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  • 1
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of vinyl chloride polymerization by titanium tetrabutoxide-ethylaluminum sesquichloride catalyst system was investigated from the view of the stereoregularity of poly(vinyl chloride). The samples were prepared at a selected temperature in the range from 23 to -78°C. The tactic triads, obtained from 220-MHz NMR spectra, show clearly the adequacy of Bernoullian statistics in describing the mechanism for stereochemical propagation. The chain propagation proceeds according to Bernoullian statistics with syndiotactic placements favored by 550 cal/mole. These results suggest that vinyl chloride polymerizes by a free-radical mechanism under the action of the present catalyst system.
    Additional Material: 7 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 12 (1974), S. 771-784 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 220-MHz proton magnetic resonance and infrared spectra of stereoregular polypropylenes polymerized with a number of Ziegler-Natta catalysts and isotactic polymers of low molecular weight obtained by thermal degradation of a highly isotactic polypropylene were measured in an attempt to obtain some information on the local regularity. The fraction of thermally degraded polymer soluble in diethyl ether shows stereorandomness (tactie sequence length is quite short), and the portion soluble in n-pentane has stereoblock character. The results so obtained provide strong evidence that racemic dyads of whole polymer consist of two models of racemic dyad isolated and racemic dyads in groups. The polymers prepared with vanadium catalyst systems show stereorandom character and these polymers have \documentclass{article}\pagestyle{empty}\begin{document}$\hbox{-\hskip-1pt-}\hskip-4pt({\rm CH}_2 \rlap{--} )$\end{document} groups formed by two propylene units in a tail-to-tail linkage. Syndiotactic polypropylene has head-to-head and tail-to-tail arrangements of two propylene units and this is the origin of randomness of syndiotacticity.
    Additional Material: 6 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 13 (1975), S. 2813-2826 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of dehydrochlorination of 2,3-dichlorobutane and chlorinated polybutadiene which are model compounds of head-to-head poly(vinyl chloride) has been investigated by pyrolysis, thermal, and ultraviolet-induced decomposition. The activation energy of dehydrochlorination for head-to-head poly(vinyl chloride) in nitrogen was 23 kcal/mole at temperatures of 150-190°C, which is slightly smaller than that (29 kcal/mole) for head-to-tail poly(vinyl chloride). The conjugated double bonds were formed by thermal and radiation decomposition of head-to-head poly(vinyl chloride), similar to head-to-tail poly(vinyl chloride). The probability of polyene formation by radiation-induced dehydrochlorination is larger than that by thermal decomposition and is affected by the conformation and the molecular motion of the main chain. This may be due to the alternative mechanism of dehydrochlorination in the thermal and radiation decomposition. The amount of head-to-head linkage of poly(vinyl chloride) samples prepared with various catalysts is dependent on polymerization temperature rather than the kinds of catalyst. Commercial poly(vinyl chloride) has 6-7 head-to-head linkages per 1000 monomeric units.
    Additional Material: 9 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 12 (1974), S. 1653-1669 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-resolution proton magnetic resonance (PMR) spectroscopy was used to determine the chlorine distribution of chlorinated polypropylenes in 1,1,2,2,-tetrachloroethane solution and suspension (5-25 wt % chlorine). The determination is based on measuring the relative amounts of methyl and methylene groups which are α, β, and γ to chlorinecontaining groups in chlorinated polypropylenes. The results obtained from the 100 MHz and 220 MHz PMR spectrometers were compared with the theoretical predictions provided by Frendsdorff and Ekiner, based on the statistics of substitution polymers. Furthermore, the PMR data were correlated with infrared and differential scanning calorimetry data to obtain the structural and crystalline properties. The comparison showed that the suspension-chlorinated polypropylenes show structure heterogeneity and thermal instability, whereas polymers chlorinated in solution with gaseous chlorine show a random chlorine distribution and thermal stability compared with the former.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 28 (1983), S. 2867-2880 
    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 morphology and dynamic mechanical properties of the composite materials [P(St-DVB)/PVC systems], prepared by copolymerization of styrene and divinylbenzene in the presence of fine PVC powder, were studied by electron microscopy and the dynamic mechanical test. The composite material (PSt/PVC composite), prepared by the polymerization of styrene in the presence of fine PVC powder, contains grafting polystyrene (PSt) onto PVC, which improves the compatibility of PSt and PVC. This result also suggests the formation of the graft copolymer of styrene-divinylbenzene onto PVC in the P(St-DVB)/PVC systems. Electron microscopy and the dynamic mechanical test indicate that P(St-DVB)/PVC systems have the two-phase nature with a styrene-divinylbenzene copolymer as the continuous phase [P(St-DVB) phase] and a PSt/PVC composite as the dispersed phase (PSt-PVC phase), in which PSt penetrates into the PVC domain. The domain size of the dispersed phase is 0.5-2μ. The crosslinking density of the P(St-DVB) continuous phase is larger than that estimated from the recipe. One of the reasons for this is ascribed to the difference of the diffusion constants of styrene and divinylbenzene into the PVC particles on the paste formation and polymerization process.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 6
    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: Effect of polymerization temperature on the phase-separated structure of the composite materials [P(St-DVB)/PVC systems] prepared by copolymerization of styrene (St) and divinylbenzene (DVB) in the presence of fine poly(vinyl chloride) (PVC) powder was studied by electron microscopy and dynamic mechanical test. P(St-DVB)/PVC systems have the two-phase nature with a styrene-divinylbenzene copolymer as the continuous phase [P(St-DVB) phase) and a PSt/PVC composite as the dispersed phase (PSt-PVC phase), in which PSt penetrates into the PVC domain. The crosslinking density of the P(St-DVB) phase is larger than that estimated from the recipe in the feed, suggesting that there exists a difference of the diffusion constants of styrene and divinylbenzene into the PVC particles on the paste formation and the polymerization process. The changes of the phase-separated structure of P(St-DVB)/PVC systems polymerized at various temperatures are also explained on the basis of the difference between the diffusion behavior of styrene and that of divinylbenzene into fine PVC particles at these temperatures.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 29 (1984), S. 75-87 
    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: Annealing of polypropylene and blends of polypropylene and poly(ethylene-co-propylene) was studied. The structural and physical properties were determined from thermal, mechanical, physicochemical, and spectral investigations. The particular emphasis was on the characteristics of structure and thermal properties of relatively amorphous components segregated from the crystalline region by annealing. Annealing of polypropylene induced an increase in crystallinity resulting in a decrease in impact strength. In contrast, by annealing a blend of polypropylene and poly(ethylene-co-propylene), the impact strength and rigidity were significantly improved with an increase in annealing temperature. The effect of annealing in a binary system was ascribed to the formation of a thicker transitional layer at the interface of the two polymers owing to the increased mobility of amorphous polymer segments. The results of tensile impact strength and brittle temperature were correlated with a deformational mechanism involving the crazing of the matrix.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 8
    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 effect of annealing on the impact strength of PP/poly(ethylene-co-propylene) (PEP) and PP/PEP/PE blends was studied with regard to the structure of PEP and the polyethylene crystallinity. The tensile impact strength of annealed blends was remarkably affected by the PEP structure such as molecular weight and comonomer composition and the annealing temperature, while the brittle temperature was scarcely affected. For the PP/PEP/PE blends, annealing at temperatures above the melting point of PE lowers the tensile impact strength in a similar manner as the PP/crystalline PEP blend. These phenomena were explained on the basis of the deformation mechanism presented in the previous article, that is, a thicker interfacial layer of PP and PEP forms by means of annealing to increase the energy needed to deform the interface. By using a scanning electron microscope, the transition layer was observed at the interface between amorphous PEP and PE in the PP/amorphous PEP/PE blend after etching with nitric acid. The formation of a thicker transition layer between amorphous PEP and PE and a sizeable increase in PE particle size by annealing was observed. The phenomena should be correlated with the impact sensitivity, especially tensile impact strength, in the PP/crystalline PEP and PP/amorphous PEP/PE blends. A reasonable explanation of the microstructure in PP/PEP blends has been developed in terms of comonomer composition and melting property of PEP.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 18 (1974), S. 3205-3217 
    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: PVC samples with different syndiotacticities were degraded at temperatures in the range of 10° to 115°C by UV radiation. The average length of polyenes increases with increase in syndiotacticity of PVC. It was found that by comparison with the long tactic sequences, on the basis of Bernoullian statistics, the propagation reaction of the polyenes at room temperature is terminated when there are more than three racemic dyads in the tactic sequences. At room temperature, the deformation of about 1.3 Å of the PVC main chain takes place, and at temperatures above the glass transition temperature the propagation rate of the polyenes is competitive with the relaxation time between the (tt) and the (tg) conformations.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 53 (1994), S. 255-255 
    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
    Type of Medium: Electronic Resource
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