jeweils 10, bei den standardmäßig ausgestatteten jeweils 20 Sekunden, um zu untersuchen, ob die von den Herstellern propagierte Zeitersparnis bei erstgenannten ohne Qualitätsverlust einhergeht. Geprüft wurden Komposite der Farbe A2, von zwei Materialien (Filtek Z250, Filtek Supreme) wurden zusätzlich dunklere Proben (A4) hergestellt. Die Lagerung der belichteten Proben betrug 7 Tage bei Trockenheit und 37 ºC. Die DHT wurde indirekt über die Knoop-Härte bestimmt und war definiert als diejenige Schicht, in der noch 80 % der maximal erzielten Knoop-Härte erreicht wurde. Voraussetzung für den Vergleich der Lichtgeräte war, dass die Maximalhärte unbeeinflusst vom Belichtungsmodus blieb, was für fast alle Materialien erfüllt wurde. Die Erkenntnisse dieser Studie lassen sich wie folgt zusammenfassen: Die DHT wurde von den Variablen Belichtungsmodus, Material, Farbe und Probenherstellungsform signifikant beeinflusst. In der Farbe A2 erzielten Filtek Z250 und TPH Spectrum die höchsten Werte. Bei den Lichtgeräten erbrachte die Halogen-Polymerisation mit Elipar Trilight für alle Materialien die höchste DHT, wobei beide LED-Lichtgeräte zum Teil äquivalente Ergebnisse erzielten. Dunkle Farben verringerten die erreichte DHT signifikant, jedoch war der Einfluss auf die Materialien unterschiedlich stark. Auch die Lichtgeräte wurden durch die dunkle Farbe beeinflusst, wobei sie die Polymerisation mit Freelight 2 am stärksten beeinträchtigte. Eine lichtundurchlässige Umgebung der Proben (Stahlform bzw. -matrize) verringerte die DHT um ca. ein Drittel gegenüber einer transparenten Begrenzung. Auch hier waren die Lichtgeräte unterschiedlich betroffen, wobei in diesem Fall Elipar Trilight stärker negativ beeinflusst wurde als Freelight 2. Die Kombinationen aus Materialien und Lichtgeräten konnten in allen Fällen eine DHT von 2 mm erzielen. In einem Fall (Definite) erwies sich die gewählte Definition des Parameters DHT jedoch als ungeeignet, Vergleiche zwischen den Lichtgeräten zu ziehen. Die Beurteilung erfolgte daher über die Knoop-Härte, wobei sich herausstellte, dass die LED-Belichtung eine signifikant geringere Härte zur Folge hatte als die Polymerisation mit Elipar Trilight. Die Ursache liegt darin begründet, dass Definite neben Kampferchinon über die beiden Initiatorsysteme Luzirin und Irgacure 651 verfügt. Diese weisen in ihrem Absorptionsmaximum eine wesentlich höhere Kongruenz mit den Emissionsspektren der Halogengeräte auf. Die LED-Technologie stellt sich jedoch insgesamt, vor allem seit der Entwicklung der zweiten Gerätegeneration, als geeignet heraus, Halogengeräte in ihrer Funktion abzulösen. Da sie ihnen qualitativ nicht nachzustehen scheinen und darüber hinaus einige zusätzliche Vorteile in sich vereinen, liegt die Vermutung nahe, dass sie die Polymerisationstechnik der Zukunft darstellen. / Polymerization of light-curing composites was so far accomplished mainly by irradiation with halogen lamps. A new curing technique based on LED units seems to unify many advantages in comparison with conventional methods: LED curing units don´t require light-filters and cooling fans, have a higher degree of efficiency and a much longer service life. The aim of this study was therefore to find out if those advantages are accompanied by reduced quality concerning the filling results and to compare LED and halogen performance. Six commercially available polymer matrix composite materials were cured with two halogen and two LED curing units. Depth of cure was determined, defined as 80% of the maximum hardness achieved in each composite specimen. Specimen were made from lighter and darker shades and fabricated in transparent and non transparent moulds. The results of the study can be summarized as follows: Using the transparent mould, depth of cure of the tested combinations ranged between 2.3 and 5.9 mm. Dark composite shades reached lower depths of cure than light shades. Using the non transparent mould reduced depths of cure by approximately 30%, but even then all the combinations appeared to be save to produce minimum depths of cure of 2 mm. The LED units didn´t always reach the high performance of the halogen lamps but produced satisfying results in all cases. With the advantages mentioned earlier, they seem to have the potential to replace conventional light curing techniques.

MSc (Eng), School of Electrical and Information Engineering, Faculty of Engineering and the Built Environment

A new β and <I>N</I>-substituted pyrrole, <I>N</I>-trimethylsilylethoxymethyl-3-methyl-4-pyrrole carboxylate ethyl ester (MPCE-SEM) is synthesised and copolymerised electrochemically with unsubstituted pyrrole to gives free-standing films for conductivity measurements. The electrochemical polymerisation of MPCE-SEM gives only soluble dimers and oligomers rather than polymers because the steric constraints stabilise the oligomeric cation radical of MPCE-SEM. The thiophene monomers containing mesogenic group at the 3-position via an alkyl chain are synthesised and polymerised chemically to give insoluble, infusible polymers and do not exhibit liquid crystalline behaviour. The conductivities of pressed-pellets of the polymer powders are lower than 10<SUP>-5</SUP>S/cm. The electrochemical polymerisation of the thiophene monomers containing mesogenic group of 4-methoxyazbenzen-4'-yloxy or 4-butylazobenzen-4'-yloxy in dichloromethane solution gives a low yield of polymers, which is accompanied by the formation of soluble dimers and oligomers as well as degradation of the resulting polymer and the mesogenic group. Poly{<I>N </I>-11-[(4-cyanobiphenyl-4'-yloxy) undecyl] pyrrole} obtained from chemical polymerisation of the corresponding monomer shows high molecule weight, is soluble in common solvents and fusible showing smectic A liquid crystalline behaviour. This polymer in the melt (175<SUP>o</SUP>C) has a conductivity of 6.6 x 10<SUP>-15 </SUP>S/cm. X-ray photoelectron spectrometry analysis on the melt processed film gives an estimated doping level of an anion every 6-7 monomer units. Electrochemical oxidation of the <I>N</I>-substituted pyrrole monomers gives the electroactive conjugated free-standing polymer films. The conductivities of the free standing polymer films are lower than 10<SUP>-4</SUP> S/cm. A conducting copolymer containing a side chain liquid crystalline group, poly{<I>N</I>-8-[(4-cyanobiphenyl-4'-yloxy)octyl]-2,5-di(2-thienyl) pyrrole} can be obtained electrochemically from the corresponding monomer. The polymer is slightly soluble in chloroform giving a dark green solution but is not liquid crystalline.

Poly(methyl methacrylate) (PMMA) homopolymers synthesised using 'classical' anionic methods and subsequently studied by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS) are discussed. Specifically, the attempts at different end-group functionalisation reactions, their varying degrees of success, and the characterisation of these functionalized polymers via MALDI are reported. Extra peaks were observed in the spectra of samples containing a tertiary amine end-group. A mechanism for the in situ elimination of H(_2)(g) involving these end-groups, which would fit the observations, is proposed. Two alternative, 'non-classical' routes to the desired materials were investigated, as difficulties in successfully performing capping reactions to give end functionalised PMMA were noted. The first method was a variation of standard anionic polymerisation that involved the use of lithium silanolates, which could be performed at a higher temperature than normal. The second was a controlled free-radical technique known as Reversible Addition-Fragmentation Chain Transfer (RAFT). A lack of control of the polymerisation to the desired degree was observed with the former method. A well-defined RAFT sample was observed to undergo in situ eliminadon also, for which a mechanism involving the dithioester end-group is proposed, and which is supported by MALDI-collision induced dissociation (CID) evidence. The synthesis of block copolymers of various compositions of MMA with r-butyl methacrylate (t-BMA) and hexyl methacrylate (HMA), along with their homopolymers, and their subsequent characterisation is reported. PHMA was analysed easily, in contrast to Pt-BMA. Only copolymers with a high PMMA content were analysed successfully and this has been rationalised in terms of the factors that affect cationisation. The characterisation of equimolar blends of various end-functionalised PMMA samples is reported also. Samples that favour the binding of a metal ion over protonation appear to have a higher ion yield. Once more, these observations are rationalised in terms of the factors that affect cationisation.

The first steps towards the long term objective of building entirely synthetic organic/inorganic composite materials in a biomimetic manner have been achieved. Following an introduction and discussion of the background to the work (Chapter 1), the syntheses and characterisation of various molecular weights of both poly(exo, exo-1,4-cyclopentenylene-5,6-ethylidene-2,3-sodium dicarboxylate) and poly(exo,endo-l,4-cyclopentenylene-5,6-ethylidene-2,3- sodium dicarboxylate) and model compounds of their repeat units have been described (Chapters 2 and 4). These compounds were used as additives in the crystallisation of CaCO(_3) from supersaturated aqueous solutions of Ca(HC0(_3))(_2) (Chapters 3 and 5). The work described in Chapter 3 showed that the diacid model compounds used as additives controlled the morphology of calcite crystals grown from supersaturated solutions of Ca(HCO(_3))(_2) over a large range of concentrations of model compound; [Ca(^2+)]: [model compound] 10 to 1000:1. The polymers of these monomers appeared to give the same type of crystal morphology as the isolated model repeat units, however, modification was observed on only one face of the CaCO(_3) crystals. This observation, and the relatively small crystal size distributions measured, indicated that the calcite crystallisation was nucleated beneath the polymer films at the truncated modified face and growth continued down into the solution.

Univ., Diss.--Regensburg, 1996.