Facile modifications of a polyimide via chloromethylation. I. Novel synthesis of a new photosensitive polyimide

A soluble aromatic polyimide was chloromethylated via a reaction with chloromethyl methyl ether in the presence of tin(IV) chloride to produce a new starting material for the modification of aromatic polyimides. The chemical structure of the resulting polymer was confirmed by ¹H NMR and Fourier transform infrared spectroscopy. The maximum number of chloromethyl groups per repeat unit was 1.81. The chloromethylated polyimide was stable up to 250 °C and soluble in both chloroform and tetrahydrofuran. So that its utilization for further modification could be demonstrated, cinnamic acid was reacted with the formed polyimide, and it produced a new photosensitive polyimide with a cinnamoyl side chain. The photosensitivity of the resulting polyimide was investigated with ultraviolet spectroscopic methods. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 22–29, 2003     

Numerical simulations of a filament in a flowing soap film

Experiments concerning the properties of soap films have recently been carried out and these systems have been proposed as experimental versions of theoretical two‐dimensional liquids. A silk filament introduced into a flowing soap film, was seen to demonstrate various stable modes, and these were, namely, a mode in which the filament oscillates and one in which the filament is stationary and aligns with the flow of the liquid. The system could be forced from the oscillatory mode into the non‐ oscillatory mode by varying the length of the filament. In this article we use numerical and computational techniques in order to simulate the strongly coupled behaviour of the filament and the fluid. Preliminary results are presented for the specific case in which the filament is seen to oscillate continuously for the duration of our simulation. We also find that the filament oscillations are strongly suppressed when we reduce the effective length of the filament. We believe that these results are reminiscent of the different oscillatory and non‐oscillatory modes observed in experiment. The numerical solutions show that, in contrast to experiment, vortices are created at the leading edge of the filament and are preferentially grown in the curvature of the filament and are eventually released from the trailing edge of the filament. In a similar manner to oscillating hydrofoils, it seems that the oscillating filaments are in a minimal energy state, extracting sufficient energy from the fluid to oscillate. In comparing numerical and experimental results it is possible that the soap film does have an effect on the fluid flow especially in the boundary layer where surface tension forces are large. Copyright © 2004 John Wiley & Sons, Ltd.     

A numerical and experimental investigation of the interactions between a non‐uniform planar array of incompressible free jets

The interaction between multiple incompressible air jets has been studied numerically and experimentally. The numerical predictions have been first validated using experimental data for a single jet configuration. The spreading features of five unequal jets in the configuration of one larger central jet surrounded by four smaller equi‐distant jets, have been studied, for different lateral spacing ratios of 1.5, 2.0 and 2.5 and a central jet Reynolds number of 1.24×105 (corresponding to a Mach number of 0.16). Flow of five equal jets has also been simulated, for the sake of comparison. The jet interactions commence at an axial distance of about 3–4 diameters and complete by an axial distance of about 10 diameters for the lowest spacing ratio of 1.5. For larger spacing ratios, the length required for the start and completion of jet interaction increase. Peripheral jets bend more towards the central jet and merge at a smaller distance, when their sizes are smaller than that of the central jet. The entrainment ratio for multiple jets is higher than that for a single jet. Excellent agreement is observed between the experimental data and theoretical predictions for both mean flow field and turbulent quantities, at regions away from the jet inlet. The potential core length and initial jet development, however, are not predicted very accurately due to differences in the assumed and actual velocity profiles at the jet inlet. Copyright © 2004 John Wiley & Sons, Ltd.     

A time‐accurate pseudo‐compressibility approach based on an unstructured hybrid finite volume technique applied to unsteady turbulent premixed flame propagation

A preconditioning approach based on the artificial compressibility formulation is extended to solve the governing equations for unsteady turbulent reactive flows with heat release, at low Mach numbers, on an unstructured hybrid grid context. Premixed reactants are considered and a flamelet approach for combustion modelling is adopted using a continuous quenched mean reaction rate. An overlapped cell‐vertex finite volume method is adopted as a discretisation scheme. Artificial dissipation terms for hybrid grids are explicitly added to ensure a stable, discretised set of equations. A second‐order, explicit, hybrid Runge–Kutta scheme is applied for the time marching in pseudo‐time. A time derivative of the dependent variable is added to recover the time accuracy of the preconditioned set of equations. This derivative is discretised by an implicit, second‐order scheme. The resulting scheme is applied to the calculation of an infinite planar (one‐dimensional) turbulent premixed flame propagating freely in reactants whose turbulence is supposed to be frozen, homogeneous and isotropic. The accuracy of the results obtained with the proposed method proves to be excellent when compared to the data available in the literature. Copyright © 2004 John Wiley & Sons, Ltd.     

Novel,biodegradable, functional poly(ester‐carbonate)s by copolymerization of trans‐4‐hydroxy‐L‐proline with cyclic carbonate bearing a pendent carboxylic group

Water‐soluble poly(ester‐carbonate) having pendent amino and carboxylic groups on the main‐chain carbon is reported for the first time. This article describes the melt ring‐opening/condensation reaction of trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline (N‐CBz‐Hpr) with 5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one (MBC) at a wide range of molar fractions. The influence of reaction conditions such as catalyst concentration, polymerization time, and temperature on the number average molecular weight (M_n) and molecular weight distribution (M_w/M_n) of the copolymers was investigated. The polymerizations were carried out in bulk at 110 °C with 3 wt % stannous octoate as a catalyst for 16 h. The poly(ester‐carbonate)s obtained were characterized by Fourier transform infrared spectroscopy, ¹H NMR, differential scanning calorimetry, and gel permeation chromatography. The copolymers synthesized exhibited moderate molecular weights (M_n = 6000–14,700 g mol^?1) with reasonable molecular weight distributions (M_w/M_n = 1.11–2.23). The values of the glass‐transition temperature (T_g) of the copolymers depended on the molar fractions of cyclic carbonate. When the MBC content decreased from 76 to 12 mol %, the T_g increased from 16 to 48 °C. The relationship between the poly(N‐CBz‐Hpr‐co‐MBC) T_g and the compositions was in approximation with the Fox equation. In vitro degradation of these poly(N‐CBz‐Hpr‐co‐MBC)s was evaluated from weight‐loss measurements and the change of M_n and M_w/M_n. Debenzylation of 3 by catalytic hydrogenation led to the corresponding linear poly(ester‐carbonate), 4 , with pendent amino and carboxylic groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2303–2312, 2004     

Photochemical attachment of polymers on planar surfaces with a covalently anchored monolayer of a novel naphthyl ketone photochemical radical generator

A monolayer of covalently anchored, novel, binaphthyl ketone is used as a surface‐confined photochemical radical generator (PRG) for anchoring a variety of polymers to silicon surfaces. The precursor PRG is synthesized by the application of a facile and novel method for the oxidation of sterically hindered benzylic hydrocarbons to carbonyl compounds. Oxidation was carried out with a stoichiometric amount of potassium peroxydisulfate, in the presence of a catalytic amount of copper sulfate in an acetonitrile/water mixture. The PRG synthesized is characterized by ¹H NMR, UV, and Fourier transform infrared (FTIR). The covalently attached monolayers are characterized by X‐ray photoelectron spectroscopy, ellipsometry, and water contact angle measurements. The method developed is applicable to the preparation of a monolayer of a variety of polymers on a wide range of substrates carrying surface hydroxyl groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5413–5423, 2004     

Generation of highly stable amidate anion in anionic polymerization of 3‐(triethylsilyl)propyl isocyanate

To study living anionic polymerization, 3‐(triethylsilyl)propyl isocyanate (TEtSPI) monomer was synthesized by hydrosilylation of allylamine with triethylsilane and treatment of the resulting amine with triphosgene. The polymerization of TEtSPI was performed with sodium naphthalenide (Na‐Naph) as an initiator and in the absence and presence of sodium tetraphenylborate (NaBPh₄) as an additive in tetrahydrofuran (THF) at ?78 and at ?98 °C. A highly stabilized amidate anion for living polymerization of isocyanates was generated for the first time with the combined effect of the bulky substituent and the shielding action of the additive NaBPh₄, extending the living character at least up to 120 min at ?98 °C. Even the anion could exist at ?78 °C for 10 min. A block copolymer, poly(n‐hexyl isocyanate)‐b‐poly[(3‐triethylsilyl)propyl isocyanate]‐b‐poly(n‐hexyl isocyanate), was synthesized with quantitative yields and controlled molecular weights via living anionic polymerization in THF at ?78 °C for TEtSPI and ?98 °C for n‐hexyl isocyanate, respectively, with Na‐Naph with three times of NaBPh₄ as a common ion salt. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 933–940, 2004