Studies in the anionic polymerization of methyl methacrylate

A study has been made of the anionic polymerization of methyl methacrylate using butyllithium and polystyryl lithium as initiators and using aluminium triisobutyl as a cocatalyst. The aspects of the polymerization that were examined were the effect of changing the order of addition of reagents, the temperature at which polymerization takes place and the polarity of the solvent. Trends were assessed in terms of molecular weight, molecular weight distribution and tacticity. In addition, a second monomer addition test was carried out to verify that the polymerization was truly a living one, and a kinetic study was attempted. Studies to investigate the effect of changing the order of addition of reagents showed that polymer with similar polydispersities and tacticities are produced whether the pre-mixing (mixing initiator and cocatalyst before addition of monomer) or the post-mixing (mixing monomer and cocatalyst before addition of initiator) method were used. However, polymerizations using the post-mixing mixing method demonstrated lower initiator efficiencies, possibly indicating a different initiating species. Investigations into the effect of changing the polymerization temperature show the molecular weight distribution to narrow as the temperature decreases, although a small amount of low molecular weight tailing was also observed at low temperature. A clear relationship between tacticity and temperature was observed with syndiotacticity increasing with decreasing temperature. Changes in solvent polarity were achieved by using mixtures of the standard solvent, toluene, with varying amounts of cyclohexane, tetrahydrofuran or dichloromethane. Experiments at low solvent polarity (using toluene/cyclohexane mixtures) showed problems with initiator solubility but produced polymer with lower polydispersity and higher syndiotacticity than in toluene alone. Experiments using toluene/THF mixtures yielded no polymer, thought to be owing to a side reaction between THF and aluminium triisobutyl. Increased solvent polarity, achieved using toluene/dichloromethane mixtures produced polymer with higher polydispersity and at lower yields than the conventional system, but also with higher syndiotacticity. Second monomer addition reactions demonstrated that the polymerization was 'living' since an increase in molecular weight was observed with no increase in polydispersity. Kinetic studies demonstrated the high speed of the polymerization but yielded no useful data.

Polymer PCF Bragg grating sensors based on poly(methyl methacrylate) and TOPAS cyclic olefin copolymer

Fibre Bragg grating (FBG) sensors have been fabricated in polymer photonic crystal fibre (PCF). Results are presented using two different types of polymer optical fibre (POF); first multimode PCF with a core diameter of 50µm based on poly(methyl methacrylate) (PMMA) and second, endlessly single mode PCF with a core diameter of 6µm based on TOPAS cyclic olefin copolymer. Bragg grating inscription was achieved using a 30mW continuous wave 325nm helium cadmium laser. Both TOPAS and PMMA fibre have a large attenuation of around 1dB/cm in the 1550nm spectral region, limiting fibre lengths to no longer than 10cm. However, both have improved attenuation of under 10dB/m in the 800nm spectral region, thus allowing for fibre lengths to be much longer. The focus of current research is to utilise the increased fibre length, widening the range of sensor applications. The Bragg wavelength shift of a grating fabricated in PMMA fibre at 827nm has been monitored whilst the POF is thermally annealed at 80°C for 7 hours. The large length of POF enables real time monitoring of the grating, which demonstrates a permanent negative Bragg wavelength shift of 24nm during the 7 hours. This creates the possibility to manufacture multiplexed Bragg sensors in POF using a single phase mask in the UV inscription manufacturing. TOPAS holds certain advantages over PMMA including a much lower affinity for water, this should allow for the elimination of cross-sensitivity to humidity when monitoring temperature changes or axial strain, which is a significant concern when using PMMA fibre.

Photosensitivity mechanism of undoped poly(methyl methacrylate) under UV radiation at 325 nm and its spatial resolution limit

In this Letter, we provide evidence suggesting that the main photosensitive mechanism of an undoped poly(methyl methacrylate)-based microstructured optical fiber under UV radiation at 325 nm is a competitive process of both photodegradation and polymerization. We found experimentally that increasing strain during photo-inscription leads to an increased photosensitivity, which is evidence of photodegradation. Likewise, refractive index change in the fiber was measured to be positive, which provides evidence for further polymerization of the material. Finally, we relate the data obtained to the spatial recording resolution of the samples. © 2014 Optical Society of America.

Humidity responsivity of poly(methyl methacrylate)-based optical fiber Bragg grating sensors

The humidity response of poly(methyl methacrylate) (PMMA)-based optical fiber Bragg gratings (POFBGs) has been studied. The characteristic wavelength of the grating is modulated by water absorption-induced swelling and refractive index change in the fiber. This work indicates that anisotropic expansion may exist in PMMA optical fiber, reducing the humidity responsivity of the grating and introducing uncertainty in the responsivity from fiber to fiber. By pre-straining a grating, one can get rid of this uncertainty and simultaneously improve the POFBG response time. © 2014 Optical Society of America.

Poly(methyl methacrylate) model study of optical surface quality after excimer laser photorefractive keratectomy

Purpose: To evaluate lenses produced by excimer laser ablation of poly(methyl methacrylate) (PMMA) plates. Setting: University research laboratory. Methods: Two Nidek EC-5000 scanning-slit excimer laser systems were used to ablate plane-parallel plates of PMMA. The ablated lenses were examined by focimetry, interferometry, and mechanical surface profiling. Results: The spherical optical powers of the lenses matched the expected values, but the cylindrical powers were generally lower than intended. Interferometry revealed marked irregularity in the surface of negative corrections, which often had a positive “island” at their center. Positive corrections were generally smoother. These findings were supported by the results of mechanical profiling. Contrast sensitivity measurements carried out when observing through ablated lenses whose power had been neutralized with a suitable spectacle lens of opposite sign confirmed that the surface irregularities of the ablated lenses markedly reduced contrast sensitivity over a range of spatial frequencies. Conclusion: Improvements in beam delivery systems seem desirable.

Direct observation of morphological development during the spin-coating of polystyrene-poly(methyl methacrylate) polymer blends

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.

Enhancing the sensitivity of poly(methyl methacrylate) based optical fiber Bragg grating temperature sensors

In poly(methyl methacrylate) (PMMA)-based optical fiber gratings (POFBGs), the temperature response is determined by thermal expansion and the thermo-optic effect of the fiber. Because thermal expansion introduces a positive change and the thermo-optic effect introduces a negative change in the Bragg wavelength of the POFBG, they cancel out each other to some extent, leading to reduced and varying temperature sensitivity. By pre-straining a POFBG, the contribution of thermal expansion can be removed, and, consequently, the temperature sensitivity of POFBG can be greatly enhanced. Theoretical analysis also indicates a reduced thermo-optic coefficient of POFBG due to restrained linear expansion that matches experimental results.

Strain and temperature sensitivity of a single mode polymer optical fiber

We have measured the optical phase sensitivity of fiber based on poly(methyl methacrylate) under near-single-mode conditions at 632.8 nm wavelength. The elongation sensitivity is 131±3×105 rad m-1 and the temperature sensitivity is -212±26 rad m-1 K-1. These values are somewhat larger than those for silica fiber and are consistent with the values expected on the basis of the bulk polymer properties.

Measurements of stress-optic coefficient in polymer optical fibers

We have systematically measured the differential stress-optic coefficient, ?C, in a number of poly(methyl methacrylate) (PMMA) fibers drawn with different stress, ranging from 2 up to 27 MPa. ?C was determined in transverse illumination by measuring the dependence of birefringence on additional axial stress applied to the fiber. Our results show that ?C in PMMA fibers has a negative sign and ranges from -4.5 to -4.5×10-12 Pa-1, depending on the drawing stress. Increase of the drawing stress results in greater initial fiber birefringence and lower ?C.

Water diffusion into UV inscripted long period grating in microstructured polymer fibre

A long period grating was photoinscribed step-by-step in microstructured poly(methyl methacrylate) fiber for the first time using a continuous wave HeCd laser at 325 nm, irradiating the fiber with a power of 1 mW. The grating had a length of 2 cm and a period of 1 mm. A series of cladding mode coupling resonances were observed throughout the spectral region studied of 600 to 1100 nm. The resonance wavelengths were shown to be sensitive to the diffusion of water into the fiber.

Quantifying hydrogel response using laser light scattering

The pH and counter-ion response of a microphase separated poly(methyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate)-block-poly(methyl methacrylate) hydrogel has been investigated using laser light scattering on an imprinted micron scale topography. A quartz diffraction grating was used to create a micron-sized periodic structure on the surface of a thin film of the polymer and the resulting diffraction pattern used to calculate the swelling ratio of the polymer film in situ. A potentiometric titration and a sequence of counter ion species, taken from the Hofmeister series, have been used to compare the results obtained using this novel technique against small angle X-ray scattering (nanoscopic) and gravimetric studies of bulk gel pieces (macroscopic). For the first time, the technique has been proven to be an inexpensive and effective analytical tool for measuring hydrogel response on the microscopic scale.

Effect of the Hofmeister anions upon the swelling of a self-assembled pH-responsive hydrogel

We report the effect of a range of monovalent sodium salts on the molecular equilibrium swelling of a simple synthetic microphase separated poly(methyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate)-block-poly(methyl methacrylate) (PMMA88-b-PDEA223-b-PMMA88) pH-responsive hydrogel. Sodium acetate, sodium chloride, sodium bromide, sodium iodide, sodium nitrate and sodium thiocyanate were selected for study at controlled ionic strength and pH; all salts are taken from the Hofmeister series (HS). The influence of the anions on the expansion of the hydrogel was found to follow the reverse order of the classical HS. The expansion ratio of the gel measured in solutions containing the simple sodium halide salts (NaCl, NaBr, and NaI) was found to be strongly related to parameters which describe the interaction of the ion with water; surface charge density, viscosity coefficient, and entropy of hydration. A global study which also included nonspherical ions (NaAce, NaNO3 and NaSCN) showed the strongest correlation with the viscosity coefficient. Our results are interpreted in terms of the Collins model,(1) where larger ions have more mobile water in the first hydration cage immediately surrounding the gel, therefore making them more adhesive to the surface of the stationary phase of the gel and ultimately reducing the level of expansion.

Atom transfer radical polymerisation - towards the synthesis of a fully-functional photorefractive polymer

Atom transfer radical polymerisation (ATRP) of styrene in xylene solution initiated with 1-phenylethyl bromide and mediated by CuBr/N-propyl-2- pyridinemethanimine catalyst complex was studied. The polymerisation was ill-controlled, yielding polymers with broad molecular weight distributions and values of number average molecular weight considerably higher than the theoretical values calculated from 100% initiator efficiency. The degree of control afforded over the polymerisation was enhanced by use of a more soluble catalyst complex, CuBr/N-octyl-2-pyridinemethanimine. Furthermore, the use of a more polar solvent, diglyme, generated a homogeneous catalyst complex that facilitated the production of polymers having narrow molecular weight distributions (1.10 < PDi < 1.20). The kinetics of the atom transfer radical polymerisation of methyl methacrylate at 90°C in diglyme solution initiated with ethyl-2-bromoisobutyrate and mediated by CuBr/N-octyl-2-pyridinemethanimine was studied and the orders of the reaction were established. The effect on the rate of polymerisation of the ratio of CuBr:N-octyl-2-pyridinemethanimine was also determined. The temperature dependencies of the rate of polymerisation of methyl methacrylate in diglyme solution and xylene solution were studied, and were found to be non-linear and dependent upon the polarity of the solvent. The use of highly polar aprotic solvents, such as N,N-dimethylformamide and dimethylsulphoxide, was found to be detrimental to the degree of control afforded over the polymerisation of methyl methacrylate. This was circumvented by use of a 5-fold excess, over that conventionally used, of catalyst complex. The atom transfer radical polymerisation of (4-nitrophenyl)-[3-[N-[2- (methacryloyloxy)ethyl]carbazolyl]]diazene in dimethyl sulphoxide solution was studied. Although homopolymerisation yielded only oligomers, copolymerisation of this monomer with methyl methacrylate was found to be readily achievable. Keywords: ATRP, Styrene; Methyl methacrylate; Polar solvents; Fully-functional photorefractive polymer. 2

Novel hydrogels for keratoprosthesis

Hydrogels may be described as cross~linked hydrophilic polymers that swell but do not dissolve in water. They have been utilised in many biomedical applications, as there is the potential to manipulate the properties for a given application by changing the chemical structure of the constituent monomers. This project is focused on the development of novel hydrogels for keratoprosthesis (KPro). The most commonly used KPro model consists of a tansparent central stem witb a porous peripheral skirt. Clear poly (methyl methacrylate) (PMMA) core material used in the Strampelli KPros prosthesis has not been the cause of failure found in other core and skirt prostheses. However, epithelialization of this kind of solid, rigid optic material is clearly impossible. The approach to the development of a hydrogeJ for potential KPro use adopted in this work is to develop soft core material to mimic the properties of the natural cornea by incorporating some hydrophilic monomers such as N, N-dimethyacrylamide (NNSMA) N~vinyl pyrrolidone (NVP) and acryloylmorpholine (AMO) with methyl methactylate (MMA). Most of these materials have been used in other ophthalmic applications, such as contact lens. However, an unavoidable limitation of simple .MMA copolymers as conventional hydrogels is poor mechanical strength. The hydrogel for use in this application must be able to withstand the stresses involved during the surgical procedure involved with KPro surgery and the in situ stresses such as the deforming force of the eyelid during the blink cycle. Thus, semi-interpenetrating polymer networks (SIPNs) based on ester polyurethane, AMO, NVP and NNDMA were examined in this work and were found to have much improved mechanical properties at water contents between 40% and 70%. Polyethylene glycol monomethacrylate (PEG MA) was successfully incorporated in order to modulate protein deposition and cell adhesion. Porous peripheral skirts were fabricated using different types of porosigen. The water content mechanical properties, surface properties and cell response of these various materials have been investigated in this thesis. These studies demonstrated that simple hydrogel SIPNs which show isotropic mechanical behaviour, are not ideal KPro materials since they do not mimic the anisotropic behaviour of natural cornea. The final stage of the work has concentrated on the study of hydrogels reinforced with mesh materials. They offer a promising approach to making a hydrogel that is very flexible but strong under tension, thereby having mechanical properties closer to the natural cornea than has been previously possible.