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  • Polymer and Materials Science  (21)
  • 1995-1999  (20)
  • 1945-1949  (1)
  • 1
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 2439-2454 
    ISSN: 0887-624X
    Schlagwort(e): radiation ; nitrile rubber ; NMR ; ESR ; radicals ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The mechanism of radiation-induced structural changes in nitrile rubber with different acrylonitrile contents were investigated by ESR, NMR, and FTIR. To investigate new structures solid-state NMR methods had to be used due to crosslinking of the irradiated rubbers, and higher probe temperatures were used to obtain better resolution. The radicals generated on the acrylonitrile groups were found to abstract hydrogen from the adjacent butadiene units resulting in the formation of allylic radicals. These allylic radicals reacted to form intermolecular crosslinks and cyclisation. Cyclisation of the butadiene units were found to occur in the initial stages of the irradiation. Radiation yields of radicals increased with acrylonitrile content from 1.42, 1.58, to 2.42 for 18, 30, and 45% acrylonitrile rubbers. The radiation yields for intermolecular crosslinking were higher in rubbers with higher acrylonitrile contents, giving G values of 17.8, 21.3, and 24.5 for 18, 30, and 45% acrylonitrile rubbers, respectively. However, the crosslink clustering was found to be less in the rubbers with a higher acrylonitrile content. © 1996 John Wiley & Sons, Inc.
    Zusätzliches Material: 15 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1627-1633 
    ISSN: 0887-624X
    Schlagwort(e): hyperbranched macromolecule ; polyester ; focal point groups ; intramolecular cyclization ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The effect of monomer structure and catalyst on the synthesis of hyperbranched polyesters based on 4,4-(4′-hydroxyphenyl)pentanoic acid has been examined. The nature of the ester group and the catalyst have a significant effect on the molecular weight of the hyperbranched polyester but do not effect the degree of branching for these materials. The fate of the single ester group at the focal point of these hyperbranched macromolecules is probed by the synthesis and polymerization of 13C labeled methyl 4,4-(4′-hydroxyphenyl)pentanoate. Comparison of the molecular weights determined by 1H- or 13C-NMR spectra with those determined by osmometry suggest that intramolecular cyclization does not occur to a significant extent in these systems. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1627-1633, 1997
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 971-984 
    ISSN: 0887-624X
    Schlagwort(e): radiation ; polyisobutylene ; NMR ; GC/MS ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: GC, GC/MS, GPC, and Solution NMR spectra were used to study the γ radiolysis of polyisobutylene (PIB) in vacuum to different total doses (0-900 kGy) and at different temperatures (77-423 K). NMR spectra show a large number of new resonances with relatively narrow line widths, and a variety of NMR techniques have been employed to determine and quantify the structures associated with these new resonances. Chemical shift assignments were made by comparison with those for small molecule model compounds and predictions based upon calculations according to several different schemes. Chain-end structures have been proposed that account well for the majority of the new resonances, all being the result of an initial chain scission reaction initiated by the radiation. These assignments support some previous proposals for the mechanism of radiation degradation of polyisobutylene and exclude others. For example, NMR provides no evidence for the formation of ethyl chain ends and some of the main chain unsaturated structures previously proposed. NMR also indicate that at higher doses the chain end products formed during initial stages undergo secondary reactions. GC/MS data show the formation of oligomers during irradiation, which may be due to a backbitting mechanism. © 1996 John Wiley & Sons, Inc.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1153-1165 
    ISSN: 0887-6266
    Schlagwort(e): even-odd nylons ; lamellar crystals ; structure ; hydrogen-bonding schemes ; Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Nylon 6 9 has been shown to have structures with interchain hydrogen bonds in both two and in three directions. Chain-folded lamellar crystals were studied using transmission electron microscopy and sedimented crystal mats and uniaxially oriented fibers studied by X-ray diffraction. The principal room-temperature structure shows the two characteristic (interchain) diffraction signals at spacings of 0.43 and 0.38 nm, typical of α-phase nylons; however, nylon 6 9 is unable to form the α-phase hydrogen-bonded sheets without serious distortion of the all-trans polymeric backbone. Our structure has c and c* noncoincident and two directions of hydrogen bonding. Optimum hydrogen bonding can only occur if consecutive pairs of amide units alternate between two crystallographic planes. The salient features of our model offer a possible universal solution for the crystalline state of all odd-even nylons. The nylon 6 9 room-temperature structure has a C-centered monoclinic unit cell (β = 108°) with the hydrogen bonds along the C-face diagonals; this structure bears a similarity to that recently proposed for nylons 6 5 and X3. On heating nylon 6 9 lamellar crystals and fibers, the two characteristic diffraction signals converge and meet at 0.42 nm at the Brill temperature, TB · TB for nylon 6 9 lamellar crystals is slightly below the melting point (Tm), whereas TB for nylon 6 9 fibers is ≅ 100°C below Tm. Above TB, nylon 6 9 has a hexagonal unit cell; the alkane segments exist in a mobile phase and equivalent hydrogen bonds populate the three principal (hexagonal) directions. A structure with perturbed hexagonal symmetry, which bears a resemblance to the reported γ-phase for nylons, can be obtained by quenching from the crystalline growth phase (above TB) to room temperature. We propose that this structure is a “quenched-in” perturbed form of the nylon 6 9 high-temperature hexagonal phase and has interchain hydrogen bonds in all three principal crystallographic directions. In this respect it differs importantly from the γ-phase models. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1153-1165, 1998
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2981-3000 
    ISSN: 0887-6266
    Schlagwort(e): sorption ; diffusion ; acetone ; poly(ethylene terephthalate) ; poly(ethylene 2,6-naphthalate) ; copolymers ; positron annihilation lifetime spectroscopy ; infrared spectroscopy ; Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Random copolymers of poly(ethylene terephthalate) (PET) and poly(ethylene 2,6-naphthalate) (PEN) were synthesized by melt condensation. In a series of thin, solvent cast films of varying PEN content, acetone diffusivity and solubility were determined at 35°C and an acetone pressure of 5.4 cm Hg. The kinetics of acetone sorption in the copolymer films are well described by a Fickian model. Both solubility and diffusivity decrease with increasing PEN content. The acetone diffusion coefficient decreases 93% from PET to PET/85PEN, a copolymer in which 85 weight percent of the dimethyl terephthalate in PET has been replace by dimethyl naphthalate 2,6-dicarboxylate. The acetone solubility coefficient in the amorphous regions of the polymer decreases by approximately a factor of two over the same composition range. The glass/rubber transition temperatures of these materials rise monotonically with increasing PEN content. Copolymers containing 20 to 80 wt % PEN are amorphous. Samples with 〈20% or 〉80% PEN contain measurable levels of crystallinity. Estimated fractional free volume in the amorphous regions of these samples is lower in the copolymers than in either of the homopolymers. Relative free volume as probed by positron annihilation lifetime spectroscopy (PALS) decreases systematically with increasing PEN content. Acetone diffusion coefficients correlate well with PALS results. Infrared spectroscopy suggests an increase in the fraction of ethylene glycol units in the trans conformation in the amorphous phase as the concentration of PEN in the copolymer increases. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2981-3000, 1998
    Zusätzliches Material: 14 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 6
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 675-688 
    ISSN: 0887-6266
    Schlagwort(e): nylons ; lamellar crystals ; diffraction ; Brill transition temperatures ; Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Four members of the even-even nylon 2 Y series, for Y = 6, 8, 10, and 12, have been crystallized in the form of chain-folded lamellar single crystals from 1,4-butanediol and studied by transmission electron microscopy (imaging and diffraction), x-ray diffraction, and thermal analysis. The structures of these 2 Y nylons are different from those of nylon 6 6 and many other even-even nylons. At room temperature, two strong diffraction signals are observed at spacings 0.42 and 0.39 nm, respectively; these values differ from the 0.44 and 0.37 nm diffraction signals observed for nylon 6 6 and most even-even nylons at ambient temperature. Detailed analyses of the diffraction patterns show that all these 2 Y nylons have triclinic unit cells. The diamine alkane segments of 2 Y nylons are too short to sustain chain folds; thus, the chain folds must be in the diacid alkane segments in all cases. On heating the crystals from room temperature to the melt, the triclinic structures transform into pseudohexagonal structures and the two diffraction signals meet at the Brill transition temperature which occurs significantly below the melting point. The room temperature structures of these 2 Y nylons are similar to the unit cell of nylon 6 6 at elevated temperature, but below its Brill temperature. The room temperature structures and behavior on heating of the nylon 2 Y family is noticeably different from that of the even-even nylon X 4 family, although the only difference between these families of polyamides is the relative disposition of the amide groups within the chains. The results show that in order to understand the structure, behavior and properties of crystalline nylons, especially as a function of temperature, the detailed stereochemistry needs to be taken into account. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 675-688, 1997
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 7
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2849-2863 
    ISSN: 0887-6266
    Schlagwort(e): nylon oligoamides ; new crystal structure ; morphology ; crystallization ; Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Three-amide oligomers of nylon 6 and nylon 6 6 have been investigated using electron microscopy (imaging and diffraction), X-ray diffraction, and computational modeling. A new crystal structure has been discovered for the three-amide oligomer of nylon 6. This material crystallizes from chloroform/dodecane solutions into an unfolded crystal form that has progressively sheared hydrogen bonding in two directions between polar (unidirectional) chains. This structure is quite different from the usual room temperature α-phase structure of chain-folded nylon 6 crystals, in which alternatingly sheared hydrogen bonding occurs between chains of opposite polarity in only one direction. The occurrence of this new structure illustrates the extent to which progressively sheared hydrogen bonding is preferred over alternatingly sheared hydrogen bonding. Indeed, the progressive hydrogen bonding scheme occurs in the three-amide nylon 6 material even though it requires a disruption to the lowest potential energy all-trans conformation of the chain backbone, and requires all the chains in each hydrogen-bonded layer to be aligned in the same direction. We believe the presence of chain folding, which necessarily incorporates adjacent chains of opposite polarity into the crystal structure, prevents the formation of this new crystal structure in the nylon 6 polymer. In contrast, the three-amide nylon 6 6 crystal structure is analogous to the polymeric nylon 6 6 α-phase structure, found in both fibers and chain-folded crystals, and consists of progressive hydrogen-bonded sheets which stack with a progressive shear. In both structures, the molecules (≈ 3 nm in length) form smectic C-like layers with well-orchestrated stacking of 2.2 nm to form a three-dimensional crystal. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2849-2863, 1998
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 8
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2329-2353 
    ISSN: 0887-6266
    Schlagwort(e): phase separation ; polyolefins ; neutron scattering ; random copolymers ; thermodynamics ; Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Saturated hydrocarbon polymers may be differentiated by the relative amount and placement of methylene, methyl, methine, and quaternary carbon moieties. While it has been known or suspected for some time that polyolefins of conventional molecular weight (Mw ≈ 100 kg/mol) with dissimilar chemical microstructures are most often immiscible in the liquid state, recent experiments with binary blends of model polyolefins have increased greatly our understanding of thermodynamic interactions between unlike chains. Model systems with methyl (-CH3) and ethyl (-C2H5) short-chain branches give results, expressed as the Flory-Huggins interaction parameter χ, that are nearly universal; repulsive interactions (χ 〉 0) are more pronounced at low temperatures, leading to liquid-liquid phase separation at an upper critical solution temperature. Phase behavior of more complex systems (with distributions of chain microstructures and/or molecular weight) is generally consistent with predictions from model systems. An interesting exception is from work at Bristol on blends of lightly branched ethylene - α-olefin copolymers with unbranched polyethylene as the minority species. Here the presence of two liquid phases is inferred under conditions not expected from model studies; effects of copolymer composition and molecular weight are also unusual. Recent theoretical work points to the importance of chain stiffness (established by short-chain branching) in determining the thermodynamics of model blends. Nonrandom mixing of chains with different stiffness gives rise to an enthalpic χ, which may be negative under certain conditions. Other limitations of the Flory-Huggins approach to describing blend energetics are considered. At present there is no theoretical basis for liquid-liquid phase separation reported by the Bristol group. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2329-2353, 1997
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 9
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1775-1791 
    ISSN: 0887-6266
    Schlagwort(e): n-alkanes ; crystallization from solution ; differential scanning calorimetry ; dissolution ; crystallization rate inversion ; Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The newly available, strictly uniform n-alkane, C246H494, has been crystallized from dilute solution. The rates of crystallization were followed by differential scanning calorimetry (DSC) as a function of temperature. Two pronounced rate inversions were registered. The dissolution temperatures of the crystals formed show a sharp discontinuity at the temperature of the rate minimum. From this it is inferred (reinforced by the precedent of previous work on C198H398) that a transition from extended to once folded crystallization is taking place at the temperature of the minimum. The methods by which the rate curves were constructed are laid out in step by step detail, leaving no possible doubt about the reality of the rate inversion. The rate inversion is attributed to “self-poisoning,” and this concept is extended to embrace the wider issue of mutually interacting competition of possible phase variants (“polymorphs”) of which the extended and folded chain crystals represent one special example. In addition, some further effects are noted and discussed regarding solubility behavior. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1775-1791, 1997
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 10
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 463-471 
    ISSN: 0887-6266
    Schlagwort(e): hydrogel ; free volume ; positron annihilation ; water ; density ; Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A copolymer of 2-hydroxyethyl methacrylate (HEMA) with 2-ethoxy ethyl methacrylate (EEMA) was synthesized and the molecular mobility, free volume, and density properties examined as a function of composition. These properties were correlated with the equilibrium water uptake in order to determine which of the properties were most influential in causing high water sorption, as these materials are suitable candidates for hydrogel systems. It was found that the polar HEMA repeat unit results in a rigid, glassy sample at room temperature due to the high degree of hydrogen bonding between chains whereas high EEMA content leads to rubbery samples with subambient glass transition temperatures. The free volume properties on the molecular scale measured by positron annihilation lifetime spectroscopy (PALS) showed that higher HEMA content led to smaller, fewer holes and a lower free volume fraction than EEMA. Therefore the high water uptake of HEEMA-containing copolymers is largely related to the high polarity of the HEMA unit compared to EEMA, despite the low content of free volume into which the water can initially diffuse. Trends in density with copolymer composition, as measured on a macroscopic level, differs to that seen by PALS and indicates that the two techniques are measuring different scales of packing. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 463-471, 1998
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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