Structure of norbornene-fused 3,1-oxazine double cycloadducts

Pentacyclic isoxazolines were obtained by the cycloaddition of benzonitrile oxide to norbornene-azetidinone-fused 3,1-oxazines. The constitutions of two of the isomers obtained, and the configurations and conformations of all products, were determined by means of ¹H and ¹³C NMR spectroscopy and DNOE experiments.     

Studies on calcium‐containing poly(urethane ether)s

The calcium salt of mono(hydroxyethoxyethyl)phthalate [Ca(HEEP)₂] was synthesized by the reaction of diethylene glycol, phthalic anhydride, and calcium acetate. Calcium‐containing poly(urethane ether)s (PUEs) were synthesized by the reaction of hexamethylene diisocyanate (HMDI) or tolylene 2,4‐diisocyanate (TDI) with a mixture of Ca(HEEP)₂ and poly(ethylene glycol) (PEG₃₀₀ or PEG₄₀₀) with di‐n‐butyltin dilaurate as a catalyst. A series of calcium‐containing PUEs of different compositions were synthesized with Ca(HEEP)₂/PEG₃₀₀ (or PEG₄₀₀)/diisocyanate (HMDI or TDI) molar ratios of 2:2:4, 3:1:4, and 1:3:4 so that the coating properties of the PUEs could be studied. Blank PUEs without calcium‐containing ionic diols were also prepared by the reaction of PEG₃₀₀ or PEG₄₀₀ with HMDI or TDI. The PUEs were well characterized by Fourier transform infrared, ¹H and ¹³C NMR, solid‐state cross‐polarity/magic‐angle‐spinning ¹³C NMR, viscosity, solubility, and X‐ray diffraction studies. The thermal properties of the polymers were also studied with thermogravimetric analysis and differential scanning calorimetry. The PUEs were applied as top coats on acrylic‐coated leather, and their physicomechanical properties were also studied. The coating properties of PUEs, such as the tensile strength, elongation at break, tear strength, water vapor permeability, flexing endurance, cold crack resistance, abrasion resistance, color fastness, and adhesive strength, were better than the standard values. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2865–2878, 2003     

功能性丙烯酸/MBAM体系共聚产物的研制

以丙烯酸和MBAM为主要原料，经聚合，合成了一种高性能的具有良好保水性能的聚合产物，其保水量达到750～1000倍．50℃以下有良好的保水性能，28℃以下有极好的保水性能，并研究了工艺条件对该产品性能的影响因素．     

Latex particles bearing hydrophilic grafted hairs with controlled chain length and functionality synthesized by reversible addition–fragmentation chain transfer

A method is described for synthesizing latex particles with anchored hairs by the grafting of hydrophilic chains, synthesized by reversible addition–fragmentation chain transfer, onto functionalized latex particles. These have the potential to bind biologically active species. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1188–1195, 2003     

Effects of tributyltin(IV) chloride on the gametes and fertilization of Ascidia malaca (Ascidiacea: Tunicata)

Ascidia malaca gametes before fertilization incubated in 10^?5 or 10^?7 M solutions of tributyltin(IV) chloride, TBTCl, for 3 h appear highly damaged under transmission electron microscopy observation. Also, the fertilization process is affected by the compound: the damaged spermatozoa are present in the vitelline coat and the egg does not cleave. An increase of microbodies, structurally similar to peroxisomes, have been detected in the egg peripheral cytoplasm, probably in relation to their role in alleviating damage to some cellular components. The results have shown that the reproduction of ascidians under unfavourable environmental conditions is prevented. Copyright © 2003 John Wiley & Sons, Ltd.     

Effect of maltodextrins on the surface activity of small-molecule surfactants

We report on the effect of commercially important polysaccharides (maltodextrins with variable dextrose equivalent (Paselli SA-2, MD-6 and MD-10) on the surface activity at the air–water interface of small-molecule surfactants (sms), possessing different hydrophobic–lipophilic balance ((SSL (Na⁺), the main component is a sodium salt of stearol–lactoyl lactic acid, and PGE (080), polyglycerol ester of C18 fatty acid), and widely used in food products. A marked change of the surface activity of sms was found in the presence of maltodextrins by tensiometry. The combined data of laser multiangle light scattering and mixing calorimetry have suggested that this result is governed by specific complex formation between maltodextrins and sms in aqueous medium. Measurements have been made of the molar mass, the second virial coefficient and the enthalpy of intermolecular interactions in aqueous solutions. The implication of a degree of polymerization of maltodextrins in this phenomenon was shown. The interrelation between the molecular parameters of the formed complexes and their surface activity at the air–water interface has been revealed and discussed.     

Amine‐blocked polyisocyanates. I. Synthesis of novel N‐methylaniline‐blocked polyisocyanates and deblocking studies using hot‐stage fourier transform infrared spectroscopy

A series of substituted N‐methylaniline‐blocked polyisocyanates based on 4,4′‐methylenebis(phenyl isocyanate) and poly(tetrahydrofuran) were prepared and characterized thoroughly with FTIR, ¹H NMR, and ¹³C NMR spectroscopy methods. Compared with unsubstituted N‐methylaniline, a blocking agent with an electron‐releasing substituent at the para position took a shorter time, whereas those with an electron‐releasing substituent at the ortho position or an electron‐withdrawing substituent at the ortho and para positions took longer times for the blocking reaction. The thermal dissociation reactions of blocked polyisocyanates were carried out with an FTIR spectrophotometer attached to hot‐stage accessories under dynamic and isothermal conditions. The dynamic method was used to determine the deblocking temperature, and the isothermal method was used to calculate the deblocking kinetics and activation parameters. The cure times of blocked polyisocyanates with hydroxyl‐terminated polybutadiene were also determined. The deblocking temperatures, the results of cure‐time studies, and the kinetic parameters revealed that the thermal dissociation of the N‐methylaniline‐blocked polyisocyanates was retarded by electron‐donating substituents and facilitated by electron‐withdrawing substituents. The action of N‐methylanilines as blocking agents for isocyanate was explained by the formation of a four‐center, intramolecularly hydrogen‐bonded ring structure during the thermal dissociation of the blocked polyisocyanates. The formation of such a hydrogen‐bonded ring structure was confirmed and supported by variable‐temperature ¹H NMR studies and entropy parameters, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1557–1570, 2007     

Physicochemical studies on hydrophobic PEO‐PPO‐PEO triblock copolymer micelles in SDS micellar environment

The shape, size, aggregation, hydration, and correlation times of water insoluble PEO‐PPO‐PEO triblock copolymer micelles with sodium dodecylsulfate (SDS) micelles were investigated using transport studies and dynamic light scattering technique. From the conductance of micellar solutions of the polymer in 25 mM SDS and 5 mM NaCl, the hydration of polymer micelles were determined using the principle of obstruction of electrolyte migration by the polymer. The asymmetry of the micellar particles of polymer and polymer‐SDS mixed micellar systems in 5 mM NaCl and their average axial ratios were calculated using intrinsic viscosity and hydration data obeying Simha–Einstein equation. Hydration number and micellar sizes were variable with temperature. The shape of the polymer micelles has been ellipsoidal rather than spherical. The micellar volume, hydrodynamic radius, radius of gyration, diffusional coefficients as well as translational, rotational and effective correlation times have been calculated from the absolute values of the axes. The partial molal volume of polymer micelles has also been determined and its comparison with the molar volume of pure polymer suggested a volume contraction due to immobilization of the water phase by the hydrophilic head groups of the polymer. The thermodynamic activation parameters for viscous flow favor a more ordered water structure around polymer micelles at higher temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2410–2420, 2007     

Solution of the hyperbolic mild‐slope equation using the finite volume method

A finite volume solver for the 2D depth‐integrated harmonic hyperbolic formulation of the mild‐slope equation for wave propagation is presented and discussed. The solver is implemented on unstructured triangular meshes and the solution methodology is based upon a Godunov‐type second‐order finite volume scheme, whereby the numerical fluxes are computed using Roe's flux function. The eigensystem of the mild‐slope equations is derived and used for the construction of Roe's matrix. A formulation that updates the unknown variables in time implicitly is presented, which produces a more accurate and reliable scheme than hitherto available. Boundary conditions for different types of boundaries are also derived. The agreement of the computed results with analytical results for a range of wave propagation/transformation problems is very good, and the model is found to be virtually paraxiality‐free. Copyright © 2003 John Wiley & Sons, Ltd.