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2.
Jeroen J. L. M. Cornelissen W. Sander Graswinckel Alan E. Rowan Nico A. J. M. Sommerdijk Roeland J. M. Nolte 《Journal of polymer science. Part A, Polymer chemistry》2003,41(11):1725-1736
The conformational properties of polymers derived from isocyanodipeptides have been investigated with a combination of model calculations, X‐ray diffraction, and circular dichroism spectroscopy. Depending on the configuration of the side chains, defined arrays of hydrogen bonds along the polymeric backbone are formed. This leads to a well‐defined conformation as, for example, expressed in the formation of lyotropic liquid‐crystalline phases and increased helical stability. Upon the disruption of the hydrogen bonds by a strong acid, a less well‐defined macromolecular conformation is observed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1725–1736, 2003 相似文献
3.
Gregory S. Constable Alan J. Lesser E. Bryan Coughlin 《Journal of Polymer Science.Polymer Physics》2003,41(12):1323-1333
An in situ ultrasonic spectroscopy technique was used to study the ring‐opening metathesis polymerization of dicyclopentadiene catalyzed by bis(tricyclohexylphosphine)benzylidene ruthenium dichloride. A reaction cell employing a flexible poly(ethylene terephthalate) window for pulse echo ultrasonic spectroscopy was used to monitor the polymerization. The changes in the density, wave speed, acoustic modulus, and attenuation were all simultaneously monitored. In comparison with Fourier transform infrared (FTIR) spectroscopy data, the changes in the density, velocity, and modulus only accurately measured the rate constant for the metathesis of the cyclopentyl unsaturation. The ultrasonic values were within 6% of the values determined by FTIR. The activation energy for metathesis of the cyclopentyl unsaturation was 84 kJ mol?1, following first‐order kinetics. Rate constants for the polymerization of the norbornyl unsaturation could not be determined by ultrasound. The gel point, vitrification, and qualitative information about the reaction rate could be determined from the change in the attenuation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1323–1333, 2003 相似文献
4.
Richard Kotek Kyeong Pang Ben Schmidt Alan Tonelli 《Journal of Polymer Science.Polymer Physics》2004,42(23):4247-4254
Poly(ethylene isophthalate) (PEI) was synthesized for this research with essentially a condensation polymerization of isophthalic acid and ethylene glycol catalyzed by zinc acetate and antimony trioxide. Several samples were obtained, and their characteristics were observed and compared with poly(ethylene terephthalate) (PET). The synthesized PEI samples were chemically identified by 1H NMR. Thermal analysis with differential scanning calorimetry (DSC) yielded results that indicate the samples were primarily amorphous, with a glass‐transition temperature of 55–60 °C. Molecular weights of these PEI samples were also obtained through intrinsic viscosity measurements (Mark–Houwink equation). Molecular weights varied with conditions of the polymerization, and the highest molecular weight achieved was 21,000 g/mol. Finally, the diffusion coefficient, solubility, and permeability of CO2 gas in PEI were measured and found to be substantially lower than in PET, as anticipated from their isomeric chemical structures. This is because in PET the phenyl rings are substituted in the para (1,4) positions, which allows for their facile flipping, effectively permitting gases to pass through. However, the meta‐substituted phenyl rings in PEI do not permit such ring flipping, and thus PEI may be more suitable for barrier applications. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4247–4254, 2004 相似文献
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Thin films of polystyrene (PS), poly(methyl methacrylate) (PMMA) and polystyrene-polyacrylonitrile copolymer (PS-AN), containing various embedded transition-metal complexes, have been studied by FTIR microscopy. The spatial distributions of the transition-metal carbonyl complexes throughout the thin organic polymer films have been determined by a two-dimensional IR mapping procedure. The spectral variations observed in the distribution of the metal carbonyls throughout the different polymer films are discussed. The IR data show that the technique used to prepare the organometallic-embedded thin films (viz. freeze-drying of solutions followed by hot mechanical pressing of the residues) does in general lead to homogeneous films which may eventually find industrial application, e.g. as membrane sensors for small molecules. 相似文献
7.
J. A. Ratto Paul T. Inglefield R. A. Rutowski K.-L. Li Alan Anthony Jones Ajoy K. Roy 《Journal of Polymer Science.Polymer Physics》1987,25(7):1419-1430
Carbon-13 and proton spin-lattice relaxation times were measured at two field strengths on solutions 10% by weight of two polycarbonates in C2D2Cl4 from ?20 to +120°C. The first polycarbonate is an asymmetrically substituted form with one chlorine on one of the two phenylene aromatic rings of the bisphenol unit, whereas the second polycarbonate is symmetrically substituted with two chlorines on each of the two rings. The nuclear spin relaxation data are interpreted in terms of several local motions likely in these polymers. Segmental motion was described by the Hall–Helfand correlation function. Segmental motion in the monosubstituted polycarbonate is somewhat slower than in unsubstituted polycarbonate, whereas segmental motion in the tetrasubstituted polycarbonate is considerably slower. Phenylene ring rotation is observed in unsubstituted polycarbonate and in the monosubstituted polycarbonate above 40°C. Below 40°C in the monosubstituted species, and at all temperatures in the tetrasubstituted species, ring rotation is replaced by ring libration as the predominant motion contributing to spin lattice relaxation. In addition, the rotational motion of the two types of rings in the asymmetric monosubstituted form are very similar although not identical. The substituted ring is slightly less mobile than the rings of unsubstituted polycarbonate. This indicates a strong coupling of ring motion, although the coupling leads to less than synchronous motion. Methyl group rotation is present in both polymers and is little affected by the various structural modifications. 相似文献
8.
Alan D. Potoff Bertrand L. Chamberland Lewis Katz 《Journal of solid state chemistry》1973,8(3):234-237
A single crystal study of hydrothermally prepared eight-layer BaMnO3 has been carried out which confirms the (Zhdanov notation) 121121 layer stacking scheme for the BaO3 layers. The MnO6 octahedra share faces in strings of four, and these strings are connected to each other by corner sharing. The compound has an hexagonal unit cell of dimensions a = 5.667 ± 0.003 and c = 18.738 ± 0.009 Å, probable space group . Its structure has been determined from 352 independent reflections, of which 242 were considered observed, collected manually by a counter technique and refined to a conventional R value of 0.079. 相似文献
9.
Alan R. Katritzky Scott A. Henderson Baozhen Yang 《Journal of heterocyclic chemistry》1998,35(5):1123-1159
Applications of benzotriazole methodology for the preparation of heterocyclic compounds are reviewed. The characteristic advantages of benzotriazole as a synthetic auxiliary are first briefly considered. This is followed by a summary of its use in ring synthesis in which the construction of small; five-membered; six-membered; and larger heterocyclic rings using benzotriazole methodology are each examined separately. Finally, consideration of the use of benzotriazole in the ring annulation - particularly benzannulation - of heterocycles. Subsequent sections deal with the introduction of substituents into aromatic heterocycles; the ring substitution of saturated heterocycles; and benzotriazole assisted modification of heterocyclic substituents. The present review supplements a recent comprehensive review of benzotriazole chemistry [1] which covers the literature through 1996. 相似文献
10.
Tetra-n-butylammonium hexachloroplatinate (IV) reacts with lithium methyl/lithium iodide in ether to give a solution containing lithium hexamethylplatinate (IV). With lithium methyl/lithium bromide in ether however, tetrabutylammonium hexamethylplatinate (IV) is precipitated together with lithium halides. Solid [Bu4N)2[Pt(Ch3)6] is stable under nitrogen at room temperature, but ether solutions of [Pt(Ch3)6]2- decompose in a few minutes at room temperature in the absence of excess lithium methyl. 相似文献