Access to nonisocyanate poly(thio)urethanes: A comparative study

This article describes the synthesis of new cyclic compounds able to react with amines to get nonisocyanate polyurethanes (NIPUs). The contribution of the most studied five‐membered cyclic carbonate was compared to five‐membered cyclic dithiocarbonate analogous and to a six‐membered cyclic carbonate. Difunctional reactive species were obtained by a simple substitution reaction or an efficient thiol–ene coupling reaction. The products, obtained with high yields, were characterized by 1H NMR, 13C NMR, and Fourier tansform infrared spectroscopy analysis. The dicyclocarbonates were then used to synthesize NIPUs by step growth polymerization with several diamines. These materials exhibited glass transition temperatures from 19 to ?29 °C, molar mass from 1800 to 20,400 g mol^?1, and a 20% mass loss temperature (T_d = 20%) between 249 and 296 °C. Such materials are interesting candidates for coating applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3284–3296     

Synthesis of low grafting density molecular brush from a poly(N‐alkyl urea peptoid) backbone

The synthesis of a molecular brush was accomplished by combining step‐growth polymerization and reversible addition fragmentation chain transfer (RAFT) polymerization in a “grafting from” methodology. A symmetrical N‐alkyl urea peptoid sixmer containing alkyne functional groups was prepared using a divergent strategy, and the structure of the product was confirmed using NMR spectroscopy and mass spectrometry. A step‐growth process was used to prepare a linear poly(N‐alkyl urea peptoid) by reacting the diamine‐functionalized N‐alkyl urea peptoid sixmer with a diisocyanate. RAFT chain transfer agents were coupled to the poly(N‐alkyl urea peptoid) backbone through a copper‐catalyzed azide/alkyne cycloaddition reaction. The afforded macro‐RAFT agent was used to sequentially polymerize styrene and tert‐butyl acrylate block copolymer arms from the poly(N‐alkyl urea peptoid) backbone. The tert‐butyl groups were removed using dilute trifluoroacetic acid affording hydrophilic polyacrylic acid segments. The molecular brushes were observed to generate micelles in aqueous solution. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of main‐chain poly(carbazole)s via CuAAC

The synthesis and characterization of a novel family of main‐chain carbazole‐containing polymers using copper‐catalyzed azide‐alkyne cycloaddition chemistry is reported. The reactions were performed under mild conditions using readily available copper catalysts and ligands, which afforded polymeric products with M_ws up to 18 kDa. Using a range of techniques, the polymers were found to exhibit a glass transition temperature (T_g) of 85 °C, high thermal stability (T_d = 274 °C), and high photoluminescent quantum efficiency (?_f = 0.29; λ_em = 448 nm), which underscore their potential for use in organic light‐emitting diodes or other emissive devices, particularly where efficient blue emission is of value. The approach described offers practical advantages over other synthetic methods used to prepare main‐chain carbazole‐containing polymers, especially with regard to the lack of need for rigorously inert conditions and the absence of byproducts generated during the polymerization reaction. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

A numerical investigation of the influence of the aspect ratio in three‐dimensional separated flows

The influence of aspect ratio in three‐dimensional, numerical experiments of separated flows is studied in the case of the backward‐facing step at Reynolds numbers 600, 800, and 950. The computational domain is designed as an actual laboratory experiment. The governing equations are the steady state, isothermal, and incompressible Navier–Stokes equations. The expansion ratio of the computational domain is 1:2. The aspect ratio varies from 1:10 to 1:40. The results of the computations focus on the spanwise variations of the length and the strength of the two eddies along the lower and upper wall. It is concluded that both numerical and laboratory experiments should be designed with an aspect ratio of at least 1:20, if only the accuracy of the position of the detachment and the re‐attachment points matters. If the accuracy of the shear‐stress distributions is also taken into account, then an aspect ratio of at least 1:30 should be chosen. Finally, if the magnitudes of the vortex centers are also considered, then only the aspect ratio of 1:40 qualifies for a realization of two‐dimensional flow conditions in the plane of symmetry. This is contrary to the common practice in the field, at least from the side of laboratory experiments, where an aspect ratio of 1:10 is still considered adequate for this purpose. Copyright © 2011 John Wiley & Sons, Ltd.     

Manganese Dioxide Mediated Stereoselective, One-step Synthesis of Novel Steroidal (6R)-Spiro-1’,2’,4’-triazoline-3’-thiones

Oxidative cyclization of 5α-cholestan-6-one thiosemicarbazone (1), its 3β-chloro (2) and 3β-acetoxy (3) analogues with active manganese dioxide at room temperature afforded selectively the corresponding (6R)-spiro-1’,2’,4’-triazoline-3’-thiones 4—6. This synthesis has the advantages of mild reaction conditions, easy handling, easily available reagent and high yields. The products have been characterized by analytical and spectral data.     

A simple mathematical model for seasonal planktonic blooms

We show how the inclusion of the defense strategy by different species can alter the prediction of simple models. One of the defense strategy by the phytoplankton population against their grazer is the release of toxic chemicals. In turn the zooplankton population reduces there predation rate over toxin producing phytoplankton (TPP) to protect themselves from those toxic chemicals. Thus, when the level of toxicity is high, the grazing pressure is low and when the level of toxicity is low or when the toxin is absent, the grazing pressure is high. Here we have considered a TPP–zooplankton system where the rate of toxin liberation and the predation rate vary with zooplankton abundance. We observe that our proposed model has the potential to show different dynamical behaviour that are similar to that seen in real‐world situations. Further, we consider three different functional forms for the distribution of the toxins and compare them using latin hypercube sampling technique and found that the functional forms seem to have no effect in determining the final outcome of the system. Copyright © 2009 John Wiley & Sons, Ltd.     

Molecular Mixing and Flowfield Measurements in a Recirculating Shear Flow. Part I: Subsonic Flow

The mixing and flowfield of a complex geometry, similar to a rearward-facing step flow but with injection, is studied. A subsonic top-stream is expanded over a perforated ramp at an angle of 30°, through which a secondary stream is injected. The mass flux of the second stream is chosen to be insufficient to provide the entrainment requirements of the shear layer, which, as a consequence, attaches to the lower guidewall. Part of the flow is directed upstream forming a re-entrant jet within the recirculation zone that enhances mixing and flameholding. A control-volume model of the flow is found to be in good agreement with the variation of the overall pressure coefficient of the device with variable mass injection. The flowfield response to changing levels of heat release is also quantified. While increased heat release acts somewhat analogously to increased mass injection, fundamental differences in the flow behaviour are observed. The hypergolic hydrogen-fluorine chemical reaction employed allows the level of molecular mixing in the flow to be inferred. The amount of mixing is found to be higher in the expansion-ramp geometry than in classical free-shear layers. As in free-shear layers, the level of mixing is found to decrease with increasing top-stream velocity. Results for a similar configuration with supersonic flow in the top stream are reported in Part II of this two-part series.     

Local Heaviside‐weighted LRPIM meshless method and its application to two‐dimensional potential flows

In this paper, the local radial point interpolation meshless method (LRPIM) is used for the analysis of two‐dimensional potential flows, based on a local‐weighted residual method with the Heaviside step function as the weighting function over a local subdomain. Trial functions are constructed using radial basis functions. The present method is a truly meshless method based only on a number of randomly located nodes. Integration over the subdomains requires only a simple integration cell to obtain the solution. No element matrix assembly is required and no special treatment is needed to impose the essential boundary conditions. The novelty of the paper is the use of a local Heaviside weight function in the LRPIM, which does not need local domain integration and integrations only on the boundary of the local domains are needed. Effects of the sizes of local subdomain and interpolation domain on the performance of the present method are investigated. The behavior of shape parameters of multiquadrics has been systematically studied. Two numerical tests in groundwater and fluid flows are presented and compared with closed‐form solutions and finite element method. The results show that the use of a local Heaviside weight function in the LRPIM is highly accurate and possesses no numerical difficulties. Copyright © 2008 John Wiley & Sons, Ltd.     

Numerical simulations of viscous flows using a meshless method

This paper uses the element‐free Galerkin (EFG) method to simulate 2D, viscous, incompressible flows. The control equations are discretized with the standard Galerkin method in space and a fractional step finite element scheme in time. Regular background cells are used for the quadrature. Several classical fluid mechanics problems were analyzed including flow in a pipe, flow past a step and flow in a driven cavity. The flow field computed with the EFG method compared well with those calculated using the finite element method (FEM) and finite difference method. The simulations show that although EFG is more expensive computationally than FEM, it is capable of dealing with cases where the nodes are poorly distributed or even overlap with each other; hence, it may be used to resolve remeshing problems in direct numerical simulations. Flows around a cylinder for different Reynolds numbers are also simulated to study the flow patterns for various conditions and the drag and lift forces exerted by the fluid on the cylinder. These forces are calculated by integrating the pressure and shear forces over the cylinder surface. The results show how the drag and lift forces oscillate for high Reynolds numbers. The calculated Strouhal number agrees well with previous results. Copyright © 2008 John Wiley & Sons, Ltd.     

Simultaneous reversible addition fragmentation chain transfer and ring‐opening polymerization

The simultaneous ring‐opening polymerization (ROP) of ε‐caprolactone (ε‐CL) and 2‐hydroxyethyl methacrylate (HEMA) polymerization via reversible addition fragmentation chain transfer (RAFT) chemistry and the possible access to graft copolymers with degradable and nondegradable segments is investigated. HEMA and ε‐CL are reacted in the presence of cyanoisopropyl dithiobenzoate (CPDB) and tin(II) 2‐ethylhexanoate (Sn(Oct)₂) under typical ROP conditions (T > 100 °C) using toluene as the solvent in order to lead to the graft copolymer PHEMA‐g‐PCL. Graft copolymer formation is evidenced by a combination of size‐exclusion chromatography (SEC) and NMR analyses as well as confirmed by the hydrolysis of the PCL segments of the copolymer. With targeted copolymers containing at least 10% weight of PHEMA and relatively small PHEMA backbones (ca. 5,000–10,000 g mol^?1) the copolymer grafting density is higher than 90%. The ratio of free HEMA‐PCL homopolymer produced during the “one‐step” process was found to depend on the HEMA concentration, as well as the half‐life time of the radical initiator used. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3058–3067, 2008