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  • 1
    Electronic Resource
    Electronic Resource
    Synthesis of a diphenylethylene derivative carrying aromatic tertiary amine groups and its use in chain end functionalization of alkyllithium-initiated polymerizations (1998)
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 2185-2191 
    Details
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1,1-Bis[(4-dimethylamino)phenyl]ethylene was successfully synthesized through the ‘Wittigtype’ reaction of 4,4′-bis(dimethylamino)benzophenone with the ‘Tebbe’ reagent. The methylenation yields were over 80 wt.-% on the basis of the initial amount of benzophenone derivative used. Terminally functionalized polymers having aromatic tertiary amine groups at one end or at both ends were prepared by the crossover reactions of n-butyllithium (n-BuLi), poly(styryl)lithium (PSLi), and poly(isoprenyl)lithium (PILi) with the diphenylethylene analogue. The functionalization yields were over 87 mol.-% based on the results of 1H NMR spectroscopic analysis. The number-average molecular weights of the polymers based on the ratio [gram of monomer]/[mole of initiator] are in good accordance with those observed from size exclusion chromatographic and 1H NMR spectroscopic analysis (3,0 × 103 ∼ 7,5 × 103 g/mol).
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Characterization of ultra low density polyethylenes (PE-ULD) (1992)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 194 (1992), S. 91-101 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In der vorliegenden Arbeit wurden die strukturellen, thermischen, rheologischen und molekularen Eigenschaften von Polyethylen ultraniedriger Dichte (PE-ULD) untersucht. Da PE-ULD hauptsächlich als Modifikator von anderen Polyolefinen verwendet wird, wurde das rheologische Verhalten besonders ausführlich untersucht.
    Notes: Ultra low density polyethylene (PE-ULD), the newest and most recently commercialized member of polyethylene family, has been characterized in terms of structure, thermal and rheological properties, and molecular parameters. Since the prime use of PE-ULD is polyolefin modifier, emphasis is put on the melt rheology of the samples to provide data base for blending with other resins.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1992.051940108
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  • 3
    Electronic Resource
    Electronic Resource
    Microstructure effect in the coupling reactions of polymeric organolithium compounds using chlorosilanes (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1743-1753 
    Details
    ISSN: 0887-624X
    Keywords: coupling reaction ; living polymer ; microstructure ; coupling yield ; 1,4-enchainment ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The most important variable affecting the yield in the coupling reactions of polymeric organolithium compounds with chlorosilane compounds has been investigated through size-exclusion chromatographic (SEC) analysis. The coupling reaction of poly(styryl)lithium with dichlorodimethylsilane as a silane-coupling agent provided 44 wt % of the coupling yield. The coupling yield, depending on the chain end reactivity of active polymers, was not greatly affected. The addition of a Lewis base such as N,N,N′,N′-tetramethylethylenediamine (TMEDA) even after complete polymerization of the dienes in hydrocarbon seems to affect the coupling reaction, resulting in decreasing the yield. The 1,2- or 3,4-enchain contents in the polydiene backbones affected the reduction of the linking efficiency in the coupling of the poly(dienyl)lithiums with chlorosilanes as the linking agent. The linking yields of the active polymers including over 75 mol % of 1,2- or 3,4-enchainment on the polydiene segment were below 20 wt %. The linking yields exhibited a dependence not only on the steric requirement of the chain end, but also the microstructure of the polydiene segment. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1743-1753, 1998
    Additional Material: 5 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Comparison of activities of homogeneous Ti-based catalysts in the presence of methylaluminoxane (MAO) for synthesis of syndiotactic polystyrene by UV/visible spectroscopic study (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1733-1741 
    Details
    ISSN: 0887-624X
    Keywords: homogeneous Ti-based catalyst ; methylaluminoxane ; catalytic activity ; UV/visible spectroscopy ; syndiotactic polystyrene ; polymorphic structure ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The catalytic activities in syndiospecific polymerization of styrene in hydrocarbon using homogeneous Ti-based catalysts in the presence of methylaluminoxane (MAO) were investigated through UV/visible spectroscopic analysis. A strong UV absorption band of CpTiCl3, itself, incipiently appeared at λmax = 400 nm in toluene, followed by a bathochromic shift with its remarkable decrease by the addition of MAO. The absorption band intensity at λmax = 400 nm arising from delocalization of π-electrons on the cyclopentadienyl ring decreased by methylation in the presence of MAO with regard to the mechanism for production of an active center (“cation-like”), for example, the change of the ionic nature. The intensity decrease at λmax = 400 nm was suppressed over 2000 of the [Al]/[Ti] ratio. In the case of Ti(OC4H9)4 having a σ-ligand, new and broad UV absorption bands were developed at λmax = 340 nm and 410 nm in the presence of MAO in contrast with the CpTiCl3/MAO system. Comparison between the relative absorption intensities at λmax = 340 nm and 410 nm led to the determination of a maximum catalytic activity of Ti(OC4H9)4 in the presence of MAO related to the polymerization yield. The maximum polymerization yield was observed with regard to the relative maximum value of the absorption intensity at λmax = 410 nm with the [Al]/[Ti] ratio (500). From observation for polymorphism of the final products via differential scanning calorimetric analysis (DSC), the thermally unstable β-form seemed to be produced by the CpTiCl3/MAO system independent of the MAO concentration, the Ti(OC4H9)4/MAO system produced a thermally stable α-form in the low MAO concentration (up to 100 of the [Al]/[Ti] ratio), and a mixture of α- and/or β-forms over 200 of the [Al]/[Ti] ratio under our experimental conditions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1733-1741, 1998
    Additional Material: 9 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Blue and green light emission from new soluble alternating copolymers (1997)
    Weinheim : Wiley-Blackwell
    Advanced Materials 9 (1997), S. 326-328 
    Details
    ISSN: 0935-9648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/adma.19970090408
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  • 6
    Electronic Resource
    Electronic Resource
    Reaction mechanisms of polyacrylonitrile on thermal treatment (1993)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 33 (1993), S. 1452-1457 
    Details
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A high-temperature radical scavenger, 2,2-diphenyl-l-picryl hydrazyl (DPPH), has been used to study the reaction mechanisms of polyacrylonitrile (PAN) on thermal treatment. The effect of DPPH on the cyclization reaction of PAN in both air and nitrogen, investigated by differential scanning calorimetry (DSC), helped to verify the proposed reaction mechanisms, i.e., the free radical and the ionic ones. For PAN homopolymer, the peak temperature of the reaction exotherm shifted to higher temperatures and the heat of reaction was decreased with increasing DPPH concentration. For PAN copolymer with methylacrylate and itaconic acid, however, the effects of DPPH on DSC thermograms were insignificant. The effects of IPPH suggest that the reaction of the nitrile groups proceeds by free radicals for the homopolymer while by ions for the copolymer. The activation energies for the thermal reactions of PAN in both air and nitrogen were also estimated by the dynamic DSC method, and they proved to be highly dependent on reaction mechanism, environment of thermal treatment, and DPPH concentration.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760332203
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  • 7
    Electronic Resource
    Electronic Resource
    Temperature dependence of the nucleation effect of sorbitol derivatives on polypropylene crystallization (1993)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 33 (1993), S. 1445-1451 
    Details
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The temperature dependence of the nucleation effect of three sorbitol derivatives on the crystallization of isotactic polypropylene (iPP) was studied by means of isothermal crystallization kinetic analysis. Isothermal crystallization thermograms obtained by differential scanning calorimetry (DSC) were analyzed based on the Avrami equation. The Avrami analysis for the nucleated iPP was carried out with DSC data collected to 35% relative crystallinity, and the rate constants were corrected assuming the heterogeneous nucleation and three dimensional growth of iPP spherulites. A semi-empirical equation for the radial growth rate of iPP spherulites was given as a function of temperature and was used to determine the number of effective nuclei at different temperatures. The number of effective nuclei in the nucleated samples was estimated to be 3 × 102 ∽ 105 times larger than that in the neat iPP. The logarithmic numbers of the effective nuclei decreased linearly with decreasing degree of supercooling in the range of crystallization temperatures tested. The temperature dependence of the effect of the nucleating agents on iPP crystallization was given quantitatively in terms of the deactivation factor defined as a fraction of the particles that are active at a particular temperature but inert at the temperature one degree higher. The nucleation activity and its temperature dependence are considered to be cooperative effects of many factors, including the dispersion and the physical or chemical nature of the agent as well as the interaction between the agent and the polymer. It is suggested that the temperature dependence of the effect of a nucleating agent should be treated as a characteristic of a given polymer/ nucleating agent mixture.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760332202
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  • 8
    Electronic Resource
    Electronic Resource
    A Raman spectroscopic study on 5′-rGMP gel and self-aggregate (1986)
    New York : Wiley-Blackwell
    Biopolymers 25 (1986), S. 753-762 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to analyze the melting behavior of 5′-rGMP gel at acidic pH and self-aggregate near neutral pH we have obtained Raman spectra of aqueous solutions of 5′-rGMP at various temperatures. At low temperature the intensities of Raman peaks at 502, 585, 1083, 1179, 1322, 1366, 1487, and 1578 cm-1 decrease due to the formation of ordered structure (Raman hypochromism). In contrast, the peaks at 671, 725, 813, and 1338 cm-1 become stronger at low temperature (Raman hyperchromism). The Raman hyperchromism of the 671- and 813-cm-1 peaks have been explained in terms of detailed structural models. Recently, the 668- and 682-cm-1 peaks in the Raman spectrum of aqueous 5′-rGMP solution have been attributed to the guanine ring breathing vibrations in C3′- and C2′-endo conformers [Benevides, J. B., Lemur, D. & Thomas, G. J., Jr. (1984) Biopolymers 23, 1011-1024]. On the basis of this information our Raman data can be interpreted to suggest that the continuous helix model of 5′-rGMP gel is right-handed. The 1487-cm-1 peak intensity has been used to monitor the melting profies at several pHs. Near neutral pH the melting profile shows a single transition, whereas at acidic pH it shows two transitions. From these observations we propose possible pathways for the melting of 5′-rGMP gel formed at acidic pH and self-aggregate formed near neutral pH.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360250415
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  • 9
    Electronic Resource
    Electronic Resource
    Controlled release of riboflavin and insulin through crosslinked poly(vinyl alcohol)/chitosan blend membrane (1992)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 44 (1992), S. 1823-1828 
    Details
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The permeation of riboflavin and insulin through poly(vinyl alcohol) (PVA) and chitosan blend membrane was conducted. The permeability coefficients of both solutes through the crosslinked PVA and chitosan blend membrane were in the order of 10-6-10-7 cm3 cm/cm2s and showed a pH dependence. The pH-dependent permeation behavior was discussed in terms of water content and water structure inside of the swollen membrane. Riboflavin and insulin were presumed to permeate through the free water region in the swollen blend membrane. The DSC thermograms of these membranes indicated that the content of free water and the amount of freezing bound water increased with the water content in the membrane. The greater permeation rate of solutes in acidic solution rather than in neutral solution was due to an increase in both water content and the amount of free water and freezing bound water.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1992.070441015
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  • 10
    Electronic Resource
    Electronic Resource
    Properties and swelling characteristics of cross-linked poly(vinyl alcohol)/chitosan blend membrane (1992)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 45 (1992), S. 1711-1717 
    Details
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Blend membrane consisting of poly(vinyl alcohol) (PVA) and chitosan was prepared from a solvent-casting technique and characterized for their intermolecular interactions using infrared and X-ray diffraction methods. Cross-linking the blend with glutaraldehyde produces a membrane with lower crystallinity and a smaller swelling degree, but having improved thermostability and mechanical properties. The present blend membrane shows a pH-dependent swelling characteristic and will be discussed in detail. © 1992 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1992.070451004
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