Experimental evidence of a relationship between monomer plasma residence time and carboxyl group retention in acrylic acid plasma polymers

Decreasing carboxyl retention in deposits from the glow region of an acrylic acid plasma was measured by X-ray photoelectron spectroscopy and chemical derivatisation as the collection distance from the monomer vapour inlet was increased. Volatilisation of plasma polymerised acrylic acid was detected after trifluoroethanol derivatisation; this is correlated with evaporation of low molecular weight components observed previously.     

Multi-site phase transfer catalyst assisted radical polymerisation of glycidyl methacrylate using potassium peroxydisulphate as initiator – a kinetic study

In this work, the kinetics and mechanism of free-radical polymerisation of glycidyl methacrylate (GMA) using potassium peroxydisulphate (PDS) as water soluble initiator in the presence of synthesized 1, 4-Bis (tributyl methyl ammonium) benzene dichloride (TBMABDC) as multi-site phase transfer catalyst (MPTC) was studied. The polymerisation reactions were carried out under inert and unstirred conditions at constant temperature of 60 ± 1°C in cyclohexane/water biphase media. The role of concentrations of monomer, initiator, catalyst and volume fraction of aqueous phase, solvent polarity and temperature on the rate of polymerisation (Rp) was ascertained. The order with respect to monomer and initiator was found to be unity. The order with respect to catalyst was found to be 0.51. The rate of polymerisation is independent of ionic strength and pH of the medium. However, an increase in the polarity of solvent has slightly increased the Rp value. Based on the results obtained, a suitable kinetic scheme has been proposed to account for the experimental observations and its significance discussed.     

Deposition mechanisms in langmuir-blodgett films

As part of a study of the possible application of polymerisable Langmuir-Blodgett (LB) films as ultra-fine-line e-beam resists, an investigation of the variation of film structure of 22-tricosenoic acid with differing deposition conditions has been made. Unexpected effects with significant implications for deposition speed and resist sensitivity have been observed, and the new techniques for film characterisation developed during the investigation have resulted in a revised model of deposition explaining the observed independence of the disorder causing optical scattering and the macroscopic features observed by polarised microscopy.     

Strawberry juice colour: The effect of some processing variables on the stability of anthocyanins

The colour stability of juice and purées made from a mixture of two strawberry varieties, stored at + 20°C or at –20°C under aerobic and anaerobic conditions, was studied. High-performance liquid chromatography and spectrophotometric analysis were used to monitor the changes in colour during storage. Pelargonidin 3-glucoside comprised 80% of the total anthocyanin content. Four other pelargonidin-based peaks were found, being 10.4%, 3.5%, 0.7% and 0.3% of the total and two cyanidin peaks were present, being 3.3% and 0.4% of the total. Clarification before storage caused considerable losses in the initial anthocyanin concentrations. Storage conditions (air versus nitrogen) did not influence the rate of loss of anthocyanins during storage or the formation of polymeric pigments. There were no losses in anthocyanins and no increase in the amount of colour measured at 510 nm due to polymers in samples stored at–20°C. Polymerisation occurred in the samples stored at + 20°C, especially in the clarified samples.     

Catalysis and plasma chemistry at solid surfaces

Heterogeneous and homogeneous non-equilibrium plasma chemistry offers a range of potential advantages compared to conventional thermal activation and synthesis methods. Some examples of how such low temperature electrical discharges can be effectively utilised for selective chemical reaction pathways are given. These include the fluorination of C-H bonds, the synthesis of polyozonides, selective ring opening polymerisation, and the conversion of alkali metal halides to nitrates using air.     

Evaluation of neural networks-based controllers in batch polymerisation of methyl methacrylate

The importance of batch reactors in today's process industries cannot be overstated. Thus said, it is important to optimise their operation in order to consistently achieve products of high quality while minimising the production of undesirables. In processes like polymerisation, these reactors are responsible for a greater number of products than other reactor types and the need for optimal operation is therefore greater.

An approach based on an offline dynamic optimisation and online control strategy is used in this work to generate optimal set point profiles for the batch polymerisation of methyl methacrylate. Dynamic optimisation is carried out from which controller set points to attain desired polymer molecular end point characteristics are achieved. Temperature is the main variable to be controlled, and this is done over finite discrete intervals of time.

For on-line control, we evaluate the performance of neural networks in two controllers used to track the derived optimal set points for the system. The controllers are generic model control (GMC), ([P.L. Lee, G.R. Sullivan, Generic model control, Comput. Chem. Eng. 12(6) (1998) 573–580]) and the neural network-based inverse model-based control (IMBC), ([M.A. Hussain, L.S. Kershenbaum, Implementation of an inverse model based control strategy using neural networks on a partially simulated exothermic reactor, Trans. IchemE 78(A) (2000) 299–311]). Although the GMC is a model-based controller, neural networks are used to estimate the heat release within its framework for on-line control. Despite the application of these two controllers to general batch reactors, no published work exists on their application to batch polymerisation in the literature. In this work, the performance of the neural networks within each controller's algorithm for tracking and setpoint regulation of the optimal trajectory and in robustness tests on the system is evaluated.     

Polymer grafted multiwalled carbon nanotubes via facile in situ solution radical polymerisation

A facile strategy to graft polymers onto the surfaces of multiwalled carbon nanotubes (MWCNTs) was developed via the free radical addition process in the solution radical polymerisation of styrene in presence of the MWCNTs without any pretreatment so that the length of the original MWCNTs remained unchanged. The polystyrene grafted MWCNTs were characterised with Fourier transform infrared spectroscopy, Raman spectroscopy, thermogravimetric analysis (TGA) and transmission electron microscopy techniques. The effect of the amount of the initiator added and of the polymerising temperature on the percentage of grafting (PG%) and conversion of monomer (C%) were calculated from the TGA results. It was found that the maximum PG% of 15.6% was achieved with 0.5% initiator added and the higher polymerising temperature favoured the grafting polymerisation. The proposed method is expected to be extended to other vinyl monomers and offers another diverse way for the sidewall functionalisation of MWCNT.     

One‐pot synthesis of {Mo6I8}4+‐doped polystyrene microspheres via a free radical dispersion copolymerisation reaction

Molybdenum octahedral clusters, when incorporated into an appropriate polymer matrix, are considered as promising agents for a range of biological applications. This work describes the one‐pot synthesis, morphology and cellular toxicity of nano‐sized polystyrene beads doped with luminescent cluster complexes [{Mo₆X₈}(NO₃)₆]^2? (X = Cl, Br or I). Specifically, the particles were obtained by free radical dispersion copolymerisation of styrene and methacrylic acid or 4‐vinylpyridine in the presence of the cluster complexes. The effects of the cluster loading in the reaction mixture on both the content of the final material and number‐average molar mass of the copolymers were evaluated. © 2017 Society of Chemical Industry     

Effect of potato presence on the degradation of extra virgin olive oil during frying

This work investigates the effect of potato presence on the degradation of extra virgin olive oil (EVOO) during repeated frying. For this reason the performance of EVOO during frying was compared with its performance during heating at frying temperatures. In order to make meaningful comparisons the temperature profiles obtained during the frying experiments were replicated during the heating experiments by means of a high energy exchange rate cooling/heating system. The effects of potato‐to‐oil ratio (1/7 and 1/35 kg_potatoes/L_oil) and number (N) of batches (N = 0, 1, 0, 20, 30, 40) were examined. EVOO was analysed using high performance size exclusion chromatography (HPSEC). It was found that polymerisation products increased linearly during frying and heating and that they were not affected by potatoes presence at low ratio. The effect of potato presence became statistically significant (yet not remarkable) at the high ratio. Decomposition products increased during frying whereas they decreased during heating.     

On the Strategic Impact of the Degenerative Transfer of Xanthates on Synthetic Planning

The present brief account relates synthetic endeavours revolving around a novel chemistry of xanthates (dithiocarbonates) being developed in our group. The degenerative reversible transfer of xanthates has a unique ability to store reactive radicals in a dormant form, and thereby to enhance their lifetime in a concentrated medium, while at the same time, regulating their absolute and relative concentrations. It allows intermolecular radical additions even to unactivated alkenes, and can promote otherwise sluggish radical processes, such as 5-endo, 6-exo, 6-endo, 7-endo, and 8-endo cyclisations, as well as ring closures on (hetero)aromatic structures. This chemistry has proved remarkably versatile and powerful, both for solving synthetic problems and for the industrial production of block copolymers through the RAFT/MADIX technology.