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  • Polymer and Materials Science  (20)
  • 1995-1999  (20)
  • 1
    Electronic Resource
    Electronic Resource
    On the mechanical properties of poly(ethylene terephthalate). Force-field parametrization and conformational analysis for the prediction of the crystal moduli (1996)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 963-973 
    Details
    ISSN: 0887-6266
    Keywords: poly(ethylene terephthalate) ; crystal modulus ; mechanical properties ; force-field parametrization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A force-field suitable for the calculation of the mechanical properties of poly(ethylene terephthalate) and their relation with the molecular structure of the polymer has been developed. The force-field parameters were derived from quantum mechanical AM1 calculations and tested against thermodynamic and vibrational spectroscopy data available for a set of closely related small molecules. The crystal moduli of the two solid phases known for poly(ethylene terephthalate) were estimated by means of this new force-field considering both the isolated chain and the chain within the unit cell. Results were qualitatively consistent with reported x-ray data showing that the triclinic crystal form is stiffer than the mesomorphic phase provided that sample heterogeneities were taken into account. Although overestimated moduli resulted for both cases, divergences with experimental values were found to be slighter than those obtained by other theoretical methods. © 1996 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Rheology of rodrun liquid-crystalline polymers (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 253-263 
    Details
    ISSN: 0887-6266
    Keywords: thermotropics ; dynamic viscoelasticity ; relaxation peaks ; gelation ; crystallization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rheological characterization of two commercial thermotropic liquid crystalline polymers based on poly(ethylene terephthalate) (PET) and para-hydroxybenzoic acid (PHB) is carried out. The thermal transitions determined by DMTA are explained by the random character of these copolyesters, in comparison with non-random copolyesters synthesized by Jackson and Kuhfuss. The evolution of the dynamic viscoelastic functions with time in the nematic state is concave in shape for the 20%PET/80%PHB copolymer, a result that leads us to treat this system as a suspension of solid spheres (unmolten crystals) where the volume fraction of crystals increases with time according to an Avrami equation. The response of 40%PET/60%PHB copolymer is similar to a chemical or physical gelation and the hypothesis that the polydomain structure gives rise to a network is considered. Continuous flow, time-independent viscosity results reveal the existence of a three-region flow curve for 40%PET/60%PHB copolymer, but a Newtonian zone followed by a shear thinning region for 20%PET/80%PHB sample. At high temperatures the isotropization of the samples leads to a very strong decrease of the activation energy of flow, which becomes zero for 40%PET/60%PHB. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 253-263, 1998
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Deorientation effects on extrusion rheometry of a thermotropic copolyester (1997)
    Weinheim : Wiley-Blackwell
    Macromolecular Rapid Communications 18 (1997), S. 591-599 
    Details
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Extrusion rheometry experiments with a commercial thermotropic liquid crystalline copolyester show concave Bagley plots and convex pressure profiles. A loss of the orientation produced at the entrance of the capillary and the slit can explain these non-linearities. Assuming that the order parameter, S, relaxes exponentially with time, the Doi-Edwards model for the shear flow of rod-like polymers is used to adjust experimental data.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/marc.1997.030180709
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  • 4
    Electronic Resource
    Electronic Resource
    The effect of mixing time on the morphology and physical properties of liquid crystalline polymer based blends (1995)
    Weinheim : Wiley-Blackwell
    Macromolecular Rapid Communications 16 (1995), S. 417-424 
    Details
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rheological and thermal analysis results of blends of a thermotropic copolyesteramide and polyarylate of bisphenol A depend on the thermo-mechanical treatment during mixing. The changes observed as mixing time increases are the following: (a) melt viscosity and loss factor increase, (b) glass transition temperature decreases. The morphological analysis of the blends shows the inability of the treated blends to form an oriented liquid crystalline polymer (LCP) phase, which explains the observed viscoelastic properties.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/marc.1995.030160603
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  • 5
    Electronic Resource
    Electronic Resource
    Poly(α-butyl β-L-aspartate): A second alkoxycarbonyl nylon-3 derivative in helical conformation (1995)
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 196 (1995), S. 253-268 
    Details
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A structural study was carried out on poly(α-butyl β-L-aspartate), which is a stereoregular nylon-3 derivative with an alkoxycarbonyl group attached to the β-carbon of the main-chain repeating unit. Two crystal forms, namely hexagonal and tetragonal, made of 13/4 and 4/1 helices, respectively, and bearing a structural resemblance to the polypeptide α-helix, were characterized by X-ray diffraction. Though these forms are basically identical to those previously reported for poly(α-isobutyl β-L-aspartate), the crystal transition from hexagonal to tetragonal known to take place in this polymer by effect of heating, was not observed in the present case. Modeling calculations revealed that although similar conformations are favoured for the two polymers in both crystal forms, the relative stability of the 13/4 helix to the 4/1 helix was found to be significantly reduced in the case of the butyl derivative. The presence of helical conformation in solution has been evidenced by both 1H NMR and circular dichroism and the helix-coil transition promoted by acids was investigated by means of these techniques.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1995.021960117
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  • 6
    Electronic Resource
    Electronic Resource
    Dynamic viscoelastic properties of blends of poly(ethylene-co-vinyl acetate) and a modified starch (1995)
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 196 (1995), S. 3133-3142 
    Details
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report dynamic viscoelastic measurements of a series of binary blends of hydroxyethyl ether of starch and ethylene-vinyl acetate copolymer (EVA), which are correlated with the granular arrangement of the starch derivative within the EVA matrix and the adhesion between both phases, studied by scanning electron microscopy. The rheological properties are similar to those of polymers filled with solid spheres, although we found a minimum in the Newtonian viscosity and a maximum in the elasticity at low starch derivative concentrations, which have been attributed to a change in the density of chain entanglements.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1995.021961005
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  • 7
    Electronic Resource
    Electronic Resource
    Synthesis of stereoregular polygluconamides from D-glucose and D-glucosamine (1995)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 299-305 
    Details
    ISSN: 0887-624X
    Keywords: polygluconamides ; stereoregular polyamides ; stereoregular nylons ; chiral polyamides ; chiral nylons ; aminoaldonic acids ; sugar polyamides ; carbohydrate monomers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two stereoregular polygluconamides, one (3) of polypeptide-type and the other (16) being a polycaproamide containing four stereocenters in the main chain of the repeating unit, have been prepared from D-glucosamine and D-glucose, respectively. The new polyamides were characterized by elemental analysis, and IR, 1H- and 13C-NMR spectroscopies. The molecular weights for 3 and 16 were estimated as 25,000 and 67,000, respectively, on the basis of viscosimetric measurements. Both polyamides display high optical activity; they are highly hydrophilic and readily soluble in water as well as in a variety of organic solvents including chloroform. Polyamide 16 is highly crystalline and yields resistant films with spherulitic texture. © 1995 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1995.080330211
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  • 8
    Electronic Resource
    Electronic Resource
    Poly(α-isobutyl-β-D,L-aspartate)s: Polymerization effects on configuration and crystal structure of the stereocopolymers (1996)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1959-1968 
    Details
    ISSN: 0887-624X
    Keywords: optically active polyamides ; helical nylons ; nylon-3 ; poly(β-amide)s ; poly(β-aspartate)s ; poly(α-isobutyl-β-L-aspartate) ; stereoselective polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Different polymerization methods were used for the preparation of poly(α-isobutyl-β-D,L-aspartate)s containing variable ratios of D- to L-aspartic units and the microstructure of the resulting stereocopolymers was examined by NMR spectroscopy. Anionic ring-opening polymerization in solution of enantiomeric mixtures of α-isobutyl-β-D- and L-aspartalactams was found to proceed stereoselectively rendering block copolymers composed of right- and left-handed helical sequences. Configurationally statistical copolymers were obtained instead when the enantiomeric lactam mixtures were polymerized in the bulk. Random stereocopolymers could be prepared also by polycondensation in solution of mixtures of pentachlorophenyl α-isobutyl-β-D and -L-aspartates. The conformation in solution and the crystal structure of the resulting copolymers were investigated in connection with their stereochemical configuration and these features compared with those displayed by optically pure poly(α-isobutyl-β-L-aspartate). © 1996 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    A theoretical study of the comonomer effect in the ethylene polymerization with zirconocene catalytic systems (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1157-1167 
    Details
    ISSN: 0887-624X
    Keywords: zirconocene catalysts ; ethylene ; 1-hexene ; copolymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The PM3(tm) semiempirical method has been used to optimize the structures for the reactants and transition states of the first and second ethylene insertion processes into zirconocene catalytic systems. The results obtained for these reactions are compared with calculations published in the literature performed at different ab-initio theoretical levels. The agreement between our calculations and those reported in the literature is satisfactory. Taking advantage of the reduced computational effort required in semiempirical calculations two additional processes related with the so-called comonomer effect were also studied: ethylene/1-hexene copolymerization, and chain termination reaction, both in the homopolymerization and in copolymerization of ethylene with 1-hexene comonomer. The calculated activation energies support some experimental findings such as the higher polymerization activities in the presence of comonomers and also the molecular weight reduction of the copolymers due to the more favorable β-elimination reactions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1157-1167, 1998
    Additional Material: 3 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Effect of the side group on the helix-forming tendency of α-alkyl-β-L-aspartamyl residues (1997)
    New York : Wiley-Blackwell
    Biopolymers 41 (1997), S. 721-729 
    Details
    ISSN: 0006-3525
    Keywords: Poly(β-L-aspartate)s ; helical conformations ; quantum mechanical calculations ; cooperative energy effects ; helix stability ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational preferences of the monomeric units of a series of poly(α-alkyl-β-L-aspartate)s were examined by quantum mechanical calculations. α-Alkyl-β-aspartamyl m-oligopeptides with a number of residues m ranging from 1 to 7 and arranged in the conformations experimentally observed for their corresponding polymers were computed. Both their total relative energies and their cooperative energy differences were compared as a function of the length of the oligopeptide and the nature of the alkyl side group. Results revealed that the 13/4 helical arrangement is the most stable structure for the isolated polymer chain for any side group, although a 17/4 helix becomes favored in the case of methyl and ethyl groups due to the packing effects. On the other hand, the stability of the 4/1 helix appears to be the preferred conformation for side groups with a branched constitution. © 1997 John Wiley & Sons, Inc. Biopoly 41: 721-729, 1997
    Additional Material: 5 Ill.
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