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  • 1
    Electronic Resource
    Electronic Resource
    Polymerizable Derivatives of Long-Chain Fatty Acids - Vinyl Stearate and Copolymerization of Vinyl Chloride with Other Vinyl Esthers (1955)
    s.l. : American Chemical Society
    Industrial & engineering chemistry 47 (1955), S. 472-480 
    Details
    ISSN: 1520-5045
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/ie50543a042
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  • 2
    Electronic Resource
    Electronic Resource
    Polymerizable derivatives of long-chain alcohols. II. Reactivity ratios for the copolymerization of some alkyl acrylatesFor part I of this series, see ref. 1.Paper presented at the Third Delaware Valley Regional Meeting, American Chemical Society, February 25, 1960. (1960)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 4 (1960), S. 203-206 
    Details
    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: Monomer reactivity ratios were determined for the copolymerization of some alkyl acrylate esters and, respectively, acrylonitrile and vinylidene chloride. For acrylonitrile (M1), the values found were: for butyl acrylate, r1 = 1.52 ± 0.03, r2 = 0.75 ± 0.18; for octyl acrylate, r1 = 1.93 ± 0.08, r2 = 0.83 ± 0.23; for octadecyl acrylate, r1 = 1.74 ± 0.04, r2 = 0.68 ± 0.18. If it is assumed that there is no change in the magnitude of the kinetic constants with chain length, a value for the generalized alkyl acrylate and acrylonitrile may be calculated and r1 = 1.61 ± 0.04, r2 = 0.50 ± 0.19. Values found with vinylidene chloride (M1) were: for butyl acrylate, r1 = 0.88 ± 0.10, r2 = 0.83 ± 0.02; for octyl acrylate, r1 = 0.87 ± 0.02, r2 = 0.70 ± 0.01; for octadecyl acrylate, r1 = 0.91 ± 0.05, r2 = 1.01 ± 0.01. For the generalized alkyl acrylate, the calculated values were r1 = 0.88 ± 0.04, r2 = 0.84 ± 0.01.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1960.070041111
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  • 3
    Electronic Resource
    Electronic Resource
    Monomer reactivity ratios of N-octadecylacrylamide and N-allylstearamide (1964)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 8 (1964), S. 527-532 
    Details
    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 monomer reactivity ratios and the corresponding copolymerization parameters for the copolymerization of N-octadecylacrylamide (M1) and several monomers in tert-butyl alcohol at 60 ± 0.1°C. were determined and were: with acrylonitrile, r1 = 1.44 ± 0.019, r2 = 1.10 ± 0.035; Q1 = 0.60, e1 = 1.20; with vinylidene chloride, r1 = 1.37 ± 0.008, r2 = 0.438 ± 0.008; Q1 = 0.65, e1 = 1.08; with vinyl acetate, r1 = 6.11 ± 0.045, r2 = 0.027 ± 0.009; Q1 = 0.72, e1 = 1.12. The mean copolymerization parameters, therefore, were Q1 = 0.66, e1 = 1.13. The reactivity ratios and the corresponding copolymerization parameters for the copolymerization of N-ally lstearamide (M1) and several monomers, polymerized in tert-butyl alcohol at 80 ± 0.1°C. (except for vinyl acetate, polymerized in bulk at 70 ± 0.1°C.) were determined and were: with acrylonitrile, r1 = 0.118 ± 0.084, r2 = 3.61 ± 0.087; Q1 = 0.058; e1 = 0.21; with vinylidene chloride, r1 = 0 ± 0.136, r2 = 5.23 ± 0.067; Q1 = 0.028, e1 = -0.80; with vinyl acetate, r1 = 0.0532 ± 0.012, r2 = 0.740 ± 0.087; Q1 = 0.043, e1 = -1.18. The mean copolymerization parameters for N-allylstearamide were, therefore, Q1 = 0.043, e1 = -0.59.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1964.070080136
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  • 4
    Electronic Resource
    Electronic Resource
    The kinetics of the heterogeneous hydrolysis of poly(vinyl formate) and of poly(vinyl formate-co-stearate)This paper was presented at the Fall Meeting of the American Chemical Society, New York, N. Y., September 13, 1957. It is Part XII in the series “Polymerizable Derivatives of Long-Chain Fatty Acids.” Paper XI is ref. 1. (1958)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 32 (1958), S. 47-56 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate of hydrolysis of formate and stearate segments from poly(vinyl formate) and from poly(vinyl formate-co-stearate) suspended in dilute aqueous hydrochloric acid was studied. Evidence was presented to show that the hydrolysis follows pseudo-first-order kinetics. The Arrhenius constants and the entropies and free energies of activation for the hydrolysis of formate and stearate groups from copolymers containing 0, 3, 5, and 10 mole-% vinyl stearate were calculated from the partially reduced reaction rate constants at three temperatures. For the hydrolysis of formate segments, ΔS
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1958.1203212404
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  • 5
    Electronic Resource
    Electronic Resource
    Allyl stearate copolymers and terpolymers: Thermal, mechanical, and solution properties of polymers incorporating vinyl chloride (1973)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 1475-1504 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(allyl stearate) and selected copolymers and terpolymers modified by allyl stearate were investigated in this work. The systems selected and studied over a wide range of composition, included copolymers with vinyl stearate and with vinyl chloride, and terpolymers containing vinyl chloride and allyl stearate, modified further by vinyl stearate or vinyl acetate. Copolymers of allyl stearate and vinyl stearate were studied incrementally across the range of composition. In the ester copolymers the effect of degradative chain transfer on crystallization and solution properties was studied. A relation was obtained between intrinsic viscosities and number-average molecular weights; a shift in molecular weight distribution with increase in allyl component was demonstrated. The crystallinity contributed by the side chains was shown to be characterized by isomorphic replacement regardless of molecular weight. Mechanical properties of internally plasticized copolymers of allyl stearate and vinyl chloride, in a limited composition range, were compared with corresponding data for copolymers of vinyl stearate and vinyl chloride. While molecular weight reduction of the allylic copolymers exceeded that for the vinyl ester system, the effect, in the useful plasticization composition range, was not enough to grossly affect ultimate properties. The glass transitions of the hypothetical amorphous homopolymers of both fatty esters were estimated to be the same. Because this Tg was low (ca. -110°C), only relatively small mole fractions of allyl stearate were needed for effective plasticization. Isochronal temperature-composition diagrams also showed both systems to be essentially identical, but marked differences were found for diluent mixtures incorporating di-2-ethylhexyl phthalate (DOP). An empirical equation, previously derived, adequately predicted the decline in degree of polymerization with increase in allyl stearate between the limits of the respective homopolymers for all copolymers studied. Terpolymers followed the trends of the copolymers and offered no special property advantage.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1973.170110703
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  • 6
    Electronic Resource
    Electronic Resource
    Terpolymers. II. Mechanical properties and transition temperatures of terpolymers of vinyl stearate, vinyl acetate, and vinyl chloride (1973)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 17 (1973), S. 1545-1568 
    Details
    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: Vinyl stearate was studied as a major internal plasticizer in terpolymers containing vinyl acetate and vinyl chloride. The terpolymers were prepared by systematically replacing vinyl acetate by close increments of vinyl stearate starting with combinations of vinyl acetate and vinyl chloride, in increments, over all compositions. For comparison of properties, a complete range of copolymers of vinyl stearate and vinyl chloride, as well as mixtures of poly(vinyl chloride) and di-2-ethylhexyl phthalate (DOP) were also made. The external plasticizer was more efficient in reducing the glass temperature than was vinyl stearate. The decline in Tg with weight fraction of plasticizer was linear for the copolymers and terpolymers but concave downward with the liquid diluent. The linear decline was shown to involve mere additivity of the free volume contributed by each side-chain methylene (or methyl) group in both vinyl esters to reducing Tg. The mechanism of the diluent system was more complex. However, the magnitude of the reduction of tensile modulus at a given weight fraction of DOP could be equaled or exceeded by the same amount of vinyl stearate, by increasing the vinyl acetate content of the base copolymer to 40 mole-% or more. Unfortunately, the ultimate strengths and elongations of internally plasticized systems were reduced more than those of the mixtures at comparable compositions. Vinyl stearate was found to markedly retard photolytic degradation compared to both vinyl acetate and the external plasticizer in unstabilized samples having nearly the same thermal treatment. The effect was greater than could be ascribed to dilution by the long alkyl group. The production of a stearoyl radical more stable than the radicals initiating dehydrochlorination is suggested as a possible mechanism.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1973.070170519
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  • 7
    Electronic Resource
    Electronic Resource
    Terpolymers. I. The mechanical properties and transition temperatures of terpolymers of n-octadecyl acrylate, ethyl acrylate, and acrylonitrile (1972)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 16 (1972), S. 3017-3034 
    Details
    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: Earlier work revealed that the internal plasticization of polyacrylonitrile by the higher n-alkyl acrylates or N-n-alkylacrylamides yielded only brittle copolymers. This difficulty was circumvented in the present work by starting with copolymers of acrylonitrile and ethyl acrylate, over the range of compositions, and further modifying these by incrementally displacing the ethyl acrylate in each recipe by n-octadecyl acrylate through terpolymerization. In this way, the stepwise small reduction in Tg for the base ethyl acrylate-acrylonitrile copolymers was greatly increased for each of the terpolymers. Compositions were obtained ranging from glassy, brittle terpolymers, with glass transitions above room temperature, to soft plasticized polymers having sufficient polar networks retained from the nitrile to confer useful properties. The decline in the glass temperature was shown to be dependent on the free volume conferred by the side-chain methylene groups of each acrylate ester. In contrast, the decline in tensile and flexural strengths and moduli for the terpolymers having glass transitions above room temperature was produced entirely by the presence of the methylene groups of the 18-carbon ester. The glass transition region corresponded to room temperature when the acrylonitrile content of the base copolymer had been reduced to 50 mole-%. Terpolymers of this nitrile content and lower had the low moduli and large elongations of plasticized compositions. An equation was developed which correlated empirically the glass transitions and the mechanical properties with the weight fraction of the acrylate esters for the glassy terpolymers.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1972.070161125
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  • 8
    Electronic Resource
    Electronic Resource
    Copolymer composition as a function of molecular weight and the effect of conversion on this relationship (1976)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 20 (1976), S. 581-589 
    Details
    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 copolymer compositions as a function of molecular weight for three poly(styrene-co-vinyl stearate) copolymers of widely varying conversion were determined. A combined gel permeation chromatography-infrared spectroscopy method was used. Theoretical changes in copolymer composition were calculated using reactivity ratios. Comparison of the calculated and observed changes in copolymer composition as a function of molecular weight showed qualitative agreement. However, the observed changes in composition were significantly larger than those calculated.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1976.070200302
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  • 9
    Electronic Resource
    Electronic Resource
    Polyblends. I. Mechanical properties of polyblends of butadiene-acrylonitrile elastomers and copolymers of vinyl stearate and vinyl chloride (1976)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 20 (1976), S. 2715-2735 
    Details
    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: Several nitrile rubber elastomers were polyblended, across the composition range, with selected polymeric compositions containing vinyl chloride. The compositions incorporated were (a) bulk poly(vinyl chloride) (PVC); (b) copolymers of vinyl stearate and vinyl chloride containing, respectively, 0.21, 0.36, and 0.47 weight fraction of the vinyl ester; and (c) mixtures containing the same weight fractions of di-2-ethylhexyl phthalate (DOP) with PVC. Mechanical, viscoelastic, optical, and volatility properties were studied on all blends in this first paper. To accurately compare the mechanical properties of polyblends of different systems, a criterion of mechanical equivalence was taken as the observance of similar stresses at break for compositions selected to have identical 100% moduli. Optimum mechanical equivalence, therefore, occurred at the largest ratios of 100% modulus to break stress for all systems compared. Optimum mechanical property equivalence was observed for NBR blends with PVC and for similar blends of both internally and externally plasticized systems containing 0.21 weight fraction of plasticizer. However, considerably more nitrile rubber was needed for PVC blends to acquire the properties of the plasticized systems. Mechanical equivalence was observed, but was not optimum for systems having more plasticizer because tensile strengths were lower. Polyblending with NBR improved the toughness and low-temperature properties of starting vinyl stearate copolymers. Improved toughness was indicated by the expansion of areas under stress-strain curves. Refractive index matching appeared to explain the transparency of the best films and their relative freedom from haze. On heating at 85°C, poly(vinyl chloride) and the copolymer polyblends suffered no volatility loss. Volatility of DOP from the blends was 1.5 times greater than for PVC-DOP mixtures. Because modulus-temperature curves and mechanical Tg values of the filler component shifted with composition, the mechanical behavior of these blends was in harmony with an accepted standard of interdomain compatibility.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1976.070201009
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  • 10
    Electronic Resource
    Electronic Resource
    Viscosity index. II. Correlation with rheological theories of data for blends containing n-octadecyl acrylate (1978)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 22 (1978), S. 1529-1545 
    Details
    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 viscosities obtained for the copolymer blends of the previous paper were correlated with several relations derived to describe more fundamental behavior of polymer-diluent mixtures at both infinite dilution and finite concentrations. Only the most efficient blends showed any appreciable expansion of hydrodynamic volume as temperature increased from 25° to 98.9°C. However, in spite of restricted coil expansion, all of the copolymers were effective viscosity index improvers. The mechanism of viscosity index improvement in multigrade oils was shown to be largely regulated by the translational friction generated by the polymer coils. This greatly increased the apparent negative entropy change of the blends; the enthalpy change characteristic of the base oil was retained. Efficiency resulted from coil contraction at low temperatures, but enthalpy decrease below that of the base oil was small. In contrast, viscosity index improvement using higher molecular weight solvents was accompanied by large enthalpy increases. Thus, undesirably high viscosities resulted at low temperatures. The structure of these blends was uncomplicated by polymer chain entanglements; unit values of the Fox-Flory exponent were obtained for the relation between viscosity and weight-average carbon backbone length. The lack of evidence for coil compression in the thermodynamically miscible blends above a critical reduced concentration was anomalous. Intermingling of side chains and their interaction may have overcome normal excluded volume effects.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1978.070220607
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