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  • Polymer and Materials Science  (57)
  • 2000-2004
  • 1995-1999  (55)
  • 1950-1954  (2)
  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 615-620 
    ISSN: 0887-624X
    Keywords: solid state ; diacetylene ; polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solid-state polymerization of a diacetylene, 1,11,13,23-tetracosatetrayne, was studied using x-ray powder diffraction and electron diffraction. It is shown that the material exhibits polymorphism. Thermochromic transitions, which are generally observed for diacetylenes, are related to the particular crystalline phase using x-ray powder diffraction. The unit cell dimensions and space group of one polymorph were determined by electron diffraction analysis: a = 20.83 Å, b = 4.84 Å, c = 10.08 Å, β = 92.4°, space group: P21/n. © 1995 John Wiley & Sons, Inc.
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 633-642 
    ISSN: 0887-624X
    Keywords: free radicals ; grafting ; kinetics ; methacrylate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of grafting a basic monomer, 2-(dimethylamino)-ethyl methacrylate (DMAEMA) to hydrocarbon substrates have been investigated. These systems were chosen as models for the grafting of a homopolymerizable monomer to polyolefins such as polyethylene. The reactions with squalane and n-eicosane were initiated by an organic peroxide, 2,5-dimethyl 2,5 dit-butylperoxy)-3-hexyne; grafting yields become significant at high reaction temperatures and low monomer concentrations. In squalane, the order of reaction with respect to monomer increased from about 1.1 for 0.22-0.44M DMAEMA to almost 2 at 0.69M DMAEMA; the order with respect to initiator was 0.56. The overall activation energy in the 130-160°C temperature range was, however, surprisingly low, 42±5 kJ mol-1. When analytical data were used to separate the overall rate into those for grafting and homopolymerization, different kinetic paths were observed for the competing reactions. These results are interpreted in terms of two different mechanisms; intramolecular chain transfer plays an important role in grafting, while depropagation becomes a major factor in homopolymerization at temperatures above 150°C. © 1995 John Wiley & Sons, Inc.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2455-2461 
    ISSN: 0887-624X
    Keywords: polyfunctional diacetylenes ; Langmuir-Blodgett multilayers ; polymerization ; characterization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Amphiphilic diacetylenes of the type HC≡C—(CH2)n—C≡C—C≡C—(CH2)8—COOH (n=6 and 12) were synthesized. The solid-state polymerization of the bulk crystals, mono-layers on the gas-water interface, and multilayers were investigated. The diacetylene moieties underwent polymerization upon irradiation by UV or γ-rays, showing different polymerizability depending on the material form. The polymerization of the terminal acetylene groups was not observed. Enhanced polymerizability and stability of the monolayers on subphases containing LiOH are explained by a proposed model of the monolayers. © 1995 John Wiley & Sons, Inc.
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1125-1132 
    ISSN: 0887-624X
    Keywords: butadiene ; polymerization ; neodymium ; molecular weight ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The homopolymerization of 1,3-butadiene in a stirred batch reactor with the catalytic system Nd octoate/diethyl-aluminium chloride/triisobutyl-aluminium in n-heptane was studied. The effect of various reaction conditions on especially high conversion and molecular weight is reported. Polymerization is shown to be first order with respect to both monomer and neodymium. Molecular weights are high and broadly distributed. Chain transfer to triisobutylaluminium is the main factor governing molecular weight development. A mechanism of polymerization is presented with the chain transfer process incorporated. © 1995 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 973-977 
    ISSN: 0887-624X
    Keywords: 1,11-dodecadiyne ; IR ; polymorphs ; γ radiation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dimer, trimer, and tetramer of 1,11-dodecadiyne, HC≡C—(CH2)8—C≡CH, were synthesized. The solid-state polymerization of the dimer was investigated by infrared (IR) spectroscopy. IR bands due to the diacetylene moiety were identified through the comparison of the IR spectra of the dimer, trimer, and tetramer. The dimer was found to have two polymorphs, melt-crystallized and solution-crystallized. Both of the polymorphs undergo solid-state polymerization by exposure to γ-ray or UV irradiation. The former has higher polymerizability for the diacetylene moiety than the latter. The solid-state polymerization of the terminal acetylene group was not observed. It is shown that the previously reported dimer structure in which both the diacetylene and terminal acetylene groups are polymerized to form an inherently electrically conducting polymer is incorrect. © 1995 John Wiley & Sons, Inc.
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1309-1316 
    ISSN: 0887-624X
    Keywords: polysulfone ; step polymerization ; end-capping ; end group titration ; multiple end groups ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of amine-terminated polysulfone by step polymerization of the monomers bisphenol A and dichlorodiphenyl sulfone in the presence of end-capping reagent 4-aminophenol was investigated. A persistent problem with end-capping strategy as applied to step polymerization is the presence of end groups other than those introduced by the end-capping reagent. These unintended end groups, which can persist in the polymer product even when 100% of the end-capping reagent has reacted, are associated with a proportionate decrease in polymer chain length. This situation renders quantitative analysis of a single type of end group invalid as a method for molecular weight determination. The presence of unintended end groups does not appear to correlate with a particular set of reaction conditions; unintended end groups were found to occur in polymerizations conducted under strong base conditions (NaOH), under weak base conditions (K2CO3), and with a wide range of monomer feed ratios. A scheme for unambiguous quantification of chain ends and molecular weight for end-capped polysulfone is described. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1309-1316, 1998
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  • 7
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 493-504 
    ISSN: 0887-624X
    Keywords: butanediol ; 4,4′-biphenyldicarboxylic acid ; characterization ; liquid crystalline polymer ; methyl substitution ; nematic ; polyester ; smectic ; synthesis ; thermal properties ; X-ray analysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Results are reported on the effect of lateral methyl groups on the thermal properties of a series of polyesters prepared from diethyl 4,4′-biphenyldicarboxylate and various methyl substituted 1,4-butanediols. The diols were 1,4-butanediol; 2-methyl-1,4-butanediol; 2,2-dimethyl-1,4-butanediol; 2,3-dimethyl-1,4-butanediol; 2,2,3-trimethyl-1,4-butanediol; and 2,2,3,3-tetramethyl-1,4-butanediol. Apart from the tetramethyl derivatve, the transition temperatures of the methyl substituted polyesters were lower with respect of the unsubstituted polyester. On the basis of polarized photomicrographs, a smectic A mesophase was found for the unsubstituted polyester, whereas a nematic mesophase was observed for the 2-methyl substituted polyster. The 2,2-dimethyl, 2,3-dimethyl, and the 2,2,3-trimethyl substituted polyesters showed no liquid crystalline behavior. The 2,2,3,3-tetramethyl derivative displayed a birefringent melt phase although the DSC measurements were not unambiguous. A copolyester based on diethyl 4,4′-biphenyldicarboxylate, 1,4-butanediol, and 2,2,3,3-tetramethyl-1,4-butanediol showed a broad nematic mesophase. Further evidence for the nematic mesophase of this copolyester and the 2-methyl substituted polyester was provided by dynamic rheological experiments. Based on thermogravimetric analysis, it was concluded that the thermal stability was affected only when four methyl side groups were present in the spacer. © 1995 John Wiley & Sons, Inc.
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 761-768 
    ISSN: 0887-6266
    Keywords: poly(ethylene terephthalate) ; poly(ethylene naphthalate) ; carbon dioxide ; diffusion ; glassy polymers ; modeling ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Finite difference modeling has been used to predict the results of gas transport experiments for a concentration-dependent diffusion coefficient. Experiments on the transport of CO2 in poly(ethylene terephthalate) and poly(ethylene naphthalate) had previously shown a difference between the effective diffusion coefficients for absorption and desorption runs of a double-sided experiment, but this effect had not been seen for single-sided experiments. The finite difference calculations show that such results are to be expected, and the parameters included in the models that attempt to describe the diffusion process in glassy polymers, such as the dual-mode model, and which lead to concentration-dependent diffusion coefficients, can be found by fitting the experimental data for the double-sided experiment using finite difference modeling. The dependence of the effective diffusion coefficient on pressure for the single-sided experiment can be correctly predicted using results from the double-sided experiment for an identical sample. © 1996 John Wiley & Sons, Inc.
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 769-780 
    ISSN: 0887-6266
    Keywords: poly(ethylene terephthalate) ; poly(ethylene naphthalate) ; carbon dioxide ; diffusion ; solubility ; permeability ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements have been made of the solubilities and effective diffusion coefficients at 25°C for carbon dioxide in random and uniaxially oriented samples of poly(ethylene terephthalate) and poly(ethylene naphthalate) (PET and PEN). Most measurements were made using a double-sided experiment in which the penetrant entered both sides of the sample simultaneously and the concentration was monitored as a function of time by means of infrared spectroscopy. Pressures of carbon dioxide from 0.125 to .5 atmospheres were employed. Finite difference modeling was used to determine concentration-dependent diffusion coefficients from the effective diffusion coefficients measured directly and to compare the results with the dual-mode and gas(SINGLEBOND)polymer matrix models. The results could be fitted slightly better by the dual-mode model than by the gas(SINGLEBOND)polymer matrix model, although the latter also provided a reasonable fit to the data. There was, however, no observed change in the spectrum of the absorbed carbon dioxide with concentration, as would be expected if it existed in two distinct states within the polymer, as required by the dual-mode model. No definite conclusion can thus be drawn about the applicability of the two models to the systems studied. © 1996 John Wiley & Sons, Inc.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 58 (1995), S. 2293-2306 
    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: To improve the fracture toughness of PMR-15 polyimide and to alleviate its high susceptibility to microcracking induced by thermal cycling, a thermoplastic polyimide, LARC-TPI, was incorporated to form a sequential semi-interpenetrating polymer network (semi-2 IPN). The imidization kinetics of LARC-TPI in the semi-IPNs were studied using a thermal gravimetric analyzer. Both the solvent and the glass transition temperature of the semi-IPN were found to have significant effects on the imidization kinetics. The kinetics could be modeled by a two-step reaction: the first step being a second-order reaction followed by a second step, which is a first-order diffusion-controlled reaction. Differential scanning calorimetry was chosen to investigate the curing of PMR-15 and PMR-15/LARC-TPI semi-IPNs. The curing process was well correlated by a first-order reaction kinetics, which suggested that the reverse Diels-Alder reaction of the Norbornene end group was the rate controlling step. The glass transition temperatures of these semi-IPNs were again found to play important an important role in dictating the curing kinetics. A higher proportion of LARC-TPI or a higher glass transition temperature of the semi-IPN prepolymer tended to result in a slower curing reaction. The optimum molding cycle of PMR-15 and PMR-15/LARC-TPI semi-IPNs were then determined from the obtained kinetics. © 1995 John Wiley & Sons, Inc.
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