31 resultados para polystyrene-poly(4-vinyl pyridine)

em Aston University Research Archive


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Poly(styrene)-block-poly(2-vinyl pyridine)-block-poly(styrene) (PS-b-P2VP-b-PS) triblock copolymers were synthesised by anionic polymerisation. Thick films were cast from solution and their structure analysed by small angle X-ray scattering (SAXS). Longer annealing times led to more ordered structures whereas short evaporation times effectively "lock" the polymer chains in a disordered state by vitrification. Well-ordered structures not only provide an isotropic network, which reduces localised stress within the material, but are also essential for fundamental studies of soft matter because their activity on the molecular scale must be analysed and understood prior to their use in technological applications. Well-characterised PS-b-P2VP-b-PS materials have been coupled to a pH-oscillating reaction and their potential application as responsive actuators is discussed. This journal is © The Royal Society of Chemistry.

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We present results of the direct observation, in real-space, of the phase separation of high molecular weight polystyrene and poly(methyl methacrylate) from ortho-xylene using our newly developed technique of high speed stroboscopic interference microscopy. Taking a fixed concentration (3 wt % in o-xylene) at a fixed composition (1:4 by weight) and by varying the rotational rate during the spin-coating process, we are able to observe the formation of a range of phase separated bicontinuous morphologies of differing length-scales. Importantly, we are able to show that the mechanism by which the final phase separated structure is formed is through domain coarsening when rich in solvent, before vitrification occurs and fixes the phase separated structure. The ability to directly observe morphological development offers a route toward controlling the length-scale of the final morphology through process control and in situ feedback, from a single stock solution. © 2013 Wiley Periodicals, Inc.

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This thesis is concerned with the investigation of transition metal (TM) ion complexation with hydrophilic membranes composed of copolymers of 4-vinyl pyridine & 4-methyl-4'vinyl- 2,2'-bipyridine with 2-hydroxyethyl methacrylate. The Cu(II), CoCII) & Fe(II) complexes with these coordinating membranes were characterised by a variety of techniques, in order to assess the effect of the polymer on the properties of the complex, and vice versa. A detailed programme of work was instigated into the kinetics of formation for the polymer-bound tris(bipyridyl) iron(II) complex; the rate and extent of complex formation was found to be anion-dependent. This is explained in terms of the influence of the anion on the transport properties and water content of the membrane, the controlling factor in the development of the tris-complex being the equilibrium concentration of Fe(II) in the gel matrix. A series of transport studies were performed with a view to the potential application of complexing hydrogel membranes for aqueous TM ion separations. A number of salts were studied individually and shown to possess a range of permeabilities; the degree of interaction between particular metal-ion:ligand combinations is given by the lag-time observed before steady-state permeation is achieved. However, when two TM salts that individually display different transport properties were studied in combination, they showed similar lag-times & permeabilities, characteristic of the more strongly coordinating metal ion. This 'anti-selective' nature thus renders the membrane systems unsuitable for TM ion separations. Finally, attempts were made to synthesise and immobilise a series of N ,0-donor macrocyclic ligands into hydrogel membranes. Although the functionalisation reactions failed, limited transport data was obtained from membranes in which the ligands were physically entrapped within the polymer matrix.

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A study has been made of the anionic polymerisation of methyl methacrylate using butyllithium and polystyryl lithium as initiators and the effects of lithium chloride and aluminium alkyls on the molecular weight and molecular weight distributions. Diblock copolymers of styrene-b-methyl methacrylate were synthesised at -78oC in THF in the presence of lithium chloride, and at ambient temperatures in toluene in the presence of aluminium alkyls. Studies in the presence of lithium chloride showed that the polymerisation was difficult to control; there was no conclusive evidence of a living system and the polydispersity indices were between 1.5 and 3. However, using relatively apolar solvents, in the presence of aluminium alkyls, homopolymerisation of methyl methacrylate showed characteristics of a living polymerisation. An investigation of the effects of the structures of the lithium and aluminium alkyls on the efficiency of initiation showed that a t-butyllithium/triisobutylaluminium initiating system exhibited an efficiency of 80%, compared with lower efficiencies (typically 30%) for systems based on butyllithium/triethylaluminium.The polydispersity index was found to decrease from ∼2.2 to ∼1.5 when butyllithium was replaced by t-butyllithium. The efficiency of the initiator was found to be solely dependent on the size of the alkyl group of the aluminium component, whereas the polydispersity index was found to be solely dependent on the size of the alkyl group on the lithium component. The aluminium alkyl is thought to be co-ordinated to the ester carbonyl groups of both the monomer and polymer. There is a critical degree of polymerisation, at which point the rate of polymerisation decreases, which probably relates to a change in structure of the active chain end. Characterisation of poly(styrene )-b-poly(4-vinylpyridine) and poly(styrene)-b-poly(4-vinylpyridine methyl iodide) diblock copolymers using static light scattering techniques, showed the formation of star-shaped 'reverse' micelles when placed in toluene. Temperature effects on micellization behaviour are only exhibited for the unquaternised micelles, which showed characterisically lower aggregation numbers than their quaternised counterparts. A suitable solvent was not obtained for characterisation of the styrene-b-methyl methacrylate diblock copolymers synthesized.

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Refractive index and structural characteristics of optical polymers are strongly influenced by the thermal history of the material. Polymer optical fibres (POF) are drawn under tension, resulting in axial orientation of the polymer molecular chains due to their susceptibility to align in the fibre direction. This change in orientation from the drawing process results in residual strain in the fibre and also affects the transparency and birefringence of the material (1-3). PMMA POF has failure strain as high as over 100%. POF has to be drawn under low tension to achieve this value. The drawing tension affects the magnitude of molecular alignment along the fibre axis, thus affecting the failure strain. The higher the tension the lower the failure stain will be. However, the properties of fibre drawn under high tension can approach that of fibre drawn under low tension by means of an annealing process. Annealing the fibre can generally optimise the performance of POF while keeping most advantages intact. Annealing procedures can reduce index difference throughout the bulk and also reduce residual stress that may cause fracture or distortion. POF can be annealed at temperatures approaching the glass transition temperature (Tg) of the polymer to produce FBG with a permanent blue Bragg wave-length shift at room temperature. At this elevated temperature segmental motion in the structure results in a lower viscosity. The material softens and the molecular chains relax from the axial orientation causing shrinking of the fibre. The large attenuation of typically 1dB/cm in the 1550nm spectral region of PMMA POF has limited FBG lengths to less than 10cm. The more expensive fluorinated polymers with lower absorption have had no success as FBG waveguides. Bragg grating have been inscribed onto various POF in the 800nm spectral region using a 30mW continuous wave 325nm helium cadmium laser, with a much reduced attenuation coefficient of 10dB/m (5). Fabricating multiplexed FBGs in the 800nm spectral region in TOPAS and PMMA POF consistently has lead to fabrication of multiplexed FBG in the 700nm spectral region by a method of prolonged annealing. The Bragg wavelength shift of gratings fabricated in PMMA fibre at 833nm and 867nm was monitored whilst the POF was thermally annealed at 80°C. Permanent shifts exceeding 80nm into the 700nm spectral region was attained by both gratings on the fibre. The large permanent shift creates the possibility of multiplexed Bragg sensors operating over a broad range. -------------------------------------------------------------------------------------------------------------------- 1. Pellerin C, Prud'homme RE, Pézolet M. Effect of thermal history on the molecular orientation in polystyrene/poly (vinyl methyl ether) blends. Polymer. 2003;44(11):3291-7. 2. Dvoránek L, Machová L, Šorm M, Pelzbauer Z, Švantner J, Kubánek V. Effects of drawing conditions on the properties of optical fibers made from polystyrene and poly (methyl methacrylate). Die Angewandte Makromolekulare Chemie. 1990;174(1):25-39. 3. Dugas J, Pierrejean I, Farenc J, Peichot JP. Birefringence and internal stress in polystyrene optical fibers. Applied optics. 1994;33(16):3545-8. 4. Jiang C, Kuzyk MG, Ding JL, Johns WE, Welker DJ. Fabrication and mechanical behavior of dye-doped polymer optical fiber. Journal of applied physics. 2002;92(1):4-12. 5. Johnson IP, Webb DJ, Kalli K, Yuan W, Stefani A, Nielsen K, et al., editors. Polymer PCF Bragg grating sensors based on poly (methyl methacrylate) and TOPAS cyclic olefin copolymer2011: SPIE.

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Refractive index and structural characteristics of optical polymers are strongly influenced by the thermal history of the material. Polymer optical fibres (POF) are drawn under tension, resulting in axial orientation of the polymer molecular chains due to their susceptibility to align in the fibre direction. This change in orientation from the drawing process results in residual strain in the fibre and also affects the transparency and birefringence of the material (1-3). PMMA POF has failure strain as high as over 100%. POF has to be drawn under low tension to achieve this value. The drawing tension affects the magnitude of molecular alignment along the fibre axis, thus affecting the failure strain. The higher the tension the lower the failure stain will be. However, the properties of fibre drawn under high tension can approach that of fibre drawn under low tension by means of an annealing process. Annealing the fibre can generally optimise the performance of POF while keeping most advantages intact. Annealing procedures can reduce index difference throughout the bulk and also reduce residual stress that may cause fracture or distortion. POF can be annealed at temperatures approaching the glass transition temperature (Tg) of the polymer to produce FBG with a permanent blue Bragg wave-length shift at room temperature. At this elevated temperature segmental motion in the structure results in a lower viscosity. The material softens and the molecular chains relax from the axial orientation causing shrinking of the fibre. The large attenuation of typically 1dB/cm in the 1550nm spectral region of PMMA POF has limited FBG lengths to less than 10cm. The more expensive fluorinated polymers with lower absorption have had no success as FBG waveguides. Bragg grating have been inscribed onto various POF in the 800nm spectral region using a 30mW continuous wave 325nm helium cadmium laser, with a much reduced attenuation coefficient of 10dB/m (5). Fabricating multiplexed FBGs in the 800nm spectral region in TOPAS and PMMA POF consistently has lead to fabrication of multiplexed FBG in the 700nm spectral region by a method of prolonged annealing. The Bragg wavelength shift of gratings fabricated in PMMA fibre at 833nm and 867nm was monitored whilst the POF was thermally annealed at 80°C. Permanent shifts exceeding 80nm into the 700nm spectral region was attained by both gratings on the fibre. The large permanent shift creates the possibility of multiplexed Bragg sensors operating over a broad range. -------------------------------------------------------------------------------------------------------------------- 1. Pellerin C, Prud'homme RE, Pézolet M. Effect of thermal history on the molecular orientation in polystyrene/poly (vinyl methyl ether) blends. Polymer. 2003;44(11):3291-7. 2. Dvoránek L, Machová L, Šorm M, Pelzbauer Z, Švantner J, Kubánek V. Effects of drawing conditions on the properties of optical fibers made from polystyrene and poly (methyl methacrylate). Die Angewandte Makromolekulare Chemie. 1990;174(1):25-39. 3. Dugas J, Pierrejean I, Farenc J, Peichot JP. Birefringence and internal stress in polystyrene optical fibers. Applied optics. 1994;33(16):3545-8. 4. Jiang C, Kuzyk MG, Ding JL, Johns WE, Welker DJ. Fabrication and mechanical behavior of dye-doped polymer optical fiber. Journal of applied physics. 2002;92(1):4-12. 5. Johnson IP, Webb DJ, Kalli K, Yuan W, Stefani A, Nielsen K, et al., editors. Polymer PCF Bragg grating sensors based on poly (methyl methacrylate) and TOPAS cyclic olefin copolymer2011: SPIE.

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The Scintillation Proximity Assay (SPA) is a method that is frequently used to detect and quantify the strength of intermolecular interactions between a biological receptor and ligand molecule in aqueous media. This thesis describes the synthesis of scintillant-tagged-compounds for application in a novel cell-based SPA. A series of 4-functianlised-2,5-diphenyloxazole molecules were synthesised. These 4-functionalised-2,5-diphenyloxazoles were evaluated by Sense Proteomic Ltd. Accordingly, the molecules were evaluated for the ability to scintillate in the presence of ionising radiation. In addition, the molecules were incorporated into liposomal preparations which were subsequently evaluated for the ability to scintillate in the presence of ionising radiation. The optimal liposomal preparation was introduced into the membrane of HeLa cells that were used successfully in a cell-based SPA to detect and quantify the uptake of [14C]methionine. This thesis also describes the synthesis and subsequent polymerisation of novel poly(oxyethylene glycol)-based monomers to form a series of new polymer supports. These Poly(oxyethylene glycol)-polymer (POP) supports were evaluated for the ability to swell and mass-uptake in a variety of solvents, demonstrating that POP-supports exhibit enhanced solvent compatibilities over several commercial resins. The utility of POP-supports in solid-phase synthesis was also demonstrated successfully. The incorporation of (4’-vinyl)-4-benzyl-2,5-diphenyloxazole in varying mole percentage into the monomer composition resulted in the production of chemically functionalised scintillant-containing poly(oxyethylene glycol) polymer (POP-Sc) supports. These materials are compatible with both aqueous and organic solvents and scintillate efficiently in the presence of ionising radiation. The utility of POP-Sc supports in solid-phase synthesis and subsequent in-situ SPA to detect and quantify, in real-time, the kinetic progress of a solid-phase reaction was exemplified successfully.In addition, POP-Sc supports were used successfully both in solid-phase combinatorial synthesis of a peptide nucleic acid (PNA)-library and subsequent screening of this library for the ability to hybridise with DNA, which was labelled with a suitable radio-isotape. This data was used to identify the dependence of the number and position of complimentary codon pairs upon the extent of hybridisation. Finally, a further SPA was used to demonstrate the excellent compatibility of POP-Sc supports for use in the detection and quantification of enzyme assays conducted within the matrix of the POP-Sc support.

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This thesis describes the synthesis of functionalised polymeric material by variety of free-radical mediated polymerisation techniques including dispersion emulsion, seeded emulsion, suspension and bulk polymerisation reactions. Organic fluorophores and nanoparticles such as quantum dots were incorporated within polymeric materials, in particular, thiol-functionalised polymer microspheres, which were fluorescently labelled either during synthesis or by covalent attachment post synthesis. The resultant fluorescent polymeric conjugates were then assessed for their utility in biological systems as an analytical tool for cells or biological structures. Quantum dot labelled, thiol-functionalised microspheres were assessed for their utility in the visualisation and tracking of red blood cells. Determination of the possible internalisation of fluorescent microspheres into red blood cells was required before successful tracking of red blood cells could take place. Initial work appeared to indicate the presence of fluorescent microspheres inside red blood cells by the process of beadfection. A range of parameters were also investigated in order to optimise beadfection. Thiol-functionalised microspheres labelled successfully with organic fluorophores were used to image the tear film of the eye. A description of problems encountered with the covalent attachment of hydrophilic, thiol-reactive fluorescent dyes to a variety of modified polymer microspheres is also included in this section. Results indicated large microspheres were particularly useful when tracking the movement of fluid along the tear meniscus. Functional bulk polymers were synthesised for assessment of their interaction with titanium dioxide nanoparticles. Thiol-functionalised polymethyl methacrylate and spincoated thiouronium-functionalised polystyrene appeared to facilitate the attachment of titanium dioxide nanoparticles. Interaction assays included the use of XPS analysis and processes such as centrifugation. Attempts to synthesise 4-vinyl catechol, a compound containing hydroxyl moieties with potential for coordination with titanium dioxide nanoparticles, were also carried out using 3,4-dihydroxybenzaldehyde as the starting material.

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The research described within this thesis is concerned with the investigation of transition metal ion complexation within hydrophilic copolymer membranes. The membranes are copolymers of 4-methyl-4'-vinyl-2,2'-bipyridine, the 2-hydroxyethyl ester of 4,4'- dicarboxy-2,2'-bipyridine & bis-(5-vinylsalicylidene)ethylenediamine with 2-hydroxyethyl methacrylate. The effect of the polymer matrix on the formation and properties of transition metal iron complexes has been studied, specifically Cr(III) & Fe(II) salts for the bipyridyl- based copolymer membranes and Co(II), Ni(II) & Cu(II) salts for the salenH2- based copolymer membranes. The concomitant effect of complex formation on the properties of the polymer matrix have also been studied, e.g. on mechanical strength. A detailed body of work into the kinetics and thermodynamics for the formation of Cu(II) complexes in the salenH2- based copolymer membranes has been performed. The rate of complex formation is found to be very slow while the value of K for the equilibrium of complex formation is found to be unexpectedly small and shows a slight anion dependence. These phenomena are explained in terms of the effects of the heterogeneous phase provided by the polymer matrix. The transport of Cr(III) ions across uncomplexed and Cr(III)-pre-complexed bipyridyl-based membranes has been studied. In both cases, no Cr(III) coordination occurs within the time-scale of an experiment. Pre-complexation of the membrane does not lead to a change in the rate of permeation of Cr(III) ions. The transport of Co(II), Ni(II) & Cu(II) ions across salenH2- based membranes shows that there is no detectable lag-time in transport of the ions, despite independent evidence that complex formation within the membranes does occur. Finally, the synthesis of a number of functionalised ligands is described. Although they were found to be non-polymerisable by the methods employed in this research, they remain interesting ligands which provide a startmg pomt for further functionalisation.

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Large-scale introduction of Organic Solar Cells (OSCs) onto the market is currently limited by their poor stability in light and air, factors present in normal working conditions for these devices. Thus, great efforts have to be undertaken to understand the photodegradation mechanisms of their organic materials in order to find solutions that mitigate these effects. This study reports on the elucidation of the photodegradation mechanisms occurring in a low bandgap polymer, namely, Si-PCPDTBT (poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5′-diyl]). Complementary analytical techniques (AFM, HS-SPME-GC-MS, UV-vis and IR spectroscopy) have been employed to monitor the modification of the chemical structure of the polymer upon photooxidative aging and the subsequent consequences on its architecture and nanomechanical properties. Furthermore, these different characterization techniques have been combined with a theoretical approach based on quantum chemistry to elucidate the evolution of the polymer alkyl side chains and backbone throughout exposure. Si-PCPDTBT is shown to be more stable against photooxidation than the commonly studied p-type polymers P3HT and PCDTBT, while modeling demonstrated the benefits of using silicon as a bridging atom in terms of photostability. (Figure Presented).

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Polymer beads have attracted considerable interest for use in catalysis, drug delivery, and photo­nics due to their particular shape and surface morphology. Electrospinning, typically used for producing nanofibers, can also be used to fabricate polymer beads if the solution has a sufficiently low concentration. In this work, a novel approach for producing more uniform, intact beads is presented by electrospinning self-assembled block copolymer (BCP) solutions. This approach allows a relatively high polymer concentration to be used, yet with a low degree of entanglement between polymer chains due to microphase separation of the BCP in a selective solvent system. Herein, to demonstrate the technology, a well-studied polystyrene-poly(ethylene butylene)–polystyrene triblock copolymer is dissolved in a co-solvent system. The effect of solvent composition on the characteristics of the fibers and beads is intensively studied, and the mechanism of this fiber-to-bead is found to be dependent on microphase separation of the BCP.

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Organic Solar Cells (OSCs) represent a photovoltaic technology with multiple interesting application properties. However, the establishment of this technology into the market is subject to the achievement of operational lifetimes appropriate to their application purposes. Thus, comprehensive understanding of the degradation mechanisms occurring in OSCs is mandatory in both selecting more intrinsically stable components and/or device architectures and implementing strategies that mitigate the encountered stability issues. Inverted devices can suffer from mechanical stress and delamination at the interface between the active layer, e.g. poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM), and the hole transport layer, e.g. poly(3,4-ethylenedioxythiophene):poly(p-styrene sulfonate) (PEDOT:PSS). This work proposes the incorporation of a thin adhesive interlayer, consisting of a diblock copolymer composed of a P3HT block and a thermally-triggerable, alkyl-protected PSS block. In this context, the synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) with controlled molar mass and low dispersity (Ð ≤ 1.50) via Reversible Addition-Fragmentation chain Transfer (RAFT) polymerisation has been extensively studied. Subsequently, Atomic Force Microscopy (AFM) was explored to characterise the thermal deprotection of P3HT-b-PNSS thin layers to yield amphiphilic P3HT-b-PSS, indicating that surface deprotection prior to thermal treatment could occur. Finally, structural variation of the alkyl protecting group in PSS allowed reducing the thermal treatment duration from 3 hours (P3HT-b-PNSS) to 45 minutes for the poly(isobutyl p-styrene sulfonate) (PiBSS) analogous copolymer. Another critical issue regarding the stability of OSCs is the sunlight-driven chemical degradation of the active layer. In the study herein, the combination of experimental techniques and theoretical calculations has allowed identification of the structural weaknesses of poly[(4,4’- bis(2-ethylhexyl) dithieno [3,2-b:2’,3’-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5’-diyl], Si-PCPDTBT, upon photochemical treatment in air. Additionally, the study of the relative photodegradation rates in air of a series of polymers with systematically modified backbones and/or alkyl side chains has shown no direct correlation between chemical structure and stability. It is proposed instead that photostability is highly dependent on the crystalline character of the deposited films. Furthermore, it was verified that photostability of blends based on these polymers is dictated by the (de)stabilising effect that [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) has over each polymer. Finally, a multiscale analysis on the degradation of solar cells based on poly[4,4' bis(2- ethylhexyl) dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-[2,5 bis(3 tetradecylthiophen 2-yl)thiazole[5,4-d]thiazole)-1,8-diyl] and PCBM, indicated that by judicious selection of device layers, architectures, and encapsulation materials, operational lifetimes up to 3.3 years with no efficiency losses can be successfully achieved.

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This thesis is concerned with the effect of polymer structure on miscibility of the three component blends based on poly(lactic acid) (PLA) with using blending techniques. The examination of novel PLA homologues (pre-synthesised poly(a-esters)), including a range of aliphatic and aromatic poly(a-esters) is an important aspect of the work. Because of their structural simplicity and similarity to PLA, they provide an ideal system to study the effect of polyester structures on the miscibility of PLA polymer blends. The miscibility behaviour of the PLA homologues is compared with other aliphatic polyesters (e.g. poly(e-caprolactone) (PCL), poly(hydroxybutyrate hydroxyvalerate) (P(HB-HV)), together with a series of cellulose-based polymers (e.g. cellulose acetate butyrate (CAB)). The work started with the exploration the technique used for preliminary observation of the miscibility of blends referred to as “a rapid screening method” and then the miscibility of binary blends was observed and characterised by percent transmittance together with the Coleman and Painter miscibility approach. However, it was observed that symmetrical structures (e.g. a1(dimethyl), a2(diethyl)) promote the well-packing which restrict their chains from intermingling into poly(L-lactide) (PLLA) chains and leads the blends to be immiscible, whereas, asymmetrical structures (e.g. a4(cyclohexyl)) behave to the contrary. a6(chloromethyl-methyl) should interact well with PLLA because of the polar group of chloride to form interactions, but it does not. It is difficult to disrupt the helical structure of PLLA. PLA were immiscible with PCL, P(HB-HV), or compatibiliser (e.g. G40, LLA-co-PCL), but miscible with CAB which is a hydrogen-bonded polymer. However, these binary blends provided a useful indication for the exploration the novel three component blends. In summary, the miscibility of the three-component blends are miscible even if only two polymers are miscible. This is the benefit for doing the three components blend in this thesis, which is not an attempt to produce a theoretical explanation for the miscibility of three components blend system.

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Co-polymerisation of α-styryl-poly(ethylene glycol)300, α,ω-bis(styryl)-penta(ethylene glycol) and 2,5-diphenyl-4-(4′-vinylbenzyl)oxazole in varying molar ratios resulted in the production of chemically functionalised scintillant-containing poly(oxyethylene glycol) polymer (POP-Sc) supports. These materials are compatible with both aqueous and organic solvents, and possess the ability to scintillate efficiently in the presence of ionising radiation, even after prolonged and repeated exposure to organic solvents. The utility of POP-Sc supports in both solid-phase peptide chemistry and a functional scintillation proximity assay has been exemplified.