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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1619-1626 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 619-638 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic study of the propagation mechanism of the alternating copolymerization of styrene (St) with methyl methacrylate (MMA) in the presence of a complexing agent (diethylaluminum chloride, DEAC) in bulk and in tetrachloroethylene solutions at a molar ratio DEAC/MMA = 0.5 has been carried out. It has been shown that the copolymerization is a chain radical process characterized by a short active-center lifetime, bimolecular termination, and high rate of chain transfer to the complexed MMA. A kinetic scheme has been proposed for the propagation mechanism of alternating copolymerization in the presence of a complexing agent not requiring independent measurements of the equilibrium constant of complexation. It has been found that spontaneous and UV-initiated copolymerizations in the system have different mechanisms of initiation and a common mechanism of propagation. The propagation proceeds by addition of single monomers as well as donor-acceptor complexes of the comonomers to the propagation radicals, with the first mechanism being predominant. Inclusion of the monomers in the complex leads to an increase of the St reactivity and to a decrease of the MMA reactivity in propagation to the corresponding macroradicals in comparison with the reactivity of the free monomers. A number of kinetic and statistical parameters of the propagation reaction have been calculated.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2903-2907 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(methyl methacrylate) has been prepared under various conditions of monomer, initiator, reaction medium, and temperature. All the 13C-NMR spectra for the polymers obtained were those to be expected for radically initiated poly(methyl methacrylates) of conventional, slightly syndiotactic-rich microstructures prepared at normal temperature. The spectra were found to be very similar to that for a radical poly(methyl methacrylate) first analyzed by Inoue et al.,8 and to those of poly(methyl methacrylates) prepared in earlier experiments of this general type. The ratios of isotactic (mm) to heterotactic (mr and rm) to syndiotactic (rr) triads were found to be close to 5:34:61. It can be concluded from the 13C-NMR spectra that the propagation steps in these polymerizations are of conventional radical type, and are uninfluenced from the steric point of view by nature of the polymerization medium by the presence of the various additives. The polydispersity for some poly(methyl methacrylate) samples determined by gel permeation chromatography was found here to vary rather widely and ranges between 1.9 and 7.9.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 385-395 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Azo compounds such as di(4-hydroxybutyl)-2,2′-azobisisobutyrate, di(3-hydroxybutyl)-2,2′-azobisisobutyrate, di(2-hydroxypropyl)-2,2′-azobisisobutyrate, and di(2-hydroxyethyl)-2,2′-azobisisobutyrate were prepared and used as initiators for the preparation of hydroxyl-terminated polybutadienes (HTPBs) of molecular weight (M̄n) ranging from 2000 to 7500 and functionality between 1.90 and 3.0. The polymers were prepared by free-radical solution polymerization in dioxane and toluene. The polymers obtained were characterized for their molecular weight, hydroxyl number, functionality, and instrinsic viscosity.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2145-2155 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rates of decomposition of di(3-hydroxybutyl)-2,2′-azobisisobutyrate, di(4-hydroxybutyl)-2,2′-azobisisobutyrate, di(2-hydroxyethyl)-2,2′-azobisisobutyrate, di(2-chloroethyl)-2,2′-azobisisobutyrate, and di(2-hydroxypropyl)-2,2, all of which are useful in the polymerization of butadiene and isoprene, were measured by nitrogen evolution technique at 60, 70, and 80°C, respectively, in each of the three solvents, namely, toluene, dioxane, and N,N-dimethylformamide. The thermal decompositions of these azo compounds in solution were first order, and the Arrhenius equation was used to calculate their activation energies.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 877-892 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Properties of linear polyesters based on azoxybenzene and 2,2′-methylazoxybenzene moieties with linear, flexible spacers based on mixtures of dodecanedioic acid (DDA) and methyladipic acid (MAA), chiral or racemic, of various compositions (system MAA/DDA-8 and MAA/DDA-9, respectively) have been described. Substitution of methyl groups in the 2,2′ or 3,3′ positions of the mesogenic core leads to soluble and relatively low-melting-point polyesters. The viscosity law for (MAA/DDA-9) polyesters in 1,1,2,2 tetrachloroethane gives an exponent 0.76, indicating well-sol-vated, coiled chain conformations in dilute solution. Calorimetric data show an increase in isotropization entropy ΔSNI with increasing average length of the spacer. This suggests a nonrandom conformation of the spacer in the nematic melt with a degree of order superior to that of low-molecular-weight analogs. X-ray data obtained with an oriented nematic glass quenched from the nematic melt of DDA-9 subjected to a magnetic field of 10-12 T also support the extended-chain model in the nematic phase of DDA-9. Oriented fibers can be produced by subjecting nematic melts of polyesters 8 and 9 either to magnetic fields of high intensity or to shear fields. The x-ray data obtained from these fibers also support the extended-chain model. Cholesteric systems do not orient in the magnetic field of 10-12 T. The study of mesophases of systems 8 and 9 indicates a dramatic influence of the position of the ester group on the stability of the mesophase in the azoxybenzene polyesters. The results are interpreted in terms of geometric factors influencing the colinearity of the mesogenic core and of the extended spacer.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 19 (1981), S. 253-272 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crazing was investigated in two commercial polystyrene/polybutadiene block copolymers made by the Phillips Petroleum Co. and marketed under the trade names of KRO-1 and KRO-3 resins. The two block copolymers each with 23% polybutadiene (PB), have radically different microstructure and radically different crazing behavior, leading to strains to fracture of 0.1 and 1.0, respectively. Of these, the KRO-1 Resin has a phase microstructure that consists of randomly wavy and often interconnected rods of PB of 20 nm diameter surrounded by polystyrene (PS). The microstructure of KRO-3 Resin consists of lamellae of PB with 20 nm thickness and large aspect ratio which range in packing from regular aligned lamellar domains with randomly varying misorientation in the annealed material, to randomly corrugated and wavy sheets in the as-received material. Crazes in KRO-1 Resin have well delineated planar shapes with a conventional, tufty craze matter structure which suggests growth by the now well-established meniscus instability mechanism proposed by one of us. In KRO-3 Resin, on the other hand, crazing involves profuse cavitation if the PB lamellae, giving rise to less well delineated zones of cavitational growth dispersed over the volume and suggests a mechanism of craze growth by stable, interfacial cavitational degradation in a process zone ahead of the craze tip. The measured stress and temperature dependences of craze velocities in these two polymers is in partial support of the suggested mechanisms which are also developed in outline.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 2425-2426 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sorption isotherms for pure CO2 and pure CH4 in Kapton H® polymide films at 60°C are reported for pressures up to 20 atm and are analyzed in terms of the dual-mode sorption model. An experimental scheme for the measurement of steady-state permeabilities of both pure and mixed gas feeds is described. Permeabilities of Kapton to the individual components at 60°C are presented for a mixture comprised of 32.2% CO2 in CH4 as functions of feed pressure up to 590 psi (absolute). The permeabilities for the individual penetrants in the mixed feed are lower than the respective purecomponent values at the corresponding partial pressures. Furthermore, the permeabilities of both penetrants drop as the feed pressure is increased at constant composition. The dual-mobility transport model used to analyze the data postulates that the observed pressure and composition dependence of the permeabilities is due to competition between penetrants for a limited microvoid sorption capacity in the glassy polymer. It is demonstrated that in addition to flux depressions due to dual-mode effects, nonideality of the gas phase must be accounted for to explain the substantial flux depressions observed for the CO2/CH4 mixtured used in this study.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 795-810 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isothermal emulsion polymerization at 60°C of styrene in a batch reactor were studied by using sodium lauryl sulfate as surfactant and potassium persulfate as initiator source. The concentrations of surfactant and initiator were varied during the runs. The polymerization evolution was followed as samples were taken at regular intervals. These emulsion samples were analyzed for monomer conversion, rate of polymerization, as well as for the size and the size distribution of the particles. The molecular weight and molecular weight distribution were obtained by gel permeation chromatography. Our study showed that fresh nucleation takes place even at high conversion, causing a continuous shifting toward broadening of particle size distribution. Contrary to the theory of Smith and Ewart, which assumes a constant number of particles during interval II of the polymerization reaction, our digital simulation of the reaction presents better experimental results with a variable number of particles, and indicates that the Hui-Hamielec model for termination constant kt as function of conversion is not applicable under our working conditions.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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