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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    ISSN: 0449-2986
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0449-2986
    Keywords: Chemistry ; 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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  • 3
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization kinetics in water of acrylylglycinamide (AG) initiated by K2S2O8 was studied over the temperature range 40.0 to 60.0°C. Monomer concentration was varied from 7.8 × 10-3 to 31.2 × 10-3M and catalyst from 1.85 × to 11.10 × 10-5M. The rate expression is -d[M]/dt = Rp, = k1.22[K2S2O8]0.5[M]1.22, and the overall empirical rate constant, k1.22 = 1.14 × 1011e-15,800/RT 1.0.72 mole-0.72 min-1. To explain the dependence on monomer, a kinetic scheme which includes a bimolecular reaction (k2) between monomer and initiator is suggested. The simplified expression which describes the initial rate of polymerization is: -d[M]/dt = Rp, = k4(2[I]/k5)1/2[M](k1 + k2[M])1/2, where k1, k2, k4 and k5 are rate constants for S2O8 = decomposition, a bimolecular reaction between monomer and initiator, propagation, and termination, respectively. Individual bimolecular rate constants are expressed in liter/mole-min. The equation predicts a dependence on monomer concentration between 1.0 and 1.5 with 1.5 being approached a t high monomer concentrations. Plots of RP2/[M]2 versus [M] are linear, as predicted by the postulated reaction route and values for k2 and k4/k51/2 were obtained from the slopes and intercepts of these plots. The temperature dependence of the bimolecular monomer-initiator reaction is k2 = 5.19 × 1021e-36,000/RT. Instead of the usual behavior, the k4/k51/2 ratio was found to decrease with temperature and the difference of activation energies, (E4 - E5/2), is -1.50 kcal. The temperature dependence of the propagation to square root of the termination rate constant ratio is k4/k51/2 = 6.16e1500/RT. These rather unusual results may be related to the ability of AG polymers in water to form thermally reversible gels; even above the gel melting points, the polymers are considerably aggregated in solution. This would tend to make the bimolecular termination reaction more temperature dependent and also account for the high values (59-69) for the k4/k51/2 ratios. For similar temperatures, the overall rate constants for AG are approximately four times those for acrylamide.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Depending on their method of preparation, polyvinylamides can have nitrogen contents which vary from the theoretical value to considerably lower values. Cyanamer P-250, a polyacrylamide, manufactured by American Cyanamid Corporation, had a nitrogen content of 17.67% compared to the theoretical value of 19.7%. A polyacrylamide prepared in dioxane at 60°C and initiated by benzoyl peroxide, had a nitrogen content of only 15.5%. These low values are ascribed to loss of ammonia via intramolecular imide formation. We have found that when the intramolecular imidization reaction in poly acrylamide and in polymethacrylamide is driven to completion by heating the polymers in dilute solution, very close to 33% of the amide groups remain unreacted. Thus, unlike poly(methyl vinyl ketone) and poly(vinyl chloride), the poly-vinylamides do not obey Flory's statistical calculation for the random reaction of 1,3 groups in a head-to-tail polymer which predicts isolation of only 13.53% of the vinyl residues. Of the various possible explanations, the hypothesis of larger ring formation seems the most plausible, since specific interactions have been shown to exist between widely spaced amide groups in low molecular weight diamides. The infrared spectra of polyacrylimide and polymethacrylimide are presented and compared with those of the corresponding polyvinylamides. When the nitrogen content of polyacrylamide falls to the 14.9-15.4% N range due to imide formation, the polymer becomes water-insoluble. Because imidization stiffens the polymer chain and introduces weakly acidic groups, the imide content of a polyvinylamide should affect its compatibility with other polymeric systems.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Substitution of several mole per cent of the hydroxyl groups of poly(vinyl alcohol) by fluorine results in marked changes in polymer properties. These fluoro poly(vinyl alcohols) (PVAF) form thermally reversible gels in water at low polymer concentrations. In solution, a helical conformation or a random coil containing helical sequences is more in accord with the experimental observations than the random coil structure of poly(vinyl alcohol). This helical hypothesis is supported by high heats of crosslinking of the aqueous thermally reversible gels, the difficult solubility of PVAF in H2O, the insolubility of the PVAF-iodine complex under conditions where the PVA-iodine complex remains soluble, the temperature-independent high value for the Huggins k ′ slope constant, the greater stability of the PVAF-iodine complex, the shear dependence of the solution viscosity and our inability to form thermally reversible gels by the introduction of fluorine into other water-soluble polymers which are capable of hydrogen bond formation. Infrared dichroism and deuteration measurements do not differentiate between PVA and PVAF. If this conclusion is correct, PVAF is the first vinyl polymer of which we are aware that maintains a helical conformation in solution.
    Additional Material: 9 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 16 (1972), S. 2709-2713 
    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
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When interpreted by network theory, equilibrium swelling measurements on poly-(vinyl chloride) (PVC) film in dioxane and moduli measurements on the equilibrium swelled films yield values for the approximate molecular weight between thermally reversible crosslinks and for the number of these crosslinks per polymer chain. These values are in reasonable agreement with the thermodynamic analysis of PVC-dioxane gels by Takahashi, Nakamura, and Kagawa and with the premise that three-dimensional network formation in these gels occurs by crystallization of a very limited number of syndiotactic sequences per chain having a sequence length of between 8 and 10. Failure to observe fusion endotherms by DTA on PVC-dibutyl phthalate gels supports the view that PVC gels have a low crystalline crosslink density and a low heat of crosslinking. The heat of crosslinking obtained by the method of Eldridge and Ferry shows only moderate agreement with expectations based on the heat of fusion of PVC and the number of repeating units per PVC chain passing through a crystalline crosslink in a PVC-dioxane gel.
    Additional Material: 1 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Certain copolymers of maleimide and N-substituted maleimides yield brilliant colors when treated with sufficiently strong basic reagents under nonhydrolytic conditions. For color generation, the copolymer must be capable of HX elimination. The chromophores which account for color probably result from the ionization of acidic protons in structures involving one or more double bonds conjugated with imide carbonyl. The analogy to the color reactions of aconitylanil is pointed out. Spectra covering the range of 330-700 mμ are presented for a number of copolymer-amine color-generating systems. The colors produced in base with radical-initiated polymaleimide and imidazole-initiated poly-N-alkylmaleimides as well as the absence of color with anionic polymaleimide and radical poly-N-alkylmaleimides are discussed in light of what is known about their polymerization kinetics and mechanisms. Corresponding maleic anhydride copolymer systems are mentioned.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Low conversion, low molecular weight homopolymers of α-trifluoromethyl vinyl acetate have been obtained by pyridine initiation and also by employing very large amounts of benzoyl peroxide. Since allylic hydrogens are not present, it appears that the limiting factor in the polymerization of isopropenyl esters is a slow rate of chain growth rather than degradative chain transfer. Copolymerization of the fluoromonomer (M2) with vinyl acetate (M1) yields values of r1 = 0.25 and r2 = 0.20, and for the fluoromonomer values of 0.069 and 1.51, respectively, for Q and e. Whereas ultraviolet initiation of equimolar mixtures of α-trifluoromethyl vinyl acetate and vinyl acetate yields low molecular weight copolymers, diisopropyl percarbonate-initiated room temperature bulk copolymerizations and emulsion copolymerizations yield polymers of high DP. Differential thermal analysis of an equimolar copolymer of vinyl acetate and the fluoromonomer surprisingly yields a sharp endotherm reminiscent of crystalline polymers. The unhydrolyzed copolymers in acetone and the alcoholyzed copolymers in 0.1N alkali exhibit Huggins k′ values of 0.3-0.4. Like ordinary poly(vinyl alcohol), the polyfluoroalcohols lose viscosity in dilute alkali due to retrograde aldol condensations. The solubilities of the polyfluoroalcohols, together with their thermal behavior, NMR spectrum, polarized infrared spectrum, refractive index, abilities to form visible polarizers, and other properties are also described.
    Additional Material: 4 Ill.
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  • 10
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Forming and conditioning thermally reversible aqueous gels of polyacrylyglycinamide (PAG) at various temperatures has little effect on either the melting point (Tm) of the gels or the heat of crosslinking (ΔHc) except at temperatures where partial hydrolysis can occur. This is added evidence that unlike with gelatin, crystallite formation does not play a role in gel formation. For unfractioned PAG, the linear relationship between the logarithm of molecular weight and 1/Tm predicted and observed for gelatin gels, does not hold. With mixed gelatin-PAG gels, a gelatin/PAG ratio of ≥4 completely inhibits the formation of a PAG gel network. At lower gelatin/PAG ratios, the PAG network forms, and if gelatin is considered as an inert diluent, normal values for the melting points and ΔHc for PAG gels are observed. At a gelatin/PAG ratio of 4, the presence of PAG reduces the ΔHc for the gelatin gel by inhibiting the formation of as large or as ordered crystallite crosslinks. To reconcile the problem of aggregation preceding gelation one can assume that M̄w of an aggregate is a linear function of C2. If this is done, the same relationship which normally relates C with Tm is obtained. The equilibrium swelling of PAG films in water at 25°C is markedly molecular weight-de-pendent and can vary from below 5 to about 40 wt-% polymer at equilibrium. It has been found that long-term dark storage of dry samples of PAG under ambient temperature conditions results in pronounced decreases in the intrinsic viscosities of their aqueous solutions. It is speculated that this results from weak links, perhaps peroxy, in the polymer backbone. The possible relationship of this phenomenon to the slow stage of the viscosity deterioration of aqueous polyacrylamide solutions is pointed out. The higher viscosity of low DP PAG in 2M NaCNS compared to H2O and the larger percentage increse of [η] with increasing temperature in the latter, verify the greater solvent power of 2M aqueous thiocyanate for PAG. At a concentration level of 3%, aqueous PAG solutions are almost Newtonian whereas at higher concentrations (5%), the viscosity decreases appreciably with increasing rates of shear. The copolymerization of AG with isopropylacrylamide has been studied and the somewhat unusual results discussed. Copolymers containing an AG mole fraction greater than 0.40 do not exhibit a cloud point up to 100°C. If the isopropylacrylamide mole fraction approaches 0.60, the solutions do not gel down to 0°C. This ability to prepare copolymers over a narrow composition range that neither gel or undergo phase separation in the temperature range 0-100°C is probably related to the random distribution of monomer units in the copolymer backbone.
    Additional Material: 3 Ill.
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