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

The use of enzymes in organic solvents in polytransesterification reactions

The aim of this research project was to identify the factors affecting the porcine pancreatic lipase (PPL.)-catalysed polytransesterification of a diester and a diol in organic solvents. It was hoped that by modifying reaction conditions a commercially acceptable polymer molecular weight (Mn) of 20,000 daltons might be attained. Exploratory investigations were carried out using 1,4-butanediolibis(2,2,2- trichloroethyl) adipate and glutarate systems in diethyl ether, with and without molecular sieves. It was found that molecular sieves promoted the reaction by reducing hydrolysis of the ester end-groups, resulting in polymer molecular weights between 1.2 and 2.2 times greater than those obtainable without molecular sieves. Investigations were then concentrated on the PPL-catalysed polytransesterification of 1,4-butanediol with divinyl adipate. The particular advantage of this system is that the reaction is irreversible. The effects of varying substrate concentration, mass of drying agent, reaction solvent, reaction temperature, mass of enzyme and also enzyme immobilisation on the 1,4-butanediolidivinyl adipate system were investigated. The highest molecular weight polymer obtained for the PPL-catalysed polytransesterification of 1,4-butanedial with divinyl adipate in diethyl ether was Mn -8,000. In higher boiling ether solvents molecular weights as high as Mn -9,200 were obtained for this system at elevated temperatures. It was found that the major factor limiting polymerisation was the low solubility of the polymer in the solvent which resulted in precipitation of the polymer onto the surface of the enzyme.

A new strategy for selecting and evaluating physical solvents for gas absorption

This work describes how the physical properties of a solvent affect the design variables of a physical gas absorption process. The role of every property in determining the capital and the running cost of a process has been specified. Direct mathematical relationships have been formulated between every item of capital or running cost and the properties which are related to that item. The accuracy of the equations formulated has been checked by comparing their outcome with some actual design data. A good agreement has been found. The equations formulated may be used to evaluate on the basis of economics any suggested new solvents. A group of solvents were selected for evaluation. Their physical properties were estimated or collected as experimental data. The selected ones include three important solvents, the first is polyethylene glycol dimethyl ether (Selexol) which represents the currently most successful one, The other two solvents are acetonyl acetone (B2) and n-formyl morpholine which have been suggested previously as potential credible alternatives to the current ones. The important characteristics of: acetonyl acetone are its high solubility and its low viscosity, while the n-formyl morpholine is characterised by its low vapour pressure and its high selectivity. It was found that acetonyl acetone (B2) is the most attractive solvent for commercial applications particularly for process configurations that:include heat exchangers and strippers. The effect of the process configuration on the selected solvent was investigated in detail and it was found that there is no universal solvent which is the best for any process configuration, but that there is a best solvent for a given process configuration. In previous work, acetonyl acetone was suggested as a commercially promising physical solvent. That suggestion was not fully based on experimental measurement of all the physical properties. The viscosity of acetonyl acetone and its solubility at 1 atm were measured but the vapour pressure and the solubility of C02 and CH4 at high pressure were predicted. In this work, the solubilities of C02, CH4 and C3H8 in acetenyl acetone were measured for a partial pressure range of (2 ~ 22) bar at 25°C, The vapour pressure of this solvent was also measured, and the Antoine equation was formulated from tbe experimental data. The experimental data were found to be not In agreement with the predicted ones, so acetonyl acetone was re-evaluated according to the experimental data. It was found that this solvent can be recommended for further trials in a pilot plant study or for small scale commercial units.

Salting out in organic solvents:a new route to carbon nanotube bundle engineering

In this study we investigate salt effects on bundle formation of carbon nanotubes (CNTs) dispersed in an organic solvent, N-methyl-2-pyrrolidone (NMP). Addition of NaI salt leads to self-assembly of CNTs into well-recognizable bundles. It is possible to control the size of the CNT bundles by varying the salt concentration. © the Owner Societies 2011.

Measurement and correlation of the solubility of telmisartan (form A) in nine different solvents from 277.85 to 338.35 K

The solubility of telmisartan (form A) in nine organic solvents (chloroform, dichloromethane, ethanol, toluene, benzene, 2-propanol, ethyl acetate, methanol and acetone) was determined by a laser monitoring technique at temperatures from 277.85 to 338.35 K. The solubility of telmisartan (form A) in all of the nine solvents increased with temperature as did the rates at which the solubility increased except in chloroform and dichloromethane. The mole fraction solubility in chloroform is higher than that in dichloromethane, which are both one order of magnitude higher than those in the other seven solvents at the experimental temperatures. The solubility data were correlated with the modified Apelblat equation and λh equations. The results show that the λh equation is in better agreement with the experimental data than the Apelblat equation. The relative root mean square deviations (σ) of the λh equation are in the range from 0.004 to 0.45 %. The dissolution enthalpies, entropies and Gibbs energies of telmisartan in these solvents were estimated by the Van’t Hoff equation and the Gibbs equation. The melting point and the fusion enthalpy of telmisartan were determined by differential scanning calorimetry.