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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2551-2558 
    ISSN: 0887-6266
    Keywords: polyethylene ; crystalline ; intermediate ; amorphous ; proton NMR ; rotating frame ; 2D time-domain analysis ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: With two-dimensional time-domain NMR analysis in the proton spin rotating frame, three phases are identifiable in the solid polyethylene. The major proton magnetization fraction is due to the polymer's crystalline region, where the motion is least isotropic and slowest. A magnetization fraction with intermediate relaxation rate is also intermediate in magnitude. This component is proposed to comprise chain loops on the surfaces of crystallites and effectively entangled chain segments. The most mobile fraction, which is most liquid-like with a T2 of near 1 ms at 120°C, is also the smallest. It is proposed that it is due to polymer chains in the amorphous phase. In the crystalline phase the chain motion is an unexpectedly effective relaxation mechanism at ∼50 KHz. This process, which involves propagation of a twisted region along the crystallite, as has been suggested before, is either not present in the other two phases of the HDPE or is less efficient because of the lower polymer density. The activation energies for the crystalline, intermediate and amorphous phases are estimated to be 34 ± 3, 13 ± 3, and 8 ± 2 Kcal/mol, respectively. The frequencies of the relaxation process at 120°C are 43 KHz, 350 KHz, and 1.5 MHz, respectively. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2551-2558, 1997
    Additional Material: 3 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 2591-2600 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of γ-radiation on aqueous polystyrene emulsions were followed by measurements by intrinsic viscosities of soluble polymer in toluene. Estimates of incipient gel dose from intrinsic viscosity data do not coincide closely with those from measurements of gel content. This uncertainty and those in molecular weight averages make it difficult to assign a precise value to G(crosslink), even when the scission crosslinking ratio in the particular system is reliably known. The intrinsic viscosity of sol polymer in the postgel region decreases with increasing dose to an asymptotic value. The decrease is as expected if larger molecules are progressively linked into the gel network and the asymptote may be attributable to cyclization. Present theories of branching do not seem to be applicable for quantitative estimation of scission/crosslinking ratios caused by irradiation of polystyrene. This is probably connected with deficiencies in the theoretical connection between radius of gyration and intrinsic viscosity in good solvents. Diallyl fumarate and diallyl maleate increased crosslinking rates, but only at low doses. Chain scission was enhanced by addition of 1,2-dichloroethylene and 2,5-dimethylhexane-2,5-dihydroperoxide.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2235-2254 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The free-radical copolymerization of α-methylstyrene and styrene has been studied in toluene and dimethyl phthalate solutions at 60°C. Gas chromatography was used to monitor the rate of consumption of monomers. For styrene alone, the measured rate of polymerization Rp and M̄n of the polymer coincided with values expected from previous studies by other workers. Solution viscosity η affected Rp and M̄n of styrene homopolymers and copolymers as expected on the basis of an inverse proportionality between η1/2 and termination rate. The rate of initiation by azobisisobutyronitrile appears to be independent of monomer feed composition in this system. Molecular weights of copolymers can be accounted for by considering combinative termination only. The effects of radical chain transfer are not significant.A theory is proposed in which the rate of termination of copolymer radicals is derived statistically from an ideal free-radical polymerization model. This simple theory accounts quantitatively for Rp and M̄n data reported here and for the results of other workers who have favored more complicated reaction models because of the apparent failure of simple copolymer reactivity ratios to predict polymer composition. This deficiency results from systematic losses of low molecular weight copolymer species in some analyses. Copolymer reactivity ratios derived with the assumption of a simple copolymer model and based on rates of monomer loss can be used to predict Rp values measured in other laboratories without necessity for consideration of depropagation or penultimate unit effects. The 60°C rate constants for propagation and termination in styrene homopolymerization were taken to be 176 and 2.7 × 107 mole/l.-sec, respectively. The corresponding figures for α-methylstyrene are 26 and 8.1 × 108 mole/l.-sec. These constants account for the sluggish copolymerization behavior of the latter monomer and the low molecular weights of its copolymers. The simple reaction scheme proposed here suggests that high molecular weight styrene-α-methylstyrene copolymers can be produced at reasonable rates at 60°C by emulsion polymerization. This is shown to be the case.
    Additional Material: 3 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1721-1732 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This investigation deals with the nature and relative abundance of stable radicals formed by gamma-irradiation of wheat starch at room temperature. Additions of equal weights of water, methanol, and ethanol were equally effective in reducing the content of stable radicals in starch which contained about 12% water before the additions. When, however, the starting material was dried starch with 2.9% initial water content additional water and methanol were better radical scavengers than ethanol. This difference is attributed to the superior ability of water and methanol to permeate the starch structure. Superficially different ESR spectra were obtained in products made by irradiating starch and starch that contained added water or methanol. Computer simulation of these spectra showed that they could be matched by superposition of the spectra of the same four component radicals, with some adjustments of relative intensities and peak widths. The structures of these radicals have been dedueed from the spectral assignments and relative effects of the three solvents used on the intensities of the respective ESR spectra.
    Additional Material: 10 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1707-1719 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Starch-g-polystyrene copolymers were made by simultaneous 60Co irradiation of mixtures of wheat starch and styrene at room temperature. The extent of conversion of monomer to polymer is increased drastically with increasing water content up to a level of about 26 wt % on starch. Methanol had approximately the same effect as water at equivalent concentrations but ethanol was clearly less effective as a promoter of homo- and graft copolymerizations. Drying the starch reduced the conversion to polymer with all promoters but caused the greatest deterioration in the ability of ethanol to promote polymerization. The effects of physically swelling the starch by freeze drying the gelatinized material were also studied, as were preirradiation graft copolymerizations. The effects of promoters on graft polymerization parallel their abilities to scavenge stable radicals in irradiated starch. Water and methanol are better radical scavengers and polymerization promoters because they are better able to disrupt hydrogen bonds and permeate the starch structure. Radiolysis of the promoter is important in the grafting reaction.
    Additional Material: 7 Tab.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1993-2006 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chain transfer constants to monomer have been measured by an emulsion copolymerization technique at 44°C. The monomer transfer constant (ratio of transfer to propagation rate constants) is 1.9 × 10-5 for styrene polymerization and 0.4 × 10-5 for the methyl methacrylate reaction. Cross-transfer reactions are important in this system; the sum of the cross-transfer constants is 5.8 × 10-5. Reactivity ratios measured in emulsion were r1 (styrene) = 0.44, r2 = 0.46. Those in bulk polymerizations were r1 = 0.45, r2 = 0.48. These sets of values are not significantly different. Monomer feed compcsition in the polymerizing particles is the same as in the monomer droplets in emulsion copolymerization, despite the higher water solubility of methyl methacrylate. The equilibrium monomer concentration in the particles in interval-2 emulsion polymerization was constant and independent of monomer feed composition for feeds containing 0.25-1.0 mole fraction styrene. Radical concentration is estimated to go through a minimum with increasing methyl methacrylate content in the feed. Rates of copolymerization can be calculated a priori when the concentrations of monomers in the polymer particles are known.
    Additional Material: 1 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1801-1810 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of solvent on the termination rate constant Kt, in the initial stages of free radical polymerizations has been estimated by considering its effect on the viscosity of the medium and on the overall dimensions of the macroradicals. The expression derived predicts that Kt is inversely proportional to the viscosity of the reaction medium, η0, and that Kt, increases as the overall dimensions of the radicals decrease in poorer solvents. The effect of solvent on the η0Kt, product depends on the average size and concentration of polymer in the system. For relatively high concentrations of high-molecular-weight polymers η0Kt can be greater in a better solvent than in a poorer solvent. This trend would be reversed for low concentrations and/or low polymer molecular weights. Good agreement has been found between experimental and estimated values of η0Kt.
    Additional Material: 2 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1557-1557 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3271-3283 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A commercially available densimeter with a vibrating stainless steel tube was used as a detector in the GPC analysis of styrene/methyl methacrylate copolymers under normal GPC operational conditions. The densimeter was thermostated to ±0.001°C and sample injection concentrations were 4.0 mg/mL. The copolymer samples were polydisperse in molecular weight but uniform in composition. A refractive index detector and the densimeter detector produced comparable estimates of the parameters of the molecular weight distributions. The densimeter is less sensitive to the effects of variations in copolymer composition than differential refractive index or ultraviolet detectors. The only serious drawback to the densimeter is a relative lack of sensitivity. Variations in composition of styrene/methyl methacrylate copolymers over a fairly wide range have no signficant effect on the relation between gel permeation chromatographic elution volume and copolymer molecular weight. In general, however, conventional means of summarizing these data are not applicable to compositionally heterogeneous mixtures. Instrumental and data-handling solutions to this problem are discussed.
    Additional Material: 1 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 19 (1981), S. 1799-1800 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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