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     

Surface polarity of cellulose derivates observed by coumarin 151 and 153 as solvatochromic and fluorochromic probes

Solvent‐dependent ultraviolet–visible (UV–vis) absorption and Stokes shifts including strong hydrogen‐bond‐donating (HBD) solvents such as 2,2,2‐trifluoroethanol and 1,1,1,3,3,3‐hexafluoro‐2‐propanol of two coumarine dyes (Co 151 and Co 153) were analyzed with multiple‐square analyses of linear solvation energy relationships and the Kamlet–Taft solvent parameter set to α (HBD capacity), β (hydrogen‐bond‐accepting capacity), and π* (dipolarity/polarizability). The UV–vis absorption and emission spectra of Co 151 and Co 153 were measured when adsorbed on various polysaccharides such as different cellulose batches, carboxymethylcelluloses with different degrees of substitution, and chitine. As a result of this evaluation, Co 153 is recommended as an alternative UV–vis probe for evaluating the dipolarity/polarizability of cellulose and cellulose derivates. Multiple adsorption of Co 153 on Linters cellulose took place indicating a wide‐surface polarity distribution, which makes the determination of a rigid polarity parameter questionable. Thus, fluorescence measurements of adsorbed Co 153 are suitable to detect inhomogenities on a surface but not for the determination of empirical polarity parameters. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1210–1218, 2003     

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     

Self‐curable polyester by a reaction of glycidol with maleic anhydride

The controlled reaction of equimolar quantities of maleic anhydride and glycidol in dimethoxyethane gives soluble polyesters with one hydroxyl group in each repeating unit. The reaction proceeds with stepwise ring opening of the components and gives highly viscous clear solutions in relatively short periods. In the first step, monomaleate ester formation takes place around 80 °C. The ring opening of the oxirane group is the second step, and it occurs at 120 °C. The overall reaction is the formation of soluble polyesters with moderate molecular weights (6000–18,000), without the elimination of water. The soluble polyesters can be crosslinked tightly by direct heating at 190 °C without additional vinyl monomer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2549–2555, 2003     

Dispersion and distribution of organically modified montmorillonite in nylon‐66 matrix

Nylon‐66 nanocomposites were prepared by melt‐compounding nylon‐66 with an alkyl ammonium surfactant pretreated montmorillonite (MMT). The thermal stability of the organic MMT powders was measured by thermogravimetric analysis. The decomposition of the surfactant on the MMT occurred from 200 to 500 °C. The low onset decomposition temperature of the organic MMT is one shortcoming when it is used to prepare polymer nanocomposites at high melt‐compounding temperatures. To provide greater property enhancement and better thermal stability of the polymer/MMT nanocomposites, it is necessary to develop MMT modified with more thermally stable surfactants. The dispersion and spatial distribution of the organic MMT layers in the nylon‐66 matrix were characterized by X‐ray diffraction. The organic MMT layers were exfoliated but not randomly dispersed in the nylon‐66 matrix. A model was proposed to describe the spatial distribution of the organic MMT layers in an injection‐molded rectangular bar of nylon‐66/organic MMT nanocomposites. Most organic MMT layers were oriented in the injection‐molding direction. Layers near the four surfaces of the bar were parallel to their corresponding surfaces; whereas those in the bulk differed from the near‐surface layers and rotated themselves about the injection‐molding direction. The influence of the spatial distribution of the organic MMT on crystallization of nylon‐66 was also investigated. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1234–1243, 2003     

Controlled/living polymerization of 2‐(diethylamino)ethyl methacrylate and its block copolymer with tert‐butyl methacrylate by atom transfer radical polymerization

Polymerization of 2‐(diethylamino)ethyl methacrylate (DEAEMA) via homogeneous atom transfer radical polymerization under various reaction conditions is described. The effects of the initiators and solvents were examined. With 1,1,4,7,10,10‐hexamethyl triethylenetetramine/copper(I) chloride/p‐toluenesulfonyl chloride as the ligand/catalyst/initiator system in methanol, poly(DEAEMA) with a polydispersity index as low as 1.07 was synthesized. Kinetic studies demonstrated the polymerization was very well controlled and exhibited the living characteristic of the process. Well‐defined block copolymers of DEAEMA and tert‐butyl methacrylate (tBMA) were successfully synthesized. The copolymers could be synthesized with equally good results by starting with either p(DEAEMA) or p(tBMA) as the macroinitiators. However, only the macroinitiators terminated with chlorine should be used. The corresponding macroinitiators with bromine as a transferable group did not yield well‐defined copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2688–2695, 2003     

Annealing behavior of gel‐spun polyethylene fibers at temperatures lower than needed for significant shrinkage

The annealing at 373 K of ultrastrong, gel‐spun polyethylene (PE) has been studied. At this temperature, the fibers show no significant shrinkage. Still, a significant decrease in the mechanical properties is observed. The fibers have been analyzed with differential scanning calorimetry (DSC), temperature‐modulated differential scanning calorimetry (TMDSC), atomic force microscopy (AFM), and small‐angle X‐ray scattering (SAXS). During the annealing, the glass transition of the intermediate phase is exceeded, as shown by DSC. When split for structure analysis by AFM, the annealed fibers undergo plastic deformation around the base fibrils instead of brittle fracture. The quasi‐isothermal TMDSC experiments are compared to the minor structural changes seen with SAXS and AFM. The loss of performance of the PE fibers at 373 K is suggested to be caused by the oriented intermediate phase, and not by major changes in the structure or morphology. The overall metastable, semicrystalline structure is shown by TMDSC to posses local regions that can melt reversibly. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 403–417, 2003     

On the number of full levels in tries

We study the asymptotic distribution of the fill‐up level in a binary trie built over n independent strings generated by a biased memoryless source. The fill‐up level is the number of full levels in a tree. A level is full if it contains the maximum allowable number of nodes (e.g., in a binary tree level k can have up to 2^k nodes). The fill‐up level finds many interesting applications, e.g., in the internet IP lookup problem and in the analysis of level compressed tries (LC tries). In this paper, we present a complete asymptotic characterization of the fill‐up distribution. In particular, we prove that this distribution concentrates on one or two points around the most probably value k = ?log_1/qn ? log log log n + 1 + log log(p/q)?, where p > q = 1 ? p is the probability of generating the more likely symbol (while q = 1 ? p is the probability of the less likely symbol). We derive our results by analytic methods such as generating functions, Mellin transform, the saddle point method, and analytic depoissonization. We also present some numerical verification of our results. © 2004 Wiley Periodicals, Inc. Random Struct. Alg., 2004     

Periodic solutions of nonlinear impulsive differential inclusions with constraints

In this paper we obtain the existence of periodic solutions for nonlinear ``invariance' problems monitored by impulsive differential inclusions subject to impulse effects.