Synthesis and characterization of poly(higher‐α‐olefin)s with a nickel(α‐diimine)/methylaluminoxane catalyst system: Effect of chain running on the polymer properties

Homopolymerization of octadecene‐1 at different reaction conditions has been studied. Significant chain running can be seen at higher polymerization temperatures. Interestingly, insertion of octadecene‐1 into a sterically hindered nickel‐cation/carbon (secondary) bond is observed. The microstructure of the polymer was established using NMR spectroscopy. The effects of chain running on polymer melting, crystallization behavior, and dynamic mechanical thermal properties were studied using DSC and DMTA. The extent of chain running (i.e., 2,ω‐, 1,ω‐enchainments) decreases with an increase in the carbon number of α‐olefins. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 191–210, 2007     

Protonation constant of salicylidene (N-benzoyl)glycyl hydrazone and its coordination behaviour towards some bivalent metal ions

Protonation constant of an unsymmetrical Schiff base, salicylidene(N-benzoyl)glycyl hydrazone (SalBzGH), and formation constants of its complexes have been determined potentiometrically at different temperatures in aqueous dioxane medium. Complexes of SalBzGH with VO(IV), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) have been prepared. Elemental analyses, pH-metric, molar conductance, magnetic susceptibility, electronic, IR, ESR, XRD (powder) and NMR studies have been carried out to study the coordination behaviour of SalBzGH toward these metal ions. pH-metric and 1H NMR studies show the presence of two dissociable protons in the ligand. IR and NMR spectra suggest the tridentate nature of the ligand, coordinating as a uninegative species in the Mn(II) complex and as a dinegative species in all the other complexes. Presence of two different conformers of the ligand at room temperature and stabilization of a single conformer upon complex formation have been established from¹H NMR spectra of the metal-free ligand, Zn(II) and Hg(II) complexes recorded at 296 K. Electronic and ESR spectra indicate highly distorted tetragonal geometry for VO(IV) and Cu(II) complexes. XRD powder patterns of the Zn(II) complexes are indexed for an orthorhombic crystal system.     

Synthesis and nuclear magnetic resonance analysis of starch‐g‐poly(1,4‐dioxan‐2‐one) copolymers

A new biodegradable starch graft copolymer, starch‐g‐poly(1,4‐dioxan‐2‐one), was synthesized through the ring‐opening graft polymerization of 1,4‐dioxan‐2‐one onto a starch backbone. The grafting reactions were conducted with various 1,4‐dioxan‐2‐one/starch feed ratios to obtain starch‐g‐poly(1,4‐dioxan‐2‐one) copolymers with various poly(1,4‐dioxan‐2‐one) graft structures. The microstructure of starch‐g‐poly(1,4‐dioxan‐2‐one) was characterized in detail with one‐ and two‐dimensional NMR spectroscopy. The effect of the feed composition on the resulting microstructure of starch‐g‐poly(1,4‐dioxan‐2‐one) was investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3417–3422, 2004     

Model-Free Analysis of Mixtures by NMR Using Blind Source Separation

The concept of blind source separation is described and examples of its use in 1D and 2D NMR spectroscopy are presented. The goal of this data processing method is to extract the spectra of components molecules when only mixtures are available.     

Multinuclear magnetic resonance study of some mesoionic oxatriazoles containing nitrogenous exocyclic groups

¹H,¹³C,¹⁴N and¹⁵N NMR measurements are reported for four mesoionic 1-oxa-2, 3, 4-triazoles containing exocyclic nitrogenous groups. The NMR signal assignments are discussed and compared with those previously published for some corresponding oxatriazoles. The results obtained support the proposed cyclic mesoionic structures for the compounds studied. The questions of possible charge delocalization and valence tautomerism are addressed. Compound with N^– H as a exocyclic group (Fig. 1) is found to be relatively unstable, this is attributed to proton migration in the corresponding non-cyclic form of this molecule.Published in Khimiya Geterotsikiicheskikh Soedinenii, No. 9, pp. 1260–1263, September, 1995.     

Dimensionally and thermally stable polymer,containing disordered graphitic structure and adamantane

In an attempt to develop a low‐k interlayer dielectric, adamantane‐diphenyldiethynyl moiety containing oligomer is prepared. Oligomerization of 1,3,5,7‐tetrakis[3/4‐ethynylphenyl]adamantane ( 4 ) is accomplished by a Glaser–Hay oxidative coupling with 1,3,5‐triethynylbenzene and phenylacetylene end‐capping agent. The CHCl₃ soluble oligomer is then thermally treated by step‐curing at 200, 300, 380, and 450 °C for 30 min at each temperature under nitrogen flow to render a shiny void‐free black polymer. TGA analysis indicates that the polymer is stable under nitrogen up to 500 °C with a marginal decomposition up to 800 °C. Solid‐state ¹³C NMR, Raman scattering, and FTIR are used to characterize the structure of the polymer. The polymer consists of amorphous carbon networks with the adamantane moieties and nanosized graphitic regions (clusters), which are generated from the thermal crosslinking of the diphenyldiethynyl units. It shows a remarkably low linear coefficient of thermal expansion (～25 ppm/°C), presumably due to the presence of the disordered graphitic structure. Its high density (～1.21 g/cm³), refractive index (～1.80 at 632 nm), and Young's modulus (～17.0 GPa) are also consistent with the interpretation. This study reveals important details about the effect of microscopic structure on the macroscopic properties of the highly crosslinked polymer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6909–6925, 2006     

Synthesis and characterization of functional gradient copolymers of allyl methacrylate and butyl acrylate

Functional spontaneous gradient copolymers of allyl methacrylate (A) and butyl acrylate (B) were synthesized via atom transfer radical polymerization. The copolymerization reactions were carried out in toluene solutions at 100 °C with methyl 2‐bromopropionate as the initiator and copper bromide with N,N,N′,N″,N″‐pentamethyldiethylenetriamine as the catalyst system. Different aspects of the statistical reaction copolymerizations, such as the kinetic behavior, crosslinking density, and gel fraction, were studied. The gel data were compared with Flory's gelation theory, and the sol fractions of the synthesized copolymers were characterized by size exclusion chromatography and nuclear magnetic resonance spectroscopy. The copolymer composition, demonstrating the gradient character of the copolymers, and the microstructure were analyzed. The experimental data agreed well with data calculated with the Mayo–Lewis terminal model and Bernoullian statistics, with monomer reactivity ratios of 2.58 ± 0.37 and 0.51 ± 0.05 for A and B, respectively, an isotacticity parameter for A of 0.24, and a coisotacticity parameter of 0.33. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5304–5315, 2006     

Liquid crystal lens with focus movable in focal plane

A liquid crystal lens with focus movable in the focal plane is reported. There are three electrodes in the cell. One electrode with a hole in the center is divided into four subelectrodes. The potential of each subelectrode is adjusted to produce a desired asymmetrical phase transformation resulting in off-axis movement of the focus. The potential of another electrode is adjusted to maintain the focus in the focal plane. Movements of the focus in three directions in the focal plane are demonstrated experimentally, and off-axis movement as large as approximately 800 μm is realized.     

Electro-optical performance of polymer stabilized cholesteric texture cell: The influence of chiral dopant and monomer concentration

Reverse-mode polymer stabilized cholesteric texture (PSCT) cells with various chiral dopant and monomer concentrations were fabricated. Experimental results indicate that the chiral dopant concentration and the monomer concentration significantly influence the threshold voltage and hysteresis of the cells. The chiral dopant and monomer deform the hysteresis loop. Increasing the monomer concentration reduces the width of the hysteresis loop of the reverse-mode PSCT cell.     

Fluorinated,crosslinkable terpolymers based on vinylidene fluoride and bearing sulfonic acid side groups for fuel‐cell membranes

The radical terpolymerization of 8‐bromo‐1H,1H,2H‐perfluorooct‐1‐ene with vinylidene fluoride (VDF) and perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene) sulfonyl fluoride is presented. Changing the feed compositions of these three fluorinated comonomers enabled us to obtain different random‐type poly[vinylidene fluoride‐ter‐perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene) sulfonyl fluoride‐ter‐8‐bromo‐1H,1H,2H‐perfluorooct‐1‐ene] terpolymers containing various sulfonyl fluoride and brominated side groups. Yields higher than 70% were reached in all cases. The hydrolysis of the sulfonyl fluoride group into the ? SO₃Li function in the presence of lithium carbonate was quantitatively achieved without the content of VDF being affected, and so dehydrofluorination of the VDF base unit was avoided. These original terpolymers were then crosslinked via dangling bromine atoms in the presence of a peroxide/triallyl isocyanurate system, which produced films insoluble in organic solvents such as acetone and dimethylformamide (which totally dissolved uncured terpolymers). The acidification of ? SO₃Li into the ? SO₃H function enabled protonic membranes to be obtained. The thermal stabilities of the crosslinked materials were higher than those of the uncured terpolymers, and their electrochemical performances were investigated. According to the contents of the sulfonic acid side functions, the ion‐exchange capacities ranged from 0.6 to 1.5 mequiv of H⁺/g, whereas the water uptake and conductivities ranged from 5–26% (±11%) and from 0.5 to 6.0 mS/cm, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4566–4578, 2006