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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 3153-3166 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolymers of styrene and ortho-vinylbenzaldehyde (o-VBA) are useful precursors to multicomponent polymer systems. Graft copolymers of poly(styrene-stat-o-VBA) can be produced by free-radical chain transfer to methyl methacrylate monomer to yield materials that display some potential as interfacial agents with binary blends of polystyrene and poly(methyl methacrylate). Significant improvements in ultimate tensile strengths and energy to rupture values have been witnessed for polystyrene/poly(methyl methacrylate) mixtures that contain various levels of the graft component. Scanning electron microscopy of representative fracture surfaces demonstrate a decrease in the particle size of the dispersed phase; it is suggested that this morphological factor contributes to the superior mechanical properties of these composites. In this regard, both the isolated and the crude graft copolymers are able to compatibilize, and thereby enhance, the material properties of polystyrene/poly(methyl methacrylate) blends.
    Additional Material: 8 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2763-2774 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polybutadienes of various microstructures and some butadiene copolymers were epoxidised to low levels (〈1 mol-%) with m-chloroperbenzoic acid. The epoxide groups functioned as initiation sites for a “grafting-from polymerization” of tetrahydrofuran (THF) catalysed by BF3. By conducting the reaction in dilute THF solution ([Monomeric unit] 〈 0,3 mol · 1-1) with a large excess of BF3 over epoxide groups, gel formation was avoided. The conversion of THF was less than 2% and the copolymers contained from 10 to 50% polytetrahydrofuran (PTHF) comprising graft chains of molar mass up to 43000 g · mol-1. The relative rate of grafting tended to decrease as the content of trans-1,4 units in the backbone polymer increased, and, unusually, there was a small increase in volume during the graft copolymerization. The graft copolymers had a two-phase morphology consisting of amorphous rubber and crystallites of PTHF. The latter function as physical crosslinks which break down above the melting point of PTHF, so that the materials behave as thermoplastic elastomers.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 30 (1985), S. 731-740 
    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 chain entanglement states in high density, linear low density, and low density polyethylenes (HDPE, LLDPE, and LDPE) have been modified by recovering the polymers from solutions in trichlorobenzene (TCB) and p-xylene. In the thermodynamically good solvent, TCB, the entanglement density is assumed to be sharply reduced, a condition which is carried over to the corresponding solids. These display transient, but large increments in tensile moduli, slight changes in stress at rupture, and decreases in dynamic mechanical parameters and in elongation at rupture. Scanning calorimetry also shows these solids to have reduced crystallinity. Much smaller property modifications are noted in corresponding samples recovered from p-xylene. This liquid is a poorer solvent, particularly for HDPE and LLDPE. The results indicate that property modifications due to deliberate changes in the entanglement states of the polymers are a general phenomenon in the polyethylenes, and the magnitude of property changes depends on parameters of the molecular weight distribution. Chain branching does not seem to be a leading factor in the sensitivity of properties to modifications in the entanglement states. The property modifications produced by the present solution treatments are viewed as guides to the magnitude and duration of shear refining effects to be expected in HDPE, LLDPE, and LDPE polymers.
    Additional Material: 5 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 31 (1986), S. 353-365 
    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: Extrusion of a hot polymer melt through a cooler die zone substantially increases the extrudate swell of some thermoplastics. This effect was examined for commercial samples of low-density polyethylene, polypropylene, and polystyrene. Two conflicting effects come into play during extrusion of a thermoplastic. Colder melt temperatures promote increased extrudate swell, but the same conditions also facilitate molecular disentanglement and reduced melt elasticity and die swell. Since the extrusion process itself may affect the relation between die swell and melt temperature, laboratory-scale measurements for the design of processes like blow molding are better carried out with small-scale screw extruders than with capillary rheometers. For some applications it may be advantageous to use a polymer whose die swell is particularly responsive or unresponsive to die temperature variations. The procedure described in this article can be used effectively to monitor this characteristic.
    Additional Material: 9 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 33 (1987), S. 2493-2501 
    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: Rheological and mechanical properties of polyvinyl chloride (PVC) compounds vary with the polymer entanglement state at the time of testing. Controlled shearing episodes and thermal histories applied to the compounds produce major property variations. These then relax toward steady-state values at rates which are consistent with diffusion-controlled processes, presumably connected with the development of steady-states in entanglement couplings. Activation energies of 4-7 kcal/mol apply to the proposed re-entanglement processes. Rates of property variation can be altered by the addition of fillers to the compounds, the interactions between polymer and filler being an important factor in this regard. CaCO3 samples with strong affinity for the PVC retard the rate of property variations (i.e., the filler tends to stabilize non-steady-state entanglement couplings). Fillers, surface treated so as not to interact strongly with the polymer, produce lesser effects on relaxation rates. The data indicate the feasibility of controlling both the sensitivity of polymer properties to processing variables, and the rates of property change associated with the attainment of steady-state polymer entanglement morphologies.
    Additional Material: 6 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 437-441 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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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. 345-357 
    ISSN: 0887-624X
    Keywords: dispersion polymerization ; nucleation, polymerization locus ; divinylbenzene, pendant vinyl groups, crosslink density ; monodisperse particles ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monodisperse, crosslinked polystyrene latexes were prepared by the dispersion technique. Some general observations regarding the effect of initial reagent concentrations on final particle size and size distribution are offered, in addition to a detailed discussion concerning the problems encountered with the use of the crosslinker divinylbenzene (DVB) in latex preparation. Particles synthesized in very polar media were found to reach their growth plateau sooner than those made in less polar surroundings. This trend was proposed to be the result of more effective nucleation in polar environments, which increases available surface area, thereby allowing the rapid replacement of monomer consumed within the particle phase during the polymerization. Attempts to favorably influence the growth rate and size distribution of particles during the reaction were unsuccessful, underlining the importance of the nucleation period in defining particle size characteristics. Up to 1% DVB was successfully incorporated in the synthesis of coagulum-free, monodisperse, 5 μm beads, by controlling the entry of the crosslinker into the particle phase during the major particle growth period. Latex stability is proposed to be largely dependent on the mobility of the adsorbed steric stabilizer. © 1995 John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2297-2304 
    ISSN: 0887-624X
    Keywords: methyl methacrylate ; emulsion polymerization ; in situ surfactant ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A “surfactant-free” emulsion polymerization of methyl methacrylate was conducted at 80°C with ammonium persulfate initiator. The water-soluble MMA-based oligomers re-maining were isolated and analyzed both as-produced and after hydrolysis. NMR analysis revealed that the mole ratio of MMA repeat units to sulfate end groups in the former is 6.5. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and gel permeation chromatography both showed that the mean number of MMA repeat units comprising the extracted material is 8-9. The hydrolysis procedure rids the oligomers of their terminal groups and converts some of the methyl ester groups to acid, greatly sim-plifying the mass spectrum. This appears to be the first direct measurement of “surfactants” produced in situ from monomer and persulfate initiator. © 1995 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 3061-3069 
    ISSN: 0887-624X
    Keywords: aggregation ; emulusion polymerization ; flocculation ; latex ; particles ; polymer ; size distribution ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The basic features of a three-step experimental process to produce supermicron polymer particles are described. First, a submicron emulsifier-free latex is prepared by a well-known technique. Second, the latex is aggregated by destabilizing with cetyl pyridinium chloride under constant stirring conditions, to yield roughly spherical clusters of 6-12 μ diameter. Third, the aggregates are stabilized with poly(vinyl alcohol) and internally coalesced by heating at or above the glass transition temperature. The final product particles have relatively smooth surfaces. Results are qualitatively interpreted in terms of a dynamic equilibrium where the aggregate size is determined by a balance between attractive interparticle potentials and stirring shear forces. Bimodal aggregate size distributions suggest the aggregate break-up mechanism may involve the erosion of individual latex particles and small fragments from the surface of aggregates. © 1996 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 24 (1986), S. 133-145 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ortho-vinylbenzaldehyde has been prepared in a three-step synthesis. Vacuum-degassed monomer was polymerized with azodiisobutyronitrile initiator in bulk and in solution in 2-butanone. The kp/kt1/2 value at 60°C is 4.7 × 10-2 L1/2 mol-1/2s-1/2. This is about twice the ratio for styrene. Chain transfer to monomer appears to be significant. Insoluble, crosslinked products were produced at high conversions, because of chain transfer to polymer. Tg of poly(ortho-vinylbenzaldehyde) was found to be 142°C.Polymers made under N2 atmosphere often contained acetal groups. These can be produced by acid catalysis in the presence of small concentrations of ortho-vinylbenzyl alcohol. A laddertype structure is produced.The monomer is capable of photoinitiation. Insoluble gels were produced in bulk monomer at all conversions. The initiation rate was very high and crosslinking resulted from combination of radicals produced from photolysis of the pendant 0-benzaldehyde groups in the macromolecules.
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