Dimerization of Poly(methyl methacrylate) Chains Using Radical Trap-Assisted Atom Transfer Radical Coupling

End-brominated poly(methyl methacrylate) (PMMABr) was prepared by atom transfer radical polymerization (ATRP) and employed in a series of atom transfer radical coupling (ATRC) and radical trap-assisted ATRC (RTA-ATRG) reactions. When coupling reactions were performed in the absence of a nitroso radical trap-traditional ATRC condition-very little coupling of the PMMA chains was observed, consistent with disproportionation as the major termination pathway for two PMMA chain-end radicals in our reactions. When 2-methyl-2-nitrosopropane (MNP) was used as the radical trap, coupling of the PMMA chains in this attempted RTA-ATRC reaction was again unsuccessful, owing to capping of the PMMA chains with a bulky nitroxide and preventing further coupling. Analogous reactions performed using nitrosobenzene (NBz) as the radical trap showed significant dimerization, as observed by gel permeation chromatography (GPC) by a shift in the apparent molecular weight compared to the PMMABr precursors. The extent of coupling was found to depend on the concentrion of NBz compared to the PMMABr chain ends, as well as the temperature and time of the coupling reaction. To a lesser extent, the concentrations of copper(I) bromide (CuBr), nitrogen ligand (N,N,N',N',N"-pentamethyldiethylenetriamine = PMDETA), and elemental copper (Cu) were also found to play a role in the success of the RTA-ATRC reaction. The highest levels of dimerization were observed when the coupling reaction was carried out at 80 degrees C for 0.5h, with ratio of 1:4:2.5:8:1 equiv of NBz: CuBr:Cu:PMDETA:PMMABr.

Osteo-odonto-keratoprosthesis (OOKP) and the testing of three different adhesives for bonding bovine teeth with optical poly-(methyl methacrylate) (PMMA) cylinder.

AIM Preparation of the lamina during osteo-odonto-keratoprosthesis (OOKP) design is complex, and its longevity and watertightness important. To date, only acrylic bone cements have been used for bonding the optical cylinder to the tooth dentine. Our aim was to evaluate different dental adhesives for OOKP preparation. METHODS Specimens of bovine teeth were produced by preparing 1.5-mm thick dentine slices with holes having a diameter of 3.5 mm. Each group (n=10 per group) was luted with either classic poly-(methyl methacrylate) (PMMA) bone cement, universal resin cement or glass ionomer cement. All specimens underwent force measurement using a uniaxial traction machine. RESULTS The highest mean force required to break the bond was measured for PMMA bone cement (128.2 N) followed by universal resin cement (127.9 N), with no statistically significant difference. Glass ionomer cement showed significantly lower force resistance (78.1 N). CONCLUSIONS Excellent bonding strength combined with easy application was found for universal resin cement, and thus, it is a potential alternative to acrylic bone cement in OOKP preparation.

Organic-inorganic poly(methyl methacrylate) hybrids with confined polyhedral oligosilsesquioxane macromonomers

We herein report the synthesis of organic-inorganic hybrid poly(methyl methacrylate) containing 1 polyhedral oligosilsesquioxanes. Octakis(3-hydroxypropyldimethylsiloxy)octasilsesquioxane (OHPS) was synthesized from octakis(hydridodimethylsiloxy)octasilsesquioxane [Si8O12(OSiMe2H)(8), Q(8)M(8)(H)] following literature procedures. Octakis(tnethacryloxypropyldimethylsiloxy) octasilsesquioxane (OMPS) was synthesized via the reaction of methacryloyl chloride or methacrylic acid anhydride with OHPS, with the latter giving improved purity. Polymerization of OMPS with methyl inethacrylate using a dibenzoylperoxide initiator gave a highly cross-linked polymer. Characterization of the polymer was performed using Fourier transform IR spectroscopy, Si-29 NMR, differential scanning calorimetry, thermogravimetric analysis, atomic force microscopy, and transmission electron microscopy with energy-dispersive X-ray analysis. The polymer was found to be largely homogeneous. Increasing the OMPS concentration in the polymer gave increased decomposition and glass transition temperatures.

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.

Chemical characterization and flexural strength of a denture base acrylic resin with monomer 2-tert-butylaminoethyl methacrylate

Purpose: The objectives of this study were to investigate the flexural strength (FS) and chemical interaction between 2-tert-butylaminoethyl methacrylate (TBAEMA) and a denture base acrylic resin. Materials and Methods: Specimens were divided into five groups according to the concentration of TBAEMA incorporated in acrylic resin Onda-Cryl (0%, 1%, 2%, 3%, 4%) and were submitted to Fourier transform infrared spectroscopy (FTIR), electron spectroscopy for chemical analysis (XPS-ESCA), and differential scanning calorimetry (DSC) analyses. FS of the specimens was tested, and results were analyzed by ANOVA/Tukey's test (α < 0.05). Results: Different nitrogen ratios were observed on specimens' surfaces: 0.36%, 0.54%, 0.35%, and 0.20% for groups 1%, 2%, 3%, and 4%, respectively. FTIR indicated copolymerization of acrylic resin and TBAEMA, and DSC results demonstrated a decrease in glass transition temperature (Tg). Significant differences were found for FS (p < 0.05). The mean values were 91.1 ± 5.5,A 77.0 ± 13.1,B 67.2 ± 12.5,B 64.4 ± 13.0,B and 67.2 ± 5.9B MPa for groups 0%, 1%, 2%, 3% and 4%, respectively (same superscript letters indicate no significant difference). Conclusions: The incorporation of TBAEMA in acrylic resin resulted in copolymerization and the presence of amine groups on specimens' surfaces, and in decreases of Tg and FS. © 2012 by the American College of Prosthodontists.

Towards the sustainable production of methyl methacrylate: A comparative analysis of industrial chemical production processes using life cycle assessment methodology

Increasing environmental awareness has been a significant driving force for innovations and process improvements in different sectors and the field of chemistry is not an outlier. Innovating around industrial chemical processes in line with current environmental responsibilities is however no mean feat. One of such hard to overhaul process is the production of methyl methacrylate (MMA) commonly produced via the acetone cyanohydrin (ACH) process developed back in the 1930s. Different alternatives to the ACH process have emerged over the years and the Alpha Lucite process has been particularly promising with a combined plant capacity of 370,000 metric tonnes in Singapore and Saudi Arabia. This study applied Life Cycle Assessment methodology to conduct a comparative analysis between the ACH and Lucite processes with the aim of ascertaining the effect of applying principles of green chemistry as a process improvement tool on overall environmental impacts. A further comparison was made between the Lucite process and a lab-scale process that is further improvement on the former, also based on green chemistry principles. Results showed that the Lucite process has higher impacts on resource scarcity and ecosystem health whereas the ACH process has higher impacts on human health. On the other hand, compared to the Lucite process the lab-scale process has higher impacts in both the ecosystem and human health categories with lower impacts only in the resource scarcity category. It was observed that the benefits of process improvements with green chemistry principles might not be apparent in some categories due to some limitations of the methodology. Process contribution analysis was also performed and it revealed that the contribution of energy is significant, therefore a sensitivity analysis with different energy scenarios was performed. An uncertainty analysis using Monte Carlo analysis was also performed to validate the consistency of the results in each of the comparisons.

Synthesis of poly(styrene-co-methyl methacrylate)-based ionomers and their Langmuir and Langmuir-Blodgett (LB) film formation

Poly(styrene-co-methyl methacrylate) (PS-PMMA) ionomers with several degrees of sulfonation were synthesized and characterized by infrared, UV-vis, and NMR spectroscopies, elemental analysis, and differential scanning calorimetry (DSC). Stable Langmuir films could be produced with PS-PMMA with 3 and 6 mol % of sulfonation, while PS-PMMA 8% exhibited material loss to the water subphase, probably due to its higher solubility. Surface pressure and surface potential isotherms with PS-PMMA 3% spread onto salt-containing subphases pointed to a film behavior characteristic of the polyelectrolyte effect, where charge repulsion governs the film properties. The Langmuir-Blodgett films of this ionomer were successfully transferred onto various substrates, as confirmed by UV-vis and FTIR spectroscopies. Using cycling voltammetry, we show that LB films from PS-PMMA 3% can be applied in selective sensing of dopamine, even in the presence of interferents such as ascorbic acid.

Miscibility and specific interactions in blends of poly(4-vinylphenol) and poly(2-ethoxyethyl methacrylate)

The properties of the hydrogen-bonded polymer blends of poly(4-vinylphenol) and poly(2-ethoxyethyl methacrylate) are presented. Spectroscopic techniques such as C-13 solid-state NMR and FT-IR are used to probe specific interactions of the blends at various compositions. Spectral features from both techniques revealed that site-specific interactions are present, consistent with a significant degree of mixing of the blend components. Changes in chemical shift and line shape of the phenolic carbon and carbonyl resonances in the C-13 CPMAS spectra of the blends as a function of composition are interpreted as resulting from changes in the relative intensities of two closely overlapped signals. A quantitative measure of hydrogen-bonded carbonyl groups using C-13 NMR has been obtained which agreed well with the results from FT-IR analyses. It is also shown that C-13 NMR can be used to measure the fraction of hydroxyl groups associated with carbonyl groups, which was not possible previously using FT-IR due to extensive overlapping of bands in the hydroxyl stretching region. The results of measurements of H-1 T-1 and 1H T-1 rho indicate that PVPh and PEEMA are intimately mixed on a scale less than 2-3 nm.